Nitric oxide binds to the proximal heme coordination site of the ferrocytochrome c/cardiolipin complex: formation mechanism and dynamics.

Mammalian mitochondrial cytochrome c interacts with cardiolipin to form a complex (cyt. c/CL) important in apoptosis. Here we show that this interaction leads to structural changes in ferrocytochrome c that leads to an open coordinate site on the central iron, resulting from the dissociation of the intrinsic methionine residue, where NO can rapidly bind (k = 1.2 x 10(7) m(-1) s(-1)). Accompanying NO binding, the proximal histidine dissociates leaving the heme pentacoordinate, in contrast to the hexacoordinate nitrosyl adducts of native ferrocytochrome c or of the protein in which the coordinating methionine is removed by chemical modification or mutation. We present the results of stopped-flow and photolysis experiments that show that following initial NO binding to the heme, there ensues an unusually complex set of kinetic steps. The spectral changes associated with these kinetic transitions, together with their dependence on NO concentration, have been determined and lead us to conclude that NO binding to cyt. c/CL takes place via an overall scheme comparable to that described for cytochrome c' and guanylate cyclase, the final product being one in which NO resides on the proximal side of the heme. In addition, novel features not observed before in other heme proteins forming pentacoordinate nitrosyl species, include a high yield of NO escape after dissociation, rapid (<1 ms) dissociation of proximal histidine upon NO binding and its very fast binding (60 ps) after NO dissociation, and the formation of a hexacoordinate intermediate. These features all point at a remarkable mobility of the proximal heme environment induced by cardiolipin

Challenges of Religious Literacy in Education : Islam and the Governance of Religious Diversity in Multi-faith Schools

This chapter seeks take part in an emerging research where religion is approached as a whole school endeavor. Previous research and policy recommendations typically focused on teaching about religion in school, but the accommodation of religious diversity in the wider school culture merits more attention. Based on observations in our multiple case studies, we discuss the multi-level governance of religious diversity in Finnish multi-faith schools with a particular focus on the challenges of religious literacy for educators. The three examples we present focus on the inclusion of Muslims in Finnish schools and in particular on the challenges for educator (1) in interpreting the distinction between religion and culture, (2) in recognizing and handling intra-religious diversity, and (3) in being aware of Protestant conceptions of religion and culture. A theme cutting across these examples is how they reflect the tendencies either to see different situations merely through the lens of religion (religionisation), or not to recognize the importance of religion at all (religion-blindness). We argue that religious literacy should be recognized and developed as a vital part of the intercultural competencies of educators.Peer reviewe

Chiral plasmonics of self-assembled nanorod dimers

Chiral nanoscale photonic systems typically follow either tetrahedral or helical geometries that require four or more different constituent nanoparticles. Smaller number of particles and different chiral geometries taking advantage of the self-organization capabilities of nanomaterials will advance understanding of chiral plasmonic effects, facilitate development of their theory, and stimulate practical applications of chiroplasmonics. Here we show that gold nanorods self-assemble into side-by-side orientated pairs and ‘‘ladders’’ in which chiral properties originate from the small dihedral angle between them. Spontaneous twisting of one nanorod versus the other one breaks the centrosymmetric nature of the parallel assemblies. Two possible enantiomeric conformations with positive and negative dihedral angles were obtained with different assembly triggers. The chiral nature of the angled nanorod pairs was confirmed by 4p full space simulations and the first example of single-particle CD spectroscopy. Self-assembled nanorod pairs and ‘‘ladders’’ enable the development of chiral metamaterials, (bio)sensors, and new catalytic processes

The Perils of Gender Beliefs for Men Leaders as Change Agents for Gender Equality

This article examines the potentially damaging role that gender beliefs can play in hindering women's equal representation in leadership positions. Based on a secondary analysis of a large‐scale EU‐wide survey (Eurobarometer 76.1), the article shows that essentialist gender beliefs lower support for equality interventions such as quotas or targets, particularly among men as leaders. The results show that discriminatory gender beliefs partially mediate this relationship and produce a more negative effect among men leaders. The paper contributes to understanding the role essentialist gender beliefs often lay the groundwork for gender discriminatory beliefs. Those in turn hinder support for effective gender equality measures. Gender essentialist beliefs can be held by everyone but are more prevalent among men leaders. We conclude that greater gender balance in leadership cannot be achieved without tackling underlying gender beliefs, particularly among men leaders since they are called upon to enact change. We thereby argue that simply asking for men to become change agents for gender equality is not an effective strategy if underlying gender beliefs are left unchallenged

Nitric oxide binding to the cardiolipin complex of ferric cytochrome

International audienceCardiolipin, a phospholipid specific to the mitochondrion, interacts with the small electron transfer heme protein cytochrome c through both electrostatic and hydrophobic interactions. Once in a complex with cardiolipin, cytochrome c has been shown to undergo a conformational change that leads to the rupture of the bond between the heme iron and the intrinsic sulfur ligand of a methionine residue and to enhance the peroxidatic properties of the protein considered important to its apoptotic activity. Here we report that the ferric cytochrome c/cardiolipin complex binds nitric oxide tightly through a multistep process in which the first step is the relatively slow displacement (5 s-1) from heme coordination of an intrinsic ligand that replaces methionine in the complex. Nanosecond photolysis of the nitrosyl adduct demonstrated that a fraction of the nitric oxide escapes from the heme pocket and subsequently recombines to the heme in second-order processes (k = 1.8 × 106 and 5.5 × 105 M-1 s-1) that, under these conditions, were much faster than recombination of the intrinsic ligand with which they compete. Ultrafast (femtosecond) laser photolysis showed that the geminate recombination of nitric oxide to the heme occurred with time constants (? = 22 and 72 ps) and that ~23% of the photolyzed nitric oxide escaped into the bulk phase. This high value for the escape fraction relative to other heme proteins indicates the open nature of the heme pocket in this complex. These results are summarized in a scheme and are discussed in terms of the possible modulation of the apoptotic activity of cytochrome c by nitric oxide. Cop. 2012 American Chemical Society

Effects of the measuring light on the photochemistry of the bacterial photosynthetic Reaction Centre from Rhodobacter sphaeroides

The bacterial reaction center (RC) has become a reference model in the study of the diverse interactions of quinones with electron transfer complexes. In these studies, the RC functionality was probed through flash-induced absorption changes where the state of the primary donor is probed by means of a continuous measuring beam and the electron transfer is triggered by a short intense light pulse. The single-beam set-up implies the use as reference of the transmittance measured before the light pulse. Implicit in the analysis of these data is the assumption that the measuring beam does not elicit the protein photochemistry. At variance, measuring beam is actinic in nature at almost all the suitable wavelengths. In this contribution, the analytical modelling of the time evolution of neutral and chargeseparated RCs has been performed. The ability of measuring light to elicit RC photochemistry induces a first order growth of the charge-separated state up to a steady state that depends on the light intensity and on the occupation of the secondary quinone (QB) site. Then the lase