Auswahl der wissenschaftlichen Literatur zum Thema „Post-Transnational modifications“

Abstract‘High skilled’ Kamma migrants from Coastal Andhra domiciled in the USA maintain strong ties with their villages and towns of origin. Since the 1990s, one key way in which they have sustained relations with their roots is through transnational philanthropy. Over the last two decades, migrant donors have diversified the modalities of their philanthropic engagements, increasingly institutionalizing them through US-based transnational associations. While the institutionalization of philanthropy may appear to be an import from the USA, closer examination reveals its historical antecedent in the caste-based Varaalu system practised by the Kammas during the late colonial period. The transnationalization of older forms of giving are marked by key modifications in the way giving is conceptualized—from being localized, need based, and individualized to being based on merit, efficiency, and professionalization. The term ‘donation’ is used to describe their philanthropy, rather than daan or charity, and the politics of semantics points to the modernizing impulse within the community to transcend caste owing to their diasporic location. Yet, by aiming to reach deserving beneficiaries while upholding meritocracy, donors often circulate philanthropic resources horizontally on a caste inflected and highly politicized transnational plane. The discourse and practices of transnational giving in post-reform India bring out the contradiction that simultaneously obscures the workings of a caste while transnationalizing its boundaries.

AbstractA consideration of political participation in early Stuart Ireland suggests modifications to the prospectus outlined by Peter Lake and Steven Pincus in “Rethinking the Public Sphere in Early Modern England.” By investigating the structures that facilitated public debates about politics in Ireland, as well as the factors that complicated it, this article challenges the periodization of the public sphere offered by Lake and Pincus and suggests that there is a clear need to integrate a transnational perspective. Unlike England, Scotland, and Wales, the majority of Ireland's population was Catholic. The flow of post-Tridentine Catholic ideas from the Continent and Anglo-Britannic political culture meant that competing ideas of what constituted the common good circulated widely in Ireland and led to debates about the nature of authority in the early modern Irish state. These divisions in Irish society created a distinctive kind of politics that created particularly unstable publics. Thus, Ireland's experience of the early modern public sphere differed considerably from concurrent developments in the wider archipelago.

Background: Use of adaptive clinical trials, particularly adaptive platform trials, has grown exponentially in response to the coronavirus disease (COVID-19) pandemic. Implementation of these trials in low- and middle-income countries (LMICs) has been fostered through the formation or modification of transnational research partnerships, typically between research groups from LMICs and high-income countries (HICs). While these partnerships are important to promote collaboration and overcome the structural and economic disadvantages faced by LMIC health researchers, it is critical to focus attention on the multiple dimensions of partnership equity. Methods: Based on informal literature reviews and meetings with leaders of one of the multinational COVID-19 adaptive platform trials, we describe what can be learned about research partnership equity from these experiences. Results: We organize these considerations into eight thematic categories: 1) epistemic structures, 2) funding, 3) ethics oversight, 4) regulatory oversight, 5) leadership, 6) post-trial access to interventions, data, and specimens, 7) knowledge translation, and 8) research capacity strengthening and maintenance. Within each category we review the normative claims that support its relevance to research partnership equity followed by discussion of how adaptive platform trials highlight new dimensions, considerations, or challenges. Conclusion: These observations provide insight into procedural and substantive equity-building measures within transnational global health research partnerships more broadly.

