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1.
Evol Hum Sci ; 6: e19, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38616986

RESUMO

A basic hypothesis is that cultural evolutionary processes sustain differences between groups, these differences have evolutionary relevance and they would not otherwise occur in a system without cultural transmission. The empirical challenge is that groups vary for many reasons, and isolating the causal effects of culture often requires appropriate data and a quasi-experimental approach to analysis. We address this challenge with historical data from the final Soviet census of 1989, and our analysis is an example of the epidemiological approach to identifying cultural variation. We find that the fertility decisions of Armenian, Georgian and Azeri parents living in Soviet-era Russia were significantly more son-biased than those of other ethnic groups in Russia. This bias for sons took the form of differential stopping rules; families with sons stopped having children sooner than families without sons. This finding suggests that the increase in sex ratios at birth in the Caucasus, which began in the 1990s, reflects a cultural preference for sons that predates the end of the Soviet Union. This result also supports one of the key hypotheses of gene-culture coevolution, namely that cultural evolutionary processes can support group-level differences in selection pressures that would not otherwise occur in a system without culture.

2.
Philos Trans R Soc Lond B Biol Sci ; 379(1897): 20230039, 2024 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-38244606

RESUMO

Applied cultural evolution includes any effort to mobilize social learning and cultural evolution to promote behaviour change. Social tipping is one version of this idea based on conformity and coordination. Conformity and coordination can reinforce a harmful social norm, but they can also accelerate change from a harmful norm to a beneficial alternative. Perhaps unfortunately, the link between the size of an intervention and social tipping is complex in heterogeneous populations. A small intervention targeted at one segment of society can induce tipping better than a large intervention targeted at a different segment. We develop and examine two models showing that the link between social tipping and social welfare is also complex in heterogeneous populations. An intervention strategy that creates persistent miscoordination, exactly the opposite of tipping, can lead to higher social welfare than another strategy that leads to tipping. We show that the potential benefits of miscoordination often hinge specifically on the preferences of people most resistant to behaviour change. Altogether, ordinary forms of heterogeneity complicate applied cultural evolution considerably. Heterogeneity weakens both the link between the size of a social planner's intervention and behaviour change and the link between behaviour change and the well-being of society. This article is part of the theme issue 'Social norm change: drivers and consequences'.


Assuntos
Evolução Cultural , Comportamento Social , Humanos , Normas Sociais
3.
Psychol Sci Public Interest ; 23(2): 50-97, 2022 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-36227765

RESUMO

Anthropogenic carbon emissions have the potential to trigger changes in climate and ecosystems that would be catastrophic for the well-being of humans and other species. Widespread shifts in production and consumption patterns are urgently needed to address climate change. Although transnational agreements and national policy are necessary for a transition to a fully decarbonized global economy, fluctuating political priorities and lobbying by vested interests have slowed these efforts. Against this backdrop, bottom-up pressure from social movements and shifting social norms may offer a complementary path to a more sustainable economy. Furthermore, norm change may be an important component of decarbonization policies by accelerating or strengthening the impacts of other demand-side measures. Individual actions and policy support are social processes-they are intimately linked to expectations about the actions and beliefs of others. Although prevailing social norms often reinforce the status quo and unsustainable development pathways, social dynamics can also create widespread and rapid shifts in cultural values and practices, including increasing pressure on politicians to enact ambitious policy. We synthesize literature on social-norm influence, measurement, and change from the perspectives of psychology, anthropology, sociology, and economics. We discuss the opportunities and challenges for the use of social-norm and social-tipping interventions to promote climate action. Social-norm interventions aimed at addressing climate change or other social dilemmas are promising but no panacea. They require in-depth contextual knowledge, ethical consideration, and situation-specific tailoring and testing to understand whether they can be effectively implemented at scale. Our review aims to provide practitioners with insights and tools to reflect on the promises and pitfalls of such interventions in diverse contexts.


