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131.
132.
Eliot P. Botosoa Virginie Silvestre Richard J. Robins Jose Manuel Moreno Rojas Claude Guillou Gérald S. Remaud 《Journal of chromatography. A》2009,1216(42):7043-7048
Quantitative isotopic 13C NMR at natural abundance has been used to determine the site-by-site 13C/12C ratios in vanillin and a number of related compounds eluted from silica gel chromatography columns under similar conditions. Head-to-tail isotope fractionation is observed in all compounds at the majority of carbon positions. Furthermore, the site-specific isotope deviations show signatures characteristic of the position and functionality of the substituents present. The observed effects are more complex than would be obtained by simply summing the individual effects. Such detail is hidden when only the global 13C content is measured by mass spectrometry. In particular, carbon positions within the aromatic ring are found to show site-specific isotope fractionation between the solute and the stationary phase. These interactions, defined as non-covalent isotope effects, can be normal or inverse and vary with the substitution pattern present. 相似文献
133.
Yogesh S. Sanghvi Steven B. Larson Roland K. Robins Ganapathi R. Revankar Pranab K. Gupta Rose D. George N. Kent Dalley 《Journal of heterocyclic chemistry》1988,25(2):623-633
Several thiazole nucleosides structurally related to tiazofurin (1) and ARPP (2) were prepared, in order to determine whether these nucleosides had enhanced antitumor/antiviral activities. Ring closure of 1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)thiourea (4) with ethyl bromopyruvate (5a) gave ethyl 2-(2,3,5-tri-O-benzoyl-β-D-ribofuranosylamino)thiazole-4-carboxylate (6a) . Treatment of 6a with sodium methoxide furnished methyl 2-(β-D-ribopyranosylamino)thiazole-4-carboxylate (9) . Ammonolysis of the corresponding methyl ester of 6a gave a unique acycloaminonucleoside 2-[(1R, 2R, 3R, 4R)(1-benzamido-2,3,4,5-tetrahydroxypentane)amino]-thiazole-4-carboxamide (7a) . Direct glycosylation of the sodium salt of ethyl 2-mercaptothiazole-4-carboxylate (12) with 2,3,5-tri-O-benzoyl-D-ribofuranosyl bromide (11) gave the protected nucleoside 10 , which on ammonolysis provided 2-(β-D-ribofuranosylthio)thiazole-4-carboxamide (3b) . Similar glycosylation of 12 with 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (13) , followed by ammonolysis gave 2-(2-deoxy-β-D-ribofuranosylthio)thiazole-4-carboxamide (3c) . The structural assignments of 3b, 7a , and 9 were made by single-crystal X-ray analysis and their hydrogen bonding characteristics have been studied. These compounds are devoid of any significant antiviral/antitumor activity in vitro. 相似文献
134.
135.
Katarzyna Kosieradzka Illa Tea Emmanuel Gentil Richard J. Robins 《Analytical and bioanalytical chemistry》2010,396(4):1405-1414
An important route for the detoxification of tropane alkaloids involves N-demethylation to the nor-compounds followed by further degradation. In order to study the mechanisms of the pertinent reactions,
a suitable means to determine the isotope ratios of the substrates and products is required. However, the polarity and functionality
of the nortropane compounds makes their analysis as free bases difficult. A method is described which allows both the quantification
of nortropane alkaloids and the determination of their natural abundance δ15N values. The protocol exploits the derivatisation of the alkaloids by reaction with ethyl chloroformate in aqueous medium
and the quantitative extraction of the ensuing ethylcarbamate esters. The improved chromatographic properties of these derivatives
gives ample separation of the isomeric nortropine and norpseudotropine for measurement of their δ15N (‰) values by isotope ratio mass spectrometry interfaced to gas chromatography. Adequate separation could not be achieved
with the underivatised compounds. Repeatability and precision are sufficient to allow differences in the δ15N values (∆δ15N) > 0.8‰ to be measured, with a standard deviation routinely ∼0.3‰. The methodology has been tested by determining the changes
in the δ15N values of nortropine and norpseudotropine during degradation by cell suspension cultures of a Pseudomonas strain expressing a specific capacity for tropine catabolism. The precision and reproducibility are shown sufficient to allow
the evolution of the δ15N values to be followed during the fermentation. 相似文献
136.