Background Use of adaptive clinical trials, particularly adaptive platform trials, has grown exponentially in response to the coronavirus disease (COVID-19) pandemic. Implementation of these trials in low- and middle-income countries (LMICs) has been fostered through the formation or modification of transnational research partnerships, typically between research groups from LMICs and high-income countries (HICs). While these partnerships are important to promote collaboration and overcome the structural and economic disadvantages faced by LMIC health researchers, it is critical to focus attention on the multiple dimensions of partnership equity. Methods Based on informal literature reviews and a meeting with leaders of one of the multinational COVID-19 adaptive platform trials, we describe some important considerations about research partnership equity in this context. Results We organize these considerations into eight thematic categories: 1) epistemic structures, 2) funding, 3) ethics oversight, 4) regulatory oversight, 5) leadership, 6) post-trial access to interventions, data, and specimens, 7) knowledge translation and dissemination, and 8) research capacity strengthening and maintenance. Within each category we review normative claims that support its relevance to research partnership equity followed by discussion of how adaptive platform trials highlight new dimensions, considerations, or challenges. Conclusion In aggregate, these observations provide insight into procedural and substantive equity-building measures within transnational global health research partnerships more broadly.

The article is devoted to the analysis of the theory and practice of the cyclical development of the economy. Revealed the relevance of studying the cyclical development of socio-economic systems; the content of key concepts used in the modern interpretation of the economic cycle (essence, content, manifestation and form of the economic cycle); classification of theories of cyclical development of the economy. The characteristics of the main types of non-cyclical fluctuations in the economy are given: seasonal fluctuations, reflecting the influence of seasonal and climatic conditions; structural fluctuations associated with changes in demand for certain types of products; transitional fluctuations due to a change in the mechanism of the functioning of the economy. The distinctive features of the economic cycles of the second half of the twentieth century, due to the third industrial revolution, the growing influence of transnational corporations and the transition to a post-industrial society, are analyzed. The main directions of modification of economic cycles in the second half of the 20th century are presented. The beginning of the XXI century. The modern features of the cyclical development of the Russian economy, related, among other things, to the influence of anti-Russian sanctions and the use of other non-market instruments in the global economy, are analyzed. The conclusion is made about the growing influence of uncertainty on the adoption of strategic decisions in modern conditions and the increasing importance of ensuring import independence for the industrial development of the economy of regions and industries in Russia.

This article studies the geo-economic paradigm of the development of the world and national economy, which should be considered as an economic interpretation of geopolitics, since we are talking about control over space, which, first of all, refers to geographical and economic space, inextricably linked with the concept of "territorial integrity". This led to the emergence of specific institutions - global and internal (often transboundary) geo-economic regions, which are interpreted as tools for implementing state economic policy in solving the problems of developing the national economy. The article discusses some theoretical aspects of the formation and development of internal geo-economic regions, in relation to modern Russia. Approaches to the interpretation of the concept of "geoeconomic region" in the context of the continuous transformation of the system of global economic interaction and the reformatting of the institutional model of the world geopolitical system are proposed. It is noted that the radical transformation of the post-war world order, expressed by the fall of the bipolar (balanced) principle of economic and political interaction and its replacement by a transnational economy, caused a response of national economic systems, expressed by regionalization. It is also argued that in the conditions of a radical transformation of the system of global economic interaction, the course of internal regionalization processes is changing, which is associated with a gradual modification of the functional role of regions in the world reproductive system. This made it possible to give a brief theoretical description of the existing internal geo-economic regions and study the prerequisites for their emergence and development. Based on the theoretical analysis of the processes of geoeconomic regionalization carried out in the study, a general classification of the internal geoeconomic regions of the country is proposed, which is based on a functional approach.

