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711.
Larsen K Worm-Leonhard K Olsen P Hoel A Jensen KJ 《Organic & biomolecular chemistry》2005,3(21):3966-3970
Current methods for glycosylation of complex alcohols, e.g. with glycosyl trichloroacetimidates, generally occur in the presence of a strong Lewis acid 'promoter', and at sub-ambient temperatures. However, the older literature reports high-temperature glycosylations, especially of phenols. We have described an efficient method for glycosylation of alcohols under neutral conditions, using as anomeric leaving group methyl 3,5-dinitrosalicylate (DISAL). Only a very few reports have described the use of microwaves to promote glycosylations, mainly of simple alcohols. Here we describe fast, high-temperature glycosylations using precise microwave heating in the synthesis of oligosaccharides, with both DISAL and widely used trichloroacetimidate glycosyl donors in the absence of strong Lewis acids. Also, we have applied microwave heating as a general protocol for evaluating new, potential glycosyl donors. 相似文献
712.
Olsen RA Struppe J Elliott DW Thomas RJ Mueller LJ 《Journal of the American Chemical Society》2003,125(39):11784-11785
Recently, we presented a novel nuclear magnetic resonance experiment for establishing through-bond connectivity in disordered solids using scalar coupling-driven correlation. This method, a variant of the popular double-quantum-filtered correlation spectroscopy experiment in liquids, is robust under fast magic-angle-spinning conditions and in the presence of dynamics. Here, we show that this new experiment, the UC2QF COSY, can be extended to 13C natural abundance correlation in moderately sized molecules, allowing the assignment of the 54 peaks of the solid-state NMR spectrum of microcrystalline vitamin-D3. In this case, comparison between the assigned peaks and ab initio calculations of the chemical shifts based on the crystal coordinates permits a refinement of the average structure in dynamic regions reported as disordered in the crystal structure. 相似文献
713.
A microstructured ionic crystal, K(3)[Cr(3)O(OOCH)(6)(H(2)O)(3)][alpha-SiW(12)O(40)].16 H(2)O (1) was synthesized by the complexation of the Keggin-type polyoxometalate of [alpha-SiW(12)O(40)](4-) with a macrocation of [Cr(3)O(OOCH)(6)(H(2)O)(3)](+). Compound 1 possessed a straight channel, with an opening of approximately 0.5x0.8 nm, which contained the water of crystallization. The use of the macrocation with large size (0.7 nm) and small charge (+1) reduced the anion-cation interaction and was essential for the channel formation. The molecular structures of the polyoxometalate and the macrocation in 1 were retained under vacuum at 473 K. Analogues of 1 were synthesized with [alpha-PVW(11)O(40)](4-) or [Fe(3)O(OOCH)(6)(H(2)O)(3)](+). The water of crystallization in 1 was removed under vacuum at room temperature to form the closely packed guest-free phase 2. Compound 2 reversibly and repeatedly included water and polar organic molecules with two carbon atoms or less. Guest inclusion was highly selective and a difference of even one methylene group in the organic guest molecule was discriminated by the host. Polar organic molecules with longer methylene chains and nonpolar molecules such as dinitrogen and methane were completely excluded. The guest-inclusion properties could be explained by the ion-dipole interaction between the host and the guest, which is proportional to the dipole moment of the guest molecule and inversely proportional to the ion-dipole (host-guest) distance. Thus, small polar molecules were selectively absorbed. These distinctive guest-inclusion properties were successfully applied to the oxidation of methanol from a mixture of C(1) and C(2) alcohols. These results show unique guest inclusion and catalysis by rationally designed ionic crystals. 相似文献
714.
Usui T Kazami S Dohmae N Mashimo Y Kondo H Tsuda M Terasaki AG Ohashi K Kobayashi J Osada H 《Chemistry & biology》2004,11(9):1269-1277
The actin-targeting toxins have not only proven to be invaluable tools in studies of actin cytoskeleton structure and function but they also served as a foundation for a new class of anticancer drugs. Here, we describe that amphidinolide H (AmpH) targets actin cytoskeleton. AmpH induced multinucleated cells by disrupting actin organization in the cells, and the hyperpolymerization of purified actin into filaments of apparently normal morphology in vitro. AmpH covalently binds on actin, and the AmpH binding site is determined as Tyr200 of actin subdomain 4 by mass spectrometry and halo assay using the yeast harboring site-directed mutagenized actins. Time-lapse analyses showed that AmpH stimulated the formation of small actin-patches, followed by F-actin rearrangement into aggregates via the retraction of actin fibers. These results indicate that AmpH is a novel actin inhibitor that covalently binds on actin. 相似文献
715.
In studies of the adsorption of surface-active molecules from organic phase on mineral surfaces in relation to wettability alterations, the system has normally been made water-free. However, since water is an inherent part of all oil-bearing formations, it is of interest to study adsorption in solid/water/oil systems. In this paper we therefore study the adsorption of benzoic (BzCOOH) and 4-heptylbenzoic (4-HBA) acid from organic solution on different silica substrates in the presence of water. The results show that the adsorption is enhanced in the presence of water and that 4-HBA has a higher affinity for the silica surface than does BzCOOH. Variations in the surface properties of the silica substrates had no significant effect on the adsorption. In studies of the adsorption of organic acids from aqueous phase, the acid has been added either as the corresponding acid salt or as the acid itself. However, the adsorption behavior of the acid salt is not necessarily representative of the adsorption behavior of the acid. To investigate this more closely, we studied the adsorption of benzoic acid added to water both as sodium benzoate (BzCOO(-)Na(+)) and as BzCOOH. The results revealed a significant increase in the maximum adsorption when BzCOO(-)Na(+) was used as adsorbate instead of BzCOOH. Copyright 2000 Academic Press. 相似文献
716.
