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71.
A nonequilibrium molecular dynamics simulation of the response of dimyristoylphosphatidylcholine (DMPC) bilayers to a solvent shear flow is presented. Application of shear flow to planar, stationary DMPC bilayers results in a redistribution of the membrane density profile along the bilayer normal due to the alignment of the lipids in the direction of flow and an increase in average lipid chain length. An increase in the intermolecular and intramolecular order of the lipids in response to the shear flow is also observed. This study provides groundwork for understanding the mechanism of the full response of lipid bilayers to externally imposed solvent shear flows, beginning with the response in the absence of collective lipid motions such as undulations and bilayer flow. 相似文献
72.
C.A. Cody R.C. Levitt R.K. Khanna Philip J. Miller 《Journal of solid state chemistry》1978,26(3):293-309
The infrared and Raman spectra of NaH3(SeO3)2 and NaD3(SeO3)2 have been recorded from 24 to 300°K. The interpretation, assignments, and analysis of the spectral studies are presented on the paraelectric α phase (proton disordered), ferroelectric β phase (proton ordered) and ferroelectric γ phase (proton ordered). A discussion of a newly proposed proton-triggered phase transition mechanism and a possible origin of the hydrogen-bonded OH stretching region of KH2PO4-type ferroelectrics is given. 相似文献
73.
Voszka I Szabó Z Csík G Maillard P Gróf P 《Journal of photochemistry and photobiology. B, Biology》2005,79(2):83-88
The effect of the symmetry and polarity of the porphyrin molecules on their membrane localization and interaction with membrane lipids were investigated by electron paramagnetic resonance (EPR). For this purpose, two glycoconjugated tetraphenyl porphyrin derivatives were selected, respectively, symmetrically and asymmetrically substituted. Small unilamellar liposomes composed of dipalmitoylphosphatidylcholine (DPPC) and spin labeled stearic acids were prepared. The spin probe was located at the 5th or 7th or 12th or 16th position of the hydrocarbon chain in order to monitor various regions of the lipid bilayer. EPR spectra of porphyrin-free and porphyrin-bound liposomes were recorded at various temperatures below and above the phase transition temperature of DPPC. The effect on membrane fluidity proved to be stronger with the asymmetrical porphyrin derivative than with the symmetrical one. The rigidity increased when the spin label was near lipid head groups. The difference observed between control and porphyrin-treated samples when measured below the main lipid transition temperature disappeared at higher temperature. When the spin label was near the end of the hydrophobic tails, the symmetrical porphyrin derivative caused increase in fluidity, while the asymmetrical one slightly decreased it. To explain this phenomenon we propose that the asymmetrical derivative exerts a stronger ordering effect caused by its fluorophenyl group located at the level of the lipid heads, which is attenuated to the hydrophobic tails. The perturbing effect of the symmetric derivative could not lead to similar extent of ordering at the head groups and looses the hydrocarbon chains deeper in the membrane. 相似文献
74.
Single-crystal Raman spectra are presented for the salt [C(NH2)3][V(OH2)6](SO4)2, displaying electronic transitions between the trigonal components of the vanadium(III) 3T1g(Oh) ground term. The 3A-->3E(C3) electronic Raman band is centered at approximately 2720 cm-1, and exhibits extensive structure, revealing the energies of the spinor components of the 3E(C3) term for the two crystallographically distinct [V(OH2)6]3+ cations. The data are interpreted in conjunction with parameters previously reported from an electron paramagnetic resonance study of the salt. A satisfactory reproduction of the electronic Raman profile and ground-state spin-Hamiltonian parameters is achieved by employing a (3A plus sign in circle3E)multiply sign in circle e vibronic coupling model, in which the spin-orbit splitting of the 3E(C3) is quenched significantly by the Ham effect, and the intensity of harmonics of the Jahn-Teller active vibration enhanced by their proximity to the electronic Raman bands. The model gives an excellent account of the intensities of the electronic Raman bands, which are shown to depend profoundly on both temperature and the selected component of the polarizability tensor. The electronic Raman profile changes notably upon deuteriation, a result that exposes deficiencies in the single-mode coupling model. 相似文献
75.
The interaction of organotin halides with lithium salts of mono-substituted phosphorus ylids and also with disubstituted ylids is described. 相似文献
76.
