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11.
Of the several stable and coloured uninegative ions examined, trans-bis(dimethylglyoximato) dinitritocobaltate(III) ([Co(C4H7O2)2(NO2)2]-, termed goldenate ion, G-) can advantageously replace the erdmannate ion in the formation of a more photochemically stable coloured anion-exchanger derived from Aliquat-336 chloride. Quantitative spectrophotometric measurements of its displacement by chloride, bromide and perchlorate ions were made and are discussed together with literature data to examine the effect of parameters such as the nature of the cation and of the anion and change in the organic solvent on the relative and absolute values of extraction constants. 相似文献
12.
Wong DM Greenblatt HM Dvir H Carlier PR Han YF Pang YP Silman I Sussman JL 《Journal of the American Chemical Society》2003,125(2):363-373
Acetylcholinesterase (AChE) inhibitors improve the cognitive abilities of Alzheimer patients. (-)-Huperzine A [(-)-HupA], an alkaloid isolated from the club moss, Huperzia serrata, is one such inhibitor, but the search for more potent and selective drugs continues. Recently, alkylene-linked dimers of 5-amino-5,6,7,8-tetrahydroquinolinone (hupyridone, 1a), a fragment of HupA, were shown to serve as more potent inhibitors of AChE than (-)-HupA and monomeric 1a. We soaked two such dimers, (S,S)-(-)-bis(10)-hupyridone [(S,S)-(-)-2a] and (S,S)-(-)-bis(12)-hupyridone [(S,S)-(-)-2b] containing, respectively, 10 and 12 methylenes in the spacer, into trigonal TcAChE crystals, and solved the X-ray structures of the resulting complexes using the difference Fourier technique, both to 2.15 A resolution. The structures revealed one HupA-like 1a unit bound to the "anionic" subsite of the active-site, near the bottom of the active-site gorge, adjacent to Trp84, as seen for the TcAChE/(-)-HupA complex, and the second 1a unit near Trp279 in the "peripheral" anionic site at the top of the gorge, both bivalent molecules thus spanning the active-site gorge. The results confirm that the increased affinity of the dimeric HupA analogues for AChE is conferred by binding to the two "anionic" sites of the enzyme. Inhibition data show that (-)-2a binds to TcAChE approximately 6-7- and > 170-fold more tightly than (-)-2b and (-)-HupA, respectively. In contrast, previous data for rat AChE show that (-)-2b binds approximately 3- and approximately 2-fold more tightly than (-)-2a and (-)-HupA, respectively. Structural comparison of TcAChE with rat AChE, as represented by the closely related mouse AChE structure (1maa.pdb), reveals a narrower gorge for rat AChE, a perpendicular alignment of the Tyr337 ring to the gorge axis, and its conformational rigidity, as a result of hydrogen bonding between its hydroxyl group and that of Tyr341, relative to TcAChE Phe330. These structural differences in the active-site gorge explain the switch in inhibitory potency of (-)-2a and 2b and the larger dimer/(-)-HupA potency ratios observed for TcAChE relative to rat AChE. The results offer new insights into factors affecting protein-ligand complementarity within the gorge and should assist the further development of improved AChE inhibitors. 相似文献
13.
H. M. N. H. Irving 《Journal of Radioanalytical and Nuclear Chemistry》1976,33(2):287-302
After summarising the techniques available generally in analytical chemistry for the separation and pre-concentration of trace
elements, reasons are given why some of these procedures have achieved greater prominence in particular radiochemical separations.
Examples of contemporary practice and current trends in a wide variety of radiochemical separation problems are then illustrated
by reference to papers that have appeared in recent literature.
Adapted from a Plenary Lecture delivered at the 4th Symposium on Recent Developments in Neutron Activation Analysis, 4–7th
August 1975, Cambridge, England. 相似文献
14.
Dynamic mechanism of photochemical induction of turing superlattices in the chlorine dioxide-iodine-malonic acid reaction-diffusion system 总被引:1,自引:0,他引:1
Berenstein I Yang L Dolnik M Zhabotinsky AM Epstein IR 《The journal of physical chemistry. A》2005,109(24):5382-5387
We study the mechanism of development of superlattice Turing structures from photochemically generated hexagonal patterns of spots with wavelengths several times larger than the characteristic wavelength of the Turing patterns that spontaneously develop in the nonilluminated system. Comparison of the experiment with numerical simulations shows that interaction of the photochemical periodic forcing with the Turing instability results in generation of multiple resonant triplets of wave vectors, which are harmonics of the external forcing. Some of these harmonics are situated within the Turing instability band and are therefore able to maintain their amplitude as the system evolves and after illumination ceases, while photochemically generated harmonics outside the Turing band tend to decay. 相似文献
15.
