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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is the driving force for the classic versions of

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇ The Management of Distinctions: ▇▇▇▇▇ ▇▇▇▇▇▇ on ▇▇▇▇’s Political Theology Abstract: Is it justified to depict ▇▇▇▇’s letters as an example of political theology, as ▇▇▇▇▇▇ did in his Heidelberg lectures on Romans in 1987? The justification lies in the fact that as a founder of non-Jewish “Christian” communities ▇▇▇▇ has to act as a politician. But he was a politician of a special kind, one who pretended to be called by God (or ▇▇▇▇▇▇) to be a spiritual leader with the task to establish a new people. To clarify this point, the author focuses on the way ▇▇▇▇ manages distinctions (between Jews and non-Jews, between followers of ▇▇▇▇▇▇ and those who stick to the world as it is, and so on) and on the impact of his theology on these distinctions. This impact relates to the intensification of distinctions. The extreme consequence of this is the distinction between friend and enemy. This possible consequence connects ▇▇▇▇▇▇’s reflections with ▇▇▇▇ ▇▇▇▇▇▇▇’▇ use of the term “political theology.” It turns out that ▇▇▇▇’s political theology cannot be taken in the sense Roman intellectuals already used the term (state cult), but points in another direction, a “Messianic” subversion of “the state.” The author ends his paper with a comment on what ▇▇▇▇▇▇ called the “Gnostic temptation” hidden in this reversed political theology. Some people do have a life after they die. Unfortunately, they do not have any- thing to say about their own fate in this afterlife. Their fate and identity is in the hands of those that tell and retell stories about those that walked the earth and left traces of their existence and above all, their actions. These stories have a life of their own. Of course, those that tell these stories or write them down are often sincere in their attempt to do justice to the person they talk about. Nevertheless, even this kind of stories differ from each other and may even become quite con- flicting. After this introduction, it must be clear that I am not going to talk about ▇▇▇▇, but will give a comment on some of these stories. It is not ▇▇▇▇ but these stories that have shaped our world view. One of these stories is put forward by ▇▇▇▇▇ ▇▇▇▇▇▇ (born in 1923), a philosopher who is as closely connected to non-orthodox Jewish thought as he also is to non-conformist and anti-capitalist movements.¹ The lectures on ▇▇▇▇, delivered shortly before he died in 1987, are a kind of personal testament, but they nevertheless have a significance that goes beyond 1 For a short but elucidating portrait see ▇▇▇▇▇▇, “Reisender in Ideen.” DOI 10.1515/9183110547467-014 252 ▇▇▇▇▇ ▇▇▇▇▇▇▇▇ that.² My aim in this paper is to pick out a single theme from these lectures, one which in my view has not gotten very much attention. This theme is the manage- ment of distinctions in a situation of regime change, a situation that is at hand when one, like ▇▇▇▇, tries to found a community or a people on the basis of a new covenant with God. As ▇▇▇▇▇▇ makes explicit in the second part of his lec- tures (“Effects. ▇▇▇▇ and Modernity: Transfigurations of the Messianic”), ▇▇▇▇’s texts show an ambivalence that is still part of contemporary philosophy because of formulations that could be read in a Gnostic way. For ▇▇▇▇▇▇, ▇▇▇▇ is not the founding father of the Christian Church, but a Jew confronted with a Messiah that tended to break away from the Jewish tradition, but was part of this tradition too. Koenders, The ambivalence of founding new communities of faith in ▇▇▇▇▇▇ P. J. T. is connected to the first attempt, in the second century, to establish an orthodox Christian Church, an attempt greatly inspired by ▇▇▇▇’s interventions. This at- tempt was made by a Gnostic “heretic,” ▇▇▇▇▇▇▇, who was then excluded from the Christian community. This orthodoxy wanted to free itself completely from the Jewish inheritance, and therefore accepted only the Gospels and the letters of ▇▇▇▇ as its foundation. The formula of this break with Israel is the rejection of the Creator-God and the God of the ▇▇▇▇▇’▇ Laws, and the sole affirmation of the Savior-God, the Father of the Messiah. The believers hope for liberation from this evil world, its political and religious order, and its worldly wisdom. If we take away the weird mythology connected to this fundamentally new theo- logical scheme, a mythology that constitutes one variety from the range of Gnos- tic world views, we can register something very familiar to the modern ear. In- deed, what we encounter may suggest that we are here at the birthplace of the very idea of modernity: the endeavor to overcome the past radically, by way of a total rupture, and to move in the direction of a new and better world. ▇▇▇▇▇▇ chose the following title for his lectures: “On the Political Theology of ▇▇▇▇: From Polis to Ecclesia (for advanced students only).”³ The theme of re- gime change is clearly present in this title, as is the reason for the concept of po- litical theology. In this case, a community inspired by a “theology” announcing the appearance of the Messiah (or the Messianic) in history is set against the es- tablished political order. My aim in this text will be to elaborate on the plausi- bility of such a reading of ▇▇▇▇. The first question is: can we read ▇▇▇▇ as a po- litical thinker? The second question is: while it is obvious that ▇▇▇▇ is a theologian (he talks about God), how can we say that his theology is connected 2 Taubes, Die politische Theologie des ▇▇▇▇▇▇. 3 Ibid., 145/117. When quoting from the translation, the second page number refers to the trans- lation and the first one to the original. The Management of Distinctions: ▇▇▇▇▇ ▇▇▇▇▇▇ on ▇▇▇▇’s Political Theology 253 to the political? The third question arises because the concept of political theol- ogy is, at least for Taubes, derived from ▇▇▇▇▇▇▇’▇ famous or notorious essay en- titled “Politische Theologie,” which was published in 1922.⁴ Thus, the question that arises is: how are ▇▇▇▇▇▇’s lectures related to ▇▇▇▇▇▇▇’▇ essay? This question is relevant because of the confrontation they had concerning ▇▇▇▇—a confronta- tion between a German lawyer who became part of the Nazi regime and a Jewish philosopher who sympathized with the 1968 student revolts. Is this reference to ▇▇▇▇▇▇▇ justified if we want to tell the story of ▇▇▇▇?I will show that the confron- tation between ▇▇▇▇▇▇▇ and ▇▇▇▇▇▇ rests on the idea of the intensification of a distinction as the connection between the political and the theological. This point will lead us finally to a short reflection on the “Gnostic temptation” that lies hidden in the problematic. Before elaborating on these questions, let me first summarize the main point. For Taubes, the current meaning of ▇▇▇▇ concerns the fate of the Jews in European history, that is, in Christian history. The revelation of ▇▇▇▇▇▇ can be seen to have the following consequence: Jews become the enemies of God (Rom. 11:25; see also1 Thess. 2:15 – 16). ▇▇▇▇▇▇’s argument with ▇▇▇▇▇▇▇ focused on this theme in ▇▇▇▇. For ▇▇▇▇▇▇▇, all distinctions in the political world finally merge into only one distinction, that between friend and enemy.⁵ So, the phrase “enemies of God” is a genuinely political one. ▇▇▇▇▇▇▇ is the ▇▇▇▇▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇- ▇▇▇▇ who proposed a sharp distinction between the Jews and the followers of ▇▇▇▇▇▇, between the first and the second covenant, between the Creator-God of the Torah and the Savior-God of the New Testament. The revival of Marcionism within liberal currents in Protestantism in the nineteenth and early twentieth century, which claimed that we can do without this authoritarian God of the Old Testament, signifies for Taubes the cultural climate in which anti-Judaism and anti-Semitism could develop.⁶ ▇▇▇▇▇▇’s distrust of liberalism in general has to do with his diagnosis that the liberal cultural climate in Germany did not prevent it to become the site of the Holocaust. Whatever one may think of this impudent assertion, this context makes clear that the core of the problem 4 The third essay in ▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is the driving force for the classic versions ofPolitical Theology.

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is the driving force for the classic versions of

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is the driving force for the classic versions ofArtikel

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k Microbial Ecology (2018) 76:1041–1052 ▇▇▇▇▇://▇▇▇.▇▇▇/10.1007/s00248-018-1183-3 SOIL MICROBIOLOGY Different Recovery Processes of Soil Ammonia Oxidizers from Flooding Disturbance Fei Ye1,2 • ▇▇▇-▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan Ma1 • Huub ▇. ▇. Op den Camp3 • ▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇▇▇▇,5 • Lei Li6 • ▇▇▇▇-▇▇▇* Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the Lv1,2 • ▇▇▇▇▇-▇▇▇▇▇ • , ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and ▇▇▇▇▇ reactions.1 The formation Received: 29 December 2017 / Accepted: 26 March 2018 / Published online: 11 April 2018 Ⓒ Springer Science+Business Media, LLC, part of Springer Nature 2018 Abstract Understanding how microorganisms respond to environmental disturbance is one of the relatively strong phosphine oxide bond key focuses in microbial ecology. Ammonia-oxidizing bacteria (PvOAOB) and archaea (AOA) are responsible for ammonia oxidation which is a crucial step in the nitrogen cycle. Although the physiology, 128 kcal mol−1distribution, and activity of AOA and AOB in soil have been extensively investigated, their recovery from a natural disturbance remains largely unknown. To assess the recovery capacities, including resistance and resilience, of AOA and AOB, soil samples were taken from a reservoir riparian zone which experienced periodically water flooding. The samples were classified into three groups (flooding, recovery, and control) is for a high-throughput sequencing and quantitative PCR analysis. We used a relative quantitative index of both the driving force for resistance (RS) and resilience (RL) to assess the classic versions ofvariation of gene abundance, alpha-diversity, and community composition. The AOA generally demonstrated a better recovery capability after the flooding disturbance compared to AOB. In particular, AOAwere more resilient after the flooding disturbance. Taxa within the AOA and AOB showed different RS and RL values, with the most abundant taxa showing in general the highest RS indices. Soil NH + and Fe2+/Fe3+ were the main variables controlling the key taxa of AOA and AOB and probably influenced the resistance and resilience properties of AOA and AOB communities. The distinct mechanisms of AOA and AOB in main- taining community stability against the flooding disturbance might be linked to the different life-history strategies: the AOA community was more likely to represent r-strategists in contrast to the AOB community following a K-life strategy. Our results indicated that the AOA may play a vital role in ammonia oxidation in a fluctuating habitat and contribute to the stability of riparian ecosystem.

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite thisPUBLISHED ONLINE: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 26 OCTOBER 2015 | DOI: 10.103910.1038/c7ob01510k NNANO.2015.243 Macromolecular crowding creates heterogeneous environments of gene expression in picolitre droplets ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders▇. Maas1, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇▇▇▇▇▇, ▇▇▇▇ ▇. ▇▇▇▇▇ and ▇▇▇▇▇▇reactions.1 The ▇. ▇. Huck1* Understanding the dynamics of complex enzymatic reactions in highly crowded small volumes is crucial for the development of synthetic minimal cells. Compartmentalized biochemical reactions in cell-sized containers exhibit a degree of randomness due to the small number of molecules involved. However, it is unknown how the physical environment contributes to the stochastic nature of multistep enzymatic processes. Here, we present a robust method to quantify gene expression noise in vitro using droplet microfluidics. We study the changes in stochasticity in the cell-free gene expression of two genes compartmentalized within droplets as a function of DNA copy number and macromolecular crowding. We find that decreased diffusion caused by a crowded environment leads to the spontaneous formation of heterogeneous microenvironments of mRNA as local production rates exceed the relatively strong phosphine oxide bond (PvOdiffusion rates of macromolecules. This heterogeneity leads to a higher probability of the molecular machinery staying in the same microenvironment, 128 kcal mol−1) directly increasing the system’s stochasticity. N oise is the driving force for the classic versions ofpresent in all living cells. It has been studied in pro- karyotes and eukaryotes1, as well as stem2,3 and cancer cells4, and cells expressing viruses5. Gene expression is a key

