161,246 research outputs found
Influence of the axial ligands on the spectral properties of P700 of photosystem I: A study of site-directed mutants
No full textTwo histidines provide the axial ligands of the two chlorophyll a (Chl a) molecules which form the primary electron donor (P700) of photosystem I (PSI). Histidine 676 in the protein subunit PsaA, His(A676), and histidine 656 in subunit PsaB, His(B656), were replaced in the green algae Chlamydomnas reinhardtii by site-directed mutagenesis with nonpolar, uncharged polar, acidic, and basic amino acid residues. Only the substitutions with uncharged polar residues led to a significant accumulation of PSI in the thylakoid membranes. These PSI complexes were isolated and the physical properties of the primary donor characterized. The midpoint potential of P700(+.)/P700 was increased in all mutants (up to 140 mV) and showed a dependence on size and polarizability of the residues when His(B656) was substituted. In the light-minus-dark absorbance spectra, all mutations in PsaB exhibited an additional bleaching band at 665 nm at room temperature comparable with the published spectrum for the replacement of His(B656) with asparagine [Webber, A. N., Su Hui, Bingham, S. E., Kass, H., Krabben, L., Kuhn, M., Jordan, R., Schlodder, E., and Lubitz, W. (1996) Biochemistry 35, 12857-12863]. Substitutions of His(A676) showed an additional shoulder around 680 nm. In the low-temperature absorbance difference spectra of P700(+.)/P700, a blue shift of the main bleaching band by 2 nm and some changes in the spectral features around 660 nm were observed for mutations of His(B656) in PsaB. The analogous substitution in PsaA showed only a shift of the main bleaching band. Similar effects of the mutations were found in the (3)P700/P700 absorbance difference spectra at low temperatures (T = 2 K). The zero-field splitting parameters of (3)P700 were not significantly changed in the mutated PSI complexes. The electron spin density distribution of P700(+.), determined by ENDOR spectroscopy, was only changed when His(B656) was replaced. In all measurements, two general observations were made. (i) The replacement of His(B656) had a much stronger impact on the physical properties of P700 than the mutation of His(A676). (ii) The exchange of His(B656) with glutamine induces the smallest changes in the spectra or the midpoint potential, whereas the other replacements exhibited a stronger but very similar influence on the spectroscopic features of P700. The data provide convincing evidence that the unpaired electron in the cation radical and the triplet state of P700 are mainly localized on the Chl a of the dimer which is axially coordinated by His(B656)
Prof. Th. W. Adorno and the author Hans Erich Nossack.
No full textProf. Th. W. Adorno and the author Hans Erich Nossack at a reception of Insel Verlag, Buchmesse Frankfurt 1966LB
Spin dynamics of light-induced charge separation in composites of semiconducting polymers and PC 60 BM revealed using Q-band pulse EPR
No full textLight-induced processes in composites of semiconducting polymers and fullerene derivatives have been widely studied due to their usage as active layers of organic solar cells. However the process of charge separation under light illumination – the key process of an organic solar cell is not well understood yet. Here we report a Q-band pulse electron paramagnetic resonance study of composites of the fullerene derivative PC60BM ([6,6]-phenyl-C61-butyric acid methyl ester) with different p-type semiconducting polymers regioregular and regiorandom P3HT (poly(3-hexylthiophene-2,5-diyl), MEH-PPV (poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]), PCDTBT (poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)]), PTB7 (poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}))), resulting in a detailed description of the in-phase laser flash-induced electron spin echo (ESE) signal. We found that in organic donor–acceptor composites the laser flash simultaneously induces species of two types: a polymer˙+/fullerene˙− spin-correlated polaron pair (SCPP) with an initial singlet spin state and (nearly) free polymer˙+ and fullerene˙− species with non-equilibrium spin polarization. Species of the first type (SCPP) are well-known for polymer/fullerene blends and are usually associated with a charge-separated state. Also, spin polarization of long-living free species (polarons in deep traps) is affected by the laser flash, which is the third contribution to the flash-induced ESE signal. A protocol for extracting the in-phase ESE signal of the SCPP based on the dependence of the microwave nutation frequency on the strength of the spin coupling within the polaron pair was developed. Nutation experiments revealed an unusual pattern of the SCPP in RR-P3HT/PC60BM composites, from which the strength of the exchange interaction between the polymer˙+ and fullerene˙− was extracted. In composites with low-efficient polymers the contribution of the SCPP to the in-phase ESE signal is high, while in composites with high-efficient polymers it is low. This finding can be used as a selection criterion of charge separation efficiency in the polymer/fullerene composites
The Magic of Disaccharide Glass Matrices for Protein Function as Decoded by High-Field EPR and FTIR Spectroscopy