Assuntos
Ecossistema , Normas Sociais , Carbono , Mudança Climática , Humanos , Políticas
4.
Nat Hum Behav ; 6(12): 1669-1679, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-36138223

RESUMO

Social tipping can accelerate behaviour change consistent with policy objectives in diverse domains from social justice to climate change. Hypothetically, however, group identities might undermine tipping in ways that policymakers do not anticipate. To examine this, we implemented an experiment around the 2020 US federal elections. The participants faced consistent incentives to coordinate their choices. Once the participants had established a coordination norm, an intervention created pressure to tip to a new norm. Our control treatment used neutral labels for choices. Our identity treatment used partisan political images. This simple pay-off-irrelevant relabelling generated extreme differences. The control groups developed norms slowly before intervention but transitioned to new norms rapidly after intervention. The identity groups developed norms rapidly before intervention but persisted in a state of costly disagreement after intervention. Tipping was powerful but unreliable. It supported striking cultural changes when choice and identity were unlinked, but even a trivial link destroyed tipping entirely.


Assuntos
Motivação , Política , Humanos , Políticas
5.
Evol Hum Sci ; 4: e13, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-37588895

RESUMO

Models of frequency-dependent social learning posit that individuals respond to the commonality of behaviours without additional variables modifying this. Such strategies bring important trade-offs, e.g. conformity is beneficial when observing people facing the same task but harmful when observing those facing a different task. Instead of rigidly responding to frequencies, however, social learners might modulate their response given additional information. To see, we ran an incentivised experiment where participants played either a game against nature or a coordination game. There were three types of information: (a) choice frequencies in a group of demonstrators; (b) an indication of whether these demonstrators learned in a similar or different environment; and (c) an indication about the reliability of this similarity information. Similarity information was either reliably correct, uninformative or reliably incorrect, where reliably correct and reliably incorrect treatments provided participants with equivalent earning opportunities. Participants adjusted their decision-making to all three types of information. Adjustments, however, were asymmetric, with participants doing especially well when conforming to demonstrators who were reliably similar to them. The overall response, however, was more fluid and complex than this one case. This flexibility should attenuate the trade-offs commonly assumed to shape the evolution of frequency-dependent social learning strategies.

6.
Bull World Health Organ ; 99(11): 819-827, 2021 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-34737474

RESUMO

Public health policy often involves implementing cost-efficient, large-scale interventions. When mandating or forbidding a specific behaviour is not permissible, public health professionals may draw on behaviour change interventions to achieve socially beneficial policy objectives. Interventions can have two main effects: (i) a direct effect on people initially targeted by the intervention; and (ii) an indirect effect mediated by social influence and by the observation of other people's behaviour. However, people's attitudes and beliefs can differ markedly throughout the population, with the result that these two effects can interact to produce unexpected, unhelpful and counterintuitive consequences. Public health professionals need to understand this interaction better. This paper illustrates the key principles of this interaction by examining two important areas of public health policy: tobacco smoking and vaccination. The example of antismoking campaigns shows when and how public health professionals can amplify the effects of a behaviour change intervention by taking advantage of the indirect pathway. The example of vaccination campaigns illustrates how underlying incentive structures, particularly anticoordination incentives, can interfere with the indirect effect of an intervention and stall efforts to scale up its implementation. Recommendations are presented on how public health professionals can maximize the total effect of behaviour change interventions in heterogeneous populations based on these concepts and examples.


