全文获取类型
收费全文 | 2584篇 |
免费 | 67篇 |
国内免费 | 18篇 |
专业分类
化学 | 1717篇 |
晶体学 | 31篇 |
力学 | 97篇 |
数学 | 413篇 |
物理学 | 411篇 |
出版年
2022年 | 14篇 |
2021年 | 21篇 |
2020年 | 26篇 |
2019年 | 22篇 |
2018年 | 19篇 |
2017年 | 16篇 |
2016年 | 55篇 |
2015年 | 52篇 |
2014年 | 47篇 |
2013年 | 103篇 |
2012年 | 146篇 |
2011年 | 178篇 |
2010年 | 90篇 |
2009年 | 74篇 |
2008年 | 149篇 |
2007年 | 149篇 |
2006年 | 127篇 |
2005年 | 126篇 |
2004年 | 113篇 |
2003年 | 96篇 |
2002年 | 102篇 |
2001年 | 62篇 |
2000年 | 42篇 |
1999年 | 33篇 |
1998年 | 29篇 |
1997年 | 15篇 |
1996年 | 36篇 |
1995年 | 26篇 |
1994年 | 28篇 |
1993年 | 25篇 |
1992年 | 28篇 |
1991年 | 34篇 |
1990年 | 29篇 |
1989年 | 37篇 |
1988年 | 23篇 |
1987年 | 14篇 |
1986年 | 23篇 |
1985年 | 28篇 |
1984年 | 36篇 |
1983年 | 31篇 |
1982年 | 41篇 |
1981年 | 33篇 |
1980年 | 29篇 |
1979年 | 17篇 |
1978年 | 21篇 |
1977年 | 21篇 |
1976年 | 25篇 |
1975年 | 31篇 |
1974年 | 15篇 |
1973年 | 22篇 |
排序方式: 共有2669条查询结果,搜索用时 62 毫秒
71.
The thermal properties of two polymorphs of the drug carbamazepine, Forms I and III, were studied using high-speed differential scanning calorimetry (DSC). Previously, accurate determination of the heat enthalpy of fusion of Form III has not been possible using DSC at typical heating rates, due to concurrent exothermic recrystallisation to the higher-melting Form I. Here, it is demonstrated that heating rates of 250° C/min altered the kinetics of the melting transition of Form III such that this concurrent exothermic recrystallisation was inhibited. This allowed direct measurement of the enthalpy of the melting endotherm for Form III from a single transition. The enthalpy of this transition was found to be 109.5 J/g. Further investigations were then performed to test the utility of this technique in quantifying relative amounts of Forms I and III in mixtures of the two polymorphs. It was demonstrated that a limit of detection of 1% (w/w) was possible in this system. However, accurate quantification was not possible due to seeding effects initiating recrystallisation to Form I in these mixtures, even at these elevated heating rates. The utility of this novel technique as a fast analytical tool for studying the polymorphic behaviour of metastable polymorphs has been successfully demonstrated. 相似文献
72.
Application of the kinetic method based on the dissociation of transition metal centered cluster ions is extended from chiral analysis (Tao, W. A.; Zhang, D.; Nikolaev, E. N.; Cooks, R. G. J. Am. Chem. Soc. 2000, 122, 10598) to quantitative analysis of isomeric mixtures, including those with Leu/Ile substitutions. Copper(II)-bound complexes of pairs of peptide isomers are generated by electrospray ionization mass spectrometry and the trimeric complex [CuII(ref)2(A) - H]+ (analyte A, a mixture of isomeric peptides; reference compound ref, usually a peptide) is caused to undergo collisional dissociation. Competitive loss of the neutral reference compound or the neutral analyte yields two ionic products and the ratio of rates of the two competitive dissociations, viz. the product ion branching ratio R is shown to depend strongly on the regiochemistry of the analyte in the precursor [CuII(A)(ref)2 - H]+ complex ion. Calibration curves are constructed by relating the branching ratio measured by the kinetic method, to the isomeric composition of the mixture to allow rapid quantitative isomer analysis. 相似文献
73.
Ion/molecule reactions were explored in a newly developed miniature mass spectrometer fitted with a rectilinear ion trap (RIT) mass analyzer. The tandem mass spectrometry performance of this instrument is demonstrated using collision induced dissociation (CID) and ion/molecule reactions. The latter includes Eberlin transacetalization reactions and electrophilic additions. Selective detection of the chemical warfare simulant dimethyl methyl phosphonate (DMMP) was achieved through selective Eberlin reactions of its characteristic phosphonium fragment ion CH3OP(+)(O)CH3 (m/z 93), with 1,4-dioxane or 1,3-dioxolane. Efficient adduct formation as a result of electrophilic attack by the phosphonium ion on various nucleophilic reagents, including 1,1,3,3-tetramethyl urea, methanesulfonic acid methyl ester, dimethyl sulfoxide and methyl salicylate, was also observed using the RIT device. The product ions of these reactions were analyzed using CID and the characteristic fragmentation patterns of the ionic addition products were recorded using multiple-stage experiments in the miniature RIT instrument. This study clearly demonstrates that a small, home-built, miniature RIT mass spectrometer can be used to perform analytically useful ion/molecule reactions and also that instruments like this have the potential to provide a portable platform for in situ detection of organophosphorus esters and related compounds with high specificity using tandem mass spectrometry. 相似文献
74.