Introdução: A transmissão SARS-CoV-2 de humano para humano pode ocorrer e o risco de propagação no ar durante os procedimentos odontológicos geradores de aerossóis permanece uma preocupação. Acredita-se que um enxaguatório bucal antimicrobiano pré-operacional reduza o número de micróbios orais. No entanto, a eficácia do enxaguatório bucal pré-procedimento na redução do número de microrganismos disseminados por meio do aerossol gerado por procedimentos odontológicos ainda não está clara. Objetivo: avaliar através de uma revisão de literatura o uso de enxaguantes bucais na redução da carga viral do SARS-CoV-2. Materiais e Método: O levantamento literário para esta pesquisa foi realizado no período de dezembro de 2019 a 10 de agosto de 2020 nas bases de dados Scielo e Medline/PubMed. Na estratégia de busca, foram utilizadas as palavras “SARS-CoV-2”, “2019-nCoV”, “COVID-19”, “Dentistry”, “Odontologia”, “Odontología”, “Mouthwashes”, “Antissépticos Bucais” e “Antisépticos Bucales”. Resultados: Uma busca sistematizada foi realizada, foram encontrados 661 artigos, após a realização da leitura criteriosa dos artigos completos foram selecionados 42 artigos. 88% dos estudos indicavam o uso de Peróxido de hidrogênio a 1%, 76% indicavam Povidine 0,2% e apenas 19% o uso da Clorexidina a 0,12%. Conclusão: Os estudos presentes na literatura apresentam divergências nas indicações e porcentagens dos enxaguantes indicados. Os protocolos clínicos devem ser avaliados para reduzir o risco de transmissão e proteger pacientes e profissionais.Descritores: Infecções por Coronavírus; Betacoronavirus; Odontologia; Antissépticos Bucais.ReferênciasGe ZY, Yang LM, Xia JJ, Fu XH, Zhang YZ. Possible aerosol transmission of COVID-19 and special precautions in dentistry. J Zhejiang Univ Sci B. 2020;21(5):361-68. Peng X, Xu X, Li Y, Cheng L, Zhou X, Ren B. Transmission routes of 2019-nCoV and controls in dental practice. 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Introduction Within wellness circles, there has been growing concern over an increasing focus on Alternative Right (or Alt-right) conspiracy (see Aubry; Bloom and Moskalenko). Greene, referring to a definition provided by the Anti-Defamation League, defines the Alt-right as a loose political network characterised by its rejection of mainstream conservatism, embrace of white nationalism, and use of online platforms (33). The “wellness revolution”, on the other hand, which marked a split from the health care sector in which “thought leaders” replaced medical experts as authorities on health (Pilzer, qtd. in Kickbusch and Payne 275), combines New Age practices with ideological movements that emphasise the “interdependence of body, mind and spirit” (Voigt and Laing 32). It has been noted that there is overlap between the circulation of conspiracy theory and New Age mysticism (see Ward and Voas; Parmigiani). Influencers following the Paleo diet, or Palaeolithic diet, such as Australian celebrity chef and Paleo diet guru Pete Evans, have also come under fire for sharing conspiracy theories and pseudoscience (see Brennan). Johnson notes that the origins of the Paleo diet can be traced back to 1975, with the publication of Dr Walter Voegtlin’s book The Stone Age Diet. This text, however, has been largely disavowed by Paleo leaders due to Voegtlin’s “white supremacist, eugenicist, and generally unpalatable politics”. Nevertheless, it is interesting to consider how white nationalism and conspiracy theory may overlap within the wellness space. A specific example occurred in 2020, when Pete Evans shared an Alt-right conspiracy meme to his Facebook account. The ‘butterfly-caterpillar meme’ contained the image of a black sun, a symbol equated with the swastika (Goodrick-Clarke 3). Though Evans later commented that the sharing of the hate symbol was unintentional, and that he misunderstood the symbol, this case raised questions about the ability of wellness influencers to amplify white nationalist messaging. This essay is concerned with the question: what makes the wellness industry a target for the spreading of white nationalist ideas? It argues that the wellness industry and far-right ideology possess a pre-occupation with bodily purity which makes it more likely that white nationalist material carrying this message will be spread via wellness networks. Through a critical examination of the media surrounding Evans’s sharing of the butterfly-caterpillar meme, this case study will examine the ideological aspects of the Paleo diet and how they