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51.
The standard potentialss
E
o of M/M+ (M=Li, Na, K, Rb, and Cs) electrodes in aqueous urea solutions containing 12, 20, 30 and 37% by weight of urea have been determined at 25°C from emf measurements on the cell M(Hg)/MCl (m), solvent/AgCl–Ag, from the activities of metals in amalgams by use of a similar type of cell in water, and from the values ofs
E
o of the Ag/AgCl electrode determined earlier. The standard free energies of transfer of MCl, G
t
o
(MCl), from water to the mixed solvents, computed by use of these values and those for the Ag–AgCl electrode, rise sharply from Li+ to Na+ but fall from Na+ to K+ and rather sharply from K+ to Cs+ with a maximum at Na+ in all the solvent compositions. This has been attributed to the superimposition of soft-soft interactions on the electrostatic interactions between the ions and the negative charge centers of the possible hydrogen-bonded solvent complexes in the mixed solvents. Comparison of G
t
o
(i) values for individual ions, obtained by a simultaneous extrapolation procedure, with those in aqueous mixtures of methanol,t-butanol, and dimethyl sulfoxide leads to the conclusion that the solvation of these ions in all these solvents is chiefly dictated by the acid-base type of ion-solvent interactions. 相似文献
52.
James V. Crivello Mingxin Fan 《Journal of polymer science. Part A, Polymer chemistry》1992,30(1):31-39
In the presence of Si? H containing cocatalysts, dicobaltoctacarbonyl has been found to very efficiently catalyze the ring-opening polymerization of cyclic ethers, especially epoxides, as well as certain vinyl monomers. The reaction conditions employed are very similar to those used in Co2(CO)8 catalyzed hydrogenation and hydrosilylation reactions. Detailed investigations have been carried out to elucidate the nature of the active species for this catalytic system. A cationic mechanism is proposed based on the experimental results of those investigations. 相似文献
53.
Triethylbenzylammonium chlorometallates [Et3NCH2Ph][MCln]m? (M = Pt, Pd, Rh, Ir, Fe, Co, Cu, m = 1–3, n = 3–6), polymer-anchored ionic metal complexes [?—CH2PBu3][MCln]n? and some other chlorometallates and complexes of platinum, rhodium, ruthenium and osmium were studied as catalysts in the hydrogermylation of phenylacetylene with triethylgermane. All the complexes containing platinum, palladium and rhodium were found to be effective catalysts. The cis/trans ratio of the products obtained is determined by the metal atom involved and decreases in the following order: Ir > Rh ? Pd > Pt. 相似文献
54.
N. S. Mosyagin A. V. Titov R. J. Buenker H.‐P. Liebermann A. B. Alekseyev 《International journal of quantum chemistry》2002,88(5):681-686
Multireference single‐ and double‐excitation configuration interaction (MRD‐CI) calculations of transition energies for the Hg atom and spectroscopic constants for the HgH molecule are carried out with the generalized relativistic effective core potential (GRECP) method. A new selection criterium for the reference configurations is discussed. The calculated spectroscopic constants are compared with experimental data and results of calculations of other groups. Improvement of accuracy is mainly observed for bond lengths from the GRECP/MRD‐CI calculations (without applying the T = 0 correction) with respect to the results of other groups. Analysis of the quality of the approximations employed is carried out. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
55.
Substituted 5-hexen-1-oxyl radicals have been generated from N-(5-hexen-1-oxy)-5-(p-methoxyphenyl)-4-methylthiazole-2(3H)-thiones under tin-free conditions and have been successfully applied as reactive intermediates in a mechanistic study on the formation of bromomethyl-substituted tetrahydropyrans via 6-exo-trig selective cyclizations. 相似文献
56.
羧甲基壳聚糖/聚乙烯醇/甘油环氧树脂蛇笼型复合螯合膜的制备及对金属离子的吸附性能 总被引:4,自引:0,他引:4
以交联甘油环氧树脂交联的聚乙烯醇(PVA)为笼树脂,羧甲基壳聚糖(CCTS)为蛇树脂制备了具有蛇笼结构的复合螯合膜,研究了其对Cu^2 、Ni^2 、Pb^2 、Fe^3 、Zn^2 ,Hg”^2 、Cd^2 等金属离子的吸附性能,研究表明,该树脂对Cu^2 、Ni^2 、Pb^2 有较好的吸附性能,其中PVA是对Cu^2 的吸附的主要贡献者,而CCTS则是在对Ni^2 的吸附中起主要作用。该树脂可以用于含Cu^2 废水的处理。 相似文献
57.
Jason R McCarthyPatricia J Melfi Steven H CapettaChristian Brückner 《Tetrahedron》2003,59(46):9137-9146
The use of AgII as a removable template in synthetic porphyrin chemistry is described. Mild procedures for the insertion of AgII into chlorins and the demetallation of the [chlorinato]AgII complexes are delineated. The UV-vis spectra of the novel [chlorinato]AgII complexes are discussed. The diol cleavage products of [meso-tetraphenyl-2,3-diolchlorinato]silver(II) under a number of conditions are characterized and compared to those resulting from the cleavage of the corresponding free base diol chlorin or its NiII complex, highlighting the unique templating effect of AgII. The scopes and limits of electrospray ionization mass spectrometry (ESI-MS) for the analysis of AgII chlorins is described. The use of AgII as a templating metal is superior over NiII or ZnII for the preparation of free base pyrrole-modified porphyrins along metal templated pathways. 相似文献
58.
V. A. D’yakonov R. K. Timerkhanov A. G. Ibragimov U. M. Dzhemilev 《Russian Chemical Bulletin》2007,56(11):2232-2235
Catalytic cycloalumination of cyclonona-1,2-diene upon treatment with Et3Al and EtAlCl2 in the presence of Cp2ZrCl2, leading to 10-ethyl-10-aluminabicyclo[7.3.01,9]dodec-8-ene (1) and 11-ethyl-11-aluminatricyclo[10.7.01,12.02,10]nonadeca-9,12-diene, respectively, was accomplished in high yields. A possibility for the selective transformation of compound
1 to 1-allyl-9-(pent-4-enyl)cyclonon-1-ene and 10-hydroxybicyclo[7.3.01,9]dodec-8-ene in one preparative step was demonstrated.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2156–2159, November, 2007. 相似文献
59.
High-energy-density batteries are in urgent need to solve the ever-increasing energy storage demand for portable electronic devices, electric vehicles, and renewable solar and wind energy systems. Alkali metals, typically lithium(Li), sodium(Na) and potassium(K), are considered as the promising anode materials owing to their low electrochemical potential, low density, and high theoretical gravimetric capacities. However, the problem of dendrite growth of alkali metals during their plating/stripping process will lead to low Coulombic efficiencies, a short lifespan and huge volume expansion, eventually hindering their practical commercialization. To resolve this issue, a very effective approach is engineering the anodes on structured current collectors. This review summarizes the development of the alkali metal batteries and discusses the recent advances in rational design of anode current collectors. First, the challenges and strategies of suppressing alkali-metal dendrite growth are presented. Then the special attention is paid to the novel current collector design for dendrite-free alkali metal anodes. Finally, we give conclusions and perspective on the current challenges and future research directions toward advanced anode current collectors for alkali metal batteries. 相似文献
60.
The synthesis and characterization of poly(4-vinyl,2′-carboxybenzophenone) ion exchange resin is described. This resin displays a remarkably high capacity for Cu2+. Control of pH permits selective adsorption and estimation of Fe3+. This ion-exchanger is quite stable to loading acid washing cycles. © 1995 John Wiley & Sons, Inc. 相似文献