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991.
Huang JS Sun XR Leung SK Cheung KK Che CM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(2):334-344
Reactions of dioxoruthenium(VI) porphyrins, [Ru(VI)O2(Por)], with p-chloroaniline, trimethylamine, tert-butylamine, p-nitroaniline, and diphenylamine afforded bis(amine)ruthenium(II) porphyrins, [Ru(II)(Por)(L)2] (L-p-ClC6H4NH2, Me3N, Por=TTP, 4-Cl-TPP; L=tBuNH2, Por = TPP, 3,4,5-MeO-TPP, TTP, 4-Cl-TPP, 3,5-Cl-TPP) and bis(amido)ruthenium(IV) porphyrins, [Ru(IV)(Por)(X)2] (X=p-NO2C6H4NH, Por=TTP, 4-Cl-TPP; X = Ph2N, Por = 3,4,5-MeO-TPP, 3,5-Cl-TPP), respectively. Oxidative deprotonation of [Ru(II)(Por)(NH2-p-C6H4Cl)2] in chloroform by air generated bis(arylamido)ruthenium(IV) porphyrins, [RuIV(Por)(NH-p-C6H4Cl)2] (Por=TTP. 4-Cl-TPP). Oxidation of [RuII(Por)-(NH2tBu)2] by bromine in dichloromethane in the presence of tert-butylamine and traces of water produced oxo(imido)ruthenium(VI) porphyrins, [RuVI-O(Por)(NtBu)] (Por=TPP, 3,4,5-MeO-TPP, TTP, 4-Cl-TPP, 3,5-Cl-TPP). These new classes of ruthenium complexes were characterized by 1H NMR, IR, and UV/visible spectroscopy, mass spectrometry, and elemental analysis. The structure of [Ru(IV)(TTP)(NH-p-C6H4Cl)2 . CH2Cl2 was determined by X-ray crystallography. The Ru-N bond length and the Ru-N-C angle of the Ru-NHAr moiety are 1.956(7) A and 135.8(6) degrees, respectively. 相似文献
992.
High-performance liquid affinity chromatography with immobilized histidine as a pseudo-biospecific ligand has been used for the fractionation of human immunoglobulin G (IgG). Histidine was immobilized onto silica in two different modes: directly onto silica after epoxy activation or using an intermediate amino derivatization of silica and then coupling histidine using water-soluble carbodiimide. The behaviours and capacities of the obtained affinity supports as well as the influence of pH, silica type, pore diameter and coupling mode have been studied. IgG was effectively separated from human plasma and high maximal binding capacities were obtained. 相似文献
993.
H. A. Al-Salah H. X. Xiao J. A. McLean Jr. K. C. Frisch 《Journal of polymer science. Part A, Polymer chemistry》1988,26(6):1609-1620
Polyurethane (PU) cationomers have been synthesized by quaternizing tertiary amine-containing linear polyurethanes using different quaternizers containing acid groups. The effect of chemical structure of PU cationomers on the physical properties was studied. The mechanical properties of PU cationomers were improved with decreasing molecular weight of poly(caprolactone) glycol, and increasing concentration of quaternary ammonium. Decreasing the carbon number in the alkyl group of the N-alkyl diethanol-amine chain-extenders, and using rigid symmetrical diisocyanates, the mechanical properties of the PU cationomers were increased. The effects of these factors on the glass transition temperature of PU cationomers were also examined. The mechanical properties of the PU cationomers decreased by immersion in water and recovered after removal of the water. 相似文献
994.
The novel ternary solid complex Gd(C5H8NS2)3(C12H8N2) has been obtained from the reaction of hydrous gadolinium chloride, ammonium pyrrolidinedithiocarbamate (APDC), and 1,10-phenanthroline
(o-phen · H2O) in absolute ethanol. The complex was described by an elemental analysis, TG-DTG, and an IR spectrum. The enthalpy change
of the complex formation reaction from a solution of the reagents, Δr
H
m
ϑ
(sol), and the molar heat capacity of the complex, c
m
, were determined as being − 15.174 ± 0.053 kJ/mol and 72.377 ± 0.636 J/(mol K) at 298.15 K by using an RD496-III heat conduction
microcalorimeter. The enthalpy change of a complex formation from the reaction of the reagents in a solid phase, Δr
H
m
ϑ
(s), was calculated as being 52.703 ± 0.304 kJ/mol on the basis of an appropriate thermochemical cycle and other auxiliary
thermodynamic data. The thermodynamics of the formation reaction of the complex was investigated by the reaction in solution.
Fundamental parameters, the activation enthalpy (ΔH
≠
ϑ
), the activation entropy (ΔS
≠
ϑ
), the activation free energy (ΔG
≠
ϑ
), the apparent reaction rate constant (k), the apparent activation energy (E), the preexponential constant (A), and the reaction order (n), were obtained by the combination of the thermochemical data of the reaction and kinetic equations, with the data of thermokinetic
experiments. The constant-volume combustion energy of the complex, Δc
U, was determined as being −17588.79 ± 8.62 kJ/mol by an RBC-II type rotatingbomb calorimeter at 298.15 K. Its standard enthalpy
of combustion, Δc
H
m
ϑ
, and standard enthalpy of formation, Δf
H
m
ϑ
, were calculated to be −17604.28 ± 8.62 and −282.43 ± 9.58 kJ/mol, respectively.
