1,080 research outputs found

    ESR, ENDOR and TRIPLE resonance studies of the primary donor radical cation P960+ in the photosynthetic bacterium Rhodopseudomonas viridis

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    The light-induced radical cation of the primary electron donor P960+‱ in photosynthetic reaction centers from Rhodopseudomonas viridis has been investigated by ESR, ENDOR and TRIPLE techniques. Both the comparison with the cation radical of monomeric bacteriochlorophyll b (BChl b) and with molecular-orbital calculations performed on P960+‱ using the results of an X-ray structure analysis, consistently show an asymmetric distribution of the unpaired electron over the two BChl b molecules which constitute P960+‱. The possible relevance of this result for the primary electron transfer step in the reaction center is briefly discussed

    Spectral diffusion and 14N quadrupole splittings in absorption detected magnetic resonance hole burning spectra of photosynthetic reaction centers

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    Zero field absorption detected magnetic resonance hole burning measurements were performed on photosynthetic reaction centers of the bacteria Rhodobacter sphaeroides R26 and Rhodopseudomonas viridis. Extrapolation to zero microwave power yielded pseudohomogeneous linewidths of 2.0 MHz for Rhodopseudomonas viridis, 1.0 and 0.9 MHz for the protonated forms of Rhodobacter sphaeroides R26 with and without monomer bacteriochlorophyll exchanged, and 0.25 MHz as an upper limit for fully deuterated reaction centers of Rhodobacter sphaeroides R26. The measured linewidths were interpreted as being due to unresolved hyperfine interaction between the nuclear spins and the triplet electron spin, the line shape being determined by spectral diffusion among the nuclei. The difference in linewidths between Rhodobacter sphaeroides R26 and Rhodopseudomonas viridis is then explained by triplet delocalization on the special pair in the former, and localization on one dimer half on the latter. In the fully deuterated sample, four quadrupole satellites were observed in the hole spectra arising from the eight 14N nitrogens in the special pair. The quadrupole parameters seem to be very similar for all nitrogens and were determined to =1.25±0.1 MHz and =0.9±0.1 MHz. The Journal of Chemical Physics is copyrighted by The American Institute of Physics

    The radical cation of bacteriochlorophyll b. A liquid-phase endor and triple resonance study

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    The previous termradical cationnext term of bacterioehlorophyll b (BChl b) is investigated by ENDOR and TRIPLE resonance in liquid solution. The experimental hyperfine coupling constants, ten proton and three nitrogen couplings, are compared with the predictions from advanced molecular-orbital calculations (RHF INDO/SP). The detailed picture obtained of the spin density distribution is a prerequisite for the investigation of the primary electron donor previous termradical cationnext term in BChl b containing photosynthetic bacteria

    Detailed studies of the subpicosecond kinetics in the primary electron transfer of reaction centers of Rhodopseudomonas viridis

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    The primary, light-induced charge separation in reaction centers of Rhodopseudomonas viridis is investigated with femtosecond time resolution. The absorption changes after direct excitation of the primary donor P at 955 nm are investigated in the time range from 100 fs to 600 ps. The experimental data, taken at various probing wavelengths, reveal one subpicosecond and two picosecond time constants: 0.65 ± 0.2 ps, 3.5 ± 0.4 ps, and 200 ± 20 ps. The previously undetected 0.65 ps kinetics can be observed clearly in the spectral range of the Qx and Qy transitions of the monomeric bacteriochlorophylls. The experimental data support the idea that the accessory bacteriochlorophyll B A participates in the electron-transfer process. Reference

    Social Freedom and Self-Actualization: “Normative Reconstruction” as a Theory of Justice