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. ChemINT J TUBERC LUNG DIS 22(9):1088–1094 Q 2018 The Union ▇▇▇▇://▇▇., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇.▇▇▇/10.5588/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent ijtld.17.0827 Computer-assisted chest radiography reading for tuberculosis screening in organophosphorus-catalysed amide bond formation† Daan people living with diabetes mellitus ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇,*† ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ,‡§ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ,* ▇. ▇▇▇▇▇▇▇▇▇▇,* ▇. ▇▇▇▇▇▇,* N. N. M. Soetedjo,¶ ▇. ▇▇▇▇▇▇▇,*† ▇. ▇▇▇▇▇▇▇▇▇,# ▇. ▇▇▇▇▇▇▇▇▇▇,# ▇. ▇. ▇▇▇▇▇▇▇▇,** ▇. ▇▇▇ ▇▇▇▇▇▇,# ▇. ▇▇▇▇▇▇▇▇▇▇▇,*¶ P. C. ▇▇▇▇†† *Infectious Disease Research Centre, and †Department of Biomedical Sciences, Faculty of Medicine Universitas Padjadjaran, Bandung, Indonesia; ‡London School of Hygiene & Tropical Medicine, London, UK; §National and Supranational Reference Laboratory, Research Centre Borstel, Germany; ¶Department of Internal Medicine, Faculty of Medicine Universitas Padjadjaran, ▇▇▇▇▇ ▇▇▇▇▇▇▇ General Hospital, Bandung, Indonesia; #Radboud University Nijmegen Medical Centre, Nijmegen, The Netherlands; **Department of Radiology, Faculty of Medicine Universitas Padjadjaran, ▇▇▇▇▇ * Development ▇▇▇▇▇▇▇ General Hospital, Bandung, Indonesia; ††Centre for International Health, University of catalytic amide bond formation reactions Otago, Dunedin, New Zealand B A C K GR O UND: Diabetes mellitus is a significant risk factor for tuberculosis (TB). We evaluated the perfor- ▇▇▇▇▇ of computer-aided detection for tuberculosis (CAD4TB) in people living with diabetes mellitus (PLWD) in Indonesia. METH O D S: PLWD underwent symptom screening and chest X-ray (CXR); sputum was examined in those with positive symptoms and/or CXR. Digital CXRs were scored using CAD4TB and analysed retrospectively using clinical and microbiological diagnosis as a reference. The area under the receiver operator curve (AUC) of CAD4TB scores was determined, and an optimal threshold score established. Agreement between CAD4TB and the radiologist’s reading was determined. R ESU LTS: Among 34ł included PLWD, seven (2.0%) had microbiologically confirmed and two (0.ł%) had clinically diagnosed TB. The highest agreement of CAD4TB with radiologist reading was achieved using a threshold score of 70 (j ¼ 0.41, P , 0.001). The AUC for CAD4TB was 0.89 (95%CI 0.73–1.00). A threshold score of ł5 for CAD4TB resulted in a sensitivity, specificity, positive predictive value and negative pre- dictive value of respectively 88.9% (95%CI 51.8–99.7), 88.5% (95%CI 84.ł–91.7), 17.0% (95%CI 7.ł–30.8) and 99.ł% (95%CI 98.2–100). With this threshold, 48 (13.9%) individuals needed microbiological examina- tion and no microbiologically confirmed cases were missed. C O N C L U SI O N S: CAD4TB has potential as a triage tool for TB screening in PLWD, thereby significantly reducing the need for microbiological examination. KEY W O R D S : CAD4TB v 5; triage tool; Indonesia IT HAS LONG BEEN RECOGNISED that people living with diabetes mellitus (PLWD) are dispropor- tionally affected by tuberculosis (TB).1 Compared with people without diabetes mellitus (DM), PLWD have an increased risk of Mycobacterium tuberculosis infection,2 at least a two-fold higher risk of develop- ing TB,3–6 and experience worse outcomes once diagnosed with TB.7 In 2015, there were approxi- mately 10.4 million new TB cases and 1.4 million deaths caused by TB worldwide.8 The six countries with the highest number of incident TB cases in 2015 were India, Indonesia, China, Nigeria, Pakistan and South Africa. Of these, Indonesia accounted for 10% of global cases, with an estimated 1 020 000 new TB cases in 2015.8 Approximately 9.5% of all TB cases in Indonesia in 2010 were attributable to DM, and this percentage is estimated to increase to 14% by 2030.9 The International Diabetes Federation pre- dicts that global DM prevalence will increase from 7% (415 million) in 2015 to 10% (642 million) by 2040.10,11 Indonesia has the seventh highest DM prevalence rate worldwide, with 10 million (6.2%) PLWD in 2015; this prevalence has been estimated to increase to 16.2 million people by 2040.10 To address the subject double burden of TB and DM and the intensive investi- gations absence of international guidelines, the World Health Organization (WHO) and the International Union Against Tuberculosis and Lung Disease devel- oped a collaborative framework setting out the principles for bidirectional screening and integrated management.12 Studies on how best to screen for TB in PLWD have mainly focused on symptom screening and chest radiography (CXR).13,14 Novel technolo- ▇▇▇▇ such as the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane)Xpertw MTB/RIF assay (Cepheid, a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the Correspondence to: Raspati C ▇▇▇▇▇▇▇▇▇▇▇▇▇▇, Faculty of Medicine, Universitas Padjadjaran, Bandung, Indonesia. e-mail: ▇.▇.▇▇▇▇▇▇▇▇▇▇▇▇▇▇@▇▇▇▇▇.▇▇.▇▇ Sunnyvale, CA, USA) and computer-assisted radiog- raphy have not been employed.15,16 Computer-aided detection for TB (CAD4TB) is a software system developed for the automated detec- tion of pulmonary TB (PTB).17 It quantifies various imaging characteristics of a CXR to compute a score from 0 to 100: higher scores indicate more abnor- malities and greater likelihood of PTB.17 Initial studies of CAD4TB have shown encouraging perfor- ▇▇▇▇▇ characteristics,18–25 although it is clear that pre-specified threshold scores are needed for different patient groups and settings.26 We conducted the first performance evaluation of CAD4TB in Indonesia and the first among PLWD, focusing on CAD4TB as a possible triage test in the screening algorithm of TB among PLWD. METHODS From December 2013 to February 2015, PLWD aged 718 years accessing DM care were offered TB screening and were recruited consecutively from the endocrine out-patient clinic at Hasan Sadikin General Hospital, Bandung, Indonesia, and 25 of 73 commu- nity health centres (CHC) in Bandung. The 25 CHCs were selected because they were 1) among the CHCs with the highest number of TB cases, and 2) had a chronic disease prevention programme in which PLWD and hypertension received routine examina- tions, medications and education. Participants who underwent digital CXR with available Digital Imag- ing and Communication in Medicine (DICOM) files were included in this study. A questionnaire was administered to collect sociode- mographic and clinical data. Clinical data included symptoms suggestive of TB and past medical history of TB and DM. Human immunodeficiency virus (HIV) testing was not routinely performed, as HIV prevalence in adults aged 15–49 years in Indonesia is 0.4% and PLWD are not considered a high HIV risk population.27 CXRs were obtained from all partici- pants and were read within 48 h by a specialist radiologist (certified by the Indonesian board) and classified as: normal, possible TB, probable TB, and abnormal, non-TB-related. All PLWD with cough .2 weeks or CXR classified as possible or probable TB were asked to submit two (spot and morning) sputum samples. Sputum samples were investigated using ▇▇▇▇▇-▇▇▇▇▇▇▇ staining and ▇▇▇▇▇ reactions.1 liquid culture for M. tuberculosis using the microscopic observation drug susceptibility assay. All results were entered into a database using Research Electronic Data Capture (REDCap; Vanderbilt University, Nashville, TN, USA).28 Digital CXRs available were scored retro- spectively using CAD4TB v5 (Delft Imaging Systems, Veenendaal, The formation Netherlands), with scores from 0 to 100 (0 being completely normal and 100 very suggestive of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is the driving force for the classic versions ofTB).

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by This article was downloaded by: [Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite thisUniversiteit Nijmegen] On: Org. Biomol. Chem.24 October 2013, 2017At: 05:37 Publisher: Routledge Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇-▇▇ ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇▇▇ ▇▇▇, ▇▇ Publication details, including instructions for authors and subscription information: ▇▇▇▇://▇▇▇.▇▇▇▇▇▇▇▇▇▇▇.▇▇▇/loi/rjpp20 ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ & ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇▇ Published online: 19 Sep 2011. To cite this article: ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ & ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇▇ (2012) Member State interest articulation in the Commission phase. Institutional pre-conditions for influencing ‘Brussels’, Journal of European Public Policy, 19:2, 179-197, DOI: 10.1080/13501763.2011.609716 To link to this article: ▇▇▇▇://▇▇.▇▇▇.▇▇▇/10.1080/13501763.2011.609716 PLEASE SCROLL DOWN FOR ARTICLE ▇▇▇▇▇▇ & ▇▇▇▇▇▇▇ makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, ▇▇▇▇▇▇ & ▇▇▇▇▇▇▇, ▇▇▇▇ ▇our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. KoendersAny opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by ▇▇▇▇▇▇ P. J. T. & ▇▇▇▇▇▇▇. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. ▇▇▇▇▇▇ and ▇▇▇▇▇▇▇ shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content. This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub- licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http:// Downloaded by [Radboud Universiteit Nijmegen] at 05:37 24 October 2013 Journal of European Public Policy 19:2 March 2012: 179 – 197 Member State interest articulation in the Commission phase. Institutional pre-conditions for influencing ‘Brussels’ Downloaded by [Radboud Universiteit Nijmegen] at 05:37 24 October 2013 ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇* Development ABSTRACT There is a large literature on Member State influence in the European Union, typically focusing on a combination of catalytic amide bond formation reactions has been the subject preferences of the intensive investi- gations in Member States and their strategies with an emphasis on Council negotiations. However, prior to Council negotiations Member States also seek to influence the past decadeCommission’s development of legislative proposals. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids This paper argues that Member States need scientific expertise, experiential knowledge and amines. Poly(methylhydrosiloxane)target group support to make this strategy work and that the availability of these resources is partly shaped by domestic institutions, a waste product such as the territorial organization of the silicon industrystate, is used as an inexpensive the recruitment principles of governmental departments, and green reducing agent the structure of government’s relationship with business groups and societal interests. As a plausibility probe for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of our argument we have conducted a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and ▇▇▇▇▇ reactions.1 The formation case study of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is Dutch government’s strategy regarding the driving force for REACH Regulation. KEY WORDS Chemicals policy; European Commission; expertise; lobbying; Member States; the classic versions ofNetherlands.

