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161.
162.
Cristina Otero Eitel Pastor Antonio Ballesteros 《Applied biochemistry and biotechnology》1990,26(1):35-44
Transesterification between ethyl butyrate and glycerol using very different lipase preparations (native, modified, and immobilized) in a two-phase system—no extra solvent added—has been investigated. Optimal conversion was obtained with the presence of 5% water in the reaction mixture. Only monobutyrin was produced in all conditions tested. The best enzyme preparations were nativeCandida cylindracea lipase,Mucor miehei lipase immobilized on a phenol-formaldehyde exchange resin (Lipozyme?), andC. cylindracea lipase immobilized on Celite. 相似文献
163.
Photodegradation of Polychlorinated Dibenzo-p-dioxins in Liquid Samples by Near UV Light Irradiation
Photodegradation of 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) in hexane solution was studied under controlled near-UV light exposure in the spectral region from 325 to 269 nm. GC-MS was used to detect the amount of unreacted dioxin and to characterize the relevant degradation products. Irradiation experiments carried out at a constant light energy (700 mJ) showed that the percentage of 1,2,3,4-TCDD left in the solution after irradiation changed from about 55 to 75%, with a minimum of 55% at 310 nm. Further irradiation experiments carried out at two wavelengths, namely 310 and 269 nm, and light energy ranging from 0 to 4000 mJ, showed that the photodegradation reaction of the TCDD always followed a pseudo-first-order kinetic, with a rate constant of 8 × 10−4and 5 × 10−4mJ−1, respectively. These experiments also showed that trichloro- and dichloro-dibenzo-p-dioxins were produced with less than 15% of the initial quantity of TCDD, leading to the conclusion that the dechlorination process is a minor photolysis pathway. 相似文献
164.
Trichochromes, the peculiar pigments of red human hair, featuring the Delta(2,2)(')-bi(2H-1,4-benzothiazine) skeleton, are known to arise from cysteinyldopas, mainly the 5-S-isomer (5). However, the mode of formation and the direct precursors have remained largely undefined. To fill this gap, we investigated the oxidation of 5 in air or with chemical and enzymatic agents under biomimetic conditions. In the presence of zinc ions, which occur in epidermal tissues at significant concentrations, the reaction course is diverted toward the formation of a labile 3-carboxy-2H-1,4-benzothiazine intermediate (11), which was identified by direct NMR analysis. Structural formulation was supported by characterization of the analogous compound 13 isolated from oxidation of the model 5-methyl-3-S-cysteinylcatechol (12) after methylation. In the further stages of the oxidation, diastereomeric 2,2'-bi(2H-1,4-benzothiazine) 15 and 14 were obtained from 5 and 12, respectively, the reaction proceeding at a higher rate and to a greater extent in the presence of acids. The dimers were shown to readily convert to each other in the presence of acids. In the case of the methylated dimers 14, a 2,2'-bi(4H-1,4-benzothiazine) intermediate (16) was isolated and characterized. In acidic media, trichochrome C (1a), the most abundant in red human hair, was smoothly formed from aerial oxidation of 15, and under similar conditions, trichochrome-related products (17 and 18) were obtained from 14 prior to or after methylation. The presence of 1a and precursors 5 and 15 was investigated by HPLC analysis of red hair samples following mild proteolytic digestion. On the basis of these data, a likely biosynthetic route to trichochrome pigments of red human hair is depicted. 相似文献
165.
Paolesse R Monti D La Monica L Venanzi M Froiio A Nardis S Di Natale C Martinelli E D'Amico A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2476-2483
Porphyrin diad 1 was synthesized by reaction of the acyl chloride of porphyrin 2 and trans-1,2-dithiane-4,5-diol. The Co complex of this diad was studied as a potential enantioselective receptor for chiral recognition in solution and in the solid state. In solution both enantiomers of limonene induce significant changes in the visible and circular dichroism (CD) spectra of [Co2(1)], while a different behavior is observed in the case of the enantiomeric pair of trans-1,2-diaminocyclohexane. A different efficiency of [Co2(1)] chiral recognition is obtained for these compounds, with a remarkable degree of enantiodiscrimination observed in the case of limonene. Self-assembled monolayers of [Co2(1)] were deposited onto the gold electrodes of quartz crystal microbalances to be used as sensing materials of nanogravimetric sensors operating in the gas phase. The enantiodiscrimination properties of these sensors towards the enantiomeric pairs of chiral analytes have been studied. While in the case of analytes bearing donor ligand atoms we did not observe a remarkable enantioselectivity, a significant degree of chiral discrimination was observed in the case of limonene; this result is particularly encouraging for the potential development of enantioselective chemical sensors for use in an array configuration. 相似文献
166.