appeal to a white nationalist agenda. Focussing on the Australian context, this essay will theorise the spreadability of memes in relation to white nationalist symbolism. It contends that the Paleo diet positions foods that are not organic as impure, and holds a preference for positive messaging. Alt-right propaganda packaged in a positive and New Age frame poses a danger in that it can operate as a kind of contagion for high-profile networks, exponentially increasing its spreadability. This is of particular concern when it is considered that diet can have an impact on people’s actions outside of the online space: it impacts what people consume and do with their bodies, as evidenced by calls for eating disorders created by algorithmic repetition to be considered a ‘cyber-pathy’. This creates the conditions for the wellness industry to be targeted using memes as recruitment material for white nationalist groups. The Paleo Diet and the Sharing of a Neo-Nazi Meme Pete Evans is a famous Australian TV Chef from the hit series My Kitchen Rules, a show that ran from 2010-2020. The show followed pairs from different households as they cooked for Evans and his co-host Manu Feildel. During the show’s run, Evans also became known for spruiking the Paleo diet, producing several cookbooks and a documentary on the topic. According to Catie Gressier, who conducted a study of Paleo dieters in Melbourne, Paleo’s aim is “to eat only those foods available prior to the agricultural revolution: meat, fish, vegetables, nuts, seeds and a small amount of fruit” and that this framed as a more “authentic” diet (3). This is seen as an ideological diet as opposed to others which may consist of rules or eating restrictions. The Paleo diet stresses “real foods” or “organic foods as close to their real state as possible” (Ramachandran et al.). Studies find that the paleo diet can be very nutritious (Cambeses-Franco et al. 2021). However, it is important to note that the presence of multiple influencers and thought leaders in the field means that there can be several variations in the diet. This article will limit its examination to that of the diet promoted by Evans. A common rationale is that the human body is incompatible with certain mass-produced foods (like grains, pulses, and dairy products, sugar, salt, and modification practices (like food processing), and that these are the cause of many modern conditions (Cambeses-Franco et al. 2021). While growing concerns over unnatural additives in foods are warranted, it can be observed that in Evans’s case, the promotion of the Paleo diet increasingly blurred the line between pseudoscience and conspiracy. In his Paleo diet book for toddlers, Evans emphasised the importance of the ideological diet and suggested that parents feed their toddlers bone broth instead of breast milk, prompting a federal investigation by the health department (Brennan). This escalated in 2020 during the global pandemic. In January, Evans promoted the work of a prominent anti-vaccine advocate (Molloy). In April, his Biocharger device, which he claimed could cure coronavirus, earned him a hefty fine from the Therapeutic Goods Administration (White). In November, several months after My Kitchen Rules was cancelled, Evans posted an Alt-right political cartoon with the image of a black sun, a symbol equated with the swastika (Goodrick-Clarke 3), to his Facebook account (Gillespie). In later news reports, it was also pointed out that the black sun symbol was emblazoned on the backpack of the Christchurch shooter (see Sutton and Molloy) who had targeted two mosques in Christchurch, New Zealand, killing 51 people and injuring 40. Initially, when a user on Facebook pointed out that the meme contained a black sun, Evans responded “I was waiting for someone to see that” (Evans, qtd. in Gillespie). Evans eventually recanted the image, writing: sincere apologies to anyone who misinterpreted a previous post of a caterpillar and a butterfly having a chat over a drink and perceived that I was promoting hatred. I look forward to studying every symbol that have ever existed and research them thoroughly before posting. Hopefully this symbol ❤️ resonates deeply into the hearts of ALL! (Evans, qtd. in Gillespie). The post was later deleted. In December of 2020, Evans’s Facebook page of around 1.5 million followers was removed due to its sharing of conspiracy theories and misinformation about the coronavirus (Gillespie). However, it should be noted that the sharing of the caterpillar-butterfly