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91.
The accepted picture of the structure of a micelle in solution arises from the idea that the surfactant molecules self-assemble into a spherical aggregate, driven by the conflicting affinity of their head and tail groups with the solvent. It is also assumed that the micelle's size and shape can be explained by simple arguments involving volumetric packing parameters and electrostatic interactions. By using wide Q-range neutron diffraction measurements of H/D isotopically substituted solutions of decyltrimethylammonimum bromide (C(10)TAB) surfactants, we are able to determine the complete, atomistic structure of a micelle and its surroundings in solution. The properties of the micelle we extract are in agreement with previous experimental studies. We find that ~45 surfactant molecules aggregate to form a spherical micelle with a radius of gyration of 14.2 ? and that the larger micelles are more ellipsoidal. The surfactant tail groups are hidden away from the solvent to form a central dry hydrophobic core. This is surrounded by a disordered corona containing the surfactant headgroups, counterions, water, and some alkyl groups from the hydrophobic tails. We find a Stern layer of 0.7 bromide counterion per surfactant molecule, in which the bromide counterions maintain their hydration shells. The atomistic resolution of this technique provides us with unprecedented detail of the physicochemical properties of the micelle in its solvent. 相似文献
92.
Chinai JM Taylor AB Ryno LM Hargreaves ND Morris CA Hart PJ Urbach AR 《Journal of the American Chemical Society》2011,133(23):8810-8813
The discovery of molecules that bind tightly and selectively to desired proteins continues to drive innovation at the interface of chemistry and biology. This paper describes the binding of human insulin by the synthetic receptor cucurbit[7]uril (Q7) in vitro. Isothermal titration calorimetry and fluorescence spectroscopy experiments show that Q7 binds to insulin with an equilibrium association constant of 1.5 × 10(6) M(-1) and with 50-100-fold selectivity versus proteins that are much larger but lack an N-terminal aromatic residue, and with >1000-fold selectivity versus an insulin variant lacking the N-terminal phenylalanine (Phe) residue. The crystal structure of the Q7·insulin complex shows that binding occurs at the N-terminal Phe residue and that the N-terminus unfolds to enable binding. These findings suggest that site-selective recognition is based on the properties inherent to a protein terminus, including the unique chemical epitope presented by the terminal residue and the greater freedom of the terminus to unfold, like the end of a ball of string, to accommodate binding. Insulin recognition was predicted accurately from studies on short peptides and exemplifies an approach to protein recognition by targeting the terminus. 相似文献
93.
94.
T. E. Hargreaves D. F. Brewer S. Chastin C. Chen N. E. Hussey A. Lappas C. S. McMenamin J. Osborne K. Prassides A. L. Thomson 《Czechoslovak Journal of Physics》1996,46(3):1215-1216
A single crystal of La2CuO4 was made superconducting after treatment in a high pressure oxygen furnace. Measurements are presented of the low temperature heat capacity of the insulating crystal in zero field between 1K and 3K, and of the superconducting crystal in fields of 0, 2 and 4 Tesla applied parallel to the ab plane between 0.2K and 3K. A linear heat capacity contribution is observed for the crystal in both the insulating and superconducting states. This linear heat capacity contribution is larger in the superconducting state and is insensitive to the applied magnetic field. 相似文献
95.
Keith Hargreaves 《Journal of polymer science. Part A, Polymer chemistry》1988,26(2):465-476
The study of the polymerization of vinyl monomers initiated by zero-valent nickel phosphite derivatives in the presence of organic halides has been extended to tetrakis (triethylphosphite) nickel (o) and tetrakis (tri 2-chloroethylphosphite) nickel (o). A kinetic study with methyl methacrylate and carbon tetrachloride shows that the polymerization proceeds by a free radical process and that the mechanism of initiation resembles that previously reported for the corresponding triphenylphosphite and carbonyl derivatives. The primary process which becomes rate determining at sufficiently high carbon tetrachloride concentration is the nonreversible SN1 scission of an alkylphosphite ligand. These alkylphosphite initiators are considerably more active than the corresponding carbonyl derivatives, but are less active than the corresponding triphenyl-phosphite derivative. The difference in activities between the aryl and alkylphosphite derivatives has been accounted for by differences in steric over-crowding of these molecules. 相似文献
96.
K. Hargreaves 《Journal of polymer science. Part A, Polymer chemistry》1987,25(12):3325-3341
The present paper describes studies carried out to determine the effect of structure on the free radical polymerization of vinyl monomers initiated by means of the hexakis(arylisocyano) derivatives of chromium (o) in which chlorine, methoxy, and methyl groups have been substituted into different positions of the benzene ring. The kinetics of the initiation reactions resembles that studied in detail for the parent compound hexakis(phenylisocyano) chromium (o). The observed changes in the initial rates of the polymerization of methyl methacrylate at 80°C in the presence of carbon tetrachloride can be accounted for by the electronic effects associated with these substituents. However, when steric overcrowding occurs, the initial rates of polymerization are reduced considerably. The results obtained confirm the mechanism of initiation proposed earlier in which the rate determining step is the Sn2 displacement of an arylisocyano ligand by a monomer or reactive solvent molecule. An attempt has been made to explain the increased rate of radical formation observed when chlorine is substituted into the benzene ring. 相似文献
97.
Clarke PA Martin WH Hargreaves JM Wilson C Blake AJ 《Organic & biomolecular chemistry》2005,3(19):3551-3563
A one-pot, multi-component reaction for the synthesis of highly substituted tetrahydropyran-4-ones, based on the long forgotten Maitland-Japp reaction has been realised. Two different aldehydes and a derivative of a beta-ketoester can be condensed regioselectively in the presence of a Lewis acid to form tetrahydropyran-4-ones in excellent yields. The diastereoselectively of the reaction was found to be dependant upon the nature of the Lewis acid and the temperature at which the reaction was carried out. This procedure was also extended to the formation of tetrahydropyran-4-ones in greater than 95% enantiomeric excess. 相似文献
98.
ICP-AES法测定色漆可溶性金属含量 总被引:1,自引:0,他引:1
用ICP-AES法测定了色漆中的“可溶性”金属铬、镉、铅元素,考察了不同酸度对分析结果的影响,优化了测试条件。进行了回收率和精密度试验。并用原子吸收光谱国标方法进行对照,结果一致。 相似文献
99.
100.