Les politiques de santé publique impliquent souvent l'organisation de campagnes rentables à grande échelle. Lorsqu'il est impossible d'imposer ou d'interdire certains comportements, les professionnels de la santé publique ont parfois recours à des actions induisant un changement de comportement afin d'atteindre des objectifs bénéfiques pour la société. Ces actions sont susceptibles d'entraîner deux effets: (i) un effet direct sur les personnes initialement visées par la campagne; et (ii) un effet indirect provoqué par la pression sociale et l'observation du comportement d'autres personnes. Néanmoins, les attitudes et croyances peuvent considérablement varier au sein de la population; ainsi, ces deux effets peuvent interagir et avoir des conséquences imprévues, inefficaces et contre-intuitives. Les professionnels de la santé publique ont besoin de mieux comprendre cette interaction. Le présent document en illustre donc les principes majeurs en examinant deux domaines clés des politiques de santé publique: le tabagisme et la vaccination. L'exemple des campagnes antitabac montre quand et comment les acteurs de la santé publique peuvent accentuer l'impact d'une action destinée à faire évoluer les comportements en optant pour l'approche indirecte. L'exemple des campagnes de vaccination met en lumière la manière dont les structures d'incitation sous-jacentes, en particulier celles favorisant l'anticoordination, peuvent interférer avec l'effet indirect d'une action et anéantir les efforts déployés pour la mettre en œuvre. Plusieurs recommandations sont formulées afin d'aider les professionnels de la santé publique à amplifier l'effet global des actions de changement comportemental au sein d'une population hétérogène, en s'appuyant sur ces concepts et exemples.


La política de salud pública suele incluir la aplicación de intervenciones rentables y a gran escala. Cuando no es posible imponer o prohibir un comportamiento específico, los profesionales de la salud pública pueden recurrir a intervenciones de cambio de comportamiento para lograr objetivos políticos que sean favorables para la sociedad. Es posible que las intervenciones generen dos efectos principales: i) un efecto directo sobre las personas a las que en principio se dirige la intervención; y ii) un efecto indirecto mediado por la influencia social y por la observación del comportamiento de otras personas. Sin embargo, las actitudes y creencias de las personas pueden ser muy diferentes en toda la población, por lo que estos dos efectos pueden interactuar y producir consecuencias inesperadas, poco útiles y contraproducentes. Los profesionales de la salud pública deben comprender mejor esta interacción. Este documento explica los principios clave de esta interacción al analizar dos áreas importantes de la política de salud pública: el tabaquismo y la vacunación. El ejemplo de las campañas antitabaco muestra cuándo y cómo los profesionales de la salud pública pueden aumentar los efectos de una intervención de cambio de comportamiento si se aprovecha el procedimiento indirecto. El ejemplo de las campañas de vacunación explica cómo las estructuras subyacentes de incentivos, en particular los incentivos de descoordinación, pueden interferir con el efecto indirecto de una intervención y detener los esfuerzos para ampliar su aplicación. A partir de estos conceptos y ejemplos, se formulan recomendaciones sobre cómo los profesionales de la salud pública pueden maximizar el efecto total de las intervenciones de cambio de comportamiento en poblaciones heterogéneas.


Assuntos
Comportamentos Relacionados com a Saúde , Abandono do Hábito de Fumar , Promoção da Saúde , Humanos , Prevenção do Hábito de Fumar
8.
Demography ; 58(5): 1737-1764, 2021 10 01.
Artigo em Inglês | MEDLINE | ID: mdl-34486643

RESUMO

Sex ratios at birth favoring boys are being documented in a growing number of countries, a pattern indicating that families selectively abort females. Son bias also explains why, in many countries, girls have more siblings and are born at relatively earlier parities compared with their brothers. In this study, we develop novel methods for measuring son bias using both questionnaire items and implicit association tests, and we collect data on fertility preferences and outcomes from 2,700 participants in Armenia. We document highly skewed sex ratios, suggesting that selective abortions of females are widespread among parents in our sample. We also provide evidence that sex-selective abortions are underreported, which highlights the problem of social desirability bias. We validate our methods and demonstrate that conducting implicit association tests can be a successful strategy for measuring the relative preference for sons and daughters when social desirability is a concern. We investigate the structure of son-biased fertility preferences within households, across families, and between regions in Armenia, using measures of son bias at the level of the individual decision-maker. We find that men are, on average, considerably more son-biased than women. We also show that regional differences in son bias exist and that they appear unrelated to the socioeconomic composition of the population. Finally, we estimate the degree of spousal correlation in son bias and discuss whether husbands are reliably more son-biased than their wives.


