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91.
Dielectric relaxation of aqueous solutions of micelles, proteins, and many complex systems shows an anomalous dispersion at frequencies intermediate between those corresponding to the rotational motion of bulk water and that of the organized assembly or macromolecule. The precise origin of this anomalous dispersion is not well-understood. In this work we employ large scale atomistic molecular dynamics simulations to investigate the dielectric relaxation (DR) of water molecules in an aqueous micellar solution of cesium pentadecafluorooctanoate. The simulations clearly show the presence of a slow component in the moment-moment time correlation function [PhiMW(t)] of water molecules, with a time constant of about 40 ps, in contrast to only 9 ps for bulk water. Interestingly, the orientational time correlation function [Cmu(t)] of individual water molecules at the surface exhibits a component with a time constant of about 19 ps. We show that these two time constants can be related by the well-known micro-macrorelations of statistical mechanics. In addition, the reorientation of surface water molecules exhibits a very slow component that decays with a time constant of about 500 ps. An analysis of hydrogen bond lifetime and of the rotational relaxation in the coordinate frame fixed on the micellar body seems to suggest that the 500 ps component owes its origin to the existence of an extended hydrogen bond network of water molecules at the surface. However, this ultraslow component is not found in the total moment-moment time correlation function of water molecules in the solution. The slow DR of hydration water is found to be well correlated with the slow solvation dynamics of cesium ions at the water-micelle interface. 相似文献
92.
A general approach to controlling the surface composition of poly(ethylene oxide)-based block copolymers for antifouling coatings 总被引:1,自引:0,他引:1
Dimitriou MD Zhou Z Yoo HS Killops KL Finlay JA Cone G Sundaram HS Lynd NA Barteau KP Campos LM Fischer DA Callow ME Callow JA Ober CK Hawker CJ Kramer EJ 《Langmuir : the ACS journal of surfaces and colloids》2011,27(22):13762-13772
To control the surface properties of a polystyrene-block-poly(ethylene oxide) diblock copolymer, perfluorinated chemical moieties were specifically incorporated into the block copolymer backbone. A polystyrene-block-poly[(ethylene oxide)-stat-(allyl glycidyl ether)] [PS-b-P(EO-stat-AGE)] statistical diblock terpolymer was synthesized with varying incorporations of allyl glycidyl ether (AGE) in the poly(ethylene oxide) block from 0 to 17 mol %. The pendant alkenes of the AGE repeat units were subsequently functionalized by thiol-ene chemistry with 1H,1H,2H,2H-perfluorooctanethiol, yielding fluorocarbon-functionalized AGE (fAGE) repeat units. (1)H NMR spectroscopy and size-exclusion chromatography indicated well-defined structures with complete functionalization of the pendant alkenes. The surfaces of the polymer films were characterized after spray coating by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS), showing that the P(EO-stat-fAGE) block starts to compete with polystyrene to populate the surface after only 1 mol % incorporation of fAGE. Increasing the incorporation of fAGE led to an increased amount of perfluorocarbons on the surface and a decrease in the concentration of PS. At a fAGE incorporation of 8 mol %, PS was not detected at the surface, as measured by NEXAFS spectroscopy. Water contact angles measured by the captive-air-bubble technique showed the underwater surfaces to be dynamic, with advancing and receding contact angles varying by >20°. Protein adsorption studies demonstrated that the fluorinated surfaces effectively prevent nonspecific binding of proteins relative to an unmodified PS-b-PEO diblock copolymer. In biological systems, settlement of spores of the green macroalga Ulva was significantly lower for the fAGE-incorporated polymers compared to the unmodified diblock and a polydimethylsiloxane elastomer standard. Furthermore, the attachment strength of sporelings (young plants) of Ulva was also reduced for the fAGE-containing polymers, affirming their potential as fouling-release coatings. 相似文献
93.
Nirmal J Saisivam S Peddanna C Muralidharan S Godwinkumar S Nagarajan M 《Chemical & pharmaceutical bulletin》2008,56(10):1455-1458
The objective of the study is to formulate bilayer tablets consisting of atorvastatin calcium (AT) as an immediate release layer and nicotinic acid (NA) as an extended release layer. The immediate release layer was prepared using super disintegrant croscarmellose sodium and extended release layer using hydroxypropylmethyl cellulose (HPMC K100M). Both the matrix and bilayer tablets were evaluated for hardness, friability, weight variation, thickness, and drug content uniformity and subjected to in vitro drug release studies. The amount of AT and NA released at different time intervals were estimated by HPLC method. The bilayer tablets showed no significant change either in physical appearance, drug content or in dissolution pattern after storing at 40 degrees C/75% relative humiding (RH) for 3 months. The release of the drug from the tablet was influenced by the polymer content and it was much evident from thermogravimetry/differential thermal analysis (TG/DTA) analysis. The results indicated that the bilayer tablets could be a potential dosage form for delivering AT and NA. 相似文献
94.
The kinetics and mechanism of Ag(I)-catalyzed oxidation of l-alanine by cerium (IV) in sulfuric acid media have been investigated by titrimetric technique of redox in the temperature range of 298–313 K. It is found that the reaction is of first order with respect to Ce(IV) and l-alanine, and it is of a positive fractional order with respect to Ag(I). It is found that the pseudo first order ([l-alanine] ? [Ce(IV)] ? [Ag(I)]) rate constant k′ increases with the increase of[H+]. The major oxidation product of alanine has been identified as acetaldehyde by an 1H NMR and IR spectroscopy. Under the experimental conditions, the kinetically active species has been found to be Ce4+. Under nitrogen atmosphere, the reaction system can initiate the polymerization of acrylonitrile, indicating generation of free radicals. On the basis of the experimental results, a suitable mechanism has been proposed. The rate constants of the rate-determining step together with the activation parameters were evaluated. 相似文献
95.
Nitin Kumar Dr. Rapelly Venkatesh Prof. Sundaram Singh Prof. Jeyakumar Kandasamy 《European journal of organic chemistry》2023,26(37):e202300679
An efficient and eco-friendly method has been developed for the preparation of functionalized 3-(S)-arylthioindoles in good to excellent yields from indoles and aryl thiols in water. The coupling reaction was prompted by K2S2O8 in the presence of glucose at room temperature. Broad substrate scope, functional group tolerance, room temperature reactions and metal-free conditions are the salient features of the developed methodology. 相似文献
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98.
The equationbelongs to the class of linear functional equations. The solutions form a linear space with respect to the usual pointwise operations. According to the classical results of the theory they must be generalized polynomials. New investigations have been started a few years ago. They clarified that the existence of non-trivial solutions depends on the algebraic properties of some related families of parameters. The problem is to find the necessary and sufficient conditions for the existence of non-trivial solutions in terms of these kinds of properties. One of the earliest results is due to Z. Daróczy [1]. It can be considered as the solution of the problem in case of n = 2. We are going to take more steps forward by solving the problem in case of n = 3.
相似文献
$$\sum^{n}_ {i=0} a_{i}f(b_{i}x + (1 - b_{i})y) = 0$$
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