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ARTICLES ▇▇▇▇▇://▇▇▇.▇▇▇/10.1038/s41588-017-0006-7 Mutations in SELENBP1, encoding a novel human methanethiol oxidase, cause extraoral halitosis ▇▇▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇▇▇▇, ▇. ▇. ▇▇▇▇ ▇▇▇▇▇▇▇ 2, ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇,5, ▇▇▇ ▇. ▇▇▇▇▇▇▇▇, Arjan P. M. ▇▇ ▇▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders▇▇▇▇▇ 7, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇P. J. T. ▇▇▇ ▇▇▇ ▇▇▇▇▇▇ and ▇▇,9, ▇▇▇▇▇▇ ▇▇▇▇▇▇▇, ▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇▇▇, Marijn Oude Elberink2, ▇▇▇▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇ 6, ▇▇▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇▇▇ 2,9, ▇▇▇▇ ▇▇▇▇▇▇ ▇▇▇▇▇▇, ▇. ▇▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇ and ▇▇▇▇▇▇▇▇▇▇, ▇. ▇▇▇▇▇▇ reactions.1 ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇ ▇. ▇. Op den Camp 1 and ▇▇▇ ▇. ▇▇▇▇▇▇ 2* Selenium-binding protein 1 (SELENBP1) has been associated with several cancers, although its exact role is unknown. We show that SELENBP1 is a methanethiol oxidase (MTO), related to the MTO in methylotrophic bacteria, that converts methanethiol to H2O2, formaldehyde, and H2S, an activity not previously known to exist in humans. We identified mutations in SELENBP1 in five patients with cabbage-like breath odor. The formation malodor was attributable to high levels of methanethiol and dimethylsulfide, the main odorous compounds in their breath. Elevated urinary excretion of dimethylsulfoxide was associated with MTO deficiency. Patient fibroblasts had low SELENBP1 protein levels and were deficient in MTO enzymatic activity; these effects were reversed by lentivirus-mediated expression of wild-type SELENBP1. Selenbp1-knockout mice showed biochemical characteristics similar to those in humans. Our data reveal a potentially frequent inborn error of metabolism that results from MTO deficiency and leads to a malodor syndrome. T he volatile sulfur-containing compounds hydrogen sulfide (H2S), methanethiol (MT, CH3-SH) and dimethylsulfide (DMS, CH3-S-CH3) have been identified as the main con- tributors to halitosis or bad breath1. The origin of halitosis can be intra- or extraoral2–4. Intraoral halitosis, the most common form, is usually caused by methanethiol and H2S produced by Gram- negative bacteria located on the dorsum of the relatively strong phosphine oxide bond tongue or in gingi- val and periodontal crevices. Extraoral halitosis has an estimated prevalence of 0.5–3% in the general population2, and its origin is not completely understood. Extraoral bad breath can be caused by conditions affecting the nose, sinuses, tonsils, and esophagus, but in some individuals, the extraoral halitosis is bloodborne3. In blood- borne halitosis, malodorant compounds, most commonly DMS, are carried to the lungs, where they enter the breath3. The DMS con- centrations in oral and nasal breath have been found to be sixfold higher in people with extraoral halitosis than in controls2. The cause of elevated DMS levels in these individuals is unknown. DMS is produced from methanethiol through methylation. Both DMS and methanethiol result from the complex microbiome and mammalian co-metabolism of volatile sulfur compounds5,6 (PvOFig. 1). Under phys- iological conditions, 128 kcal mol−1methanethiol has three sources in the human body7,8: synthesis from sulfur-containing amino acids by intestinal bacteria; synthesis in intestinal cells through methylation of H2S by thiol S-methyltransferase; and synthesis from methionine through the transamination pathway in human endogenous metabolism. Under pathological conditions, increased levels of DMS can lead to high concentrations of dimethylsulfoxide (DMSO) and dimethyl- sulfone (DMSO2)9. The enzymes involved in these conversions are largely unknown, and gut bacteria are also thought to contribute to the conversion process5,6. Interestingly, people with cancer pro- duce methanethiol and DMS as prominent volatile organic com- pounds10,11. DMS is produced in substantial amounts by lung and liver cancer cell lines10,12 and has been found in lung tumor tissue13. A methanethiol oxidase (MTO) has been purified from the driving force Hyphomicrobium strain VS14,15. This enzyme has 26% similarity at the amino acid level to human SELENBP1, a protein that can bind selenium but whose function is unknown16–18. Low expression of the human gene has been found in several tumors, and a tumor- suppressor function has been suggested for this gene19–21. We hypoth- esized that mutations in SELENBP1 might cause extraoral halitosis. Through studying five patients with extraoral halitosis caused by elevated levels of DMS in the blood, we identified SELENBP1 as the human MTO catalyzing the conversion of methanethiol into formaldehyde, H2S, and hydrogen peroxide (H2O2). Mutations in SELENBP1 cause extraoral halitosis and define a novel inborn error of metabolism. 1Department of Microbiology, IWWR, Faculty of Science, Radboud University, Nijmegen, The Netherlands. 2Translational Metabolic Laboratory, Department of Laboratory Medicine, Radboud University Nijmegen Medical Centre (RUNMC), Nijmegen, The Netherlands. 3Department of Internal Medicine, RUNMC, Nijmegen, The Netherlands. 4Center for Dentistry and Oral Hygiene, University Medical Center Groningen, University of Groningen, Groningen, The Netherlands. 5Clinic for Periodontology, Amsterdam, The Netherlands. 6Department of Human Genetics, RUNMC, Nijmegen, The Netherlands. 7Department of Surgery, School of Medicine, and Mouse Biology Program, University of California, ▇▇▇▇▇, Davis, CA, USA. 8Mouse Biology Program, University of California, ▇▇▇▇▇, Davis, CA, USA. 9Department of Pediatrics, RUNMC, Nijmegen, The Netherlands. 10Klinik für Kinder und Jugendmedizin, Universitätsklinikum Münster, Münster, Germany. 11Bioanalytics and Biochemistry, Department of Natural Sciences, Bonn-▇▇▇▇▇- ▇▇▇▇ University of Applied Sciences, Rheinbach, Germany. 12Department of Pediatrics and Adolescent Medicine, University Hospital Freiburg, Freiburg, Germany. 13School of Life Sciences, University of Warwick, Coventry, UK. 14Centre for Molecular and Biomolecular Informatics, RUNMC, Nijmegen, The Netherlands. 15Metabolic Unit–Pediatric Department, Hospital de Dona Estefânia, CHLC, Lisbon, Portugal. ▇▇▇▇▇ ▇▇▇ and ▇. ▇▇▇▇▇ ▇▇▇▇▇▇▇ contributed equally to this work. Huub ▇. ▇. Op den Camp and ▇▇▇ ▇. ▇▇▇▇▇▇ jointly directed this work. *e-mail: ▇▇▇.▇▇▇▇▇▇@▇▇▇▇▇▇▇▇▇▇.▇▇ NATURE GENETICS | VOL 50 | JANUARY 2018 | 120–129 | ▇▇▇.▇▇▇▇▇▇.▇▇▇/▇▇▇▇▇▇▇▇▇▇▇▇▇▇ H2O2 HS CH3 CH2O Bacterial flora Methionine catabolism H3C CH3 MTO H2S Dietary sources H3C CH3 H3C CH3 Dimethyl sulfone (DMSO2) affected individuals in the Dutch family are from a nonconsanguin- eous marriage, and the malodor was their only clinical symptom. The mother of CII-1 and CII-2 had some complaints of halitosis. The parents of the other affected individuals were consanguineous. The affected female in family A had malodor as the only symptom, whereas her brother had a broader spectrum of clinical symptoms with neurological features. The Portuguese affected individual also had neurological sequelae. Breath and body-fluid analyses. For breath and body-fluid analy- ses, we used complementary methods (NMR spectroscopy and gas chromatography) (Table 1). Because of the malodorous body fluid, Hydrogen Formaldehyde Hydrogen NMR spectroscopy was requested for the classic versions ofindex patients in the three peroxide sulfide HS CH3 + Methanethiol H2O Water + O2 MTO CH2O + Formaldehyde H2S + Hydrogen sulfide H2O2 DMSO and DMSO2 in the body fluids (Fig. 2b,c). Using gas chromatography with a sulfur-specific detector, we detected high concentrations of an additional sulfur-containing compound, DMS, in the affected individuals (Table 1b). Elevated‌ Fig. 1 | Sulfur metabolism. Diet, bacterial metabolism, and endogenous metabolism contribute to the levels of MT, DMS, DMSO, DMSO2, and catabolites in the body. The main conversion of MT to H2O2, formaldehyde, and H2S by the enzyme MTO is deficient in the patients (indicated by X). Bottom, MTO reaction. All underlined metabolites were confirmed in our assay. Results‌ Patients with extraoral halitosis. We studied five affected individ- uals from three unrelated families with extraoral halitosis causing a cabbage-like breath odor (Fig. 2a). The affected individuals had high levels of DMS in their oral and nasal breath. Known causes, such as intake of DMS-containing food, use of sulfur-containing medication, lower-gastrointestinal problems, and known metabolic defects, such as methionine adenosyltransferase deficiency and tyrosinemia, were excluded. Family A is a German family of Turkish origin and has two affected children (AII-2 and AII-3); family B is Portuguese and has one affected child (BII-2); and family C is Dutch and has two affected children (CII-1 and CII-2). The unifying clini- cal feature across families was the pungent breath malodor. Other clinical signs and symptoms of the affected individuals differed considerably (full description in Supplementary Note). The two blood DMS concentrations have been described in people with extraoral halitosis3,4. Elevated concentrations of DMSO2, an oxida- tion product of DMS, have been observed in the blood of individu- als with methionine adenosyltransferase deficiency9. DMSO2 also occurs in cerebrospinal fluid after intake of DMSO2 as a dietary sup- ▇▇▇▇▇▇▇▇▇. Additional investigation of breath samples from AII-3 and CII-2 identified elevated levels of a fourth sulfur-containing compound, methanethiol. The methanethiol concentration in the breath of these patients was ten times higher than the highest values in control individuals and unaffected family members. Specialized dental clinics may use portable gas chromatography to detect this specific form of halitosis (breath analysis of CII-2 in Supplementary Fig. 1). We detected elevated methanethiol levels in the urine in some of our patient samples. Because methanethiol is highly volatile and reactive, reproducible quantification of urinary methanethiol was not possible. Patient BII-2 was treated for 5 d with the antibiotic metronida- zole (500 mg oral; three times per day), after which the concentra- tion of DMS in the breath decreased to just above the detection limit. DMS and methanethiol in the urine decreased to 65% after 5 d of metronidazole administration. After cessation of treatment, the DMS levels in the breath and urine returned to pretreatment values. In patient AII-3, a methionine-loading trial was performed. Family A DMSO2 Citric acid Creatinine Creatine DMSO 1 2 4 II 1 3 B I 2 II 1 2 Family Family C 1 2 I II 1 2 3.10 3.00 Creatinine Citric acid Creatine 3.10 3.00 p.p.m. p.p.m.

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the & ▇▇▇▇▇▇▇▇▇▇, D. (2012). Member State Interest Articulation in the Com- mission Phase. Institutional Preconditions for Influencing “Brussels”. Journal of Euro- pean Public Policy, 19 (2), 179-197. Er is veel literatuur over ▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and waarop de lidstaten proberen invloed uit te oefe- nen op de besluitvorming in de Europese Unie (EU). Deze richt zich vooral op de preferenties en strategieën van lidstaten tij- dens de onderhandelingen in ▇▇ ▇▇▇▇ van Ministers. Maar ook in de daaraan voor- afgaande fase van beleidsvoorbereiding door de Commissie proberen lidstaten in- vloed uit te oefenen. Dit artikel onderzoekt ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) hulpbronnen nodig zijn om in deze fase van belangenbehartiging succesvol te zijn en hoe de beschikbaarheid van deze hulpbronnen afhangt van de binnenlandse institutionele context. Het onderzoek is the driving force ge- baseerd op een studie naar de Nederlandse pogingen tot het beïnvloeden van het voor- stel voor de ‘Regulation for the classic versions ofRegistra- tion, Evaluation, Authorization and Re- striction of Chemical Substances’ (REACH) in de periode 2000-2003. Dit artikel onderscheidt drie hulpbron- nen die tijdens de beleidsvoorbereiding door de Commissie van bijzonder belang zijn: – wetenschappelijke kennis; – ervaringskennis, d.w.z. kennis over de beleidspraktijk, mogelijke implemen- tatieproblemen, enz.; deze ▇▇▇▇▇▇ ▇▇▇ afkomstig zijn van (nationale) overhe- den of direct van de doelgroep van het beleid; – draagvlak (legitimiteit), in het bijzon- der het draagvlak bij de doelgroep van het beleid.

