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91.
The growth of crystals in solution 总被引:3,自引:0,他引:3
George H. Nancollas 《Advances in colloid and interface science》1979,10(1):215-252
The crystallization of sparingly soluble salts from their aqueous supersaturated solutions is discussed from the standpoint of two important applications; scale formation and biological mineralization. Theories of crystal growth are outlined and the importance of kinetic factors in determining the nature of the growing phases is discussed. The kinetic factors can be studied by using a highly reproducible seeded growth technique and under certain conditions secondary nucleation can also be induced on the surface of the inoculating seed crystals. The kinetics of crystallization of the alkaline earth surfaces and the calcium phosphates is discussed. In the latter systems, temperature, supersaturation, surface concentration, pH, ionic strength and the presence of foreign ions are important in determining the nature of the phase which grows on the added seed crystals. The mechanism of the retardation of crystal growth by added crystallization inhibitors is illustrated by the influence of organic phosphonate molecules upon the precipitation of calcium carbonate. 相似文献
92.
Commodari F Sclavos G Ibrahimi S Khiat A Boulanger Y 《Magnetic resonance in chemistry : MRC》2005,43(6):444-450
The NMR-derived structure of estrogen (17beta-estradiol, E2), the drug of choice for postmenopausal women, was compared with a recent literature crystal x-ray structure of Fab-bound E2. 1H and 13C NMR spectra of E2 were acquired in DMSO-d6. Assignments were obtained from an analysis of DQF-COSY, TOCSY, HETCOR, HMQC and HMBC 2D NMR spectra. The 1H and 13C NMR assignments are the first reported for E2 in DMSO-d6. Two solution structures, S1 and S2, were obtained with molecular modeling using NOE constraints. S1 overlaps with the crystal structure for all rings. S2 shows prominent differences in the C-ring (C9--C11--C12--C13) segment, which deviates from a chair conformation, and excellent overlap in the A-, B- and D-rings of E2. The C-ring in S2 adopts a boat conformation as opposed to a chair conformation in the x-ray and S1 structures. The S2 structure is about 6 degrees more twisted than the bound x-ray and S1 models. The S1, S2 and x-ray structures had ring bowing values of 10.1 +/- 0.3, 11 +/- 1 and 10.37 degrees , respectively. Of the 100 solution conformers generated, 83 had S1 conformation and 17 had S2 conformation, with average internal energies of 112 +/- 2 and 141 +/- 2 kcal mol(-1), respectively. The 100 S1- and S2- derived conformers showed a r.m.s.d. of 0.72 A for all atoms. The x-ray, S1 and S2 C18--O17 distances were 2.93, 2.92 +/- 0.01 and 2.93 +/- 0.01 A, respectively, and the O3--O17 distances were 11.06, 11.18 +/- 0.12, and 10.89 +/- 0.05 A, respectively. 相似文献
93.
Henry DJ Yiapanis G Evans E Yarovsky I 《The journal of physical chemistry. B》2005,109(36):17224-17231
This study examines the adhesion of graphite to functionalized polyester surfaces using a range of qualitative and quantitative measures of theoretical adhesion. Modifications to the polyester surfaces include the addition of hydroxyl, carboxyl, or fluorine substituents with coverages of 0.4 and 0.9 groups per nm(2). In each case, the introduction of substituents to the surface of the polyester was calculated to lead to reduced adhesion to graphite. Effects of surface relaxation on adhesion are studied by employing different simulation protocols. The theoretical results suggest one mechanism to reduce adhesion to carbonaceous solids is to increase atomic roughness using strongly hydrophilic or alternatively strongly hydrophobic substituents. 相似文献
94.
Love JC Urbach AR Prentiss MG Whitesides GM 《Journal of the American Chemical Society》2003,125(42):12696-12697
Metallic rods with submicron diameters that contain disklike ferromagnetic sections self-assemble into highly stable, hexagonally close-packed arrays of rods. The rods were fabricated by electrodeposition in porous alumina membranes and comprised alternating sections of gold and nickel. The thicknesses of the ferromagnetic nickel sections were approximately one-half the diameter of the rods (400 nm); this geometry orients the "easy" axis of magnetization perpendicular to the long axis of the rod. After magnetization of the rods with a rare-earth magnet, followed by sonication of the suspension, the rods spontaneously assembled into three-dimensional (3D) bundles that, on average, contained 15-30 rods. A macroscopic model of the rods suggests that the most stable orientation of the magnetic dipoles for rods in a defect-free, hexagonally close-packed arrangement is in concentric rings with the dipoles oriented head-to-tail. This configuration minimizes the energy of the bundle and does not generate a net dipole for the structure. This work provides a simple demonstration that magnetic interactions between ferromagnetic objects can direct and stabilize the formation of ordered, 3D structures by self-assembly. 相似文献
95.
