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91.
Garcia-Galdo JE Cobas-Rodriguez J Jáuregui-Haza UJ Guiochon G 《Journal of chromatography. A》2004,1024(1-2):9-14
This work presents a modification to the real adsorbed solution model using a Flory-Huggins type of expression that was reported previously. This modification consists in replacing the Flory-Huggins activity coefficient by the spreading pressure dependent approach. This new model takes into account explicitly the adsorbate-adsorbate interactions taking place in the adsorbed phase. It provides an excellent prediction of the competitive, ternary adsorption equilibrium of benzyl alcohol, 2-phenylethanol and 2-methyl benzyl alcohol observed in a reversed-phase liquid chromatographic system using information merely derived from the single-component adsorption experimental data. 相似文献
92.
de Oliveira MC Scarpellini M Neves A Terenzi H Bortoluzzi AJ Szpoganics B Greatti A Mangrich AS de Souza EM Fernandez PM Soares MR 《Inorganic chemistry》2005,44(4):921-929
The crystal structures and redox and UV-vis/EPR spectroscopic properties of two new mononuclear copper(II) complexes, [Cu(HL1)Cl2] (1) and [Cu(L1)Cl] (2), prepared through the reaction between copper(II) chloride and the ligand 2-[(bis(pyridylmethyl)amino)methyl]-4-methyl-6-formylphenol (HL1) under distinct base conditions, are reported along with solution studies. Also, we demonstrate that these CuII complexes are able to cleave unactivated peptide bonds from bovine serum albumin (BSA) and the thermostable enzyme Taq DNA polymerase at micromolar concentration, under mild pH and temperature conditions. The cleavage activity seems to be specific with defined proteolytic fragments appearing after protein treatment. The location of the specific cleavage sites was tentatively assigned to solvent-accessible portions of the protein. These are two of the most active Cu(II) complexes described to date, since their cleavage activity is detected in minutes and evidence is here presented for a hydrolytic mechanism mediating protein cleavage by these complexes. 相似文献
93.
Quantitative investigation of the reaction of the ferri-heme model compound Fe(III)(TPPS)(H(2)O)(2) (1) to give Fe(II)(TPPS)(NO) (2) (TPPS = tetra(4-sulfonato-phenyl)porphinato) in buffered aqueous solution demonstrates a slow pH-independent reductive nitrosylation pathway in the pH range 4-6. The rate of this reaction is subject to modest general base catalysis. In the course of this study, a surprising catalytic pathway whereby nitrite ion (NO(2)(-)) strongly catalyzes the reduction of 1 to 2 under reductive nitrosylation conditions was demonstrated. 相似文献
94.
Bismuth(III) salts are efficient catalysts for the selective allylic oxidation using tert-butyl hydroperoxide. BiCl3 is especially effective and can be easily recovered and reused as BiOCl. Using BiCl3/K-10 as catalyst, an increase in the reaction rate was observed. 相似文献
95.
Abstract— The triplet state characteristics (spectrum, lifetime and quantum yield) for four dye sensi tisers [methylene blue (MB), erythrosin (ER), haematoporphyrin (HP) and riboflavin (RF)] were determined in methanol by laser flash photolysis and singlet oxygen yields (0.60 to 0.48) from time-resolved measurements of the 1270 nm near infrared emission. The reaction of singlet oxygen with four long chain unsaturated phenyl esters [oleate (18: 1), linoleate (18: 2), linolenate (18: 3) and arachidonate (20: 4)] was followed quantitatively using the singlet oxygen luminescence technique and also, after continuous420–700 nm irradiation, by HPLC and other analysis of the isomeric product monohydroperoxides. The overall quantum yield of photooxidation (∼10-2 ) was shown to be consistent with the observed singlet oxygen quenching constants(2–12 times 104 dm3 mol-1 s-1 ) for the four esters studied and the singlet oxygen lifetime in methanol (τ∼ 9 μs). The isomer product distribution was interpreted in terms of a dual singlet oxygen and radical mechanism, the radical contribution increasing with sensitiser in the order ER = MB < HP ≪ RF, but also showing some dependence on substrate unsaturation. Evidence is presented for singlet oxygen quenching by MB and RF ( kO = 1.6 and 6.0 times 107 dm3 mol-1 s-1 ) and for the accelerated photobleaching of the dye sensitisers in the presence of the unsaturated esters. 相似文献
96.
