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21.
Novel complexing processes in the CuII–dithiooxamide–methanal, CuII–dithiooxamide–ethanal and CuII–dithiooxamide–propanone triple systems proceeding under specific conditions, to copper(II)hexacyanoferrate(II) gelatin-immobilized matrix systems in contact with aqueous-alkaline (pH 12) solutions containing dithiooxamide and methanal, ethanal or propanone, have been studied. It has been shown that template synthesis leading to the formation of macrocyclic coordination compounds (2,8-dithio-3,7-diaza-5-oxanonandithioamide-1,9)copper(II), (2,8-dithio-3,7-diaza-4,6-dimethyl-5-oxanonandithio-amide-1,9)copper(II) and (4,4,6-trimethyl-2,8-dithio-3,7-diazanonen-6-dithioamide-1,9)copper(II), respectively, takes place under such conditions. Dithiooxamide, methanal, ethanal and propanone act as ligand synthons in these processes. 相似文献
22.
Barriga S Fuertes P Marcos CF Rakitin OA Torroba T 《The Journal of organic chemistry》2002,67(18):6439-6448
We report the synthesis of some new polysulfur-nitrogen heterocycles by cycloaddition reactions to readily available tricyclic condensed 1,2-dithiole-3-thiones. Thus, treatment of bis[1,2]dithiolopyrrole ketothione 1 with diacyl acetylenes gave the bis-aducts 2a-d. On the other hand, cycloaddition of bis[1,2]dithiolo[1,4]thiazine ketothione 3 with 1 equiv of acyl or diacyl acetylenes gave [1,3]dithiolylidenyl[1,2]dithiolo[1,4]thiazines 4a-f in fair to high yields. Catalysis by scandium triflate was used in the reactions that implied the less reactive dipolarophiles. Treatment of 3 with 2 equiv of DBA gave the bis-aduct 5a, and reaction of 4c with DMAD gave the mixed bis-adduct 5b. Cyclic voltammetry of selected examples showed irreversible processes that were influenced by the electrochemical activity of peripheral groups bonded to the heterocyclic system. 相似文献
23.
Oleg V. Voinov 《Journal of colloid and interface science》1998,200(2):197
Equilibrium of a capillary meniscus near a wetting film on a solid in a gravitational field is considered. Unlike previous studies, the present study proves that the fine meniscus structure in a gravitational field is a universal feature—it takes place in a wide variety of problems. In the general case, the capillary meniscus is at a certain distance from the wetting film and does not intersect it. The relation for the minimum distance from the arbitrary meniscus to the solid generalizes the Derjaguin formula for a flat slit. An equation that optimally approximates the meniscus with due account of the contribution of the meniscus/film transition region is derived. A refined solution to the problem of a meniscus on a vertical plate is derived within the perturbation theory. Both gravity and nonuniformity of the vertical static film above a capillary–gravitational meniscus do not affect the minimum distance (the influence is less than 0.0001). A general method for solving sophisticated problems of capillary equilibrium in gravitational field is proposed. 相似文献
24.
Svyatoslav V. Katyurin Oleg B. Glinkin 《International journal of quantum chemistry》1992,43(2):251-258
A quantum chemical study of the two low-lying quartet states of seven model compound I iron–porphyrin complexes with varying axial ligands has been carried out using the INDO method. The varying axial ligands included in this study are five that are models for those in the intact enzymes: imidazole and imidazolate (model peroxidase HRP and CCP), CH3CONH2 (Gln175 mutant of CCP), PhO?1 (catalase), CH3S?1 (P450), and two that have been used in biomimetics of these enzymes: Cl?1 (hemin) and PhS?1 (model P450s). The purpose of these studies was to determine the role of the axial ligands in determining (i) the relative energies of the two nearly degenerate quartet electronic states of compound I, involved either as an a1u or a2u porphyrin π cation radical and (ii) the electron and spin distributions in the a1u and a2u radical cations of compound I. For most of the model complexes, including both HRP-I and CAT-I, a moderate effect of the axial ligand on the relative energy of these two states was observed and the a1u radical cation was found to be the ground state. The energy order of these two radical cations, however, was reversed in the P450-I model complexes, indicating an association of the unique property of the Fe?O bond breaking with an a2u radical cation. The symmetry-allowed overlap between the Fe?O and 3a2u orbitals may lower the activation energy for the Fe?O bond cleavage in P450-I. However, the calculated electronic and spin properties, including the unpaired spin and net charge on the oxygen and the Fe?O bond overlap density, important determinants of the reactivity of this complex in the ligand–Fe?O region, are very similar for all complexes and in both cation states. © 1992 John Wiley & Sons, Inc. 相似文献
25.
Vyacheslav I. Boyko Volodymyr V. Pyrozhenko Oleg V. Shishkin 《Tetrahedron letters》2006,47(44):7775-7778
Calix[4]arenes bearing a methoxy and an R or S α-phenylethylacetamido group at the narrow rim of macrocycles are stereoselectively acylated with 1 equiv of trichloroacetyl isocyanate to give chiral asymmetrically substituted calix[4]arenecarbamates in preparative yields and high diastereomeric excess. 相似文献
26.