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇ Peer Scheepers ▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇ ▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is the driving force for the classic versions of

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite thisInternational Edition: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.103910.1002/c7ob01510k ▇▇▇.▇▇anie.201609437 German Edition: DOI: 10.1002/▇▇▇ Poly(methylhydrosiloxane) as ange.201609437 Low-Frequency CH Stretch Vibrations of Free Alkoxide Ions Many introductory texts begin the discussion of molecular vibrations by treating the elongation and contraction of CH bonds. CH stretches tend to couple to only a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇slight extent with : motions of other atoms besides carbon and hydrogen, and few other vibrations overlap the CH stretch region. ▇. ▇▇▇▇▇▇▇Because nitrogen and oxygen bind more strongly to hydrogen than does carbon (and other elements bind more loosely), ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ * Development the low mass of catalytic amide bond formation reactions has been the subject hydrogen causes excitation of CH stretches to occupy a distinctive domain of the intensive investi- gations electromagnetic spectrum, 3040 cm@1 11 % for an uncharged molecule. Here we describe experiments, which demonstrate that adding electric charge (in anions) has the past decadesame effect as removing electron density (in cations): to lower CH stretching frequencies by hundreds of wavenumbers. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids Removing electron density diminishes bond strengths. CH stretches occur at lower frequencies in positively charged ions such as protonated methane,[1] protonated ethylene,[2] pro- tonated acetylene,[3] or the radical cations of hydrocarbons, alcohols, and aminesethers.[4] For instance, in gaseous CH5+, whose lowest CH stretch occurs near 2500 cm@1,8 valence electrons have to form 5 bonds, if all bonds become equivalent. Poly(methylhydrosiloxane)In these cations fewer than 2 electrons are available for each bond, rendering CH bonds weaker than in neutrals. We present data to reveal that in isolated, negatively charged alkoxide ions the charged oxygen tends to donate electron density to the adjacent carbon to form a waste product of the silicon industrypartial C=O linkage, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide causing that carbon atomQs bond to phosphinehydrogen to weaken. The reported method enables net result of increased electron density in anions lowers the synthesis of a wide range of secondary and tertiary amides a-CH stretch fundamentals in very good these cases, to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is the driving force for the classic versions ofan extent comparable to the

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite thisCoHLA: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇Design Space Exploration and Co-simulation Made Easy The Netherlands ▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, @▇▇.▇▇.▇▇. The Netherlands ▇▇▇▇▇▇▇, @▇▇.▇▇.▇▇ The Netherlands . Koenders, .▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ .▇▇▇▇▇▇▇▇@▇▇▇▇▇▇▇.▇* Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the Netherlands ▇.▇.▇▇▇▇▇▇▇▇▇▇, @▇▇▇▇▇▇▇.▇▇, ▇▇▇▇▇▇ and ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is the driving force for the classic versions of

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k Dat de beslispraktijk binnen de EU ▇▇▇.▇/▇ nationale verschillen kent in de toepassing van de definities en toekenning van de status van vluchteling ▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent wel subsidiair beschermde, bevestigt dat de beschermingsbehoefte van deze twee groepen niet altijd even goed te onderscheiden is, of in organophosphorus-catalysed amide bond formation† Daan elk geval aan verschillende interpretaties onderhevig. Het duidelijkste voorbeeld daarvan is de behandeling van Syrische asielzoekers: alle EU lidstaten verlenen Syrische vluchtelingen bescherming vanwege de verwoestende oorlog in hun land, maar de grondslag waarop die bescherming wordt verleend verschilt per lidstaat.60 Ook in andere vluchtsituaties blijkt het lastig om bij de toeken­ ning van bescherming de noodzakelijke beschermingsduur in . . ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇en wordt de tijd die gemoeid is met een veilige terugkeer na een gewijzigde situatie in het herkomstland vooraf ▇▇▇▇▇ ▇▇▇▇▇- ▇▇▇ overschat. Mede in dat licht geldt de rechtvaardiging die de Gezinsherenigingsrichtlijn noemt voor de soepeler toelatings­ regels voor gezinsleden van vluchtelingen, in dezelfde mate voor subsidiair beschermden.61 De jurisprudentie van het EHRM over gelijke behandeling en discriminatie, heeft niet alleen zijn weerslag op het recht op gezinshereniging. Op grond van artikel 1 van het Twaalfde Protocol bij het EVRM, geldt het verbod op discriminatie ook als de materiële rechten van het EVRM niet van toepassing zijn. Artikel 21 lid 1 EU Handvest bevat een soortgelijk discrimina­ tieverbod bij de toepassing van het Unierecht, dat niet ▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇, mag ▇▇▇▇▇▇ and geïnterpreteerd ▇▇▇ het EVRM en de uitleg ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO60 Zie COM(2016)466, 128 kcal mol−1) is the driving force for the classic versions ofp. 4. voetnoot 12. 61 Considerans punt 8: 'De situatie van vluchtelingen vraagt b jzondere aandacht vanwege de redenen die hen ertoe hebben gedwongen hun land te ontvluchten en die hen beletten aldaar een gezinsleven te leiden. Om die reden moeten er voor hen gunstiger voorwaarden ▇▇▇▇▇▇ geschapen voor de uitoefening van hun recht op gezinshereniging." 302 - A&MR door het EHRM.62 Ook bij de toekenning van andere rechten zullen lidstaten voor een onderscheid tussen vluchtelingen en subsidiair beschermden dus een voldoende zwaarwegende rechtvaardiging moeten aanvoeren. ▇▇▇▇▇ op het voorgaande, zullen ze daar maar moeilijk in kunnen slagen.

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k REVIEWS Encoding information into polymers ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇. Rutten1, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇. . ▇. Elemans1 and Abstract | Defined-sequence polymers have great potential as durable and high-density data-storage media. DNA already fulfils this role in nature, ▇▇▇▇▇▇ using the sequence of its four nucleobases to store genetic information. Synthetic DNA can be used to store binary codes, and ▇▇▇▇▇ reactions.1 The formation it is both more durable and can store information at a much higher density than conventional silicon-based storage systems. Other defined-sequence synthetic polymers have properties that make them even more suitable for data storage, at least in principle, assuming that complete control over their composition, that is, their monomer sequence, can be achieved. This Review addresses the current status of data storage in DNA, proteins and synthetic polymers, with the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is objective to overcome the driving force for the classic versions ofproblems of current data storage technology.

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇.▇▇ ▇▇/▇▇▇▇▇(✉), ▇▇▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ,3, and ▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇ 1 Digital Security Group, Radboud University, Nijmegen, The Netherlands {▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the .▇▇▇▇▇▇▇▇▇▇, ,▇▇▇▇▇,▇▇▇▇, }@▇▇.▇▇.▇▇ and ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO2 3 STMicroelectronics, 128 kcal mol−1) is the driving force for the classic versions ofDiegem, Belgium

