1,215 research outputs found
Collective exchange processes reveal an active site proton cage in bacteriorhodopsin
Proton translocation across membranes is vital to all kingdoms of life. Mechanistically, it relies on characteristic proton flows and modifications of hydrogen bonding patterns, termed protonation dynamics, which can be directly observed by fast magic angle spinning (MAS) NMR. Here, we demonstrate that reversible proton displacement in the active site of bacteriorhodopsin already takes place in its equilibrated dark-state, providing new information on the underlying hydrogen exchange processes. In particular, MAS NMR reveals proton exchange at D85 and the retinal Schiff base, suggesting a tautomeric equilibrium and thus partial ionization of D85. We provide evidence for a proton cage and detect a preformed proton path between D85 and the proton shuttle R82. The protons at D96 and D85 exchange with water, in line with ab initio molecular dynamics simulations. We propose that retinal isomerization makes the observed proton exchange processes irreversible and delivers a proton towards the extracellular release site
Finite group actions on reductive groups and buildings and tamely-ramified descent in Bruhat-Tits theory
The purpose of the paper is to give a new approach to tamely-ramified descent
in Bruhat-Tits theory. This descent was first studied by Guy Rousseau in his
thesis.Comment: 28 pages. arXiv admin note: text overlap with arXiv:1611.0743
Accommodation of transpressional strain in the Arabia-Eurasia collision zone: new constraints from (U-Th)/He thermochronology in the Alborz mountains, north Iran
The Alborz range of N Iran provides key information on the spatiotemporal evolution and characteristics of the Arabia-Eurasia continental collision zone. The southwestern Alborz range constitutes a transpressional duplex, which accommodates oblique shortening between Central Iran and the South Caspian Basin. The duplex comprises NW-striking frontal ramps that are kinematically linked to inherited E-W-striking, right-stepping lateral to obliquely oriented ramps. New zircon and apatite (U-Th)/He data provide a high-resolution framework to unravel the evolution of collisional tectonics in this region. Our data record two pulses of fast cooling associated with SW-directed thrusting across the frontal ramps at ~ 18–14 and 9.5-7.5 Ma, resulting in the tectonic repetition of a fossil zircon partial retention zone and a cooling pattern with a half U-shaped geometry. Uniform cooling ages of ~ 7–6 Ma along the southernmost E-W striking oblique ramp and across its associated NW-striking frontal ramps suggests that the ramp was reactivated as a master throughgoing, N-dipping thrust. We interpret this major change in fault kinematics and deformation style to be related to a change in the shortening direction from NE to N/NNE. The reduction in the obliquity of thrusting may indicate the termination of strike-slip faulting (and possibly thrusting) across the Iranian Plateau, which could have been triggered by an increase in elevation. Furthermore, we suggest that ~ 7-6-m.y.-old S-directed thrusting predated inception of the westward motion of the South Caspian Basin
Ceramide remodeling and risk of cardiovascular events and mortality
BackgroundRecent studies suggest that circulating concentrations of specific ceramide species may be associated with coronary risk and mortality. We sought to determine the relations between the most abundant plasma ceramide species of differing acyl chain lengths and the risk of coronary heart disease (CHD) and mortality in community‐based samples. Methods and ResultsWe developed a liquid chromatography/mass spectrometry assay to quantify plasma C24:0, C22:0, and C16:0 ceramides and ratios of these very–long‐chain/long‐chain ceramides in 2642 FHS (Framingham Heart Study) participants and in 3134 SHIP (Study of Health in Pomerania) participants. Over a mean follow‐up of 6 years in FHS, there were 88 CHD and 90 heart failure (HF) events and 239 deaths. Over a