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191.
A simple and sensitive method was developed using hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry
for determination of monosaccharides liberated from marine polysaccharides by acidic hydrolysis. Optimal separation of diastereomeric
monosaccharides including hexoses, pentoses, and deoxyhexoses was achieved using an aminopropyl bonded column with mobile
phase containing ternary solvents (acetonitrile/methanol/water) in conjunction with MS/MS in SRM mode. Mechanisms for fragmentation
of deprotonated monosaccharides with regard to cross-ring cleavage were proposed. Matrix effects from coeluting interferences
were observed and isotopic-labeled internal standard was used to compensate for the signal suppression. The method demonstrated
excellent instrumental limits of detection (LOD), ranging from 0.7 to 4.2 pg. Method LODs range from 0.9 to 5.1 nM. The proposed
method was applied to the analysis of polysaccharides in seawater collected from the open leads of the central Arctic Ocean
in the summer of 2008. 相似文献
192.
Roe C Moragas Solá T Sasraku-Neequaye L Hobbs H Churcher I MacPherson D Stockman RA 《Chemical communications (Cambridge, England)》2011,47(26):7491-7493
The synthetic utility of S-mesitylsulfinimines for the synthesis of chiral amines and aziridines was examined through their reactions with Grignard reagents, with the ylides derived from trimethylsulfonium iodide and S-allyl-tetrahydrothiophenium bromide and through an aza-Darzens manifold, affording convenient access to a diverse range of highly substituted chiral amines and aziridines in high yields and excellent stereoselectivities. 相似文献
193.
194.
Carlos Guerrero‐Sanchez Caroline Abeln Ulrich S. Schubert 《Journal of polymer science. Part A, Polymer chemistry》2005,43(18):4151-4160
Anionic polymerization techniques have been implemented successfully in a commercial automated synthesizer. The main problems for a successful adaptation of the experimental technique in the automated synthesizer are addressed, as well as some simple potential applications, such as the anionic polymerization of styrene, isoprene, and methyl methacrylate. The obtained results were reproducible and in concordance with literature knowledge. The apparent rate constant of the anionic polymerization of styrene in cyclohexane initiated by sec‐butyllithium could be determined at two different concentrations of the monomer and initiator in a temperature range of 10–60 °C. All the synthesis and characterization experiments of the polymers were performed within a short time period. Moreover, the syntheses of poly(styrene‐b‐isoprene) and poly(styrene‐b‐methyl methacrylate) block copolymers were also successfully carried out within the automated synthesizer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4151–4160, 2005 相似文献
195.
Caroline Brayer Ebby 《The Journal of Mathematical Behavior》2005,24(1):73-87
This study examines one child's use of computational procedures over a period of 3 years in an urban elementary school where teachers were using a standards-based curriculum. From a sociocultural perspective, the use of standard algorithms to solve mathematical problems is viewed as a cultural tool that both enables and constrains particular practices. As this student appropriated and mastered procedures for addition, subtraction, multiplication and division, she could solve problems that involved fairly straightforward computations or where she could easily model the action to determine an appropriate computation. At the same time, her use of these algorithms, along with other readily available tools, such as her fingers or multiplication tables, constrained her ability to reflect on the tens-structure of the number system, an effect that had serious consequences for her overall mathematical achievement. The results of this study suggest that even when not directly introduced, algorithms have such strong currency that they can mediate more reform-oriented instruction. 相似文献
196.
Ronald K. Russell Richard A. Rampulla Caroline E. van Nievelt Dieter H. Klaubert 《Journal of heterocyclic chemistry》1990,27(6):1761-1770
The synthesis of thieno[4,3,2-de] tricyclic compounds is described. The N-1 alkylation of I produced the alkanoic ester precursors. After hydrolysis, the corresponding carboxylic acids were cyclized to the title compounds II . This cyclization step was accomplished with 1:10 phosphorus pentoxide-methanesulfonic acid. The ketones II were further modified to introduce additional functionality onto this novel tricyclic ring system. 相似文献
197.
198.
Baker CD Fawcett J Insley CD Messenger DS Newland CL Overend HL Patel AB Shah M Vara B Virdee D Rawlings BJ 《Chemical communications (Cambridge, England)》2005,(14):1883-1885
6-Benzoyl-3,4-dihydro-(2H)-pyran will protect 1,2,3-triols such as glycerol as their corresponding spiro-[5-phenyl-3,6,8-trioxabicyclo[3.2.1]octane-4,2[prime or minute]-tetrahydropyran]s and 1,2,4-triols (less efficiently) as the corresponding trioxabicyclo[3.2.2]nonanes; the hexol mannitol is converted into the corresponding bis-protected product. 相似文献
199.
Bailey PJ Dick CM Fabre S Parsons S Yellowlees LJ 《Dalton transactions (Cambridge, England : 2003)》2006,(13):1602-1610
Treatment of dimethylmagnesium with the alpha-diimine ligands Ar'N=C(R)C(R)=NAr' [R = naphth-1,8-diyl (1), H (2), CH3 (3); Ar' = 2,6-diisopropylphenyl] in diethyl ether provides the neutral methyl-bridged dimeric complexes [(alpha-diimine-.)Mg+(mu-CH3)]2 via single electron transfer (SET) to the coordinated diimine and elimination of a methyl radical. These biradical species have been characterised by EPR spectroscopy and, for the ligand , X-ray crystallography. In the presence of THF the reaction of ligand proceeds to the diamagnetic [(ene-1,2-diamide)Mg(THF)3] complex in which the diimine ligand has been doubly reduced to an ene-diamide by two successive SET processes. Comparison of the structural data for the free ligand with that obtained for the alpha-diimine radical anion and ene-diamide complexes shows the expected increases in C-N, and decreases in C-C, bond lengths within the N-C-C-N unit consistent with the progressive reduction of the ligand. In the case of ligand , reaction at low temperature provides the complex [Mg(mu2-Me){Ar'NC(Me)2C(Me)NAr'}]2 in which methyl transfer to a ligand imine carbon atom has occurred. This species has also been structurally characterised. This contrasts with the formation of the radical species at room temperature, and indicates the involvement of an intermediate in which the radical products of the SET process are held in close proximity by the solvent cage. Two competing processes of methyl radical escape and methyl transfer to the ligand account for the formation of the observed products at different temperatures. 相似文献
200.
[reaction: see text] Phosphoramidites based on BINOL readily react with trimethylaluminum in "noncoordinating" solvents, leading to the corresponding aminophosphine which is the real ligand in copper-catalyzed asymmetric transformations. This artifact explains the experimental differences in the asymmetric ring opening of meso bicyclic hydrazines using dialkylzinc or trialkylaluminum reagents as nucleophiles. 相似文献