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic Journal of Environmental Policy & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite thisPlanning ISSN: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI1523-908X (Print) 1522-7200 (Online) Journal homepage: 10.1039/c7ob01510k ▇▇▇▇://▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇.▇▇▇/loi/cjoe20 Following Old Paths or Shaping New Ones in Natura 2000 Implementation? Mapping Path Dependency in Instrument Choice ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇▇, ▇▇* Development ▇▇▇ ▇▇▇▇▇▇▇▇▇ & Bas Arts To cite this article: ▇▇▇▇▇ ▇▇▇▇▇▇, ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇▇, ▇▇▇ ▇▇▇ ▇▇▇▇▇▇▇▇▇ & Bas Arts (2016) Following Old Paths or Shaping New Ones in Natura 2000 Implementation? Mapping Path Dependency in Instrument Choice, Journal of catalytic amide bond formation reactions has been Environmental Policy & Planning, 18:2, 214-233, DOI: 10.1080/1523908X.2015.1070334 To link to this article: ▇▇▇▇://▇▇.▇▇▇.▇▇▇/10.1080/1523908X.2015.1070334 Published online: 14 Aug 2015. Submit your article to this journal Article views: 136 View related articles View Crossmark data Citing articles: 3 View citing articles Download by: [Radboud Universiteit Nijmegen] Date: 05 October 2016, At: 00:48 Full Terms & Conditions of access and use can be found at ▇▇▇▇://▇▇▇.▇▇▇▇▇▇▇▇▇▇▇.▇▇▇/action/journalInformation?journalCode=cjoe20 Journal of Environmental Policy & Planning, 2016‌ Vol. 18, No. 2, 214 – 233, ▇▇▇▇://▇▇.▇▇▇.▇▇▇/10.1080/1523908X.2015.1070334 Following Old Paths or Shaping New Ones in Natura 2000 Implementation? Mapping Path Dependency in Instrument Choice ▇▇▇▇▇ ▇▇▇▇▇▇∗, ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇▇∗∗, ▇▇▇ ▇▇▇ ▇▇▇▇▇▇▇▇▇∗ & BAS ARTS† ∗Alterra, Wageningen UR, Wageningen, The Netherlands ∗∗Department of Environmental Policy Sciences, Nijmegen School of Management, Radboud University Nijmegen, Nijmegen, The Netherlands Abstract This article reviews the subject influence of two specific European Union (EU) laws, the Birds and Habitats Directives, on the choice of national policy instruments by Member States. Both Directives leave the choice for policy instruments to manage the sites desig- nated under the Directives to the Member States. Using path dependency as a leading concept, this article analyses the continuity or changes in policy instruments due to the implementation of the intensive investi- gations Directives in 15 countries. This article shows that the tendency to use existing instruments to implement EU policy is limited, as in almost all countries new instruments were developed. Yet, states do tend to choose instruments from their pre- dominant policy instrument mix and preferred implementation style to address the man- agement requirements of the Directives. Additionally, in Central and Eastern European countries where the implementation of EU policy coincided with a process of transition to a market economy, new instruments were introduced outside the existing implemen- tation style. The introduction of new policy instruments is the result of historical turns, domestic pressure and a shift to new modes of governance. National case studies are needed to shed more light on the interaction between EU policy and domestic factors during the process of instrument choice. KEY WORDS: Path dependency, Natura 2000, policy instruments, conservation management, policy implementation, EU legislation, instrument choice, nature conservation Introduction As part of its ambitious goal to halt the loss of biodiversity, the European Union (EU) developed the network of Natura 2000 sites, which at present covers approxi- Correspondence Address: ▇▇▇▇▇ ▇▇▇▇▇▇, Alterra, ▇▇▇▇▇▇▇▇▇▇▇▇▇▇▇▇▇▇ ▇, ▇▇▇▇ ▇▇ ▇▇▇▇▇▇▇- ▇▇▇, ▇▇▇ ▇▇▇▇▇▇▇▇▇▇▇. Tel.: +▇▇▇▇▇▇▇▇▇▇▇; Email: ▇▇▇▇▇.▇▇▇▇▇▇@▇▇▇.▇▇ Ⓒ 2015 ▇▇▇▇▇▇ & ▇▇▇▇▇▇▇ mately 18.4% of the European territory (European Commission, 2014). After the phase of site designation, all Member States are now in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product challenging phase of organizing the management of the silicon industrysites. In order to derive lessons for future policy development, it is used as an inexpensive important to consider how they address this challenge and green reducing agent for in situ reduction of phosphine oxide whether they are using their exist- ing planning, financial and regulatory instruments to phosphinemanage the Natura 2000 sites, are adapting these or developing new ones. The reported method enables requirement to designate Natura 2000 sites stems from two European Directives, the synthesis Birds Directive (79/ 409/EEC)1 and the Habitats Directive (92/43/EEC). Contrary to some other direc- tives, the two Directives do not prescribe the use of specific policy instruments. The Birds Directive only states that measures need to be taken without providing any guidance on which policy instruments to apply. The Habitats Directive suggests a wide range array of secondary instruments for implementation from which Member States can choose freely. Available literature on the effect of EU policy on national policy suggests that Member States prefer to follow their existing national repertoire of institutional procedures and tertiary amides organizational forms (▇▇▇▇, ▇▇▇▇▇▇, & ▇▇▇▇▇▇▇▇▇▇, 2007; ▇▇▇▇▇, 2001; ▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇▇, & ▇▇▇▇▇▇▇, 2005). It is not often that a policy choice is made that breaks with established rules, procedures and policy instru- ments. This phenomenon in very good public policy is referred to excellent yieldsas ‘path dependency’ (▇▇▇▇▇ & North, 1971; ▇▇▇▇▇▇ & ▇▇▇▇▇▇, 1967; ▇▇▇▇▇▇▇, 2000). Over However, descriptive studies on the past decadeimplementation practice of Natura 2000 in EU Member States show that some countries have developed new policy instruments although there is no obligation to do so (▇▇▇▇, there has been a significant interest ▇▇ ▇▇▇▇▇, Van Apeldoorn, Bouwma, & ▇▇▇▇, 2010). At first glance, this seems to contradict mainstream and empirically grounded the- ories explaining the influence of EU law on national administrations. Given the cost (in social, political or economic terms) associated with the development of catalytic versions new policy instruments, this behaviour would not be expected (▇▇▇▇▇▇▇ & ▇▇▇▇▇▇, 2006). Therefore, one may wonder whether the instrument choice made by these Member States is an exception to the ‘path dependency rule’, or that the majority of phosphinethe Member States have indeed changed their policy instrumenta- tion. Therefore, the question this article addresses is whether Member States tend to use their existing instruments, that is, show path-mediated reactions that dependent behaviour when implementing the Birds and Habitats Directives. Based on the results of this study, more general conclusions on instrument choice by Member States under the influence of EU policy are often used formulated. In policy instrument choice, the monitoring and enforcement of policy instru- ments plays a role (Tosun, 2012). The expected level of compliance to new regu- lations as well as costs of enforcement might determine the choice for regulation versus other instruments. However, as this article deals with the initial choice of governments for policy instruments, the issue of monitoring and enforcement is not elaborated further. This article is structured as follows. After a presentation of the relevant the- ories, the key hypothesis for this article is presented. This article then tests this hypothesis through an analysis of policy instrument choices for the management of Natura 2000 sites in organic synthesis15 Member States. Following the presentation of the results, the discussion puts the findings in a broader context of path dependency research. Policy Instrument Choice, Europeanization and Policy Change In order to develop a hypothesis about whether EU policy influences the choice of Member States at the level of policy instruments, we combine insights from three fields of research: studies on instrument choice, on policy change including path dependency and Europeanization studies. In so doing, this article takes a historic institutional viewpoint on policy instrument development. Policy instru- ments are defined as the tools at the disposal of the government to implement their policy objectives (Bemelmans-Videc & ▇▇▇▇, 1998; ▇▇▇▇▇▇▇, 1991). However, policy instruments are part of a larger framework of established gov- ernance modes and policy regime logics (▇▇▇▇▇▇▇, 2009). The historical policy context has shaped the present policy instrument mix and will influence its further development. As such, this article pays less attention to sociological argu- ments explaining the selection process of policy instruments (▇▇▇▇▇▇▇▇ & ▇▇▇▇▇, 2000; Hall, 1993). The literature describes a broad array of policy instruments and typologies (Bemelmans-Videc & ▇▇▇▇, 1998; ▇▇▇▇▇▇▇▇ & ▇’▇▇▇▇▇ ▇▇, 1998; ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇, & ▇▇▇▇▇▇▇▇, 1998; ▇▇▇▇▇▇▇, 2002) such as legal and regulatory instru- ments, economic and fiscal instruments as well as policy instruments based on information, communication or agreement (Lascoumes & ▇▇ ▇▇▇▇▇, 2007). One of the major challenges in assessing policy instrument change is that policy instru- ments are multifaceted. This has resulted in a multitude of typologies using differ- ent ordering principles (▇▇▇▇▇▇▇, 2002). In this study, a distinction is made between individual instruments, types of instruments and policy instrument mix. Individual instruments are detailed in a law or particular regulation, such as a subsidy, tax, planning system or certification standard. In the existing classifications, individual instruments are grouped in different types based on a particular analytical perspective. Each type consists of ‘families’ of individual instruments sharing similar characteristics. As a result, the variety within a type can still be high. Consequently, only major changes of instruments will result in a shift of an instrument from one type to another type. We opted for the classification as presented by ▇▇▇▇▇▇ (1998). This typology distinguishes three types of instruments based on their coercive nature, being (1) legal and regulatory instruments, (2) economic instruments and (3) information instruments and communication-based instruments.2 A policy instrument mix is a combination of individual policy instruments applied within a particular policy field, which may belong to different types of instruments. Existing instrument choice theories assume that administrators can choose from a wide variety of policy instruments to implement a specific policy and adapt them over time to improve policy implementation (▇▇▇▇▇▇▇- ▇▇▇ et al., 1998; ▇▇▇▇▇▇▇, 2002). In practice, their choice is often limited by the his- torically determined policy context (▇▇▇▇▇▇▇ & ▇▇▇▇▇, 2008; ▇▇▇▇▇▇▇, 2009; ▇▇▇ ▇▇▇▇▇▇, Arts, & ▇▇▇▇▇▇▇▇, 2010). Often, the choice for particular policy instru- ments follows more general governance patterns in a country such as the type of state– society relations, the level of state intervention or the importance attached to the law (▇▇▇▇▇▇▇▇ et al., 2005). Recently, much attention has been paid to agreement-based policy instruments. Several authors have suggested that these instruments result from a shift to new modes of governance (▇▇▇▇▇▇▇, Hill, & ▇▇▇▇▇▇▇, 2005; ▇▇▇▇▇▇, ▇▇▇▇▇▇, & ▇▇▇▇, 2003; ▇▇▇▇▇▇, 2000; ▇▇▇▇▇▇▇, 2002). Although the extent of the shift is debated, the shift itself has been generally acknowledged (▇▇▇▇▇▇, ▇▇▇▇▇▇, ▇▇▇▇, & ▇▇▇▇▇▇▇▇, 2003; ▇▇▇▇▇▇-▇▇▇▇ & ▇▇▇▇▇▇▇▇▇▇, 2006; ▇▇▇▇▇▇, 2007). Besides generic national governance systems or governance modes, the socio- economic development also has been proposed to influence policy instrument choice, particularly in the field of the environment. Also in Europeanization literature, the socio-economic development of Member States has been used to explain the response to EU policy (▇▇▇▇▇▇▇▇▇, Knill, & Arts, 2008; ▇▇▇▇▇▇▇▇ et al., 2005; ▇▇▇▇▇▇▇▇▇▇, Arts, ▇▇▇▇▇▇▇, & Ooijevaar, 2009). ▇▇▇▇▇▇ and ▇▇▇▇▇▇reactions.1 The formation (2005) provide another explanation by underlining the importance of policy trans- fer in the EU. States, which were Members of the relatively strong phosphine oxide bond EU when the Directive was drafted, were able to influence the EU policy to include or reflect their own policy goals and instrumentation, thus limiting the need to revise their instru- ments. Over time, governments usually develop a preference for specific policy instruments and a specific policy mix to implement their policy (PvOBressers & ▇’▇▇▇▇▇ ▇▇, 128 kcal mol−11998; ▇▇▇▇▇▇▇, 2009; ▇▇▇▇▇▇ et al., 2003). ▇▇▇▇▇▇▇ (2009) has intro- duced the term ‘implementation style’ to describe this process. ‘An implemen- tation style is usually composed of a combination, or mix, of substantive and procedural instruments, at minimum two’ (▇▇▇▇▇▇▇, 2009, p. 81). Despite this preference for a specific implementation style, changes to policy instruments may occur during the driving force recurrent process of policy instrument selection. Hall (1993) defined different sorts of changes: at the level of settings, at the level of the type of instruments and at the level of the goals underlying the policy instruments. Changes at the level of settings usually refer to small incremental changes, for instance the classic versions ofmaximum permissible concentration of a toxic sub- stance. Changes regarding the type of instruments may, for instance, involve a shift from regulatory instruments to voluntary ones. Changes at the level of policy goals, finally, may impact both the level of settings as well as the type of instruments applied. Based on Hall’s definition of instrument change, the EU through its policy may influence settings, types of instruments or underlying goals. Although EU directives, according to the EU Treaty, set common goals and leave the choice of means to achieve them to the Member States, in practice, this can also involve the prescription of certain policy instruments (Jordan & ▇▇▇▇▇▇, 2012; ▇▇▇▇▇▇ & ▇▇▇▇▇▇▇▇▇▇, 2004) and even settings. Furthermore, the EU may not set legal require- ments but promote the use of particular policy instruments, such as market-based instruments or voluntary agreements (Jordan et al., 2003). The influence of the EU on the policy instrument choice of Member States has not received much scholarly attention so far. The majority of the existing studies on the influence of EU law on the policies of the Member States have focused on the stage of formal transposition (Bo¨ rzel, 2000; ▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇, & Treib, 2007; ▇▇▇▇▇▇▇▇▇ & ▇▇▇▇▇▇▇, 2007; ▇▇▇▇▇▇▇▇▇▇▇, 2005; Treib, 2014). Only a few case studies for individual countries and for a limited number of policy fields on the practical side of implementation of EU-law exist (cf. ▇▇▇▇ et al., 2007; cf. ▇▇▇▇▇ & ▇▇▇▇▇, 2009; Treib, 2014). Nevertheless, Europeanization studies provide important insights on how Member States might respond to EU influence. In general, Member States prefer to follow their existing national repertoire of institutional procedures and organ- izational forms (▇▇▇▇▇, 2001; ▇▇▇▇▇▇▇▇ et al., 2005). In

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent Het oude en nieuwe Rome in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is the driving force for the classic versions ofde Latijnse poëzie rond het jaar 400

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Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017‘Democracy is the official religion of the West. Downloaded by Now is as good a time as any to question the faith.’1 Godsdienst en geloofsbeleving, zeker in het institutionele verband van een kerk, mag ▇▇▇ in Nederland (en datzelfde geldt voor vele westerse ▇▇▇▇▇▇) de laatste halve eeuw in rap tempo naar de zijlijn van de maat- schappij zijn verschoven,2 dat betekent niet dat religieuze voorstellin- gen of een gelovige geesteshouding zomaar het veld hebben geruimd. De echo’s van godsdienstige tradities en religieuze praktijken kunnen nog lang nagalmen of in andere gedaanten voortleven. De kerken hebben niet ▇▇▇▇▇▇ een belangrijke rol in het vormgeven van geloof, maar dat is niet hetzelfde als het verdwijnen van het geloof als gees- teshouding. ▇▇▇▇▇▇ we begrijpen wat geloven is, en waarop een religi- euze beleving van de wereld berust, ▇▇▇ moeten we verder kijken ▇▇▇ de inhoud van een bepaald geloof alleen. Het minste dat we hierover kunnen zeggen is dat geloven of religie één oplossing is voor de onze- kerheid die het menselijk bestaan onvermijdelijk begeleidt. Andere oplossingen zijn de relatieve terugdringing van onzekerheid door wetenschap, technologie of maatschappelijke regels, of het erkennen van en leren leven met onzekerheid. * ▇▇. ▇▇▇▇▇ ▇▇▇▇▇▇▇▇, universitair docent praktische filosofie, Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. ChemUniversiteit (▇., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇▇▇▇▇▇@▇▇▇.▇▇/.▇▇). 1 Deze uitspraak is afkomstig uit een samenvatting van ▇▇▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇▇▇- ▇▇▇, Against Democracy, Princeton University Press, Princeton/Oxford 2016, publiek gemaakt op ▇▇▇▇://▇▇▇▇▇▇▇▇▇▇▇▇▇▇▇▇.▇▇▇/feature/against- democracy-17605 (bezocht op 9 februari 2017). 2 Het meest recente overzicht biedt . ▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇, God in Nederland 2006-2015, Ten Have, Utrecht 2016. ▇▇▇* Development III Vanuit de filosofie Zolang deze en andere oplossingen niet geschikt zijn, zal religie een ordeningsvorm in of catalytic amide bond formation reactions has been the subject van de maatschappij blijven – ▇▇▇▇▇ inhoud en vorm ze ook krijgt. Het woord religio werd oorspronkelijke geasso- cieerd met het strikt voortzetten van een traditie, gewoonte, ritueel of the intensive investi- gations tekst, maar ook met het verbinden of verenigen ▇▇▇ ▇▇▇▇▇▇ door deelname aan dezelfde eredienst.3 Beide zorgen voor het wegnemen van de onzekerheid die met het bestaan van uiteenlopende levenswij- zen en overtuigingen te maken heeft. Dat men vandaag nog in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the bepaal- ▇▇ ▇▇▇▇▇▇▇ spreekt over de vraag of religie een rol moet spelen in de sociale cohesie heeft vooral te maken met de moderne betekenis van religie: deze verwijst naar een kerkgemeenschap en de daarbij horen- de confessio (bekentenis of belijdenis). Oorspronkelijk betekent religie zoveel als sociale cohesie; hoe ▇▇▇▇, ▇ ook gaat het om een vormgevend beginsel van maatschappelijke verbanden. Bijna anderhalve eeuw geleden stelde het Britse parlementslid ▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and al vast dat onderwerping aan een eredienst ook in de democratie een plaats kan behouden: ‘De aangeboren drift tot aanbidding heeft ons nog steeds zo ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvOin ▇▇ ▇▇▇▇▇, 128 kcal mol−1) dat we bereid zijn – nadat ons vermogen om koningen en anderen voor gewijde personen ▇▇ ▇▇▇▇▇▇ net is the driving force for the classic versions ofversleten – een meerderheid van onze soort- genoten dezelfde soort eerbiedwaardigheid te verlenen. En zonder dat we onderkennen hoe ongerijmd de tegenstelling is waarin we terecht zijn gekomen, zijn we bereid een menigte mensen onbeperk- te rechten te geven, terwijl we ▇▇ ▇▇▇▇ toekennen aan de enkelingen zelf die deze menigte uitmaken.’4 De uitspraak past goed in het