Assuntos
Fertilidade , Núcleo Familiar , Armênia , Características da Família , Feminino , Humanos , Recém-Nascido , Masculino , Gravidez , Razão de Masculinidade
9.
Nat Hum Behav ; 4(1): 55-68, 2020 01.
Artigo em Inglês | MEDLINE | ID: mdl-31792402

RESUMO

For a policy-maker promoting the end of a harmful tradition, conformist social influence is a compelling mechanism. If an intervention convinces enough people to abandon the tradition, this can spill over and induce others to follow. A key objective is thus to activate such spillovers and amplify an intervention's effects. With female genital cutting as a motivating example, we develop empirically informed analytical and simulation models to examine this idea. Even if conformity pervades decision-making, spillovers can range from irrelevant to indispensable. Our analysis highlights three considerations. First, ordinary forms of individual heterogeneity can severely limit spillovers, and understanding the heterogeneity in a population is essential. Second, although interventions often target samples of the population biased towards ending the harmful tradition, targeting a representative sample is a more robust way to achieve spillovers. Finally, if the harmful tradition contributes to group identity, the success of spillovers can depend critically on disrupting the link between identity and tradition.


Assuntos
Cultura , Tomada de Decisões , Modelos Psicológicos , Conformidade Social , Identificação Social , Adulto , Circuncisão Feminina/psicologia , Feminino , Humanos
10.
Proc Biol Sci ; 285(1879)2018 05 30.
Artigo em Inglês | MEDLINE | ID: mdl-29794048

RESUMO

The importance of culture for human social evolution hinges largely on the extent to which culture supports outcomes that would not otherwise occur. An especially controversial claim is that social learning leads groups to coalesce around group-typical behaviours and associated social norms that spill over to shape choices in asocial settings. To test this, we conducted an experiment with 878 groups of participants in 116 communities in Sudan. Participants watched a short film and evaluated the appropriate way to behave in the situation dramatized in the film. Each session consisted of an asocial condition in which participants provided private evaluations and a social condition in which they provided public evaluations. Public evaluations allowed for social learning. Across sessions, we randomized the order of the two conditions. Public choices dramatically increased the homogeneity of normative evaluations. When the social condition was first, this homogenizing effect spilled over to subsequent asocial conditions. The asocial condition when first was thus alone in producing distinctly heterogeneous groups. Altogether, information about the choices of others led participants to converge rapidly on similar normative evaluations that continued to hold sway in subsequent asocial settings. These spillovers were at least partly owing to the combined effects of conformity and self-consistency. Conformity dominated self-consistency when the two mechanisms were in conflict, but self-consistency otherwise produced choices that persisted through time. Additionally, the tendency to conform was heterogeneous. Females conformed more than males, and conformity increased with the number of other people a decision-maker observed before making her own choice.


Assuntos
Tomada de Decisões , Conformidade Social , Normas Sociais , Adulto , Idoso , Idoso de 80 Anos ou mais , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Sudão , Adulto Jovem
11.
SSM Popul Health ; 3: 283-293, 2017 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-29302613

RESUMO

Worldwide, an estimated 200 million girls and women have been subjected to female genital cutting. Female genital cutting is defined as an intentional injury to the female genitalia without medical justification. The practice occurs in at least 29 countries in Africa, the Middle East, and Asia. In addition, globalization and migration have brought immigrants from countries where cutting is commonly practiced to countries where cutting is not traditionally practiced and may even be illegal. In countries receiving immigrants, governments and development agencies would like to know if girls with parents who immigrated from practicing countries are at risk of being cut. Risk assessments, for example, could help governments identify the need for programs promoting the abandonment of cutting among immigrants. Extrapolating from the prevalence and incidence rates in practicing countries, however, is generally not sufficient to guarantee a valid estimate of risk in immigrant populations. In particular, immigrants might differ from their counterparts in the country of origin in terms of attitudes toward female genital cutting. Attitudes can differ because migrants represent a special sample of people from the country of origin or because immigrants acculturate after arriving in a new country. To examine these possibilities, we used a fully anonymous, computerized task to elicit implicit attitudes toward female genital cutting among Sudanese immigrants living in Switzerland and Sudanese people in Sudan. Results show that Sudanese immigrants in Switzerland were significantly more positive about uncut girls than Sudanese in Sudan, and that selective migration out of Sudan likely contributed substantially to this difference. We conclude by suggesting how our method could potentially be coupled with recent efforts to refine extrapolation methods for estimating cutting risk among immigrant populations. More broadly, our results highlight the need to better understand how heterogeneous attitudes can affect the risk of cutting among immigrant communities and in countries of origin.