Fedushkin IL Morozov AG Rassadin OV Fukin GK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(19):5749-5757
Compounds [Sr(dpp-bian)(thf)4] (2), [Ba(dpp-bian)(dme)2.5] (3) and [Mg(dtb-bian)(thf)2] (4) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene; dtb-bian = 1,2-bis[(2,5-di-tert-butylphenyl)imino]acenaphthene) were prepared by reduction of dpp-bian and dtb-bian with an excess of metallic Mg, Sr, or Ba in THF or DME. Reactions of [Mg(dpp-bian)(thf)3], 3, and 4 with diphenylacetonitrile gave keteniminates [Mg(dpp-bianH)(NCCPh2)(thf)2] (5), [Mg(dtb-bianH)(NCCPh2)(thf)2] (6), and [Ba(dpp-bianH)(NCCPh2)(dme)2] (7), respectively. The reaction of 2 with CH3C[triple chemical bond]N in THF gave [{Sr(dpp-bianH)[N(H)C(CH3)C(H)CN](thf)}2] (8). The compounds 2, 3, 5-8 were characterized by elemental analysis, and IR and NMR spectroscopy. Molecular structures of 2, 3, 7, and 8 were determined by single-crystal X-ray diffraction. In contrast to reactions of alkali-metal reagents, magnesium amides, or yttriumalkyls with alpha-H acidic nitriles, which are accompanied by an amine or an alkane elimination, the reactions of [Mg(dpp-bian)(thf)3] (1), 2, 3, and 4 with such nitriles proceeded with formation of Mg, Sr, and Ba keteniminates and simultaneous protonation of one nitrogen atom of the bian ligand. The NMR spectroscopic data obtained for complex 5 indicated that in solution the amino hydrogen atom underwent the fast (on the NMR timescale) shuttle transfer between both nitrogen atoms of the dpp-bianH ligand. 相似文献
27.
Varnavski OP Ostrowski JC Sukhomlinova L Twieg RJ Bazan GC Goodson T 《Journal of the American Chemical Society》2002,124(8):1736-1743
Measurements of ultrafast fluorescence anisotropy decay in model branched dendritic molecules of different symmetry are reported. These molecules contain the fundamental branching center units of larger dendrimer macromolecules with either three (C(3))- or four (T(d), tetrahedral)-fold symmetry. The anisotropy for a tetrahedral system is found to decay on a subpicosecond time scale (880 fs). This decay can be qualitatively explained by F?rster-type incoherent energy migration between chromophores. Alternatively, for a nitrogen-centered trimer system, the fluorescence anisotropy decay time (35 fs) is found to be much shorter than that of the tetramers, and the decay cannot be attributed to an incoherent hopping mechanism. In this case, a coherent interchromophore energy transport mechanism should be considered. The mechanism of the ultrafast energy migration process in the branched systems is interpreted by use of a phenomenological quantum mechanical model, which examines the two extreme cases of incoherent and coherent interactions. 相似文献
28.
Oleg V. Mikhailov Marina A. Kazymova Tatyana A. Shumilova Galina A. Chmutova Svetlana E. Solovieva 《Transition Metal Chemistry》2005,30(3):299-304
The complexing process proceeding in the NiII–thiocarbohydrazide (H2N–H–NC(=S)–NH–NH2)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of NiII with (N,N,S,S)-donor tetradentate ligands having NiL1, NiL2 and NiL3compositions where L1 is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L2 is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L3 is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur. 相似文献
29.
Oleg N. Obrezkov Andrey V. Pirogov Igor V. Pletnev Oleg A. Shpigun 《Mikrochimica acta》1991,103(5-6):293-302
A new optimization criterion for chromatography is presented. It was designed to evaluate the quality of chromatograms in a way similar to human estimation. Selectivity, efficiency, and time of analysis as well as the number of peaks were taken into account. The criterion has been tested in comparison with expert estimations and some modern criteria. A better agreement of the new criterion with human estimation of chromatographic quality compared to some literature criteria is shown. A number of successful optimization runs has been performed using the criterion together with simplex optimization. 相似文献
30.
Kostko O Wrigge G Cheshnovsky O von Issendorff B 《The Journal of chemical physics》2005,123(22):221102
We present photoelectron spectroscopy studies on Zn(n) (-) in the size range of n=3-117. We show that zinc clusters exhibit a distinct transition in their electronic structure as a function of size. At small sizes (up to n=18) the clusters follow the Bloch-Wilson picture of the development of a metal from closed-shell atoms, exhibiting a gradual decrease of the gap between the fully occupied s band and the empty p band. For large sizes (n approximately or > 32) the band overlap allows the valence electrons to fully delocalize. This leads to an almost perfect free-electron density of states, as is demonstrated by discussing the spectra in the light of standard free-electron models and by comparison to the results obtained on sodium clusters. 相似文献