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    In Freedom's Right Axel Honneth seeks to provide a theory of justice by appropriatingHegel's account of ethical substance in the Philosophy of Right, but hewants to do sowithout endorsingHegel'smore robust idealist commitments. I argue that this project can only succeed if Honneth can offer an alternative, comparatively robust demonstration of the rationality and normative coherence of existing social institutions. I contend that the grounds Honneth provides for this claimare insufficient for his purposes. In particular, I argue that Honneth's claim that "justice and individual self-determination are mutually referential," even were it to be accepted, would be insufficient to underwrite hismore robust identification between the normative foundations of justice, autonomy and reciprocal self-realization. In the final section of the paper, I turn to Honneth's analysis of the "social institution" of friendship,which he, followingHegel, holds up as a paradigmatic instantiation of social freedom understood as, in Hegel's words, "being with oneself in another" (Beisichselbstsein in einem Anderen). I argue that an analysis of the normative import of friendship wholly in terms of mutual recognition misses an important aspect of the kind of self-realization that friendship makes possible

    Temperature dependence of the primary electron transfer in photosynthetic reaction centers from Rhodobacter sphaeroides

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    The primary electron transfer (ET) in reaction centers (RC) of Rhodobacter sphaeroides is investigated as a function of temperature with femtosecond time resolution. For temperatures from 300 to 25 K the ET to the bacteriopheophytin is characterized by a biphasic time dependence. The two time constants of τ1=3.5±0.4 ps and τ2=1.2±0.3 ps at T=300 K decrease continously with temperature to values of τ1=1.4±0.3 ps and τ2=0.3±0.15 ps at 25 K. The experimental results indicate that the ET is not thermally activated and that the same ET mechanisms are active at room and low temperatures. All observations are readily rationalized by a two-step ET model with the monomeric bacteriochlorophyll as a real electron carrier

    The unacknowledged legacy

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    This paper presents a critical discussion of the treatment of mimetic art, and particularly poetry and the theatre, in the work of the Athenian philosopher Plato (427-347 BC). It centres on Plato's discussion of the corrupting powers of the arts in the Republic, and the implications that his fierce attack on poetry and theatre have for his construction of the ideal polity. The legacy of Platonic ideas in later elaborations of the corrupting power of the arts is discussed. Furthermore, the paper investigates the relationship between current debates on cultural policy and the Platonic idea that the transformative powers of the arts ought to be harnessed by the state to promote a just society. The conclusion thus reached is that “instrumental cultural policy”, rather then being a modern invention, was in fact first theorized precisely in Plato's Republic

    Markovian Master Equations: A Critical Study

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    We derive Markovian master equations of single and interacting harmonic systems in different scenarios, including strong internal coupling. By comparing the dynamics resulting from the corresponding Markovian master equations with exact numerical simulations of the evolution of the global system, we precisely delimit their validity regimes and assess the robustness of the assumptions usually made in the process of deriving the reduced dynamics. The proposed method is sufficiently general to suggest that the conclusions made here are widely applicable to a large class of settings involving interacting chains subject to a weak interaction with an environment.Comment: 40 pages, 14 figures, final versio

    Have Anglo-Saxon concepts really influenced the development of European qualifications policy?

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    This paper considers how far Anglo-Saxon conceptions of have influenced European Union vocational education and training policy, especially given the disparate approaches to VET across Europe. Two dominant approaches can be identified: the dual system (exemplified by Germany); and output based models (exemplified by the NVQ ‘English style’). Within the EU itself, the design philosophy of the English output-based model proved in the first instance influential in attempts to develop tools to establish equivalence between vocational qualifications across Europe, resulting in the learning outcomes approach of the European Qualifications Framework, the credit-based model of European VET Credit System and the task-based construction of occupation profiles exemplified by European Skills, Competences and Occupations. The governance model for the English system is, however, predicated on employer demand for ‘skills’ and this does not fit well with the social partnership model encompassing knowledge, skills and competences that is dominant in northern Europe. These contrasting approaches have led to continual modifications to the tools, as these sought to harmonise and reconcile national VET requirements with the original design. A tension is evident in particular between national and regional approaches to vocational education and training, on the one hand, and the policy tools adopted to align European vocational education and training better with the demands of the labour market, including at sectoral level, on the other. This paper explores these tensions and considers the prospects for the successful operation of these tools, paying particular attention to the European Qualifications Framework, European VET Credit System and European Skills, Competences and Occupations tool and the relationships between them and drawing on studies of the construction and furniture industries
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