12.
Nature ; 538(7626): 506-509, 2016 10 27.
Artigo em Inglês | MEDLINE | ID: mdl-27732586

RESUMO

As globalization brings people with incompatible attitudes into contact, cultural conflicts inevitably arise. Little is known about how to mitigate conflict and about how the conflicts that occur can shape the cultural evolution of the groups involved. Female genital cutting is a prominent example. Governments and international agencies have promoted the abandonment of cutting for decades, but the practice remains widespread with associated health risks for millions of girls and women. In their efforts to end cutting, international agents have often adopted the view that cutting is locally pervasive and entrenched. This implies the need to introduce values and expectations from outside the local culture. Members of the target society may view such interventions as unwelcome intrusions, and campaigns promoting abandonment have sometimes led to backlash as they struggle to reconcile cultural tolerance with the conviction that cutting violates universal human rights. Cutting, however, is not necessarily locally pervasive and entrenched. We designed experiments on cultural change that exploited the existence of conflicting attitudes within cutting societies. We produced four entertaining movies that served as experimental treatments in two experiments in Sudan, and we developed an implicit association test to unobtrusively measure attitudes about cutting. The movies depart from the view that cutting is locally pervasive by dramatizing members of an extended family as they confront each other with divergent views about whether the family should continue cutting. The movies significantly improved attitudes towards girls who remain uncut, with one in particular having a relatively persistent effect. These results show that using entertainment to dramatize locally discordant views can provide a basis for applied cultural evolution without accentuating intercultural divisions.


Assuntos
Circuncisão Feminina/educação , Circuncisão Feminina/etnologia , Características Culturais , Conhecimentos, Atitudes e Prática em Saúde/etnologia , Filmes Cinematográficos , Mudança Social , Circuncisão Feminina/efeitos adversos , Evolução Cultural , Feminino , Direitos Humanos/educação , Humanos , Casamento/etnologia , Sudão , Saúde da Mulher/etnologia
13.
PLoS One ; 11(2): e0149542, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-26882013

RESUMO

Economic exchange between strangers happens extremely frequently due to the growing number of internet transactions. In trust situations like online transactions, a trustor usually does not know whether she encounters a trustworthy trustee. However, the trustor might form beliefs about the trustee's trustworthiness by relying on third-party information. Different kinds of third-party information can vary dramatically in their importance to the trustor. We ran a factorial design to study how the different characteristics of third-party information affect the trustor's decision to trust. We systematically varied unregulated third-party information regarding the source (friend or a stranger), the reliability (gossip or experiences), and the valence (positive or negative) of the information. The results show that negative information is more salient for withholding trust than positive information is for placing trust. If third-party information is positive, experience of a friend has the strongest effect on trusting followed by friend's gossip. Positive information from a stranger does not matter to the trustor. With respect to negative information, the data show that even the slightest hint of an untrustworthy trustee leads to significantly less placed trust irrespective of the source or the reliability of the information.