An ion trap mass spectrometer, equipped with a membrane/jet separator interface, is used for the direct detection of volatile and semi-volatile organic compounds in aqueous solutions. Aqueous sample is passed through a capillary membrane, the outside surface of which is continuously purged by helium. The permeate is pneumatically transported to the mass spectrometer via a jet separator which acts as an additional enrichment device. The performance and response characteristics of non-porous silicone and microporous polytetrafluoroethylene (PTFE) membranes are studied. The microporous membrane allows sufficient water to pass for it to be used as a reagent gas for chemical ionization. Both types of membranes provide detection limits in the parts per trillion (pptr) to parts per billion (ppb) range with a linear dynamic range of 3 orders of magnitude for some volatile organic compounds. Results show that there is no detectable matrix effect on response in the selected cases examined. The use of microporous membranes to analyze more polar compounds, such as 5-hydroxymethyl furfuraldehyde and lactic acid, is also demonstrated. The effects of other experimental parameters, such as membrane temperature and length, on sensitivity are also investigated. 相似文献
77.
The stereochemistry of istanbulin-B has been defined by X-ray crystal-structure analysis. Rings A and B are transfused, with the Me groups at C(4) and C(5) cis. The α,β-unsaturated,γ -lactone ring is essentially planar. Crystals of istanbulin-B are orthorhombic, space group P2121,21, with a = 6.729(2), b = 13.447(3), c = 14.721(3)Â,and Z = 4. The crystal structure was determined by direct phasing and the atomic parameters were subsequently adjusted by least-squares calculations that converged at R 38% over 1179 diffractometer |Fa| values 相似文献
78.
Philip J. Cox Olga A. Melvin Simon J. Garden James L. Wardell 《Journal of chemical crystallography》1995,25(8):469-475
The title organotin carbohydrate, C31H36O6Sn, has been synthesized and its molecular structure has been determined in solution and in the solid state. NMR, infrared, mass and X-ray crystallographic techniques were used. The chiral molecules crystallize in the monoclinic space group P21 withZ=2. The triphenyltin and carbohydrate moieties are linked by a trans methylene-oxygen-methylene arrangement. The pyranosyl ring adopts a twist-boat conformation and the isopropylidene rings adopt different (half-chair and envelope) forms. Solution and solid-state conformations are similar as only three 13C shift values are greater than 2ppm; the 119Sn value is 12 ppm. 相似文献
79.
In this paper, we prove the first approximate max-flow min-cut theorem for undirected multicommodity flow. We show that for a feasible flow to exist in a multicommodity problem, it is sufficient that every cut's capacity exceeds its demand by a factor ofO(logClogD), whereC is the sum of all finite capacities andD is the sum of demands. Moreover, our theorem yields an algorithm for finding a cut that is approximately minimumrelative to the flow that must cross it. We use this result to obtain an approximation algorithm for T. C. Hu's generalization of the multiway-cut problem. This algorithm can in turn be applied to obtain approximation algorithms for minimum deletion of clauses of a 2-CNF formula, via minimization, and other problems. We also generalize the theorem to hypergraph networks; using this generalization, we can handle CNF clauses with an arbitrary number of literals per clause.Most of the results in this paper were presented in preliminary form in Approximation through multicommodity flow,Proceedings, 31th Annual Symposium on Foundations of Computer Science (1990), pp. 726–737.Research supported by the National Science Foundation under NSF grant CDA 8722809, by the Office of Naval and the Defense Advanced Research Projects Agency under contract N00014-83-K-0146, and ARPA Order No. 6320, Amendament 1.Research supported by NSF grant CCR-9012357 and by an NSF Presidential Young Investigator Award. 相似文献
80.
Elliott H. Lieb Jan Philip Solovej Jakob Yngvason 《Communications in Mathematical Physics》1994,161(1):77-124
The ground state energy of an atom of nuclear chargeZe in a magnetic fieldB is exactly evaluated to leading order asZ in the following three regions:BZ
4/3,BZ
4/3 andZ
4/3BZ3. In each case this is accomplished by a modified Thomas-Fermi (TF) type theory. We also analyze these TF theories in detail, one of their consequences being the nonintuitive fact that atoms are spherical (to leading order) despite the leading order change in energy due to theB field. This paper complements and completes our earlier analysis [1], which was primarily devoted to the regionsBZ
3 andBZ3 in which a semiclassical TF analysis is numerically and conceptually wrong. There are two main mathematical results in this paper, needed for the proof of the exactitude of the TF theories. One is a generalization of the Lieb-Thirring inequality for sums of eigenvalues to include magnetic fields. The second is a semiclassical asymptotic formula for sums of eigenvalues that isuniform in the fieldB.Work partially supported by U.S. National Science Foundation grant PHY90-19433 A02Work partially supported by U.S. National Science Foundation grant DMS 92-03829Work partially supported by the Heraeus Stiftung and the Research Fund of the University of Iceland. 相似文献