How does huperzine A enter and leave the binding gorge of acetylcholinesterase? Steered molecular dynamics simulations 总被引:9,自引:0,他引:9
Xu Y Shen J Luo X Silman I Sussman JL Chen K Jiang H 《Journal of the American Chemical Society》2003,125(37):11340-11349
The entering and leaving processes of Huperzine A (HupA) binding with the long active-site gorge of Torpedo californica acetylcholinesterase (TcAChE) have been investigated by using steered molecular dynamics simulations. The analysis of the force required along the pathway shows that it is easier for HupA to bind to the active site of AChE than to disassociate from it, which for the first time interprets at the atomic level the previous experimental result that unbinding process of HupA is much slower than its binding process to AChE. The direct hydrogen bonds, water bridges, and hydrophobic interactions were analyzed during two steered molecular dynamics (SMD) simulations. Break of the direct hydrogen bond needs a great pulling force. The steric hindrance of bottleneck might be the most important factor to produce the maximal rupture force for HupA to leave the binding site but it has a little effect on the binding process of HupA with AChE. Residue Asp72 forms a lot of water bridges with HupA leaving and entering the AChE binding gorge, acting as a clamp to take out HupA from or put HupA into the active site. The flip of the peptide bond between Gly117 and Gly118 has been detected during both the conventional MD and SMD simulations. The simulation results indicate that this flip phenomenon could be an intrinsic property of AChE and the Gly117-Gly118 peptide bond in both HupA bound and unbound AChE structures tends to adopt the native enzyme structure. At last, in a vacuum the rupture force is increased up to 1500 pN while in water solution the greatest rupture force is about 800 pN, which means water molecules in the binding gorge act as lubricant to facilitate HupA entering or leaving the binding gorge. 相似文献
16.
Daniel Ammann Ren Bissig Marc Güggi Ern Pretsch Wilhelm Simon Irving J. Borowitz Louis Weiss 《Helvetica chimica acta》1975,58(6):1535-1548
The preparation of a series of non-cyclic, uncharged ligands able to selectively complex alkali and alkaline earth metal cations is described. These molecules are designed to be used as carriers for cations through membranes. Some of the compounds show high Ca2+ and Na+ selectivity, respectively, in liquid membrane electrodes. 相似文献
17.
Buddy D. Ratner Irving F. Miller 《Journal of polymer science. Part A, Polymer chemistry》1972,10(8):2425-2445
The interaction of poly(2-hydroxyethyl methacrylate) [poly(HEMA)] and other similar hydrogels with dilute urea solution has been studied by a variety of techniques, including swelling experiments, fluorescence quenching, near infrared spectroscopy and fundamental band infrared spectroscopy. The results obtained indicate that the anomalous swelling behavior of poly(HEMA) gels in the presence of such dilute urea solutions is probably not due to the disruption of a secondary hydrophobic bond structure as has been generally believed. Although poly(HEMA) gels do contain sites that can participate in hydrophobic bonding, the evidence gathered indicates that dilute urea solutions have no effect on such bonds. A plausible model that does fit all the data involves the interaction of urea with a secondary structure composed of hydrogen-bonded hydroxyl groups, stabilized by the exclusion of water molecules from the regions containing the bonds. 相似文献
18.
Haiwen Zhang David W. Norman Tracey M. Wentzell Alison M. Irving Janet P. Edwards Susan L. Wheaton Christopher M. Vogels Stephen A. Westcott Felix J. Baerlocher Andreas Decken 《Transition Metal Chemistry》2005,30(1):63-68
Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na2PdCl4 afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC6H4C(O)H) with H2NC6H4Bpin (pin=1,2-O2C2Me4) afforded the boron-containing Schiff bases, 2-HOC6H4C(H)=NC6H4Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na2PdCl4 afforded complexes of the type PdL2
(4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus. 相似文献
19.
Infrared multiple-photon dissociation of CTCl3 was investigated using a pulsed CO2 laser-pumped NH3 laser at 12.08 μm. No evidence of any CDCl3 depletion or decomposition product was observed in photolyzed CTCl3/CDCl3 mixtures. A lower limit of the single-step T/D enrichment factor, β, was found to be ≈ 165, based on the sensitivity in measuring CDCl3 depletion. The low-fluene CTCl3/CDCl3 optical selectivity in absorptions is > 9000 at the 835 cm?1 CTCl3 ν4 peak. 相似文献
20.
Heat capacities of concentrated multicomponent aqueous electrolyte solutions at various temperatures
Boris S. Krumgalz Ilan A. Malester Irving J. Ostrich Frank J. Millero 《Journal of solution chemistry》1992,21(7):635-649
The specific heat capacities of the aqueous multicomponent system NaCl +KCl+MgCl2+CaCl2 with ionic strength between 8.3 and 9.6 (resembling Dead Sea waters) were measured between 15°C and 45°C. The obtained data were fitted to an empirical equation as a function of concentration and temperature. The thermodynamic functions of the studied multicomponent system were found to be strongly influenced by changes in MgCl2 concentrations. The application of Young's rule to such concentrated systems was checked at 25°C. The calculated (by Young's rule) specific heat capacitiesC
p and apparent molar heat capacities Cp, of these multicomponent electrolyte solutions were in reasonable agreement with the measured values (–0.008 J-g–1-K–1 and –2.6 J-mol–1-K–1, respectively). 相似文献