meme was different from the previous instances of conspiracy sharing, in that Evans stated that it was unintentional, and it included imagery associated with neo-Nazi ideology (the black sun). Evans’s response implies that, while the values of the Paleo diet are framed in terms of positivity, the symbols in the butterfly-caterpillar meme are associated with “promoting hatred”. In this way, Evans frames racism as merely and simplistically an act of hatred, rather than engaging in the ways in which it reinforces a racial hierarchy and racially motivated violence. According to Hartzell (10), white nationalists tend to position themselves as superior to other races and see themselves as protectors of the “white race”. “White” in this context is of European descent (Geary, Schofield and Sutton). There are conspiracy theories associated with this belief, one of which is that their race is under threat of extinction because of immigration from ‘undesirable’ countries of origin. This can also be observed in the Alt-right, which is a white nationalist movement that was created and organised online. According to Berger, this movement “seeks to unify the activities of several different extremist movements or ideologies”. This is characterised by anti-immigrant sentiment, conspiracy theories, and support for former US President Donald Trump. It can be argued, in this case, that the symbol links to a larger conspiracy theory in which whiteness must be defended against some perceived threat. The meme implies that there is an ‘us’ versus ‘them’, or ‘good’ versus ‘evil’, and that some people are ‘in the know’ while others are not. Spreadable Memes An important aspect of this case study is that this instance of far-right recruitment used the form of a meme. Memes are highly spreadable, and they have very complex mechanisms for disseminating ideas and ideology. This can have a dramatic impact if that ideology is a harmful one, such a white supremacist symbol. While the digital meme, an image with a small amount of text, is common today, Richard Dawkins originally used the term meme to describe the ways in which units of culture can be spread from person to person (qtd. in Shifman 9). These can be anything from the lyrics of a song to a political idea. Jeff Hemsley and Robert Mason (qtd. in Shifman) see virality as a “process wherein a message is actively forwarded from one person to other, within and between multiple weakly linked personal networks, resulting in a rapid increase in the number of people who are exposed to the message” (55). This also links to Jenkins, Ford, and Green’s notions of spreadability (3-11), a natural selection process by which media content continues to exist through networked sharing, or disappears once it stops being shared. Evans’s response indicates that he merely shared the image. Despite the black sun imagery, a Make America Great Again (MAGA) hat is clearly present. A political presence, and one that is associated with white nationalism, is present despite Evans’s attempts to frame the meme in the language of innocence and positivity. This is not to say Evans is extremist or supports a white nationalist agenda. However, in much the same way that sharing of imagery may not necessarily indicate agreement with its ideological messaging, this framing creates a way in which wellness influencers may avoid criticism (Ma 1). Furthermore, the act of sharing the meme, regardless of intention, amplifies its message exponentially. The Paleo Diet, the Far Right and Purity This overlap between wellness and white nationalist ideology is not new. In Jules Evans’s exploration of why QAnon is popular with New Age and far-right followers, she points to the fact that many Nazi leaders – Hitler, Hess, Himmler – “were into alternative medicine, organic and vegetarian diets, homeopathy, anti-vaxxing, and natural healing”. Similarly, Bernhard Forchtner and Ana Tominc argue that a natural diet which focussed on food purity was favoured by the Nazis (421). In their examination of the German neo-Nazi YouTube channel Balaclava Küche they argue add that “present-day extreme right views on environment and diet are often close to positions found in contemporary Green movements and foodie magazines” (422). Like neo-Nazi preoccupations with food, the Paleo diet’s ideology has its basis in the concept of purity. Gressier found that the Paleo diet contains an “embedded moralism” that “filters into constructions of food as either pure or polluting” (1). This is supported by