No full textThe structural and dynamical interaction of proteins with their microenvironment in disordered matrices plays a decisive role for their function; EPR spectroscopy is a powerful tool for shading light onto the molecular mechanisms of this protein-matrix interplay. To clarify the molecular mechanisms of disaccharide bioprotection, we studied the structure and dynamics of spin-labeled systems and photosynthetic reaction centers (RCs) in sucrose and trehalose matrices at different hydration levels by means of cw and pulse high-field 95 GHz (W-band) EPR as well as by FTIR. In this minireview, we summarize and discuss EPR and FTIR experiments showing that the anhydrobiotic state of the RC-trehalose system (1) is not the result of matrix-induced changes of the local structure of the charge-separated radical-pair cofactors, and , and (2) is not the result of changes of local dynamics and local hydrogen bonding of Q(A) in its binding pocket. Rather, the extreme impairment of RC dynamics caused by incorporation into the dehydrated trehalose matrix, which also protects it against thermal denaturation, originates in the high rigidity, already at room temperature, of the dry trehalose glass matrix coating the RC protein surface. This surface hydrogen-bonding scaffold shifts the correlation time of thermal conformational fluctuations into the non-biological time domain. Another intriguing aspect of disaccharide bioprotection is the superior efficiency of trehalose versus sucrose matrices in stabilizing the anhydrobiotic state of proteins. To clarify the molecular basis of this specificity, glassy trehalose-water and sucrose-water binary systems, incorporating a nitroxide radical as spin probe, have been studied by high-field W-band EPR spectroscopy at different water contents. Analysis of the EPR spectra revealed a different structural and dynamical organization in the sucrose and trehalose matrix, only the trehalose being homogeneous in terms of residual water and nitroxide distribution
Nowe spojrzenie na planowanie architektury mieszkaniowej w afryce subsaharyjskiej
No full textThe author shares his reflections on state of art in housing and urban planning, deficiencies, expectations and possibilities in the Sahel region of Africa. He notices, that the housing problem in Africa is one of the challenges, which should be solved in order to recover life dignity of African people and secure their rights to traditional family life in acceptable conditions. The paper describes the studies on the typical dispersed urban structures and the need to foster this type of settlement structure and proposals of introduction of new on light steel frame housing system in the area of Sahel, combining the traditional way of building houses with modern technology. The particularly analysed case, is the housing problem in the Republic of Chad. The author presents the basic discussion on this topic and his architectural proposals. Unfortunately, the gap between the needs and the financial feasibility of housing construction in this area, makes this project already at the starting point extremely difficult to be realized without external subventions.Problem mieszkaniowy w Afryce jest jednym z wyzwań, które należy rozwiązać, aby Afrykanie mogli odzyskać godność życiową i zabezpieczyć swoje prawa do tradycyjnego życia rodzinnego w akceptowalnych warunkach. W artykule opisano badania nad typowymi rozproszonymi strukturami miejskimi i potrzebą wspierania tego typu struktur osadniczych oraz propozycji wprowadzenia nowego systemu konstrukcji domów, opartym na lekkim szkielecie stalowym, łączącym tradycyjny sposób budowania domów z nowoczesną technologią. Przypadkiem szczególnie analizowanym jest problem mieszkaniowy w Republice Czadu. Autor przedstawia podstawową dyskusję na ten temat i swoje propozycje architektoniczne. Niestety luka między potrzebami mieszkaniowymi w Czadzie a finansową wykonalnością budownictwa mieszkaniowego w tym obszarze sprawia, że projekt ten, już w punkcie wyjścia, jest niezwykle trudny do realizacji bez uzyskania zewnętrznych dotacji
Structural and dynamical characteristics of trehalose and sucrose matrices at different hydration levels as probed by FTIR and high-field EPR
No full textSome organisms can survive complete dehydration and high temperatures by
adopting an anhydrobiotic state in which the intracellular medium contains
large amounts of disaccharides, particularly trehalose and sucrose. Trehalose
is most effective also in protecting isolated in vitro biostructures. In an
attempt to clarify the molecular mechanisms of disaccharide bioprotection, we
compared the structure and dynamics of sucrose and trehalose matrices at
different hydration levels by means of high-field W-band EPR and FTIR
spectroscopy. The hydration state of the samples was characterized by FTIR
spectroscopy and the structural organization was probed by EPR using a
nitroxide radical dissolved in the respective matrices. Analysis of the EPR
spectra showed that the structure and dynamics of the dehydrated matrices as
well as their evolution upon re-hydration differ substantially between
trehalose and sucrose. The dehydrated trehalose matrix is homogeneous in terms
of distribution of the residual water and spin-probe molecules. In contrast,
dehydrated sucrose forms a heterogeneous matrix. It is comprised of sucrose
