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71.
Milen Raytchev Elke Mayer Nicole Amann Hans-Achim Wagenknecht Torsten Fiebig 《Chemphyschem》2004,5(5):706-712
5-(Pyren-1-yl)-2'-deoxyuridine (PydU) and 5-(Pyren-1-yl)-2'-deoxycytidine (PydC) were used as model nucleosides for DNA-mediated reductive electron transport (ET) in steady-state fluorescence and femtosecond time-resolved transient absorption spectroscopy studies. Excitation of the pyrene moiety in PydU and PydC leads to an intramolecular electron transfer that yields the pyrenyl radical cation and the corresponding pyrimidine radical anion (dU.- and dC.-. By comparing the excited state dynamics of PydC and PydU, we derived information about the energy difference between the two pyrimidine radical anion states. To determine the influence of protonation on the rates of photoinduced intramolecular ET, the spectroscopic investigations were performed in acetonitrile, MeCN, and in water at different pH values. The results show a significant difference in the basicity of the generated pyrimidine radical anions and imply an involvement of proton transfer during electron hopping in DNA. Our studies revealed that the radical anion dC.- is being protonated even in basic aqueous solution on a picosecond time scale (or faster). These results suggest that protonation of dC.- may also occur in DNA. In contrast, efficient ET in PydU could only be observed at low pH values (< 5). In conclusion, we propose--based on the free energy differences and the different basicities--that only dT.- but not dC.- can participate as an intermediate charge carrier for excess electron migration in DNA. 相似文献
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Cremer GA Bureaud N Lelièvre D Piller V Piller F Delmas A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6353-6360
Our goal was to develop mimics of MUC1, highly immunogenic to induce an efficient immune response against the tumor-associated form of MUC1, and sufficiently different from the natural antigen to bypass the tolerance barrier in humans. With the aim of obtaining a well-defined peptide construct as a means of evoking the precise immune responses required in immunotherapy, we synthesized artificial mimics of the MUC1 protein composed of two MUC1 repeat units of inverse orientation and a universal T-helper epitope. To synthesize these heteromeric peptide constructs, we followed a convergent approach using chemoselective ligation based on oxime chemistry. A stem peptide was first synthesized bearing two orthogonally masked aldehydes. After successive deprotection, two oxime bonds can be specifically generated. The proposed strategy proved to be concise and robust, and allowed the synthesis of the tri-branched protein in a very satisfactory yield. The different constructs were tested for their ability to generate antibodies able to recognize the MUC1 protein. 相似文献
74.
Zusammenfassung Das früher beschriebene1 Succinylzellulose-Papier wird als Ionenaustauscher zur weiteren papierchromatischen Trennung von Basengemischen verwendet. Getrennt wurden die Alkaloide der Morphingruppe und deren Abwandlungsprodukte, ferner die Alkaloide der Strychnin-, der Tropin-, der Cocaingruppe und andere Alkaloide.
Summary The succinyl-cellulose paper described previously1 is used as ion exchanger for additional paper chromatographic separations of mixtures of bases. Separations were accomplished of the alkaloids of the morphine group and their modification products, and also of the alkaloids of the strychnine-, tropine- and cocaine groups and other alkaloids.
Résumé On utilise le papier à la succinyl-cellulose déjà décrit1, comme écharigeur d'ions pour d'autres séparations par chromatographie sur papier de mélanges basiques. On a séparé ainsi les alcaloïdes du groupe de la morphine et leurs produits d'évolution, et en outre, les alcaloïdes des groupes de la strychnine, de la tropine et de la cocaïne et d'autres alcaloïdes.相似文献
75.
Fritz Keinert 《Advances in Computational Mathematics》1995,4(1):1-26
For orthogonal wavelets, the discrete wavelet and wave packet transforms and their inverses are orthogonal operators with perfect numerical stability. For biorthogonal wavelets, numerical instabilities can occur. We derive bounds for the 2-norm and average 2-norm of these transforms, including efficient numerical estimates if the numberL of decomposition levels is small, as well as growth estimates forL . These estimates allow easy determination of numerical stability directly from the wavelet coefficients. Examples show that many biorthogonal wavelets are in fact numerically well behaved. 相似文献
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Cyrille Ceugniet Ltitia Lepetit Nancy Lauth De Viguerie Henry Jammes Nicole Peyrot Monique Rivire 《Journal of chromatography. A》1998,810(1-2):237-240
A high-performance liquid chromatographic (HPLC) procedure was developed to allow the rapid separation, in a single run, of a mixture of the main retinal isomers (all-trans, 13-cis, 9-cis), all-trans-retinol, and of the two major photooxygenated photoproducts (5,8-peroxyretinal and 5,6-epoxyretinal). The mixture was separated by HPLC on an octadecyl (ODS) column with 16% (v/v) diethyl ether in hexane as mobile phase and anthracene as the internal standard. A commercial type cosmetic formulation containing 0.05% all-trans-retinal was analyzed successfully for this analyte. 相似文献
80.
Nicole Desrosiers Gérald Perron John G. Mathieson Brian E. Conway Jacques E. Desnoyers 《Journal of solution chemistry》1974,3(10):789-806
The apparent molal volume φv, expansibility φE, compressibility φK, and heat capacity φc of NaCl were measured in urea-water mixtures, as a function of salt (<1.5m) and urea (<13m) concentrations at 25°C. At a fixed urea concentration, the transfer functions from H2O to 3m urea are linear functions of the NaCl aquamolality. At a fixed salt aquamolality, (0.1m), the sign of the transfer functions is in the direction of a decrease in the structure-breaking effect, and the absolute values of the transfer functions tend to level off at high urea concentrations (13m). The functions φv, φE, φK, φc, and (?φv/?T)p were measured for the sodium halides and alkali, bromides (chlorides in the case of φK) at a fixed salt aquamolality of 0.1m and fixed urea molality of 3m. The corresponding transfer functions from H2O to 3m urea are opposite those from H2O to D2O and similarly are relatively independent of ionic size. This suggests that urea, shows no specific interaction affinity for ions and that the overall number of water molecules influenced by the ions is relatively constant for all alkali halides. The lithium halides are an exception in that Li+ seems to have hardly any structure-breaking effect. 相似文献