The text was submitted by the authors in English. 相似文献
995.
The chelate compounds K[Fe(hyc)3] and N2H5[Fe(hyc)3]·H2O (hyc = N2H3COO) were studied by the Mössbauer effect of 57Fe at various temperatures. At room temperature the quadrupole splitting parameter is 2.77 mm/sec for K[Fe(hyc)3] and 2.35 mm/sec for N2H5[Fe(hyc)3]·H2O, and the center shift is 1.08 mm/sec for both compounds. The temperature dependences of the quadrupole parameters yielded the crystal field splittings of the 5T2g levels of the Fe2+ ions which indicate large trigonal distortion of the Fe(hyc)3 anion. Using a molecular crystal-like treatment of the ferrous ion vibrations the temperature dependence of the recoilless fraction gave an effective Debye temperature ΘD = 71°K for K[Fe(hyc)3] and ΘD = 90°K for N2H5[Fe(hyc)3]·H2O. No evidence for magnetic ordering was found down to 4.5°K in either compound. 相似文献
996.
T. L. Wang H. W. Tong X. Y. Yan L. Q. Sheng J. Yang S. M. Liu 《Chromatographia》2005,62(11-12):631-636
An effective and rapid method, use of a 2,4-dinitrophenylhydrazine (DNPH)-treated Cambridge filter and high-performance liquid chromatography (HPLC) with diode-array detection (DAD), has been used for determination of low-molecular-mass carbonyl compounds in cigarette smoke. Different chromatographic mobile phases were investigated and the optimized mobile phase was a gradient prepared from water–acetonitrile–tetrahydrofuran (THF)–iso-propanol, 59:30:10:1 (v/v) (mixture A) and acetonitrile–water, 65:35 (v/v) (mixture B). Under the optimized chromatographic conditions, the 2,4-dinitrophenylhydrazones of formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, 2-butanone, and iso-butyraldehyde were separated completely in an 18 min chromatographic run. The concentration of acid, which has large effect on carbonyl-DNPH derivatization, was investigated by adding different volumes of perchloric acid. The DNPH-treated Cambridge filter was convenient and effective compared with conventional methods used to collect and derivatize the carbonyl compounds present in cigarette smoke. Validation of the method showed it to be effective, precise, accurate, and linear over the range of concentrations of analyzed. 相似文献
997.
Deng JK Li GQ Wang F Su GL Ning CG Zhang T Ren XG Wang Y Zheng Y 《The Journal of chemical physics》2004,120(21):10009-10014
The binding energy spectra and electron distributions in momentum space of the valence orbitals of cyclopentane (C(5)H(10)) are studied by Electron Momentum Spectroscopy (EMS) in a noncoplanar symmetric geometry. The impact energy was 1200 eV plus binding energy and energy resolution of the EMS spectrometer was 1.2 eV. The experimental momentum profiles of the outer valence orbitals are compared with the theoretical momentum distributions calculated using Hartree-Fock and density functional theory (DFT) methods. The shapes of the experimental momentum distributions are generally quite well described by both the Hartree-Fock and DFT calculations when the large and diffuse basis sets are used. 相似文献
998.
Xu QM Wang D Han MJ Wan LJ Bai CL 《Langmuir : the ACS journal of surfaces and colloids》2004,20(8):3006-3010
Scanning tunneling microscopy (STM) combined with cyclic voltammetry has been employed to investigate the adsorption of cinchonine on Cu(111). Similar to cinchonidine, cinchonine forms a long-range ordered adlayer with (4 x 4) symmetry on the substrate. The structural details on molecular adsorption were obtained by high-resolution STM images. On the basis of the previous results and obtained STM images, the quinoline ring is proposed to lie parallel to Cu(111) and serve as an anchoring group. The chiral quinuclidine moiety extends out of the surface to facilitate the interaction with the prochiral reactants. 相似文献
999.
Lam WH Gaspar PP Hrovat DA Trieber DA Davidson ER Borden WT 《Journal of the American Chemical Society》2005,127(27):9886-9894
CASSCF, CASPT2, CCSD(T), and (U)B3LYP electronic structure calculations have been performed in order to investigate the thermal fragmentation of P-phenylphosphirane (1) to phenylphosphinidene (PhP) and ethylene. The calculations show that generation of triplet PhP via a stepwise pathway is 21 kcal mol(-1) less endothermic and has a 12 kcal mol(-1) lower barrier height than concerted fragmentation of 1 to give singlet PhP. The formation of singlet PhP via a concerted pathway is predicted to be stereospecific, whereas formation of triplet PhP is predicted to occur with complete loss of stereochemistry. However, calculations on fragmentation of anti-cis-2,3-dimethyl-P-mesitylphosphirane (cis-1Me) to triplet mesitylphosphinidene (MesP) indicate that this reaction should be more stereospecific, in agreement with the experimental results of Li and Gaspar. Nevertheless, with a predicted free energy of activation of 42 kcal mol(-1), the formation of MesP from cis-1Me is not likely to have occurred in an uncatalyzed reaction at the temperatures at which this phosphirane has been pyrolyzed. 相似文献
1000.
HACCP体系的原理 总被引:8,自引:0,他引:8
论述了美国从1997年12月18日零时起执行的并被国际认同的HACCP体系的原理,对我国水产品加工企业出口产品与编制产品的HACCP计划有重要指导作用。 相似文献