Ramachandran et al.’s study, which found that the diet “promoted ‘real food’ – or the shift to consuming organic whole foods that are as close to their natural state as possible, with an avoidance of processed foods”. This framing of the food as real creates a binary – if one is real, the other must not be. Another example can be seen in Pete Evans’s Webpage, which lists about 33 Paleo recipes. The Butter Chicken recipe states: the paleo way of life is not meant to be restrictive, as you can see from this lovely butter chicken recipe. All the nasties have been replaced with good-quality ingredients that make it as good, if not better, than the original. I prefer chicken thighs for their superior flavour and tenderness. The term “nasties” here can be seen to create a dichotomy between real and fake, the west and the east. We see these foods are associated with impurity, the foods that are not “real foods” are positioned as a threat. It can be seen as an orientalist approach, othering those not associated with the west. As can be observed in this Butter Chicken recipe that is “getting rid of the nasties”, it appropriates and ‘sanitises’ ingredients. In her article on the campaign to boycott Halal, Shakira Hussein points out that “ethnic food” presents as multiculturalism in the context of white chefs and homecooks, but the opposite is true if the roles are switched (91). Later in her essay “Halal Chops and Fascist Cupcakes”, she discusses the “weaponisation of food” and how specific white nationalist groups express disgust at the thought of consuming Muslim food. This ethnocentric framing of butter chicken projects a western superiority, replacing traditional ingredients with ‘familiar’ ingredients, making it more palatable to nationalistic tastes. Spreading Consumption I have established that the Paleo diet, with its emphasis on ‘real foods’, is deeply embedded with nationalist ideology. I have also discussed how this is highly spreadable in the form of a meme, particularly when it is framed in the language of positivity. Furthermore, I have argued that this is an attempt to escape criticism for promoting white nationalist values. I would like to turn now to how this spreadability through diet can have an impact on the physical actions of its followers through its digital communication. The Paleo diet, and how to go about following it as described by celebrity influencers, has an impact on what people do with their bodies. Hanganu-Bresch discusses the concept of orthorexia, a fixation with eating proper foods that operates as a cyber-pathy, a digitally propagated condition targeting media users. Like the ‘viral’ and ‘spreadable’ meme, this puritanical obsession with eating can also be considered both a spreadable condition and ideology. According to Hanganu-Bresch, orthorexia sees this diet as a way to overcome an illness or to improve general health, but this also begins to feel righteous and even holy or spiritual. This operates within the context of neoliberalism. Brice and Thorpe talk about women’s activewear worn in everyday settings, or ‘athleisure’, as a neoliberal uniform that says, ‘I’m taking control of my body and health’. To take this idea a step further, this uniform could be extended out into digital spaces as well in terms of what people post on their profiles and social media. This ideological aspect operates as not only a highly spreadable message, but one that is targeted at the overall health of its followers. It encourages not only the spreading of ideology, in this case, white nationalist ideology, but also the modification of food consumption. If this were then to be used as a vehicle to spread messages that encourage white nationalist ideology, it can be seen to be not only a kind of contagion but a powerful one at that. White nationalist iconography that is clearly associated with white supremacist propaganda has the potential to spread extremism. However, neoliberal principles of discipline and bodywork operate through “messages of empowerment, choice, and self-care” (Lavrence and Lozanski, qtd. in Brice and Thorpe). While racist extremism does not necessarily equate to neoliberal and ethnocentric values, a frame of growth, purity, and positivity create an overlap that allow extremist messaging to spread more easily through these networks. Conclusion The case of Pete Evans’s sharing of the butterfly-caterpillar meme exemplifies a concerning overlap between white nationalist discourse and wellness. Ideologically based diets that emphasise real