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161.
Fátima Nunes Serralha José Madeira Lopes Francisco Lemos Duarte Prazeres Maria Aires-Barros Joo Rocha Joaquim Cabral Fernando Ramôa Ribeiro 《Reaction Kinetics and Catalysis Letters》2000,69(2):217-222
Novel [CrIII(amp)(bipy)(Cl)] (1) (H2amp = N-(hydroxyphenyl)salicyldimine; bipy = 2,2-bipyridyl) and [CrIII(app)(bipy)(Cl)]+ (2) (H2app = N-(hydroxyphenyl)pyridine-2-carboxaldimine; bipy = 2,2-bipyridyl) complexes have been synthesized and characterized by physico-chemical methods. Complexes 1 and 2 have been employed as catalysts in the oxidation of both saturated and unsaturated hydrocarbons using tert-butylhydroperoxide (t-BuOOH). The significance of the results with respect to oxo-functionalization of C-H bonds both in unsaturated and saturated hydrocarbons is noted. 相似文献
162.
高锰酸根离子氧化烯烃反应机理的研究王磊(淮北煤炭师范学院化学系,淮北235000)关键词烯烃高锰酸根离子氧化机理碳碳双键是烯烃分子的官能团,通常情况下此官能团较活泼、易受亲电和亲核试剂的进攻。碱性的高锰酸根离子MnO-4是烯烃羟化的经典试剂,同时导致... 相似文献
163.
CuO/Ce-Zr-La-O催化剂的表征及CO氧化活性 总被引:5,自引:3,他引:5
采用柠檬酸溶胶-凝胶法制备的Ce-Zr-La-O固溶体为载体,制备CuO/Ce-Zr-La-O催化剂,用XRD,Raman,TPR等实验技术对Ce-Zr-La-O固溶体及CuO/Ce-Zr-La-O的物相、Redox性能进行了表征。实验结果表明,Ce0.7Cr0.3-yLayO固溶体的还原性能与La含量有关,适量的La能促进固溶体的氧化还原。CuO的负载量为6%时,CuO/Ce0.7Zr0.15La0.15O的活性最高,高分散且与载体相互作用的CuO是CO氧化活性相。 相似文献
164.
The biomimetic catalytic enantioselective addition of aldehydes to amines is reported. This was accomplished by combining biomimetic coupled catalytic aerobic oxidation of amines involving ruthenium-induced dehydrogenation and organocatalytic asymmetric Mannich reactions. The novel one-pot reactions furnished β-amino aldehyde and α-amino acid derivatives in high yields with excellent chemoselectivity and up to >99% ee. 相似文献
165.
A kinetic method for the determination of selenium(IV) traces is proposed, based on its inhibitory action on the oxidation of Nile Blue A by hydrogen peroxide in phosphate buffer (pH 10.5). A linear dependence was established between the rate of the proposed indicator reaction and selenium concentration in the range 9.5 × 10–2-1.58 ng cm–3. The experimental conditions of maximal selenium effect were established. Selenium, determined by the tangent method, was determined at concentrations over the range 0.22–1.26 ng cm–3, with relative standard deviations up to 4.5%. The reaction rate was followed spectrophotometrically. The effect of foreign ions on the accuracy of this method was also investigated. The method was applied to the determination of selenium in pharmaceutical preparations and wheat flour. 相似文献
166.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(2):352-362
Coenzyme B12 initiates radical chemistry in two types of enzymatic reactions, the irreversible eliminases (e.g., diol dehydratases) and the reversible mutases (e.g., methylmalonyl‐CoA mutase). Whereas eliminases that use radical generators other than coenzyme B12 are known, no alternative coenzyme B12 independent mutases have been detected for substrates in which a methyl group is reversibly converted to a methylene radical. We predict that such mutases do not exist. However, coenzyme B12 independent pathways have been detected that circumvent the need for glutamate, β‐lysine or methylmalonyl‐CoA mutases by proceeding via different intermediates. In humans the methylcitrate cycle, which is ostensibly an alternative to the coenzyme B12 dependent methylmalonyl‐CoA pathway for propionate oxidation, is not used because it would interfere with the Krebs cycle and thereby compromise the high‐energy requirement of the nervous system. In the diol dehydratases the 5′‐deoxyadenosyl radical generated by homolysis of the carbon–cobalt bond of coenzyme B12 moves about 10 Å away from the cobalt atom in cob(II )alamin. The substrate and product radicals are generated at a similar distance from cob(II )alamin, which acts solely as spectator of the catalysis. In glutamate and methylmalonyl‐CoA mutases the 5′‐deoxyadenosyl radical remains within 3–4 Å of the cobalt atom, with the substrate and product radicals approximately 3 Å further away. It is suggested that cob(II )alamin acts as a conductor by stabilising both the 5′‐deoxyadenosyl radical and the product‐related methylene radicals. 相似文献
167.