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 201722 December 2016. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 4/8/2019 9:07:29 AM. Biomolecular Chemistry PCCP PAPER Cite this: Org. BiomolPhys. Chem. Chem. Phys., 2017, 1519, 6426 2974 Received 22nd June 20177th December 2016, Accepted 15th July 2017 22nd December 2016 DOI: 10.1039/c7ob01510k c6cp08349h ▇▇▇.▇▇▇.▇▇▇/▇▇Poly(methylhydrosiloxane) as a green reducing agent Facile pentagon formation in organophosphorus-catalysed amide bond formation† Daan the dissociation of polyaromatics† ▇▇▇▇▇ ▇. de Haas,a . ▇▇ ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ * Development ‡*a Energetic processing of catalytic amide bond formation gaseous polycyclic aromatic hydrocarbons (PAHs) plays a pivotal role in the chemistries of inter- and circumstellar environments, certain planetary atmospheres, and also in the chemistry of combustion and soot formation. Although the precursor PAH species have been extensively characterized, the products from these gaseous breakdown reactions have received far less attention. It has been the subject particularly challenging to accurately determine their molecular structure in gas-phase experiments, where comparisons against theoretical modeling are best made. Here we report on a combined experimental and theoretical study of the intensive investi- gations dissociative ionization of two nitrogen containing polycyclic aromatic hydrocarbons of C13H9N composition, acridine and phenanthridine. The structures of HCN-loss fragments are resolved by infrared multiple-photon dissociation (IRMPD) spectroscopy of the mass-isolated products in an ion trap mass spectrometer. Quantum-chemical computations as well as reference IRMPD spectra are employed to unambiguously identify the molecular structures. Furthermore, computations at the density functional level of theory provide insight into chemical pathways leading to the observed products. Acenaphthylene●+ and benzopentalene●+ – two aromatic species containing pentagons – are identified as the main products, suggesting that such species are easily formed and may be abundant in regions where thermal or photoprocessing of polyaromatics occurs. 1 Introduction Polycyclic aromatic hydrocarbons (PAHs) and their nitrogen con- taining analogs (PANHs) are known as very stable molecular entities explaining their pivotal role in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxanechemistries of diverse environ- ments, ranging from the interstellar medium (ISM), a waste product planetary atmospheres, to combustion environments.1–7 Here we focus on these gas-phase environments, where energetic processing of PA(N)Hs induced by photo- and/or collisional excitation is common and may cause isomerization or dissociation to occur.8,9 The dissociation of large PAHs in the ISM has been suggested to lead to the formation of fullerenes,9–11 but spectroscopic evidence supporting this hypothesized conversion has not yet been reported. The loss of C2H2 units from PAHs or the loss of an isoelec- tronic HCN unit from PANHs constitute the most common carbon loss channel for irregular PAHs. Recently, our group identified the structure of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest product formed in the development of catalytic versions of phosphinedissociative E-mediated reactions that are often used in organic synthesis, including the mail: ▇▇▇▇▇▇▇@▇▇▇▇.▇▇▇▇▇▇▇▇▇▇, .▇▇; Tel: +▇▇(▇)▇▇ ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇and ▇▇▇▇▇ reactions.1 The formation ionization of the relatively strong phosphine oxide bond smallest PAH, naphthalene, by infrared multiple-photon dissociation (PvOIRMPD) spectroscopy.12 We con- firmed theoretical predictions that suggest that isomerization to azulene●+ precedes the loss of a C2H2-unit, 128 kcal mol−1yielding pentalene●+ as the main product.13–15 The products that form from the dissociation of larger PAHs remain elusive.16–20 Identification of these products and the characterization of the underlying potential energy surface (PES) is critical to fully understand the driving force chemical networks involving polyaromatics. The high degree of symmetry of homocyclic PAHs consisting of three or more aromatic rings hampers unique identification of the underlying chemical mechanism, as a number of indis- tinguishable C2H2 units can be removed. Here, we address this challenge by investigating the loss of an isoelectronic HCN-unit from N-heterocyclic PAHs (PANHs). The nitrogen atom is placed at a specific position in the molecule and traced back in the [M—27] mass loss channel, allowing for an unambiguous deter- mination of the classic versions ofunderlying dissociation mechanism. Additionally, the loss of HCN from nitrogen heterocycles typically requires less energy than C2H2 removal from their carbon-only counter- parts,20,21 having the added advantage of enhanced dissocia- tion resulting in larger ion intensities in the experiment. We chose to study HCN-loss products from two PANHs of † Electronic supplementary information (ESI) available: Detailed description of experiments. See DOI: 10.1039/c6cp08349h C13 H9N composition, acridine and phenanthridine (Fig. 1), as ‡ Present address: Sackler Laboratory for Astrophysics, Leiden Observatory, Leiden University, P.O. Box 9513, 2300 RA Leiden, The Netherlands. they comprise the smallest representatives of two classes of polyaromatics: PAHs with zigzag and with armchair edges,

