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1.
Recent discoveries about functional mechanisms of proteins in the TMEM16 family of phospholipid scramblases have illuminated the dual role of the membrane as both the substrate and a mechanistically responsive environment in the wide range of physiological processes and genetic disorders in which they are implicated. This is highlighted in the review of recent findings from our collaborative investigations of molecular mechanisms of TMEM16 scramblases that emerged from iterative functional, structural, and computational experimentation. In the context of this review, we present new MD simulations and trajectory analyses motivated by the fact that new structural information about the TMEM16 scramblases is emerging from cryo-EM determinations in lipid nanodiscs. Because the functional environment of these proteins in in vivo and in in vitro is closer to flat membranes, we studied comparatively the responses of the membrane to the TMEM16 proteins in flat membranes and nanodiscs. We find that bilayer shapes in the nanodiscs are very different from those observed in the flat membrane systems, but the function-related slanting of the membrane observed at the nhTMEM16 boundary with the protein is similar in the nanodiscs and in the flat bilayers. This changes, however, in the bilayer composed of longer-tail lipids, which is thicker near the phospholipid translocation pathway, which may reflect an enhanced tendency of the long tails to penetrate the pathway and create, as shown previously, a nonconductive environment. These findings support the correspondence between the mechanistic involvement of the lipid environment in the flat membranes, and the nanodiscs. © 2019 Wiley Periodicals, Inc.  相似文献   
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Carbon nanotubes yield to mechanical force by a primary dislocation dipole whose formation energy describes the thermodynamic stability of the tubule. However, the real-time strength is determined by the rate of defect formation, defined in turn by the activation barrier for the bond flip. First extensive computations of the kinetic barriers for a variety of strain-lattice orientations lead to predictions of the yield strength. Its value depends on nanotube chiral symmetry, in a way very different from the thermodynamic assessment.  相似文献   
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The palladium/phosphine-catalyzed productive chloroarene C-Cl bond activation provides general, efficient, and functional group friendly methods for the selective oxidation of alcohols and the hydrodechlorination of chloroarenes.  相似文献   
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Guram AS  Bei X  Turner HW 《Organic letters》2003,5(14):2485-2487
[reaction: see text] The palladium/ligand-catalyzed activation of chlorobenzene provides a general, efficient, and functional group friendly method for the selective oxidation of alcohols to carbonyl compounds.  相似文献   
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The European Physical Journal A - The divergent part of the one-loop effective action in Chiral Perturbation Theory with virtual photons has been evaluated in an arbitrary covariant gauge. The...  相似文献   
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The notion of n-fold Čech derived functors is introduced and studied. This is illustrated using the n-fold Čech derived functors of the nilization functors Zk. This gives a new purely algebraic method for the investigation of the Brown–Ellis generalised Hopf formula for the higher integral group homology and for its further generalisation. The paper ends with an application to algebraic K-theory. (Received: December 2004)  相似文献   
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When we interpret modal ? as the limit point operator of a topological space, the Gödel-Löb modal system GL defines the class Scat of scattered spaces. We give a partition of Scat into α-slices S α , where α ranges over all ordinals. This provides topological completeness and definability results for extensions of GL. In particular, we axiomatize the modal logic of each ordinal α, thus obtaining a simple proof of the Abashidze–Blass theorem. On the other hand, when we interpret ? as closure in a topological space, the Grzegorczyk modal system Grz defines the class HI of hereditarily irresolvable spaces. We also give a partition of HI into α-slices H α , where α ranges over all ordinals. For a subset A of a hereditarily irresolvable space X and an ordinal α, we introduce the α-representation of A, give an axiomatization of the α-representation of A, and characterize H α in terms of α-representations. We prove that ${X \in {\bf H}_{1}}When we interpret modal ◊ as the limit point operator of a topological space, the G?del-L?b modal system GL defines the class Scat of scattered spaces. We give a partition of Scat into α-slices S α , where α ranges over all ordinals. This provides topological completeness and definability results for extensions of GL. In particular, we axiomatize the modal logic of each ordinal α, thus obtaining a simple proof of the Abashidze–Blass theorem. On the other hand, when we interpret ◊ as closure in a topological space, the Grzegorczyk modal system Grz defines the class HI of hereditarily irresolvable spaces. We also give a partition of HI into α-slices H α , where α ranges over all ordinals. For a subset A of a hereditarily irresolvable space X and an ordinal α, we introduce the α-representation of A, give an axiomatization of the α-representation of A, and characterize H α in terms of α-representations. We prove that X ? H1{X \in {\bf H}_{1}} iff X is submaximal. For a positive integer n, we generalize the notion of a submaximal space to that of an n-submaximal space, and prove that X ? Hn{X \in {\bf H}_{n}} iff X is n-submaximal. This provides topological completeness and definability results for extensions of Grz. We show that the two partitions are related to each other as follows. For a successor ordinal α = β + n, with β a limit ordinal and n a positive integer, we have Ha ?Scat = Sb+2n-1 èSb+2n{{\bf H}_{\alpha} \cap {\bf Scat} = {\bf S}_{\beta+2n-1} \cup {\bf S}_{\beta+2n}} , and for a limit ordinal α, we have Ha ?Scat = Sa{{\bf H}_{\alpha} \cap {\bf Scat} = {\bf S}_{\alpha}} . As a result, we obtain full and faithful translations of ordinal complete extensions of Grz into ordinal complete extensions of GL, thus generalizing the Kuznetsov–Goldblatt–Boolos theorem.  相似文献   
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