foods, such as the Paleo diet, have a preoccupation with purity and consumption that appeals to white nationalism. They also share a tolerance for the promotion of conspiracy theory and tendency to create an ‘us’ versus ‘them’ dichotomy. Noting these points can provide insight into a potential targeting of the wellness industry to spread racist ideology. As research into spreadability shows, memes are extremely shareable, even if the user does not grasp the meaning behind the symbolism. This article has also extended the idea of the cyberpathy further, noting a weaponisation of the properties of the meme, for the purposes of radicalisation, and how these are accelerated by celebrity influence. This is more potent within the wellness industry when the message is packaged as a form of growth and positivity, which serve to deflect accusations of racism. Furthermore, when diet is combined with white nationalist ideology, it may operate like a contagion, creating the conditions for racism. Those exposed may not have the intention of sharing or spreading racist ideology, but its amplification contributes to the promotion of a racist agenda nevertheless. As such, further investigation into the far-right infiltration of the wellness industry would be beneficial as it could provide more insight into how wellness groups are targeted. 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Les enzymes à radical S-adénosyl-L-méthionine (SAM), constituent une superfamille majeure d'enzymes intervenant dans de nombreux processus biologiques essentiels du vivant. Ces enzymes utilisent la chimie radicalaire pour catalyser une grande diversité de modifications biochimiques non conventionnelles sur différents types de molécules, notamment des métabolites secondaires, l'ADN ou l'ARN ainsi que sur les protéines et peptides. Pour catalyser ces réactions uniques, ces enzymes emploient un centre métallique [4Fe-4S] radical SAM, ainsi qu'un cofacteur, la S-adénosyl-L-méthionine (SAM), qui se lie à celui-ci. La réduction de ce centre induit le clivage homolytique de la SAM et la formation d'un intermédiaire radicalaire 5'-deoxyadenosyl, indispensable à l'activité de ces enzymes.L'une des plus grandes familles d'enzymes à radical SAM, est la famille des enzymes à radical SAM dépendantes de la vitamine B12 (cobalamine). Cette famille émergente catalyse diverses réactions biochimiques complexes incluant principalement des réactions de méthylations sur des atomes de carbone inactifs chimiquement. Ces enzymes, comme les autres membres de cette superfamille, utilisent la chimie radicalaire pour le clivage de la SAM mais aussi la méthylcobalamine comme accepteur et donneur de groupements méthyles. Néanmoins, le mécanisme de ces enzymes reste encore largement mal compris. Récemment, la glutamine C‐méthyltransférase (QCMT), une nouvelle enzyme appartenant à ce groupe a été décrite comme catalysant la méthylation d'un résidu de glutamine dans le site actif de la méthyl-coenzyme M réductase (MCR), un complexe enzymatique jouant un rôle majeur dans la méthanogenèse.L'un des objectifs de ma thèse a consisté à déterminer le mécanisme et la structure de cette nouvelle enzyme. Nous avons notamment montré que QCMT est non seulement capable de catalyser in vitro la méthylation d'une glutamine sur son atome de carbone Cα, mais également l'épimérisation de ce résidu. En outre, QCMT catalyse également la méthylation d'un grand nombre d'acides aminés, comprenant la conversion directe d'une Gly en D-Ala sur un peptide mimant la séquence de MCR. L'étude structurale de cette enzyme nous a permis de montrer qu'en solution, des changements conformationnels ont lieu lors de la liaison de la cobalamine. Grâce à une étude par cristallographie, nous avons également résolu une structure de cette enzyme et proposé un modèle structural.Le second groupe majeur d'enzymes à radical SAM est celui des enzymes possédant un domaine SPASM, leur permettant de coordonner, en plus du centre radical SAM, d'autres centres [4Fe-4S] auxiliaires. La grande majorité de ces enzymes catalyse des MPTs sur des peptides de la famille des RiPPs (Ribosomally-Synthesized and Post-translationally-modified Peptides). Les RiPPs appartiennent à une famille majeure de produits naturels possédants de multiples fonctions biologiques, dont par exemple des activités antibiotiques ou encore anti-cancéreuses, faisant de ces molécules des composés d'intérêt dans le domaine de la santé. La biosynthèse des RiPPs débute généralement par la traduction d'un peptide