Self-assembly is a versatile bottom-up approach for fabricating novel supramolecular materials with well-defined nano- or micro-structures associated with functionalities. The oil-water interface provides an ideal venue for molecular and colloidal self-assembly. This paper gives an overview of various self-assembled materials, including nanoparticles, polymers, proteins, and lipids, at the oil-water interface. Focus has been given to fundamental principles and strategies for engineering the self-assembly process, such as control of pH, ionic strength and use of external fields, to achieve complex soft materials with desired functionalities, such as nanoparticle surfactants, structured liquids, and proteinosomes. It has been shown that self-assembly at the oil-water interface holds great promise for developing well-structured complex materials useful for many research and industrial applications. 相似文献
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
Pulse radiolysis with kinetic spectroscopic detection was applied to study the kinetics of the first steps of radiation induced polymerization of cyclohexyl acrylate and cyclohexyl methacrylate in cyclohexane solvent. The reactions were initiated by cyclohexyl radicals produced in the radiolysis of the solvent. The transient absorption spectra of the -carboxyalkyl type radicals produced in addition reaction show maxima around 300 nm. This shifts to longer wavelength with time after the pulse. This phenomenon was explained by the oligomerization reaction. From the kinetic curves average rate coefficients of termination for the oligomer radicals (2kt) were determined as a function of time elapsed after the electron pulse. The values obtained were compared with those calculated for other (acrylate and methacrylate type) monomers. 相似文献
Organometallic compounds Cp2TiCl2, (EtC5H4)2NbCl2, and (PriC5H4)2WCl2 were assessed as additives that control polymer chain growth in the polymerization of methyl methacrylate. In the presence of compounds mentioned in amounts comparable with that of the initiator, a uniform process with no gel-effect occured and respective linear increase in the molecular weight of the polymer up to high degrees of the monomer conversion was observed. 相似文献
The local and the terminal velocities, the size and the degree of bubbles’ shape deformations were determined as a function of distance from the position of the bubble formation (capillary orifice) in solutions of n-octyltrimethylammonium bromide, n-octyldimethylphosphine oxide, n-octyl-β-D-glucopyranoside and n-octanoic acid.
These surface-active compounds have different polar groups but an identical hydrocarbon chain (C8) in the molecule. The motion of the bubbles was monitored and recorded using a stroboscopic illumination, a CCD camera, and a JVC professional video. The recorded bubble images were analyzed by the image analysis software. The bubbles accelerated rapidly and their shape was deformed immediately after detachment from the capillary. The extent of the bubbles’ shape deformation (ratio of horizontal and vertical diameters) was 1.5 in distilled water and dropped rapidly down to a level of ca. 1.05–1.03 with increasing surfactant concentration. After the acceleration period the bubbles either attained a constant value of the terminal velocity (distilled water and high concentrations of the solutions), or a maximum in the velocity profiles was observed (low concentrations). The values of the terminal velocity diminished drastically with increasing concentration, from the value of 35 cm/s in water down to about 15 cm/s, while the bubble diameter decreased by ca. 10% only. The surfactant adsorption at the surface of the bubbles was evaluated and the minimum adsorption coverages required to immobilize the bubbles’ surface were determined. It was found that this minimum adsorption coverage was ca. 4% for n-octyldimethylphosphine oxide, n-octyl-β-D-glucopyranoside, n-octanoic acid and 25% for n-octyltrimethylammonium bromide. The difference in the adsorption coverage together with the surfactants’ surface activities indicate that it is mainly the adsorption kinetics of the surfactants that governs the fluidity of interfaces of the rising bubbles. 相似文献
The paper addresses the problem of a semi-infinite plane crack along the interface between two isotropic half-spaces. Two methods of solution have been considered in the past: Lazarus and Leblond [1998a. Three-dimensional crack-face weight functions for the semi-infinite interface crack-I: variation of the stress intensity factors due to some small perturbation of the crack front. J. Mech. Phys. Solids 46, 489-511, 1998b. Three-dimensional crack-face weight functions for the semi-infinite interface crack-II: integrodifferential equations on the weight functions and resolution J. Mech. Phys. Solids 46, 513-536] applied the “special” method by Bueckner [1987. Weight functions and fundamental fields for the penny-shaped and the half-plane crack in three space. Int. J. Solids Struct. 23, 57-93] and found the expression of the variation of the stress intensity factors for a wavy crack without solving the complete elasticity problem; their solution is expressed in terms of the physical variables, and it involves five constants whose analytical representation was unknown; on the other hand, the “general” solution to the problem has been recently addressed by Bercial-Velez et al. [2005. High-order asymptotics and perturbation problems for 3D interfacial cracks. J. Mech. Phys. Solids 53, 1128-1162], using a Wiener-Hopf analysis and singular asymptotics near the crack front.The main goal of the present paper is to complete the solution to the problem by providing the connection between the two methods. This is done by constructing an integral representation for Lazarus-Leblond's weight functions and by deriving the closed form representations of Lazarus-Leblond's constants. 相似文献
Historical perspectives for the chemistry of diene complexes of early transition metals developed at Osaka University in the period after 1970s were reviewed briefly and personally. Preparative chemistry of this field commenced from the magnesium-diene 1:1 compounds and quickly extended to almost all the early transition metals. By the studies operated together with other researchers, unique features of these diene complexes, especially their bonding and structure, selective reactions, and catalysis performances are described. 相似文献