Assuntos
Confiança , Tomada de Decisões , Feminino , Humanos , Masculino , Análise Multivariada , Reprodutibilidade dos Testes
14.
Evol Hum Behav ; 37(1): 1-9, 2016 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-26766895

RESUMO

For cooperation to evolve, some mechanism must limit the rate at which cooperators are exposed to defectors. Only then can the advantages of mutual cooperation outweigh the costs of being exploited. Although researchers widely agree on this, they disagree intensely about which evolutionary mechanisms can explain the extraordinary cooperation exhibited by humans. Much of the controversy follows from disagreements about the informational regularity that allows cooperators to avoid defectors. Reliable information can allow cooperative individuals to avoid exploitation, but which mechanisms can sustain such a situation is a matter of considerable dispute. We conducted a behavioral experiment to see if cooperators could avoid defectors when provided with limited amounts of explicit information. We gave each participant the simple option to move away from her current neighborhood at any time. Participants were not identifiable as individuals, and they could not track each other's tendency to behave more or less cooperatively. More broadly, a participant had no information about the behavior she was likely to encounter if she moved, and so information about the risk of exploitation was extremely limited. Nonetheless, our results show that simply providing the option to move allowed cooperation to persist for a long period of time. Our results further show that movement, even though it involved considerable uncertainty, allowed would-be cooperators to assort positively and eliminate on average any individual payoff disadvantage associated with cooperation. This suggests that choosing to move, even under limited information, can completely reorganize the mix of selective forces relevant for the evolution of cooperation.

16.
Sci Rep ; 3: 1047, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23308340

RESUMO

The evolution of cooperation requires some mechanism that reduces the risk of exploitation for cooperative individuals. Recent studies have shown that men with wide faces are anti-social, and they are perceived that way by others. This suggests that people could use facial width to identify anti-social men and thus limit the risk of exploitation. To see if people can make accurate inferences like this, we conducted a two-part experiment. First, males played a sequential social dilemma, and we took photographs of their faces. Second, raters then viewed these photographs and guessed how second movers behaved. Raters achieved significant accuracy by guessing that second movers exhibited reciprocal behaviour. Raters were not able to use the photographs to further improve accuracy. Indeed, some raters used the photographs to their detriment; they could have potentially achieved greater accuracy and earned more money by ignoring the photographs and assuming all second movers reciprocate.

17.
Mol Cell Endocrinol ; 351(2): 337-41, 2012 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-22269094

RESUMO

BACKGROUND: Elevated levels of C-peptide have been found in patients with insulin resistance and early type 2 diabetes. These patients are at greater risk to develop micro- and macrovascular complications. Since diabetic nephropathy involves glomerular hyperproliferation, the present study evaluates the role of C-peptide on human renal mesangial cell proliferation. METHODS AND RESULTS: C-peptide induces proliferation of human renal mesangial cells in a concentration-dependent manner with a maximal 2.6±0.4-fold induction at 10 nmol/L (P<0.05 compared with unstimulated cells; n=6), as revealed by [3H]-thymidine incorporation experiments. The proliferative effect of C-peptide is prevented by Src-kinase inhibitor-PP2, PI-3 kinase inhibitor-LY294002, and the ERK1/2 inhibitor-U126. Moreover, C-peptide induces phosphorylation of Src, as well as activation of PI-3 kinase and ERK1/2. Furthermore, C-peptide induces cyclin D1 expression as well as phosphorylation of retinoblastoma protein (Rb). CONCLUSIONS: These results demonstrate an active role of C-peptide on the proliferation of human renal mesangial cells in vitro involving PI-3 kinase and MAP kinase signaling pathways, suggesting a possible role of C-peptide in glomerular hyperproliferation in patients with diabetic nephropathy.