Benoit Gay Rodolphe Vaillon M. P?nar Mengüç 《Journal of Quantitative Spectroscopy & Radiative Transfer》2010,111(2):287-294
A new integral-vector Monte Carlo method (IVMCM) is developed to analyze the transfer of polarized radiation in 3D multiple scattering particle-laden media. The method is based on a “successive order of scattering series” expression of the integral formulation of the vector radiative transfer equation (VRTE) for application of efficient statistical tools to improve convergence of Monte Carlo calculations of integrals. After validation against reference results in plane-parallel layer backscattering configurations, the model is applied to a cubic container filled with uniformly distributed monodispersed particles and irradiated by a monochromatic narrow collimated beam. 2D lateral images of effective Mueller matrix elements are calculated in the case of spherical and fractal aggregate particles. Detailed analysis of multiple scattering regimes, which are very similar for unpolarized radiation transfer, allows identifying the sensitivity of polarization imaging to size and morphology. 相似文献
137.
Glycosylation of 6-(substituted-imidazol-1-yl)purine sodium salts with 2-deoxy-3,5-di-O-(p-toluoyl)-alpha-D-erythro-pentofuranosyl chloride proceeds with regiospecific formation of the N9 isomers. Base substrates with lipophilic substituents on the C6-linked imidazole moiety are more soluble in organic solvents, and the solubility is further increased with binary solvent mixtures. Selective solvation also diminishes the extent of anomerization of the chlorosugar. Stirred reaction mixtures of the modified-purine sodium salts generated in a polar solvent and cooled solutions of the protected 2-deoxysugar chloride in a nonpolar solvent give 2'-deoxynucleoside derivatives with N9 regiochemistry and enhanced beta/alpha configuration ratios. Application of the binary-solvent methodology with 2-chloro-6-(substituted-imidazol-1-yl)purine salts in cold acetonitrile and the chlorosugar in cold dichloromethane gives essentially quantitative yields of the N9 isomers of beta-anomeric 2'-deoxynucleoside intermediates. Direct ammonolysis (NH(3)/MeOH) of such intermediates or benzylation of the imidazole ring followed by milder ammonolysis of the imidazolium salt gives high yields of the clinical anticancer drug cladribine (2-chloro-2'-deoxyadenosine). 相似文献
138.
Gary E. Martin Russell H. Robins Frank W. Crow Wayne K. Duholke Jane E. Guido Chad E. Hadden Brian D. Kaluzny Thomas J. Thamann Bruce A. Pearlman 《Journal of heterocyclic chemistry》1999,36(4):1107-1114
TipranavirTM (PNU-140690) is a protease inhibitor under clinical investigation for the treatment of human acquired immunodeficiency syndrome (AIDS). During scale-up synthesis of clinical quantities of the bulk drug, a colored, transient by-product of the final coupling reaction was observed. Quantities of this colored, transient chemical species were too low (<<0.1%) for characterization by conventional spectroscopic methods. It was, however, possible to isolate sufficient material for characterization based on mass spectrometry and submicro inverse-detection gradient (SMIDG) nmr methods by methanol stripping of silica gel that had been used in purification of bulk drug. This process afforded an enriched feedstock from which small quantities of this highly colored and unstable (halflife < 18 hours in methanol and < 10 minutes in acetone) trace contaminant could be isolated by semi preparative reversed phase hplc. The impurity was identified as an unstable Zincke salt formed by the condensation of two molecules of the anilino precursor and the pyridine used as a base in the final step of the synthetic process. Following identification of this impurity, efforts were undertaken to engineer it out of the synthetic process. 相似文献
139.
Alves GA Amato S Anjos JC Appel JA Astorga J Bernard T Bracker SB Cremaldi LM Darling CL Dixon RL Errede D Gay C Green DR Jedicke R Karchin PE Kwan S Lueking LJ de Mello Neto JR Metheny J Milburn RH de Miranda JM da Motta Filho H Napier A Passmore D Rafatian A dos Reis AC Ross WR Santoro AF Sheaff M Souza MH Spalding WJ Stoughton C Streetman ME Summers DJ Takach SF Wallace A Wu Z 《Physical review letters》1994,72(6):812-815
140.
UPS studies are reported for carbon monoxide chemisorbed, at varying coverages, on a clean Pt(100) surface. A new assignment of surface states is obvious from the broadening and resolution of the emission peak, positioned at ca. 8 eV below the Fermi level, following pre-adsorption of propene and pyridine. The valence band density of states, determined by He(I) and He(II) emission spectroscopy, is compared with that reported earlier by X-ray electron emission spectroscopy. 相似文献