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11.
Zou Q Bennion BJ Daggett V Murphy KP 《Journal of the American Chemical Society》2002,124(7):1192-1202
Trimethylamine n-oxide (TMAO) is a naturally occurring osmolyte that stabilizes proteins and offsets the destabilizing effects of urea. To investigate the molecular mechanism of these effects, we have studied the thermodynamics of interaction between TMAO and protein functional groups. The solubilities of a homologous series of cyclic dipeptides were measured by differential refractive index and the dissolution heats were determined calorimetrically as a function of TMAO concentration at 25 degrees C. The transfer free energy of the amide unit (-CONH-) from water to 1 M TMAO is large and positive, indicating an unfavorable interaction between the TMAO solution and the amide unit. This unfavorable interaction is enthalpic in origin. The interaction between TMAO and apolar groups is slightly favorable. The transfer free energy of apolar groups from water to TMAO consists of favorable enthalpic and unfavorable entropic contributions. This is in contrast to the contributions for the interaction between urea and apolar groups. Molecular dynamics simulations were performed to provide a structural framework for the interpretation of these results. The simulations show enhancement of water structure by TMAO in the form of a slight increase in the number of hydrogen bonds per water molecule, stronger water hydrogen bonds, and long-range spatial ordering of the solvent. These findings suggest that TMAO stabilizes proteins via enhancement of water structure, such that interactions with the amide unit are discouraged. 相似文献
12.
Various poly(macromonomer)s containing sugars have been prepared by ROMP of norbornene macromonomers substituted with ROMP block copolymers containing acetal-protected sugars as the side chain, which upon removal of the protecting group affords a novel amphiphilic architecture. 相似文献
13.
14.
A rapid and simple fractionation procedure using solid-phase extraction (SPE) cartridges was developed for an accurate determination of aliphatic and polycyclic aromatic hydrocarbons in petroleum residues and further application in chemical fingerprinting of oil spills by gas chromatography-mass spectrometry (GC-MS). Among the adsorbents evaluated, SiO2/C3-CN exhibited the best selectivity, providing, by elution with n-hexane (4 ml) and n-hexane-CH2Cl2 (1:1) (5 ml), two well-resolved aliphatic and aromatic hydrocarbon fractions, with recoveries of 97 +/- 7.2 and 99.7 +/- 13.9%, respectively. The SPE fractionation procedure was compared with the conventional silica-alumina adsorption chromatography showing similar results but practical advantages in terms of reproducibility, analysis time, solvent reduction and cost. Moreover, is particularly suitable for routine analysis with a high sample throughput. The developed methodology was tested in the characterization of fuel-oil samples collected along the Spanish north-west coast, after the Prestige oil spill accident. 相似文献
16.
M.J. Grosskopf R.P. Drake C.C. Kuranz E.M. Rutter J.S. Ross N.L. Kugland C. Plechaty B.A. Remington A. Spitkovsky L. Gargate G. Gregori A. Bell C.D. Murphy J. Meinecke B. Reville Y. Sakawa Y. Kuramitsu H. Takabe H.-S. Park 《High Energy Density Physics》2013,9(1):192-197
Experiments investigating the physics of interpenetrating, collisionless, ablated plasma flows have become an important area of research in the high-energy-density field. In order to evaluate the feasibility of designing experiments that will generate a collisionless shock mediated by the Weibel instability on the National Ignition Facility (NIF) laser, computer simulations using the Center for Radiative Shock Hydrodynamics (CRASH) radiation-hydrodynamics model have been carried out. This paper reports assessment of whether the experiment can reach the required scale size while maintaining the low interflow collisionality necessary for the collisionless shock to form. Comparison of simulation results with data from Omega experiments shows the ability of the CRASH code to model these ablated systems. The combined results indicate that experiments on the NIF are capable of reaching the regimes necessary for the formation of a collisionless shock in a laboratory experiment. 相似文献
17.
Thomas AG Mangles SP Najmudin Z Kaluza MC Murphy CD Krushelnick K 《Physical review letters》2007,98(5):054802
Spectral analysis of radiation emitted transverse to laser propagation in laser-wakefield acceleration experiments shows broadband emission when electrons are accelerated to relativistic energies. The region over which emission occurs is short compared with the overall interaction length. The energy of the emission and location along the interaction length both vary with plasma density. A model for the radiation from self-trapped electrons indicates that the emission is a signature of the violent initial acceleration, and hence can be used as a diagnostic of the self-injection mechanism. 相似文献
18.
Nativitat Valls Josep Bonjoch Carlos Del Alamo Joan Bosch 《Helvetica chimica acta》1992,75(1):137-144
A stereodivergent synthesis of enantiomerically pure E-nor-15-azayohimbines via condensation of tryptamine with derivatives of pyroglutamate 4 is reported. When the Pictet-Spengler reaction was induced in refluxing aqueous AcOH a nearly equimolar ratio of lactams 7 and 8 was obtained, whereas under kinetic control (TFA, room temperature) the trans-derivative 8 was the major product. In contrast, cyclization of amido acetal 12 with TsOH gave the cis-derivative 7 as preponderant component. 相似文献
19.
生物测定在环境毒物学研究中普遍用于检测人为污染物对个别生物体和生态系统的影响.这些测定适用于个别化学品或复杂的混合物(如废水)对有代表性的生物系统或整个生物体所引起的影响,并普遍应用于环境监测项目.生物测定可在生物体外或生物体内进行,前者是在实验室内利用细胞培养技术,后者除可在实验室内进行还可应用在真实的环境中.体外生物测定往往是用来研究环境样品中的污染物对生物机制的具体影响,如受体结合特性.而体内活性生物测定则提供了一个更加具体化的综合生物反应.然而,这两种类型的生物测定法可以测量许多不同的生物指标,如对生物生长及发育的影响、内分泌功能和DNA损伤.无论是在体内和体外生物测定都分别有其特有的优点和缺点,其中一些测定法可以使用于毒性鉴定和评价程序.本文简要介绍了体内和体外生物测定方法的基本特点及其在环境监测中的应用实例,指出化学物质如何影响有机体及生态系统的结构和功能,认为广泛发展更能充分反映生态系统生物多样性的生物测定方法,将有助于更准确地了解环境污染物对环境的潜在影响. 相似文献
20.
We employ spin-polarized STM to study the spin-dependent tunneling between a magnetite (111) sample and an antiferromagnetic tip through a vacuum barrier at room temperature. Atomic scale STM images show significant magnetic contrast corresponding to variations in the local surface states induced by oxygen vacancies. The estimated variations in tunneling magnetoresistance of 250% suggest that the spin-transport properties are significantly altered locally by the presence of surface defects. 相似文献