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k De zevenkoppige draak van ongelijkheid Heldinnen en hindernissen in de queeste naar inclusiviteit1 ▇▇▇.▇/▇▇▇ Poly(methylhydrosiloxane▇▇▇ ▇▇▇ ▇▇▇▇▇ TVGN 21 (2): 113–129 DOI: 10.5117/TVGN2018.2.BRIN Abstract Diversity in the workforce – in terms of social identity categories such as gender, race, ethnicity, age, and class – has become a prime concern for organisations in both the public and private sectors. Despite decades of equal-opportunities legislation and numerous initiatives, progress towards equality, diversity, and inclusion in organisations remains – at best – slow. Inequality in organisations seems to be an unbeatable seven-headed dragon that has a multitude of faces in different economic, social, and cultural contexts. In this essay, ▇▇▇▇▇▇▇ ▇▇▇ ▇▇▇ ▇▇▇▇▇ questions whether we have the right swords or bravest heroines to beat this tenacious dragon of inequality. She proposes to unravel the complexity and polyvocality of change by distinguishing between inequality practices – the routinised organisational practices that produce inequality regimes – and equality practices – the planned change interventions aiming for gender equality. Greater insight into the ways that gender equality practices and gender practices interact with, conflict with, and anticipate each other can further our knowledge and understanding of the slow rate of change that gender equality policies have managed to achieve. Keywords: inclusion, diversity policy, organisational change, organisational memory, diversity professionals Inleiding Het vakgebied ‘gender en diversiteit in organisaties’ bestudeert de proces- sen van machtsongelijkheid in organisaties, de factoren die ermee samen- VOL. 21, NO. 2, 2018 113 ▇▇▇▇▇▇ en de structuren die deze bestendigen. Echter, na ruim 50 jaar van onderzoeken, documenteren en theoretiseren van machtsongelijkheid tus- sen de meerderheid en van oudsher ondervertegenwoordigde groepen in organisaties (Calás, Smircich, & Holvino, 2014), is onze kennis over hoe organisaties daadwerkelijk meer gelijkheid kunnen creëren nog altijd te- leurstellend ▇▇▇▇▇ (Benschop, Mills, Mills, & ▇▇▇▇▇▇▇, 2012; ▇▇▇▇▇▇▇▇ & ▇▇▇▇▇▇, 2014; Vinkenburg, 2017). Organisaties voelen zich genoodzaakt di- versiteit op de agenda te plaatsen, maar tegenvallende resultaten lijken meer ▇▇▇▇▇ ▇▇▇ uitzondering. De vele pogingen van overheden, organisaties en individuen om veranderingen te bewerkstelligen, hebben slechts in be- perkte mate effect gehad (▇▇▇▇▇, 2012; ▇▇▇▇▇▇ & Kalev, 2016). We kunnen ons afvragen waarom, na jaren van wet- en regelgeving (zie Bleijenbergh, Van Engen, Terlouw, & ▇▇▇▇▇▇, 2014) as a green reducing agent en commitment van organisaties en leiders, onze organisaties nog steeds geen betere afspiegeling zijn van de maatschappij. Ongelijkheid in organophosphorus-catalysed amide bond formation† Daan organisaties blijkt niet eenvoudig te bestrijden. Ik ver- geleek het in mijn oratie met een zevenkoppige draak, waarbij ▇▇▇ ▇▇▇ een andere economische, culturele of structurele praktijk representeert die de ongelijkheid hardnekkig in stand houdt (Van den Brink, 2017). Een monster waarvan ▇ ▇▇▇▇▇▇ steeds bewegen en waarvan, afhankelijk van context en tijd, ▇▇▇ ▇▇▇▇ de ene of de andere kop domineert over de andere. En als het ▇▇ ▇▇▇▇ is gelukt om met veel inspanning een van die zeven ▇▇▇▇▇▇ ▇▇ ▇▇ ▇▇▇▇▇▇, steekt meteen weer een nieuwe kop op, op een ander gebied. Het is dus noodzakelijk om strategieën te bedenken die ▇▇ ▇▇▇▇▇▇ gaan met de dynamiek tussen de verschillende ▇▇▇▇▇▇ ▇▇ succesvol met de draak af te rekenen. Dat is een langdurig en moeizaam proces. In dit essay analyseer ik of we wel de juiste zwaarden hanteren en de juiste heldinnen en helden hebben om deze hardnekkige draak van ongelijkheid te verslaan. Het zwaard is niet scherp genoeg Laten we eerst eens kijken naar de instrumenten die we hebben ▇▇ ▇▇▇▇- lijkheid te bestrijden. Zijn onze zwaarden scherp genoeg? Oftewel, deugt onze wetenschappelijke kennis en waar zitten de lacunes? Hoe kan het dat al die kennis niet leidt tot ▇▇▇▇▇ veranderingen, en dat de ongelijkheid in organisaties, ondanks onze mooie modellen en theorieën, hardnekkig blijft bestaan? Effectiviteit is moeilijk vast te stellen Om te beginnen is het erg moeilijk om de effectiviteit van beleidsmaat- regelen vast te stellen (▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇, & ▇▇▇▇▇▇▇▇, ▇▇▇▇ ▇2014). Koenders, Er zijn slechts enkele studies die deze effectiviteit bestuderen (zie bijvoorbeeld ▇▇▇▇▇▇ P. J. T. & Kalev, 2016; ▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ * Development & ▇▇▇▇▇▇▇, 2012; Verbeek & Groeneveld, 2012) en die leren ons ▇▇▇▇▇ maatregelen de numerieke toename van on- dervertegenwoordigde groepen in organisaties vergroten op ▇▇▇▇▇ termijn. Ze bieden ons echter weinig inzicht in de langdurige effecten op de diversi- teitscultuur of catalytic amide bond formation reactions has been the subject of the intensive investi- gations mate van inclusie die wordt ervaren. Juist dit type informa- tie is echter noodzakelijk voor een langdurige verankering van diversiteit in the past decadeorganisaties (Mor Barak, 2015). Herein Bovendien is de effectiviteit van maat- regelen, zoals netwerken, diversiteitstrainingen en mentorprogramma’s, ▇▇▇▇▇ afhankelijk van de context waarin ▇▇ ▇▇▇▇▇▇ toegepast; en die is in elke organisatie anders (Ahonen, Tienari, ▇▇▇▇▇▇▇▇▇▇, & ▇▇▇▇▇▇, 2014; Heres & Benschop, 2010). In een laboratoriumonderzoek kunnen we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amineszorgen dat alle condities gelijk zijn, en kunnen we meten ▇▇▇▇▇ veranderingen het gevolg zijn van door onszelf opzettelijk aangebrachte variaties. Poly(methylhydrosiloxaneMaar in de dagelijkse realiteit is geen organisatie hetzelfde. Allemaal hebben ze verschillende, met elkaar verweven werkwijzen; allemaal hebben ze speci- fieke groepen werknemers; en allemaal zijn ze ingebed in specifieke cultu- rele en institutionele contexten (Heres & Benschop, 2010), a waste product of the silicon industry. Omdat die ▇▇▇▇- tijken zo complex en rommelig zijn, is used as an inexpensive and green reducing agent for het ontzettend lastig om empirische casestudies te vertalen naar abstracte theoretische inzichten die altijd toe- pasbaar zijn, in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇ context ▇▇▇ ook. Zo bleek uit mijn eerdere onder- zoek dat diversiteitsstrategieën die ontworpen zijn voor professionele bu- reaucratieën zoals accountantskantoren en banken, totaal niet aanslaan bij bijvoorbeeld een dynamisch mediabedrijf, een adhocratie (Van den Brink, 2014a). Waar ▇▇▇▇▇ bedrijven ruimte hebben voor uitgebreide diversiteits- plannen en professionals, moeten kleinere organisaties het hebben van informele dagelijkse praktijken. ▇▇ ▇▇▇▇▇▇ niet zomaar uitspraken gedaan ▇▇▇▇▇▇ of diversiteitstraining of mentorprogramma’s ‘werken’, het is af- hankelijk van de context en de wijze waarop deze programma’s ▇▇▇▇▇▇ opgezet en uitgevoerd (zie ▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇▇, ▇▇▇ ▇▇▇ ▇▇▇▇▇, & ▇▇▇▇, 2015). We moeten in ons onderzoek dus meer rekening houden met de specifieke organisatiekenmerken en de wijze waarop diversiteitsinitiatie- ven ontworpen en geïmplementeerd ▇▇▇▇▇▇, ook ▇▇ ▇▇▇▇▇ dit haaks op de wens naar best practices (▇▇▇▇▇ & ▇▇▇▇▇▇▇, 2014). Samenhang met ongelijkheidspraktijken Gaan we dieper in op de specifieke context, ▇▇▇ ▇▇▇▇ mij op dat we in ons onderzoek ook ▇▇ ▇▇▇▇▇▇ rekening houden met de bestaande ongelijkheids- praktijken in organisaties. Een organisatie is immers geen tabula rasa. Iedere organisatie kent praktijken die ongelijkheid produceren in termen van gender, etniciteit, seksualiteit en leeftijd. De aard en sterkte van deze ongelijkheidspraktijken hebben invloed op de effectiviteit van diversiteits- interventies – de maatregelen die we inzetten om meer diversiteit, gelijk- ▇▇▇▇ en inclusie te creëren (▇▇▇▇ & ▇▇▇▇▇▇, 2011). Hierdoor hebben maat- regelen die gelijkheid moeten bevorderen, vaak tragere en soms ook an- dere effecten ▇▇▇ bij de invoering ▇▇▇▇▇ was voorzien (Dobusch, 2014; Holck, 2015). Initiatieven voor meer gendergelijkheid en diversiteit ▇▇▇▇▇▇ ▇▇▇▇▇▇ ▇▇▇▇▇▇ of nooit bestudeerd in samenhang met initiatieven tegen gendergelijkheid en diversiteit. We moeten diversiteitsmaatregelen dus onderzoeken in hun complexe relatie met ongelijkheidspraktijken. Een voorbeeld: in een eerder onderzoek over genderongelijkheid bin- nen de academische wereld, hebben we bekeken hoe praktijken van gen- dergelijkheid en -ongelijkheid samenkomen, met elkaar conflicteren en op elkaar anticiperen (▇▇▇ ▇▇▇ ▇▇▇▇▇ & Benschop, 2012). Om genderbias tij- dens werving en selectie te voorkomen, stellen universiteiten protocollen in met de bedoeling de transparantie van deze processen te vergroten. Deze protocollen, de gelijkheidspraktijk, houden echter geen rekening met de bestaande micropolitiek in deze procedures. In de meest extreme gevallen werken deze beleidsmaatregelen zelfs contraproductief; commis- sieleden gebruiken micropolitieke technieken en strategieën om transpa- rantie te ‘faken’ terwijl ze het systeem naar hun hand zetten. De interventie om gendergelijkheid te bevorderen, maskeert dus als het ware de ongelijk- ▇▇▇▇ die plaatsvindt. Dit is in lijn met wat de Brits-Australische diversiteits- onderzoeker ▇▇▇▇ ▇▇▇▇▇ ‘doing diversity is doing the document’ noemt (▇▇▇▇▇, 2007, p. 590). Het simpelweg ‘hebben’ van een diversiteitsbeleid wordt gezien als een succesvol bewijs van commitment, maar dit zegt helemaal niets over de werkelijke praktijken van in- en uitsluiting die in een organisatie plaatsvinden. Niet lineair Wat de zaak extra ingewikkeld maakt, is dat het veranderproces in de richting van meer diversiteit en inclusie niet altijd lineair verloopt. Toch bevragen we in het onderzoek ▇▇ ▇▇▇▇▇▇ ons eigen theoretisch begrip van organisatieverandering in relatie tot gender en diversiteit, hoe deze plaats- vindt en hoe we deze kunnen herkennen. Veel onderzoeken houden vast aan een lineaire kijk in termen van uitkomsten. De onderliggende assump- tie is dat we diversiteitsveranderingen in zekere mate kunnen sturen en dat diversiteitstrategieën en initiatieven automatisch resulteren in een meer divers personeelsbestand. Maar deze lineaire kijk is wellicht niet realistisch en belemmert onze theoretische kennis over de effectiviteit van beleidsmaatregelen. Wellicht zijn we te ongeduldig of te goed getraind in het zien van ongelijkheid, zodat we ▇▇ ▇▇▇▇▇▇ stappen die gemaakt zijn, niet zien. Transformatieve verandering is een continu en iteratief proces waarin een omgeving wordt gecreëerd waar mensen kunnen leren, reflec- teren en experimenteren. We moeten incalculeren dat het ook de andere ▇▇▇▇ op kan gaan. Zo zien we vaak dat onder het bewind van een bestuurs- voorzitter diversiteitsbeleid op de agenda komt. Deze neemt ▇▇▇ enkele maatregelen, maar zodra een opvolger aantreedt, bestaat het gevaar dat deze maatregelen op de achtergrond raken. Ook macrofactoren, zoals de economische crisis, hebben de diversiteitsagenda bij veel organisaties tij- delijk doen verdwijnen, terwijl we zien dat veel organisaties nu weer meer aandacht besteden aan dit thema (De meerderheid en de buitenbeentjes, 2017). Hiervoor stellen ze vaak nieuwe diversiteitsmanagers aan die het wiel opnieuw uitvinden, maar daar kom ik later nog op terug. Mijn punt is dat we in het onderzoek meer gebruik moeten maken van non-lineaire en procesgerichte perspectieven op verandering in organisaties uit de or- ganisatiewetenschappen, die meer ruimte bieden voor het analyseren van fluctuaties, tegenslagen en weerstanden (Hernes, 2008; ▇▇▇▇▇▇ & ▇▇▇▇▇▇, 2005). Gluren bij de ▇▇▇▇▇ ▇▇▇▇ effect heeft dit gebrek aan ▇▇▇▇▇ ▇▇▇▇▇▇ over effectieve interventies op het gedrag van organisaties? Ze gaan gluren bij de buren (▇▇▇▇▇, 2014) wat leidt tot isomorfisme: organisaties kijken wat concurrenten in dezelfde branche doen, en kopiëren dat (▇▇▇▇▇▇ & ▇▇▇▇▇▇▇, 2005). Daarbij zijn voor- al diversiteitsmaatregelen in trek die je veel bij ▇▇▇▇▇ ondernemingen in Angelsaksische landen ziet; ▇▇▇▇▇▇ met een sterke wetgeving op het gebied van gelijke kansen en positieve discriminatie (Boxenbaum, 2006; Syed & Özbilgin, 2009). Zij gebruiken die maatregelen echter voornamelijk om te laten zien hoe netjes het betreffende bedrijf voldoet aan de institutionele normen (▇▇▇▇▇▇▇, 2005; ▇▇▇▇▇ & Noon, 2004), de welbekende ‘lip service’ ten opzichte van diversiteitsbeleid (zie ook Benschop, 2007). Gelijkheid, diversiteit en inclusie zijn mooie termen die moderne organisaties graag als uithangbord gebruiken (Singh & Point, 2006), maar dit pleidooi blijft vaak oppervlakkig (▇▇▇▇▇▇▇, 2005; ▇▇▇▇▇ & Noon, 2004), of in elk geval eenzijdig (▇▇▇▇▇▇▇▇▇▇▇ & Erlingsdóttir, 2005). Zo zijn in de loop van de tijd mentorprogramma’s, leiderschapsontwikkeltrajecten, awarenesstrainingen en diversiteitsnetwerken populaire diversiteitsinstrumenten geworden (▇▇▇▇▇▇▇▇▇, Benschop, & ▇▇▇ ▇▇▇ ▇▇▇▇▇, 2014; ▇▇▇, ▇▇▇▇▇▇ and ▇, & ▇▇▇▇, 2011; ▇▇▇▇▇▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond & ▇▇▇▇▇▇▇, 2006). Maar ondanks die populariteit weten we nog steeds ▇▇ ▇▇▇▇▇▇ over hun effectiviteit en hun mogelijke ongewenste gevolgen. Het blijkt dat deze instrumenten niet vanzelfsprekend zorgen voor meer gelijkheid (PvO▇▇▇▇▇▇ & ▇▇▇▇▇, 128 kcal mol−1) 2016; ▇▇▇▇▇, 2014). ▇▇▇▇▇▇▇ nog, ze werken soms averechts, in die zin dat ze stereotypen bevestigen en de vijandigheid van de meerderheid ten opzichte van minderheden vergroten (▇▇▇▇▇, 2016; ▇▇▇▇▇▇▇▇ & ▇▇▇▇▇▇, 1999; Noon, 2017). ▇▇▇▇ in dit verband aan zogenaamde gendertrainingen die teruggrijpen op ideeën als ‘mannen komen van ▇▇▇▇’ en ‘vrouwen komen van ▇▇▇▇▇’. Dit zijn ideeën die meer kapotmaken ▇▇▇ wij genderwetenschappers de rest van ons leven kunnen goedmaken, omdat ze de verschillen tussen mannen en vrouwen bena- drukken, tot onveranderlijke natuur verklaren en hiermee seksestereotype opvattingen niet bekritiseren, maar bevestigen (▇▇▇ ▇▇▇ ▇▇▇▇▇ & ▇▇ ▇▇▇▇▇, 2014). De laatste tien jaar is the driving force for the classic versions ofeen pluriform landschap ontstaan van aanbie- ders van vrouwen-, gender- en diversiteitstrainingen, -coaches en -oplei- dingen. Dit landschap wordt gekenmerkt door trainers met de nodige ex- pertise op dit gebied, maar ook door aanbieders die de hang naar diver- siteit zien als een gat in de markt en zonder een gedegen kennis van de structurele aard van ongelijkheid wat betreft gender, etniciteit en sekse (Kaiser et al., 2013). Het gevolg hiervan is dat veel van dit type interventies zich weer richten op de ‘deficiënte’ vrouwen, en niet op het systeem van ongelijkheid. Een slechte strategie We hebben dus meer en betere wetenschappelijke kennis nodig voor een duurzaam en effectief diversiteitsbeleid; maar daarmee hebben we de or- ganisaties nog niet veranderd. Wat gebeurt er uiteindelijk met onze weten- schappelijke kennis en ▇▇▇▇▇ zwaarden hanteren organisaties zelf? Het lijkt erop dat een moderne organisatie best goede ▇▇▇▇ ▇▇▇

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite this: Org. Biomol. ChemINT J TUBERC LUNG DIS 21(8):880–886 Q 2017 The Union ▇▇▇▇://▇▇., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇▇.▇▇▇/10.5588/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent ijtld.16.0851 Automatic versus human reading of chest X-rays in organophosphorus-catalysed amide bond formation† Daan ▇. the Zambia National Tuberculosis Prevalence Survey ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇ * Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ,*† R. H. H. M. ▇▇▇▇▇▇▇▇▇,*† , . ▇▇▇▇▇▇▇▇▇, -▇▇▇▇▇▇ and ▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO, 128 kcal mol−1) is the driving force for the classic versions of,‡§ V. Sunkutu,¶ N. Kapata,‡§