Complete geometry optimizations, employing a minimal STO-3G basis set, have been applied to the recently-prepared cyanogen isocyanate [NCNCO] and to the isomeric dicyanoether [NCOCN]. Cyanogen isocyanate is found to be a rather flexible molecule with the computed barrier to inversion about the central nitrogen being ~5 k cal mol?1. In addition, the inversion motion is found to be coupled to the bending of the NCN and OCN linkages away from colinearity. On the other hand, dicyanoether is predicted to be a fairly rigid molecule, with no important inversion motions. Both molecules are predicted to have planar trans bent equilibrium structures similar to that found for the simpler HNCO-HOCN isomers. Cyanogen isocyanate is predicted to be the more stable isomer. Electronic structures of these molecules are discussed in the light of the results of a Mulliken population analysis. 相似文献
717.
Detailed formulae for the implementation of the multi-configuration SCF spinor optimization in a basis of Kramers pair 2-spinors
– i.e. exploiting time-reversal symmetry – are presented. Full expressions for the spinor gradient and spinor Hessian elements
are given in abstract form as well as within the usual CASSCF subspace division. As far as possible, the resulting terms are
grouped to relativistic inactive and active Fock matrices, which have been introduced previously. Approximations for the Hessian
are introduced so as to initialize it in an inverse Hessian update algorithm for a diagonal first approximation within the
standard quasi-Newton-Raphson procedure. The effects of double group symmetry arising from spin dependence on Fock matrices
and therefore gradient and Hessian are discussed and a group scheme for the implementation is proposed.
Received: 14 January 1997 / Accepted: 3 February 1997 相似文献
718.
We utilize classical trajectory calculations to study the reaction dynamics of the dissociative adsorption of H2 on the stepped Pt(211) surface. The potential-energy surface has been obtained through an accurate interpolation of density-functional theory data at the generalized gradient approximation level, using the corrugation reduction procedure. New techniques for visualizing the collective dynamics of trajectories are introduced to elucidate the reaction mechanisms involved. Reaction exhibits a nonmonotonic dependence on collision energy, first decreasing with energy, and then increasing. A strong component of direct nonactivated reaction exists at the top edge of the step over the entire range of energies. The inverse relationship between reaction and collision energy at low energies is attributed to trapping in weak chemisorption wells. These wells also influence the direct reaction at the step, leading to a strong asymmetric dependence on incidence angle. Reaction on the terrace is activated, and only contributes significantly at high energies. Agreement with experiments on Pt(533) [A. T. Gee, B. E. Hayden, C. Mormiche, and T. S. Nunney, J. Chem. Phys. 112, 7660 (2000); Surf. Sci. 512, 165 (2002)] is good, and we are able to suggest new interpretations of the experimental data. 相似文献
719.
We present shear mechanical and dielectric measurements taken on seven liquids: triphenylethylene, tetramethyltetra-phenyltrisiloxane (Dow Corning 704 diffusion pump fluid), polyphenyl ether (Santovac 5 vacuum pump fluid), perhydrosqualene, polybutadiene, decahydroisoquinoline (DHIQ), and tripropylene glycol. The shear mechanical and dielectric measurements are for each liquid performed under identical thermal conditions close to the glass transition temperature. The liquids span four orders of magnitude in dielectric relaxation strength and include liquids with and without Johari-Goldstein beta relaxation. The shear mechanical data are obtained by the piezoelectric shear modulus gauge method giving a large frequency span (10(-3)-10(4.5) Hz). This allows us to resolve the shear mechanical Johari-Goldstein beta peak in the equilibrium DHIQ liquid. We moreover report a signature (a pronounced rise in the shear mechanical loss at frequencies above the alpha relaxation) of a Johari-Goldstein beta relaxation in the shear mechanical spectra for all the liquids which show a beta relaxation in the dielectric spectrum. It is found that both the alpha and beta loss peaks are shifted to higher frequencies in the shear mechanical spectrum compared to the dielectric spectrum. It is in both the shear and dielectric responses found that liquids obeying time-temperature superposition also have a high-frequency power law with exponent close to -12. It is moreover seen that the less temperature dependent the spectral shape is, the closer it is to the universal -12 power-law behavior. The deviation from this universal power-law behavior and the temperature dependencies of the spectral shape are rationalized as coming from interactions between the alpha and beta relaxations. 相似文献
720.
Seth Olsen Mark Prescott Pascal Wilmann Jion Battad Jamie Rossjohn Sean C. Smith 《Chemical physics letters》2006,420(4-6):507-511
The red fluorescent protein Rtms5H146S displays a transition from blue (absorbance λmax 590 nm) to yellow (absorbance λmax 453 nm) upon titration to low pH. The pKa of the reaction depends on the concentration of halide, offering promise for new expressible halide sensors. The protonation state involved in the low pH form of the chromophore remains, however, ambiguous. We report calculated excitation energies of different protonation states of an RFP chromophore model. These suggest that the relevant titration site is the phenoxy moiety of the chromophore, and the relevant base and conjugate acid are anionic and neutral chromophore species, respectively. 相似文献