Fernandez Romero AJ López Cascales JJ Fernandez Otero T 《The journal of physical chemistry. B》2005,109(2):907-914
Polypyrrole/poly(vinyl sulfonate) (PPy/PVS) films in acetonitrile containing 0.1 M LiClO4 were studied by cyclic voltammetry. Consecutive voltammograms pointed to a continuous increase in the charge involved in the process, suggesting a rise in the number of the electroactive participants involved in the redox process. However, voltammograms obtained for the PPy/ClO4 films in analogous conditions pointed to a steady-state behavior from the very early cycles. Theoretical studies based on the Nernst and Butler-Volmer equations indicated that perchlorate ions are involved during the oxidation/reduction process of the PPy/PVS films when the steady state is reached. This result was confirmed by "ex situ" energy-dispersive X-ray analysis of the films. In this regard, the electrochemical behavior of PPy/PVS polymers was similar to that of PPy/ClO4 films when a high number of cycles were carried out. The exchange of ClO4- during the redox reaction of the PPy/PVS films made it necessary to incorporate Li+ cations inside the polymer during the initial voltammetric cycles to compensate for the negative charges of PVS polyanions. Li+ cations are mainly stabilized inside the polymer by the ion pairs formed with the sulfonated groups of the PVS. An increase and shift of the voltammetric cycles indicated a restructuring of the polymeric chains with consecutive scans. 相似文献
97.
98.
[reaction: see text] As a hybrid of the N,N-dibenzylammonium and 1,2-bis(pyridinium)ethane axles, various N-benzylanilinium cations were investigated as suitable axles for the formation of [2]pseudorotaxanes with the 24-membered crown ethers 24C8 and DB24C8. The effect of electron-donating OCH(3) and electron-withdrawing CF(3) groups on both the anilinium and benzyl aromatic rings was studied. Formation constants and structural details were compared to the [2]pseudorotaxanes formed by the two aforementioned dibenzylammonium and 1,2-bis(pyridinium)ethane axles. 相似文献
99.
Diego R. Pérez Susana H. Tarulli Oscar V. Quinzani Dr. Jorge Dristas Ricardo Faccio Leopoldo Suescun Alvaro W. Mombrú 《无机化学与普通化学杂志》2007,633(7):1066-1073
Four new lead(II) thiosaccharinate complexes: [Pb(tsac)2H2O] (1) (tsac: thiosaccharinate anion), [Pb2(tsac)4(py)4] (2) (py: pyridine), [Pb(tsac)(o‐phen)2](tsac)·CH3CN (3) (o‐phen: 1,10‐phenantroline), and [Pb(tsac)2(bipy)] (4) (bipy: 2,2′‐bipyridine) were prepared. The infrared and electronic spectra as well as the thermal analysis of all the compounds were recorded and discussed. The thiosaccharinate anion acts in three different coordination forms, one of then reported for the first time. The crystal structures of complexes 2 and 3 have been determined by single crystal X‐ray diffractometry. In complex 2 , two monomeric moieties are joined together forming a symmetric bis‐μ‐sulphur bridged dimer by interaction of two lead(II) atoms through the exocyclic sulphur atoms of two thiosaccharinate ligands. The seven‐fold coordination sphere of each lead atom is completed by two pyridine nitrogen atoms and by another sulfur and two nitrogen atoms of the thiosaccharinate anions. In complex 3 , the lead(II) atom is coordinated by four nitrogen atoms of two 1,10‐phenantroline molecules and by the sulfur and nitrogen atoms of one thiosaccharinate ion. The second anion has an electrostatic interaction with the nucleus. 相似文献
100.
Development of a bionematicide with Paecilomyces lilacinus to control Meloidogyne incognita 总被引:1,自引:0,他引:1
Brand D Roussos S Pandey A Zilioli PC Pohl J Soccol CR 《Applied biochemistry and biotechnology》2004,118(1-3):81-88
Root-knot disease caused by Meloidogyne incognita is a matter of grave concern because it affects several economically important crop plants. The use of solid-state fermentation
(SSF) may help to elaborate efficient formulations with fungi to be employed in the biologic control of nematodes. Attempts
were made to select low-cost substrates for spore production of a strain of Paecilomyces lilacinus with known nematicide capacity. Coffee husks, cassava bagasse, and defatted soybean cake were utilized as substrates, and
sugarcane bagasse was used as support. Fermentations were carried out in flasks covered with filter paper at 28°C for 10 d.
The products obtained by SSF were evaluated for their nematicide activity in pot experiments containing one seedling of the
plant Coleus inoculated with the nematode M. incognita. The plants were evaluated 2 mo after inoculation. Fermented products showed a reduction in the number of nematodes. The
best results were obtained with defatted soybean cake, which showed almost 100% reduction in the number of nematodes; the
reduction with coffee husk was 80% and with cassava bagasse was about 60%. 相似文献