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Inl eiding  Ruimtelijke interventies in de stad zijn noodzakelijk om maatschappelijke en econo- mische belangen te realiseren. Downloaded by Radboud University Nijmegen on 3/8/2019 8:23:31 AMMaar hoe ▇▇▇ ▇▇ het beste de stedelijke ruimte ordenen? Dat is een fundamentele vraag voor de planologische wetenschap. Biomolecular Chemistry PAPER Cite this: Org. Biomol. Chem., 2017, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k Decennialang is de ruimtelijke ordening gebaseerd geweest op de gedachte dat de ruimte in de stad een soort publiek goed is dat door de overheid moet ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent aangeboden en beheerd. De planologie gaat vooral over de vraag hoe de overheid dat ▇▇▇ ▇▇▇ moeten doen. Nederlandse steden zijn daarbij vaak ondernemend ▇▇ ▇▇▇▇ gegaan en hebben naar hartenlust voor ontwikkelaar gespeeld. Zij hebben zelf bouwgrond gerealiseerd, op basis van een actief gemeentelijk grondbeleid. Inmiddels is ook bekend dat daaraan de nodige risico’s verbonden zijn en dat de uitkomst van dit proces niet altijd succes- vol is. Veel steden hebben tientallen miljoenen euro’s verlies geleden op hun investe- ▇▇▇▇▇▇ in organophosphorus-catalysed amide bond formation† Daan grond doordat ze de bouwgrond niet kunnen verkopen of tegen een veel lagere prijs . . ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇▇▇▇▇▇, ▇▇▇▇ ▇Uit de economische wetenschap kunnen we leren dat er op z’n minst twee alternatie- ven zijn voor de ‘ruimtelijke orde als publiek goed’-benadering. Koenders, ▇▇▇▇▇▇ P. J. T. ▇▇▇▇▇▇ and Nobelprijswinnaar ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇* Development of catalytic amide bond formation reactions has been the subject of the intensive investi- gations in the past decade. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxane), a waste product of the silicon industry, is used as an inexpensive and green reducing agent for in situ reduction of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the ▇▇▇▇▇leert ons dat publieke goederen het gevolg zijn van onvolledig gefor- muleerde eigendomsrechten (▇▇▇▇▇, 1960). Omdat deze rechten niet goed zijn afge- bakend, blijft het goed in het publieke domein. Voorbeelden hiervan zijn de openbare ruimte en het parkeren in een binnenstad. Particulieren zullen niet snel ‘de openbare ruimte’ gaan produceren, omdat het gebruik van die openbare ruimte moeilijk af te bakenen is. Je kunt voor de toegang tot de openbare ruimte moeilijk een prijs heffen. De oplossing ▇▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇ and voor goederen in het publieke domein is de toekenning van volledige eigendomsrechten door de overheid aan de markt, waarmee het een privaat goed wordt. Voortbouwend op de ▇▇▇▇▇ reactions.1 The formation of the relatively strong phosphine oxide bond (PvO▇▇▇ ▇▇▇▇▇ kunnen planologen de ruimte ordenen door ‘markten in rechten’ te creëren, 128 kcal mol−1) is the driving force for the classic versions ofvergelijkbaar met markten in

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End User Agreement. This publication is distributed under the terms of Article 25fa of the Dutch Copyright Act (Auteurswet) with explicit consent by the author. Dutch law entitles the maker of a short scientific work funded either wholly or partially by Dutch public funds to make that work publicly available for no consideration following a reasonable period of time after the work was first published, provided that clear reference is made to the source of the first publication of the work. This publication is distributed under The Association of Universities in the Netherlands (VSNU) ‘Article 25fa implementation’ pilot project. In this pilot research outputs of researchers employed by Dutch Universities that comply with the legal requirements of Article 25fa of the Dutch Copyright Act are distributed online and free of cost or other barriers in institutional repositories. Research outputs are distributed six months after their first online publication in the original published version and with proper attribution to the source of the original publication. You are permitted to download and use the publication for personal purposes. Please note that you are not allowed to share this article on other platforms, but can link to it. All rights remain with the author(s) and/or copyrights owner(s) of this work. Any use of the publication or parts of it other than authorised under this licence or copyright law is prohibited. Neither Radboud University nor the authors of this publication are liable for any damage resulting from your (re)use of this publication. If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the ma terial inaccessible and/or remove it from the website. Please contact the Library through email: ▇▇▇▇▇▇▇▇▇@▇▇▇.▇▇.▇▇, or send a letter to: University Library Radboud University Copyright Information Point PO Box 9100 6500 HA Nijmegen You will be contacted as soon as possible. Organic & Published on 17 July 2017. Downloaded by This article was downloaded by: [Radboud University Nijmegen on 3/8/2019 8:23:31 AM. Biomolecular Chemistry PAPER Cite thisUniversiteit Nijmegen] On: Org. Biomol. Chem.19 November 2013, 2017At: 04:33 Publisher: Routledge Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 15, 6426 Received 22nd June 2017, Accepted 15th July 2017 DOI: 10.1039/c7ob01510k ▇▇-▇▇ ▇▇▇.▇▇/▇▇▇ Poly(methylhydrosiloxane) as a green reducing agent in organophosphorus-catalysed amide bond formation† Daan ▇. ▇. ▇▇▇▇▇▇▇, ▇▇▇▇▇ ▇. ▇▇ ▇▇▇, ▇▇ Publication details, including instructions for authors and subscription information: ▇▇▇▇://▇▇▇.▇▇▇▇▇▇▇, ▇▇▇▇ ▇. Koenders, ▇▇▇▇▇▇ P. J. T. .▇▇▇/loi/cjud20 ▇▇ and ▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇a & ▇▇▇▇▇▇ ▇▇▇ ▇▇▇▇▇ b a Centre for Urban Studies, University of Amsterdam , Amsterdam , The Netherlands b Nijmegen School of Management, Radboud University Nijmegen , Nijmegen , The Netherlands Published online: 14 Jun 2013. To cite this article: ▇▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇▇ & ▇▇▇▇▇▇ ▇▇▇ ▇▇▇▇▇ (2013) Challenging the ‘End of Public Space’: A Comparative Analysis of Publicness in British and Dutch Urban Spaces, Journal of Urban Design, 18:3, 429-448, DOI: 10.1080/13574809.2013.800451 To link to this article: ▇▇▇▇://▇▇.▇▇▇.▇▇▇/10.1080/13574809.2013.800451 PLEASE SCROLL DOWN FOR ARTICLE ▇▇▇▇▇▇ & ▇▇▇▇▇▇▇ makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, ▇▇▇▇▇▇ & ▇▇▇▇▇▇▇, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. 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Terms & Conditions of access and use can be found at ▇▇▇▇://▇▇▇.▇▇▇▇▇▇▇▇▇▇▇.▇▇▇/page/terms- and-conditions Vol. 18, No. 3, 429–448, ▇▇▇▇://▇▇.▇▇▇.▇▇▇/10.1080/13574809.2013.800451 Challenging the ‘End of Public Space’: A Comparative Analysis of Publicness in British and Dutch Urban Spaces ▇▇▇▇▇▇▇ ▇▇▇▇▇▇▇▇▇▇* Development & ▇▇▇▇▇▇ ▇▇▇ ▇▇▇▇▇** Downloaded by [Radboud Universiteit Nijmegen] at 04:33 19 November 2013 *Centre for Urban Studies, University of catalytic amide bond formation reactions Amsterdam, Amsterdam, The Netherlands; **Nijmegen School of Management, Radboud University Nijmegen, Nijmegen, The Netherlands Abstract The increasing involvement of the private sector in the design and management of urban public space has prompted some critical scholars to predict the ‘end of public space’. This study reassesses the implications of private sector involvement through a comparative analysis of British and Dutch urban spaces, based on a threefold critique of the existing literature on the privatization of public space. The analysis is governed by a new model of pseudo-public space that consists of four dimensions of ‘publicness’: ownership, management, accessibility and inclusiveness (OMAI). The findings suggest that, while there are significant differences between the British and the Dutch cases, neither context supports the notion of a possible ‘end of public space’ in any literal sense. Introduction Urban public spaces, such as squares, streets, plazas and parks, have been the subject of considerable debate over the intensive investi- gations last two decades. Some critical urban scholars have argued that public space is under threat (▇▇▇▇▇▇ 1992; ▇▇▇▇▇▇▇▇ 1995, 2003; ▇▇▇▇▇▇▇▇ 2001; ▇▇▇▇▇ 2006; Madden 2010). They paint a rather bleak picture of modern urban life, one that is characterized by social exclusion, sanitized consumerism and restrictive security measures. In his critique of American urbanism, ▇▇▇▇▇▇ (1992) even spoke in terms of the past decade‘end of public space’ when he compared the contemporary American urban landscape to Disneyland: a place that provides regulated pleasure for its target group, but at the same time a soulless place which is stripped of its sting, cleaned of undesirables, heavily controlled and, ultimately, a place that proves to be an illusion. Herein we report an efficient organophosphorus-catalysed amidation reaction between unactivated carboxylic acids and amines. Poly(methylhydrosiloxaneRecently, some popular media, such as Britain’s The Guardian (2012), a waste product have also raised concerns about “new outdoor spaces [that] favour business over community”. If we are convinced by this depiction of contemporary public space, an important question is why its nature is changing. One of the silicon industry, main reasons the literature points to is used as an inexpensive and green reducing agent for the increasing involvement of the private sector; in situ reduction other words the ‘privatization’ of phosphine oxide to phosphine. The reported method enables the synthesis of a wide range of secondary and tertiary amides in very good to excellent yields. Over the past decade, there has been a significant interest in the development of catalytic versions of phosphine-mediated reactions that are often used in organic synthesis, including the public space (Loukaitou-▇▇▇▇▇▇▇ 1993; ▇▇▇▇▇▇▇▇ 2001; ▇▇▇▇ 2004; ▇▇▇▇▇ 2006; see also London Assembly 2011). Local authorities have Correspondence Address: ▇▇▇▇▇▇ ▇▇▇ ▇▇▇▇▇, Nijmegen School of Management, Radboud University Nijmegen, PO Box ▇▇▇▇, ▇▇▇▇ ▇▇, ▇▇▇▇▇▇▇▇, ▇▇▇▇▇▇▇▇▇▇▇▇▇. Email: ▇.▇▇▇▇▇▇▇▇@▇▇.▇▇.▇▇ Downloaded by [Radboud Universiteit Nijmegen] at 04:33 19 November 2013 traditionally been responsible for managing the public spaces of city centres. However, they are increasingly unable and unwilling to bear the sole responsibility of the provision of public goods. They are unable because confronted with decentralization, deindustrialization, rising structural unemployment and a shrinking fiscal capacity of the state, their financial abilities to invest in public space are limited (▇▇▇▇▇▇▇ 2002; De Magalha˜es 2010). They are unwilling because the increasingly ‘entrepreneurial’ local authorities realize they need to cooperate with the private sector in order to not just offer public goods, but to create spectacular, well-designed public spaces that help to attract higher-income residents, tourists, investments and businesses to the city (▇▇▇▇▇▇▇▇▇▇ reactions.1 The formation 2003). Handing over responsibility for providing public space to the private sector would thus save government expenses on the one hand, and lead to more spectacular and well-maintained spaces on the other hand, following the argument that it is more efficient to put the production of goods and services in the hands of the relatively strong phosphine oxide bond market (PvO▇▇▇▇▇▇▇ 2006). An ever-growing number of urban parks, 128 kcal mol−1) plazas and shopping centres worldwide are now both owned and managed by for-profit enterprises. The crucial point here is that, while these spaces may look like public spaces on first sight, they are always managed and controlled with private interests in mind, and are therefore not truly public. As ▇▇▇▇▇▇▇▇ stated: There is a presumption of ‘publicness’ in these pseudopublic spaces. But in reality they are in the driving force for private realm Access to and use of the classic versions ofspace is only a privilege, not a right Any expectation that such spaces are open to all is fanciful at best. (Banerjee 2001, 12)

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