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71.
Two enzymes, Mucor javanicus lipase and subtilisin Carlsberg (SC), catalyzed the nonaqueous acylation of doxorubicin (DOX). Compared to the untreated enzyme the rate of DOX acylation at the C-14 position with vinyl butyrate in toluene was 25-fold higher by lipase ion-paired with Aerosol OT (AOT) and 5-fold higher by lipase activated by 98% (w/w) KCl co-lyophilization (3.21 and 0.67 mumol/min g-lipase, respectively, vs 0.13 mumol/min g-lipase). Particulate subtilisin Carlsberg (SC) was nearly incapable of DOX acylation, but ion-paired SC (AOT-SC) catalyzed acylation at a rate of 2.85 mumol/min g-protease. The M. javanicus formulations, AOT-SC, and SC exclusively acylated the C14 primary hydroxyl group of DOX. Co-lyophilization of SC with 98% (w/w) KCl expanded the enzyme's regiospecificity such that KCl-SC additionally acylated the C4' hydroxyl and C3' amine groups. The total rate of DOX conversion with KCl-SC was 56.7 mumol/min g-protease. The altered specificity of KCl-SC is a new property of the enzyme imparted by the salt activation, and represents the first report of unnatural regioselectivity exhibited by a salt-activated enzyme. Using AOT-SC catalysis, four unique selectively acylated DOX analogues were generated, and KCl-SC was used to prepare DOX derivatives acylated at the alternative sites. Cytotoxicities of select derivatives were evaluated against the MCF7 breast cancer cell line (DOX IC50 = 27 nM) and its multidrug-resistant sub-line, MCF7-ADR (DOX IC50 = 27 muM). The novel derivative 14-(2-thiophene acetate) DOX was relatively potent against both cell lines (IC50 of 65 nM and 8 muM, respectively) and the 14-(benzyl carbonate) DOX analogue was as potent as DOX against the MCF7 line (25 nM). Activated biocatalysts and their novel regioselectivity differences thus enabled single-step reaction pathways to an effective collection of doxorubicin analogues. 相似文献
72.
73.
Heating a toluene solution of dicarhomethoxyacetylenebis(triphenylphosphine)platinum(0) at 130°C gives the ortho-metalated complex (Ph3P)(Ph2t-trans-(COOMe)CCHCOOMe. 相似文献
74.
A solid-phase extraction method is described for the separation of alachlor, atrazine and metolachlor from groundwater using solid-phase disposable columns. The method is rapid, reproducible and uses considerably fewer reagents than classical liquid-liquid methods. The average recoveries were greater than 90% for all three compounds. 相似文献
75.
The reaction of a racemic perhydroisoquinolene derivative 9 with the homochiral lithium amide basse 3 in the presence of Me3SiCl in an regiodivergent fashion to give the two non-racemic regioisomeric enol silanes 10 and 11. Conversion of 10 into enone 15, an intermediate useful in the synthesis of the alkaloid (+)-yohimbine, was also possible. 相似文献
76.
Lisa D. Harris 《Tetrahedron letters》2005,46(10):1627-1629
The enantiomeric excess observed for the exo-adduct from the Lewis acid catalysed Diels-Alder reaction between cyclopentadiene and methacrolein can be increased up to 21% by simple modification of the electronics of the aromatic ring in a series of stilbene-derived diol ligands, suggesting that the proposed face-face π-π interaction between the catalyst and the dienophile can be modulated by altering the electron density on the aromatic ring. 相似文献
77.
D. T. Clark M. Z. Abrahman 《Journal of polymer science. Part A, Polymer chemistry》1981,19(11):2689-2703
A systematic investigation has been made of the composition, gross structural features, and rates of deposition of plasma polymer films produced from the excitation of inductively coupled RF plasmas in the isomeric tetrafluorobenzenes. ESCA data reveal that the dominant reaction involves rearrangement such that under a wide variety of experimental conditions the composition of the crosslinked products remains essentially the same as that of the starting material. Small differences in rates of deposition are observed for the different isomers, and theoretical SCF MO studies at the MNDO level provides a basis for discussion of the experimental data. 相似文献
78.
D. T. Clark B. J. Cromarty A. Dilks 《Journal of polymer science. Part A, Polymer chemistry》1978,16(12):3173-3184
Nonempirical LCAO MO SCF computations (in the ΔSCF formalism) have been carried out of binding energies and relaxation energies for an extensive series of oxygen-containing organic systems encompassing most of the common functionalities. The molecules for which experimental data are available for comparison demonstrate the adequacy of the treatment for describing the relative binding energies for both the Cls and Ols core levels. A sound basis is therefore provided for the discussion of relative core binding energies (Cls and Ols) for functionalities for which experimental data are not available, that is, hydroperoxides, peroxides, peroxyacids, and peroxyesters, a knowledge of which is essential for investigations of the surface oxidation of polymers by means of ESCA. Cls shifts are discussed in terms of primary and secondary substituent effects of oxygen, which greatly simplify the analysis of complex unresolved spectra, whereas for the Ols levels a similar but less straightforward situation exists. The relaxation energies associated with both Cls and Ols core ionization follow a dependence on the binding energy for a given structural type. 相似文献
79.
80.
W.John Albery David Clark Humphrey J.J. Drummond Anthony J.M. Coombs William K. Young Clive E.W. Hahn 《Journal of Electroanalytical Chemistry》1992,340(1-2)
A novel electrochemical sensor for the determination of CO2 in expired breath is described. The sensor works by generating
from the reduction of O2 in dimethyl sulphoxide (DMSO) in a generating pulse. There is a rapid titration reaction between the
and any CO2 present. In the recovery pulse the amount of unreacted
is determined. The larger the concentration of CO2 the less
is found in the recovery pulse. The solubilities and diffusion coefficients of O2 and CO2 in DMSO have been determined using rotating disc voltammetry and rotation speed step experiments. The stoichiometry, the product, and the rate constant of the titration reaction have been determined using ring—disc voltammetry and laser Raman spectroscopy. The operation and the effect of adventitious water on the sensor are described. Results are presented which show that the sensor can indeed measure the breath-by-breath rhythm of expired CO2 from a human subject. 相似文献