Assuntos
Peptídeo C/metabolismo , MAP Quinases Reguladas por Sinal Extracelular/metabolismo , Células Mesangiais/citologia , Células Mesangiais/metabolismo , Fosfatidilinositol 3-Quinases/metabolismo , Quinases da Família src/metabolismo , Butadienos/farmacologia , Peptídeo C/farmacologia , Proliferação de Células/efeitos dos fármacos , Células Cultivadas , Cromonas/farmacologia , Ciclina D1/biossíntese , Ativação Enzimática , MAP Quinases Reguladas por Sinal Extracelular/antagonistas & inibidores , Mesângio Glomerular/efeitos dos fármacos , Mesângio Glomerular/metabolismo , Humanos , Sistema de Sinalização das MAP Quinases/efeitos dos fármacos , Morfolinas/farmacologia , Nitrilas/farmacologia , Inibidores de Fosfoinositídeo-3 Quinase , Fosforilação/efeitos dos fármacos , Pirimidinas/farmacologia , Proteína do Retinoblastoma/metabolismo , Quinases da Família src/antagonistas & inibidores
19.
Dalton Trans ; 39(12): 3057-64, 2010 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-20221540

RESUMO

The [Fe]-hydrogenase is an ideal system for studying the electronic properties of the low spin iron site that is common to the catalytic centres of all hydrogenases. Because they have no auxiliary iron-sulfur clusters and possess a cofactor containing a single iron centre, the [Fe]-hydrogenases are well suited for spectroscopic analysis of those factors required for the activation of molecular hydrogen. Specifically, in this study we shed light on the electronic and molecular structure of the iron centre by XAS analysis of [Fe]-hydrogenase from Methanocaldococcus jannashii and five model complexes (Fe(ethanedithiolate)(CO)(2)(PMe(3))(2), [K(18-crown-6)](2)[Fe(CN)(2)(CO)(3)], K[Fe(CN)(CO)(4)], K(3)[Fe(III)(CN)(6)], K(4)[Fe(II)(CN)(6)]). The different electron donors have a strong influence on the iron absorption K-edge energy position, which is frequently used to determine the metal oxidation state. Our results demonstrate that the K-edges of Fe(II) complexes, achieved with low-spin ferrous thiolates, are consistent with a ferrous centre in the [Fe]-hydrogenase from Methanocaldococcus jannashii. The metal geometry also strongly influences the XANES and thus the electronic structure. Using in silico simulation, we were able to reproduce the main features of the XANES spectra and describe the effects of individual donor contributions on the spectra. Thereby, we reveal the essential role of an unusual carbon donor coming from an acyl group of the cofactor in the determination of the electronic structure required for the activity of the enzyme.


Assuntos
Hidrogenase/química , Proteínas Ferro-Enxofre/química , Ferro/química , Modelos Moleculares , Proteínas de Bactérias/química , Carbono/química , Hidrogênio/química , Estrutura Molecular , Oxirredução , Espectroscopia por Absorção de Raios X
20.
FEBS Lett ; 583(3): 585-90, 2009 Feb 04.
Artigo em Inglês | MEDLINE | ID: mdl-19162018

RESUMO

[Fe]-hydrogenase is one of three types of enzymes known to activate H(2). Crystal structure analysis recently revealed that its active site iron is ligated square-pyramidally by Cys176-sulfur, two CO, an "unknown" ligand and the sp(2)-hybridized nitrogen of a unique iron-guanylylpyridinol-cofactor. We report here on the structure of the C176A mutated enzyme crystallized in the presence of dithiothreitol (DTT). It suggests an iron center octahedrally coordinated by one DTT-sulfur and one DTT-oxygen, two CO, the 2-pyridinol's nitrogen and the 2-pyridinol's 6-formylmethyl group in an acyl-iron ligation. This result led to a re-interpretation of the iron ligation in the wild-type.


Assuntos
Hidrogenase/química , Hidrogenase/metabolismo , Proteínas Ferro-Enxofre/química , Proteínas Ferro-Enxofre/metabolismo , Ferro/química , Ferro/metabolismo , Adenina/metabolismo , Domínio Catalítico , Cristalografia por Raios X , Citosina/metabolismo , Holoenzimas/química , Holoenzimas/genética , Holoenzimas/metabolismo , Hidrogenase/genética , Proteínas Ferro-Enxofre/genética , Methanococcales/enzimologia , Methanococcales/genética , Mutação/genética , Estrutura Quaternária de Proteína
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