polycrystalline clusters and several bulk water domains. The amorphous form
was found only in 30% (volume) of the sucrose matrix. Re-hydration leads to a
structural homogenization of the sucrose matrix, whilst in the trehalose
matrix several domains develop differing in the local water/radical content
and radical mobility. The molecular model of the matrices provides an
explanation for the different protein–matrix dynamical coupling observed in
dried ternary sucrose and trehalose matrices, and accounts for the superior
efficacy of trehalose as a bioprotectant. Furthermore, for bacterial
photosynthetic reaction centers it is shown that at low water content the
protein–matrix coupling is modulated by the sugar/protein molar ratio in
sucrose matrices only. This effect is suggested to be related to the
preference for sucrose, rather than trehalose, as a bioprotective disaccharide
in some anhydrobiotic organisms
Site-directed mutagenesis of Thr A739 of photosystem I in Chlamydomonas reinhardtii alters significantly the excitonic and electronic coupling of the primary electron donor P700
No full textThe primary electron donor P700 of photosystem I is a dimer comprised of one chlorophyll (Chl) a (PB) and one Chl a ́ (PA). To investigate the influence of protein-cofactor interactions on the properties of P700, we constructed a series of site-directed mutants in the surrounding of P700. The most interesting effects were obtained for the replacement of Thr A739, a possible hydrogen bond donor to the 9-keto group of PA, against Val. The low-energy exciton absorption band of P700 observed as a shoulder at about 700 nm in the absorption spectrum of PS I complexes from wild type is not visible in the mutant TV A739. The main bleaching band in the (P700+-P700) and (3P700-P700) absorption difference spectra is blue shifted by 9 nm. Both results imply that the excitonic coupling of P700 is severely disturbed. A similar blue shift is observed for the main bleaching in the Soret region. Redox titrations yielded a decrease of the midpoint potential for the oxidation of P700 by 32 mV. ENDOR spectroscopy revealed a change of the electron spin densitiy distribution of P700+. The data provide evidence that P700 is a Chl-dimer with an asymmetric spin/charge density distributio
Seeing the world anew : the radical vision of Martin Waldseemüller's 1507 & 1516 world maps /
No full text9781929154470 (ISBN). 192915447X (ISBN). First edition 2012. Accompanied by 2 foldeds map in front and back pockets: 1507 map -- 1516 map.; Includes bibliographical references: pages 98-107.; Maps from pockets also available online http://nla.gov.au/nla.map-vn6254227; Original version of the 1507 map: Universalis cosmographiae secundum Ptholomaei traditionem et Americi Vespucii alioru que lustrationes. [St. Dié, France? : s.n., 1507]; Original version of the 1516 map: Carta marina, navigatoria Portugallen, navigationes atque tocius cogniti orbis terre marisque formam naturamq[u]e situs et terminos nostris temporibus recognitos et ab antiquorum traditione differentes eciam quor[um] vetusti non meminerunt auctores hec generaliter indicat / consumatum est in oppido S. Deodati compositione et digestione Martini Waldseemuller Ilacomili. [St. Dié, France? : s.n., 1516]. Prologue: In a Renaissance Vision, a Glimpse of the Modern / John W. Hessler -- "An island surrounded on all sides by sea" : The World Map, 1507 / John W. Hessler -- "Land of Cuba, part of Asia" : The Carta marina, 1516 / Chet Van Duzer -- Epilogue: A Renaissance That Resonates Still / John W. Hessler -- Notes -- Afterword / Ralph E. Ehrenberg -- About the authors -- Acknowledgments -- The Maps: The 1507 World Map, 12 sheets, with commentary -- Composite: front pocket -- The 1516 Carta marina, 13 sheets, with commentary -- Composite: back pocket
Klimat społeczny w szkole inkluzyjnej
No full textAuthor presented in this paper theoretical approach to the building of social climate in an inclusive school. The publication indicatessome tendencies and directions of changes to improve the functioning of these institutions and to implement the idea of inclusive education.Autorka przedstawiła w artykule teoretyczne ujęcie zagadnienia związanego z budowaniem klimatu społecznego w szkole inkluzyjnej. W publikacji ukazano pewne dążenia i kierunki zmian, jakich należy dokonywać w masowych szkołach, aby poprawić jakość funkcjonowania tych placówek, tak by kierowały się one ideą edukacji włączającej
Ewolucja programowa FDP w polityce wschodniej w latach 1949-1969 w świetle nowych zasobów Archiwum Niemieckiego Liberalizmu
No full textZasadniczym celem artykułu jest analiza działalności programowej FDP w polityce wschodniej Republiki Federalnej Niemiec w latach 1949-1969. Autor wykorzystał nowe zasoby Archiwum Niemieckiego Liberalizmu w Gummersbach, co umożliwiło przedstawienie nowej oceny wpływu FDP na politykę wschodnią Republiki Federalnej Niemiec.The main goal of the article is to analyze the FDP's program activities in the eastern policy of the Federal Republic of Germany in the years 1949-1969. Of great importance here is the fact that the author used in this work new archives from the Archives of German Liberalism in Gummersbach. This enabled him to present a new assessment of the FDP's impact on the eastern policy of the Federal Republic of Germany
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