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191.
Duffy DJ Quenneville J Baumbaugh TM Kitchener SA McCormick RK Dormady CN Croce TA Navabi A Stidham HD Hsu SL Guirgis GA Deng S Durig JR 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(3):659-671
Ab initio calculations are reported for three of four possible conformers of 1,3-dichloropropane. The fourth conformer, with Cs symmetry, has a predicted enthalpy difference of more than 1500 cm(-1) from the most stable conformer from each calculation regardless of the basis set used, so there is little chance of observing it. Thus, there is no evidence in the infrared or Raman spectrum of the presence of a fourth conformer. The order of stability given by the ab initio calculations is C2(GG)>C1(AG)>C2v(AA)>Cs(GG'), where A indicates the anti form for one of the CH2Cl groups and G indicates the gauche conformation for the other CH2Cl group relative to the plane of the carbon atoms. Almost every band observed can be confidently assigned to one or another of the conformers. Many observed bands proved to be of a composite nature, with several nearly coincident vibrations of different conformers contributing to the band contour. Nonetheless, a complete assignment of fundamentals is possible for the most stable C2 conformer, and 5 of the fundamentals of the C2v conformer and 13 those of the C1 conformer can be confidently assigned. 相似文献
192.
The reduction of ReCl4(THF)2 in the presence of excess t-butylisocyanide by sodium amalgam produces pentakis(t-butylisocyanide)chlororhenium(I), which has been converted to the corresponding methyl and ethyl derivatives. The reaction of pentakis(trimethylphosphine)chlororhenium(I) with ButNC gives partially substituted complexes, ReCl(CNBut)2(PMe3)3 and ReCl(CNBut)3(PMe3)2. The structures of both compounds have been determined by X-ray methods. Octahedral ReCl(CNBut)2(PMe3)3 has trans isocyanide groups with one linear [C---N---C = 175(1)°] and one slightly bent [C---N---C = 159(1)°]. The Re---C bond lengths are equal within experimental error [2.004(7), 2.003(7)Å]. In the octahedral ReCl(CNBut)3(PMe3)2, for which the structure is not well defined, due to disorder, the unique isocyanide trans to chlorine is considerably bent at the nitrogen atom [C---
---C = 141(6)°] and appears to show the shortest Re---C bond length, 1.94(5) vs 2.02(5)Å for the other two isocyanides which are mutually trans. Protonation of these two isocyanide complexes with fluoroboric acid gives, respectively, the salts [ReCl(CNBut)CNHBut(PMe3)3]BF4 and [ReCl(CNBut)2CNHBut(PMe3)2]BF4, whose configurations have been determined by NMR spectroscopy. The reduction by sodium amalgam of Cr2(CO2Me)4 in tetrahydrofuran in presence of ButNC gives a high yield of Cr(CNBut)6 while similar reduction of the dimeric tungsten(II) complex of the anion (mhp) of 2-methyl-6- hydroxypyridine gives W(CNBut)6. Interaction of W2(mhp)4 in methanol-ether with ButNC gives a tungsten(I) complex W2(η-mhp)2(ButNC)4, which may be an intermediate in the reductive cleavage reaction. Interaction of cis-PtMe2(PMe3)2 with ButNC leads only to replacement of one PMe3 group to give the complex cis-PtMe2(PMe3)(CNBut). 相似文献
193.
Ajay K. Saini Clifford M. Carlin Howard H. Patterson 《Journal of polymer science. Part A, Polymer chemistry》1992,30(3):419-427
New model compounds for poly[N,N′-bis(phenoxyphenyl)pyromellitimide] have been synthesized in order to investigate the formation of imine bonds which are proposed to form during the curing process and lead to crosslinking in the bulk polymer. Raman studies show that terminal amines can react with imide carbonyls during curing to form C?N bonds. The Raman band due to C?N appears at 1656 cm?1 and the band due to C?O closest to the imine bond is observed at 1742 cm?1. These results are in agreement with previously published results on vapor deposited polyimide films. 相似文献
194.
FrankH. Allen Raju Mondal NigelA. Pitchford JudithA.K. Howard 《Helvetica chimica acta》2003,86(4):1129-1139
Symmetry‐modified principal‐component analysis has been used to visualise the geometrical distortions of three‐coordinate metal centres observed in crystal structures retrieved from the Cambridge Structural Database. It is shown that compounds of Cu, Ag, Hg, Zn, and Au dominate the dataset, and exhibit distortions away from the trigonal planar archetype towards a) T‐shaped and b) Y‐shaped geometries. A small number of compounds, principally of Cu and Ag, also show distortions towards trigonal pyramidal geometries. The interconversions from Y‐shaped geometries, through the trigonal planar form to T‐shaped geometries are clearly mapped by the PC analysis. For HgII complexes, it is possible to interpret the transition from T‐shaped geometries to the trigonal planar form in terms of a reaction pathway for ligand addition to linear L1? HgII? L2 species. 相似文献
195.
196.
Dmitrii S. Yufit Judith A. K. Howard Sergei I. Kozhushkov Rafael R. Kostikov Armin de Meijere 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(8):968-969
The central three‐membered ring in the title compound, trans‐1,1′,1′′‐cyclopropane‐1,2,3‐triyltris(cyclopropanol), C12H18O3, shows pronounced asymmetry of the bond lengths, which is induced by the different orientations of the substituents. A network of hydrogen bonds links the molecules into sheets. 相似文献
197.
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199.
Carrie A. Delcomyn Howard S. Weinberg Philip C. Singer 《Journal of chromatography. A》2001,920(1-2):213-219
A user-friendly ion chromatography method in conjunction with a post-column reaction (PCR) achieves practical quantitation limits for the oxyhalides bromate and chlorite of 0.05 μg/l and 0.10 μg/l, respectively. This level of measurement allows for the accurate assessment of bromate contributed to finished drinking waters that have been chlorinated using sodium hypochlorite. The target sensitivity of oxyhalides in the presence of other major ion species typically found in drinking water is achieved by PCR using excess bromide under acidic conditions to form a tribromide species that is detected by ultraviolet spectrometry. The method setup involves non-hazardous materials, as opposed to other recently developed methods that employ somewhat hazardous chemicals for generating the reaction necessary for the detection of bromate at sub-μg/l levels. No pretreatment of the samples is required, other than filtration and quenching of oxidant residual. 相似文献
200.