median follow‐up time in SHIP of 5.75 years for CHD and HF and 8.24 years for mortality, there were 209 CHD and 146 HF events and 377 deaths. In meta‐analysis of the 2 cohorts and adjusting for standard CHD risk factors, C24:0/C16:0 ceramide ratios were inversely associated with incident CHD (hazard ratio per average SD increment, 0.79; 95% confidence interval, 0.71–0.89; P<0.0001) and inversely associated with incident HF (hazard ratio, 0.78; 95% confidence interval, 0.61–1.00; P=0.046). Moreover, the C24:0/C16:0 and C22:0/C16:0 ceramide ratios were inversely associated with all‐cause mortality (C24:0/C16:0: hazard ratio, 0.60; 95% confidence interval, 0.56–0.65; P<0.0001; C22:0/C16:0: hazard ratio, 0.65; 95% confidence interval, 0.60–0.70; P<0.0001). ConclusionsThe ratio of C24:0/C16:0 ceramides in blood may be a valuable new biomarker of CHD risk, HF risk, and all‐cause mortality in the community
Optimal eigenvalue estimate for the Dirac-Witten operator on bounded domains with smooth boundary
Eigenvalue estimate for the Dirac-Witten operator is given on bounded domains
(with smooth boundary) of spacelike hypersurfaces satisfying the dominant
energy condition, under four natural boundary conditions (MIT, APS, modified
APS, and chiral conditions). This result is a generalisation of Friedrich's
inequality for the usual Dirac operator. The limiting cases are also
investigated.Comment: 2007, 18 pages, submitted 02 June 200
Terrestrial solar radiation driven photodecomposition of ciprofloxacin in clinical wastewater applying mesostructured iron(III) oxide
Cationic cylindrical polymer brushes based on polybutadiene-block-poly(2-vinylpyridine) were applied as structure-directing agent for mesostructuring F
Raltitrexed (Tomudex): an alternative drug for patients with colorectal cancer and 5-fluorouracil associated cardiotoxicity.
Two patients with proven 5-fluorouracil (5-FU)-associated cardiotoxicity were treated with the specific thymidylate synthase inhibitor raltitrexed safely, without evidence of cardiotoxicity. Raltitrexed might be an alternative for patients with advanced colorectal cancer and 5-FU-associated cardiotoxicity. 5-FU cardiotoxicity is not due to the antineoplastic mechanisms via thymidilate synthase
Interconversion of one-dimensional Thiogallates Cs2[Ga2(S2)2-xS2+x] (x = 0, 1, 2) by using high-temperature Decomposition and Polysulfide-Flux Reactions
The potential of cesium polysulfide-flux reactions for the synthesis of chalcogenogallates was investigated by using X-ray diffraction and Raman spectroscopy. An investigation of possible factors influencing the product formation revealed that only the polysulfide content x in the Cs2Sx melts has an influence on the crystalline reaction product. From sulfur-rich melts (x > 7), CsGaS3 is formed, whereas sulfur-poor melts (x < 7) lead to the formation of Cs2Ga2S5- In situ investigations using high-temperature Raman spectroscopy revealed that the crystallization of these solids takes place upon cooling of the melts. Upon heating, CsGaS3 and Cs2Ga2S5 release gaseous sulfur due to the degradation of S-2(2-) units. This decomposition of CsGaS3 to Cs2Ga2S5 and finally to CsGaS2-mC16 was further studied in situ by using high-temperature X-ray powder diffraction. A combination of the polysulfide reaction route and the high-temperature decomposition leads to the possibility of the directed interconversion of these thiogallates. The presence of disulfide units in the anionic substructures of these thiogallates has a significant influence on the electronic band structures and their optical properties. This influence was studied by using UV/vis-diffuse reflectance spectroscopy and DFT simulations, revealing a trend of smaller band gaps with increasing S-2(2-) content
Synthese und Charakterisierung von Cs4Ga6Q11 (Q = S, Se) – Neue Chalkogenogallate mit außergewöhnlichen polymeren Anionen = Synthesis and Characterization of Cs4Ga6Q11 (Q=S, Se): Chalcogenometalates with Exotic Polymeric Anions
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