précurseur qui va ensuite subir diverses MPTs catalysées par des enzymes de maturation, dont font partie les enzymes à radical SAM à domaine SPASM.Afin de mieux comprendre les mécanismes et fonctions de ces enzymes, j'ai étudié la biosynthèse d'un peptide RiPPs, la ruminococcine C. L'enzyme de maturation de ce peptide (MC2), catalyse la formation de quatre ponts α-thioéthers, conférant à la ruminococcine C sa structure en double épingle à cheveux et son activité contre Clostridium perfringens. En particulier, je me suis intéressé au rôle des centres [4Fe-4S] auxiliaires chez cette enzyme dans la formation des ponts α-thioéthers. Nous avons ainsi caractérisé par spectroscopie RPE les trois centres [4Fe-4S] de cette enzyme et avons montré que le centre auxiliaire II pourrait jouer un rôle rédox dans le mécanisme de l'enzyme
S-adenosyl-L-methionine (SAM) radical enzymes are a major superfamily of enzymes involved in many of life's essential biological processes. These enzymes use radical chemistry to catalyze a wide variety of unconventional biochemical modifications on different types of molecules, including secondary metabolites, DNA or RNA, as well as proteins and peptides. To catalyze these unique reactions, these enzymes require a [4Fe-4S] radical SAM cluster, as well as a cofactor, S-adenosyl-L-methionine (SAM), which binds to the SAM radical cluster. One electron reduction of this center induces homolytic cleavage of SAM and the formation of a radical intermediate, the 5'-deoxyadenosyl radical, which is essential for the activity of these enzymes.One of the largest families of radical SAM enzymes is the family of B12 vitamin (cobalamin)-dependent radical SAM enzymes. This emerging family catalyzes a variety of complex biochemical reactions, including mainly methylation reactions on chemically inactive carbon atoms. These enzymes, like the other members of this superfamily, use radical chemistry for SAM cleavage, but also methylcobalamin as acceptor and donor of methyl groups. Nevertheless, the mechanism of these enzymes remains largely poorly understood. Recently, glutamine C-methyltransferase (QCMT), a new enzyme belonging to this group, was described as catalyzing the methylation of a glutamine residue in the active site of methyl-coenzyme M reductase (MCR), an enzyme complex playing a major role in methanogenesis.One of the objectives of my thesis was to determine the enzymatic mechanism and structure of this new enzyme. In particular, we have shown that QCMT is not only able to catalyze in vitro the methylation of a glutamine on its Cα carbon atom, but also the epimerization of this residue. In addition, QCMT also catalyzes the methylation of a large number of amino acid residues, including the direct conversion of a Gly to D-Ala on a peptide mimicking the MCR sequence. The structural study of this enzyme enabled us to show that, in solution, conformational changes take place during cobalamin binding. Thanks to a crystallographic study, we have also solved the structure of this enzyme, and proposed a structural model.The second major group of radical SAM enzymes are those containing a SPASM domain, allowing them to coordinate other [4Fe-4S] auxiliary clusters in addition to the radical SAM cluster. The vast majority of these enzymes catalyze MPTs on peptides of the RiPPs (Ribosomally-Synthesized and Post-translationally-modified Peptides) family. RiPPs represent a major family of natural products with multiple biological functions, including antibiotic, toxin and anti-cancer activities, making these molecules of interest in the healthcare field. The biosynthesis of RiPPs generally begins with the translation of a precursor peptide, which then undergoes various MPTs catalyzed by maturation enzymes, including radical SAM enzymes with SPASM domains.To better understand the mechanisms and functions of these enzymes, I studied the biosynthesis of a peptide belonging to the RiPPs family, produced by the human microbiota, ruminococcin C. The maturation enzyme for this peptide (MC2) catalyzes the formation of four α-thioether bonds, giving ruminococcin C its double hairpin structure and its activity against Clostridium perfringens, a Gram-positive human pathogen. In particular, I investigated the role of [4Fe-4S] auxiliary clusters in this enzyme in the formation of α-thioether bonds. Using EPR spectroscopy, we characterized the three [4Fe-4S] clusters of this enzyme and showed that auxiliary center II could play a redox role in the enzyme's enzymatic mechanism