Riccò M Shiroka T Carretta S Bolzoni F Femoni C Iapalucci MC Longoni G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2856-2861
The magnetic behaviour of the even-electron [Ni16Pd16(CO)40]4- cluster, in its [NnBu4]+ salt, has been investigated by magnetometry and muon spin rotation/relaxation (muSR) spectroscopy. The susceptibility measurements show an exceptionally high magnetic moment corresponding to a total spin value J=2. This suggests a Hund filling of a quadruplet ground state, quite unique in carbonyl-metal clusters. SQUID magnetometry shows a departure from the Curie-Weiss law, for T>150 K, and strong deviation from a Brillouin behaviour of the magnetisation curves. muSR spectroscopy in zero applied field shows a temperature independent decay of the muon spin polarisation, similar to that of a purely paramagnetic system. The observed muon spin repolarisation in a moderate external longitudinal field, however, invalidates this simple picture and suggests the presence of a local anisotropy field acting on the cluster's magnetic moment. A consistent interpretation of magnetometry and muSR results implies the occurrence of an additional interaction of the cluster spin with an effective crystalline field. The inclusion of this interaction in a model Hamiltonian allows us to successfully reproduce both the susceptibility and magnetisation data. 相似文献
167.
Aurora González-Portal F. Bermejo-Martínez C. Baluja-Santos María Cristina Diez-Rodríguez 《Microchemical Journal》1985,31(3):368-374
A new method for the Spectrophotometric determination of bismuth using N-(2-acetamido)iminodiacetic acid as complexometric agent is proposed. The complex is formed in a wide pH range, 5.5–7.5, and has a maximum absorption at 265 nm. Beer's law is obeyed in the interval 3.8–17.9 μg of bismuth(III)/ml, with a minimum photometric error of 2.3. The molar absorptivity is 9.1 × 103 liters/cm mol. The stoichiometry of the reaction takes place in the metal-to-ligand ratio 1:2. The interferences produced by the more common ions are studied. The method has been successfully applied to the determination of bismuth in pharmaceutical formulations. 相似文献
168.
Iodine-poly(2-vinylpyridine-co-styrene-co-divinylbenzene) charge transfer complexes with antibacterial activity 总被引:1,自引:0,他引:1
Angela Cristina Jandrey Mônica Regina Marques Palermo de Aguiar José Luiz Mazzei 《European Polymer Journal》2007,43(11):4712-4718
In this work, we have developed three different copolymers based on 2-vinylpyridine, styrene and crosslinked with divinylbenzene (10-30 mol%). The copolymers were morphologically and chemically characterized by apparent density, swelling degree, elemental analysis, Fourier transform infrared spectrophotometry and optical microscopy. The formation of iodine complexes with these copolymers was carried out by two different procedures: with solvent, or not. The influence of the copolymers structure on the capacity of anchoring iodine has been investigated. The antibacterial properties of polymeric charge transfer complexes were determined towards 103-107 cells/mL dilutions from the auxotrophic AB1157 Escherichia coli strain. 相似文献
169.
The reductive alkylation of amine with carbonyl compounds usingsodium hydrogen telluride has been investigated in recent years.Application of this method to the synthesis of N-alkyl derivativesof biologically important amino acids and their esters is described. 相似文献
170.
We computed by spin-polarized DFT the structure and the electronic properties of an infinite periodic wire constituted of planar Cu-bridged hydroxypyridone chelator base pairs and of a similarly stacked finite dimer. The Cu centers undergo electronic hybridization with the bases. There is an unpaired spin per plane, and the majority-spins manifest ordering: The ferromagnetic and antiferromagnetic phases are energetically degenerate. The total magnetization of the ferromagnetic wire depends linearly on the number of planes in the stack. The combination of interplane spin coupling and intraplane metal-hydroxypyridone coupling makes this system very appealing for electronic and magnetic device exploitation. 相似文献