Akira Matsumoto Hisako Mano Masayoshi Oiwa George B. Butler 《Journal of polymer science. Part A, Polymer chemistry》1989,27(6):1811-1816
The radical polymerization of tetraallyl ammonium chloride (TAAC) was carried out in water using azo-initiator as compared to that of diallyl dimethyl ammonium chloride (DADMAC); the rate of polymerization was quite low for TAAC, around one-third of DADMAC. Kinetic discussion revealed the importance of degradative chain transfer in the polymerization of TAAC. The cyclopolymerizability of TAAC was estimated kinetically as the ability of 5-membered monocyclic radical to form a bicyclic ring, giving the cyclization constant of 21 mol/L at [M] = 2 mol/L. Gelation occurred at around 20% conversion. 相似文献
96.
The o-, m-, and p-phenylene bis(1,3-dioxolanium) dications (4-6) and 2,4,6-triphenylene tris(1,3-dioxolanium) trication (7) have been prepared by the ionization of the corresponding 2-methoxyethyl benzoates in FSO(3)H or CF(3)SO(3)H at 40 and 60 degrees C, respectively. The charge delocalization in these carbocations was probed by (13)C NMR chemical shifts and substantiated by GIAO/DFT calculations. Relatively less charge is delocalized into the aromatic ring of the carbotrication 7. The rotational barrier around the C(+)-Ar bond for carbodications 4 and 5 was also estimated to be 8-10 kcal/mol. 相似文献
97.
K. Adibi M. H. George J. A. Barrie 《Journal of polymer science. Part A, Polymer chemistry》1981,19(1):57-64
A relatively high-molecular-weight polyurethane based on MDI and ethylene glycol was prepared and characterized. This polymer was metalated with sodium hydride in N,N-dimethylformamide (DMF) at about 0°C. Metalation was confirmed principally by spectroscopic identification of the N-methyl derivative obtained by coupling the metalated polymer with methyl iodide. Under appropriate reaction conditions the metalated polyurethane was used for the anionic graft polymerization of the reactive monomers acrylonitrile and ethylene and propylene sulfides. Attempted anionic graft polymerizations with other monomers, including styrene and ethylene and propylene oxides, were unsuccessful. The polyurethane grafted with acrylonitrile was separated by fractionation from accompanying small amounts of polyacrylonitrile, a low-molecular-weight homopolymer. One sample of polyurethane grafted with acrylonitrile was identified by microanalysis, IR, NMR, and increase in weight and was also characterized by differential thermal analysis. 相似文献
98.
1,1-Difluoroethysilanes (R3SiCF2CH3, R = Me or Et) were synthesized from 1,1-difluoroethyl phenyl sulfone and chlorosilanes using magnesium metal via reductive 1,1-difluoroethylation. It was confirmed that 1,1-difluoroethylsilanes were effective 1,1-difluoroethylating reagents for carbonyl compounds. 相似文献
99.
George P. Scott Abdelaziz M. R. Elghoul 《Journal of polymer science. Part A, Polymer chemistry》1970,8(8):2255-2263
Chain-transfer constants for radicals one to five units in length were determined for the methyl acrylate–isopropanethiol system. Effects of varying ester alkyl group, mercaptan solvent and initiator on three-unit diastereomer ratio were also investigated. It was found that the proportion of syndiotactic isomer increased as the size of either the ester alkyl group or the mercaptan increased, the latter result being equivalent to a penultimate effect. Polar solvents, on the other hand, favored the formation of the isotactic form. This effect was observed in the free-radical telomerization and to an even greater degree in the base-initiated anionic telomerization. Possible reasons for solvent effects are discussed. 相似文献
100.
Studies of extractions of yttrium from aqueous solution into chloroform, benzene, methyl isobutyl ketone, and mixtures of these solvents, containing thenoyltrifluoroacetone are described. The effects of reagent concentration, added n-butylamine, and added fluoride were investigated. Values of pH and Pe were determined, and identifications of the involved species are suggested. 相似文献