Fausi?RassoulEmail author Heinz?L?ster Volker?Richter 《Monatshefte für Chemie / Chemical Monthly》2005,136(8):1501-1507
Summary. L-Carnitine, L-(−)-β-hydroxy-γ-trimethylaminobutyrate, plays an important role as a factor necessary for the transport of long-chain fatty acids into the mitochondria. In order to investigate the influence of L-carnitine on hyperlipidaemias, the experimental model of the sucrose-induced hypertriglyceridaemia of the rat was used. In these experiments L-carnitine in the dose of 11 mg per day and 100 g body weight (over the period of 1 week) was able to antagonize the sucrose-induced hypertriglyceridaemia and the increase of serum free fatty acid level in female rats of the Wistar strain. Carnitine administration did not change the activities of lipogenic enzymes and fatty acid synthesis in the liver. However, L-carnitine increases the rate of hepatic fatty acid oxidation. Our results indicate a hypotriglyceridemic and free fatty acid lowering effect of L-carnitine, and suggest the use of this compound in the therapy of hyperlipidaemias. 相似文献
168.
A. A. Tyshchenko O. F. Filatova S. M. Khodzhibaeva K. D. Davranov 《Chemistry of Natural Compounds》2004,40(1):75-78
The ability to bind reversibly molecular oxygen was established for a free-radical product of gossypol oxidation. Conversion of dianhydrogossypol into the stable biradical dioxodianhydrogossypol was viewed as the reason for interruption of the gossypol redox conversion cycle in the extracellular milieu of cotton steles. 相似文献
169.
This account describes the results collected by our group during the last years on some themes of environmental/mechanistic
interest. Theoretical quantum-mechanical investigations have been carried out to help clarifying the mechanism of some oxidation
reactions, which involve mainly unsaturated but also saturated organics as substrates, and, as reactive oxidants, triplet
or singlet dioxygen, hydroxyl, ozone, and nitrogen oxides. Depending on the problem, the calculations are either multi-configurational
(as CAS-MCSCF, CAS-PT2, MC-QDPT2), or based on the Density Functional Theory for the heavier systems. Research work has thus
been developed along the following lines: hydrocarbon oxidations under atmospheric or combustion conditions; definition of
a model for soot particles and their interaction with species as HO, O2, O3, NO, NO2, NO3, etc.; investigation on the reaction mechanism of 1Δg dioxygen with organic unsaturated systems (cycloaddition and ene reactions). 相似文献
170.
The electrocatalytic oxidation of hydrazine at the aluminum electrode, modified by electroless deposition of nickel pentacyanonitrosylferrate
(NiPCNF) on the surface of the electrode has been studied by cyclic voltammetry, chronoamperometry and rotating disk electrode
voltammetry and the kinetics of the catalytic reaction were investigated. The results were explained using the theory of electrocatalytic
reactions at chemically modified electrodes. It was found that a one-electron charge-transfer process is rate limiting and
that the average values of the rate constant for the catalytic reaction and the diffusion coefficient, evaluated by different
approaches, are 5.2×103 M–1s–1 and 8.5×10–6 cm2s–1, respectively. Further examinations of the modified electrodes show that the modifying layers (NiPCNF) on the aluminum substrate
have reproducible behavior and a high level of stability, after exposing them in air and hydrazine solutions for a long time.
Electronic Publication 相似文献