Apparent pK values of the wine pigment, 5-carboxypyranomalvidin-3-glucoside (vitisin A), were determined using UV-vis spectroscopy, viz. pKa1=0.98 (±0.10), pKH1=4.51 (±0.03) and pKH2=7.57 (±0.02). An additional ionisation constant at high pH (pKa4=8.84±0.06) was established by high-voltage paper electrophoresis. These data in conjunction with previously published pKa values determined by high-voltage electrophoresis suggest that in wine (pH 3.2-3.8), 5-carboxypyranomalvidin-3-glucoside exists as a complex mixture of hydrated and non-hydrated, partially ionised species with the predominant species being the quinonoidal base (λmax 498 nm). 相似文献
75.
Hanna C. Wentz Grigorii Skorupskii Ana B. Bonfim Jenna L. Mancuso Christopher H. Hendon Evan H. Oriel Graham T. Sazama Michael G. Campbell 《Chemical science》2020,11(5):1342
Redox-active metal–organic frameworks (MOFs) are promising materials for a number of next-generation technologies, and recent work has shown that redox manipulation can dramatically enhance electrical conductivity in MOFs. However, ligand-based strategies for controlling conductivity remain under-developed, particularly those that make use of reversible redox processes. Here we report the first use of ligand n-doping to engender electrical conductivity in a porous 3D MOF, leading to tunable conductivity values that span over six orders of magnitude. Moreover, this work represents the first example of redox switching leading to reversible conductivity changes in a 3D MOF.Redox-active ligands are used to reversibly tune electrical conductivity in a porous 3D metal–organic framework (MOF). 相似文献
76.
Assembly of well-aligned multiwalled carbon nanotubes in confined polyacrylonitrile environments: electrospun composite nanofiber sheets 总被引:5,自引:0,他引:5
Ge JJ Hou H Li Q Graham MJ Greiner A Reneker DH Harris FW Cheng SZ 《Journal of the American Chemical Society》2004,126(48):15754-15761
Highly oriented, large area continuous composite nanofiber sheets made from surface-oxidized multiwalled carbon nanotubes (MWNTs) and polyacrylonitrile (PAN) were successfully developed using electrospinning. The preferred orientation of surface-oxidized MWNTs along the fiber axis was determined with transmission electron microscopy and electron diffraction. The surface morphology and height profile of the composite nanofibers were also investigated using an atomic force microscope in tapping mode. For the first time, it was observed that the orientation of the carbon nanotubes within the nanofibers was much higher than that of the PAN polymer crystal matrix as detected by two-dimensional wide-angle X-ray diffraction experiments. This suggests that not only surface tension and jet elongation but also the slow relaxation of the carbon nanotubes in the nanofibers are determining factors in the orientation of carbon nanotubes. The extensive fine absorption structure detected via UV/vis spectroscopy indicated that charge-transfer complexes formed between the surface-oxidized nanotubes and negatively charged (-CN[triple bond]N:) functional groups in PAN during electrospinning, leading to a strong interfacial bonding between the nanotubes and surrounding polymer chains. As a result of the highly anisotropic orientation and the formation of complexes, the composite nanofiber sheets possessed enhanced electrical conductivity, mechanical properties, thermal deformation temperature, thermal stability, and dimensional stability. The electrical conductivity of the PAN/MWNT composite nanofibers containing 20 wt % nanotubes was enhanced to approximately 1 S/cm. The tensile modulus values of the compressed composite nanofiber sheets were improved significantly to 10.9 and 14.5 GPa along the fiber winding direction at the MWNT loading of 10 and 20 wt %, respectively. The thermal deformation temperature increased with increased MWNT loading. The thermal expansion coefficient of the composite nanofiber sheets was also reduced by more than an order of magnitude to 13 x 10(-6)/ degrees C along the axis of aligned nanofibers containing 20 wt % MWNTs. 相似文献
77.
Paul L. Coe Simon E. Sellers J.Colin Tatlow Graham Whittaker 《Journal of fluorine chemistry》1980,16(6):612
As part of a programme to prepare and evaluate a series of perfluoro- chemicals for use as inert fluids, the fluorinations of some tetrafluoroethylene oligomers over cobalt (III) fluoride have been studied.Fluorination of perfluoro-3,4-dimethylhex-3-ene (tetramer) and perfluoro-4-ethyl-3,4-dimethylhex-2-ene (pentamer) over CoF3 at 230°C and l45°C respectively afforded the corresponding saturated fluorocarbons however, at 250°C, pentamer gave predominantly the saturated tetramer. The thermal behaviour of these saturated fluorocarbons alone and in the presence of bromine and toluene has been studied.Pyrolysis of pentamer over glass beads at 500°C gave perfluoro-1,2,3- trimethylcyclobutene and isomers of perfluoro-2,3-dimethylpenta-1,3- diene. Under similar conditions perfluoro-2-(1-ethyl-1-methylpropyl). 3-methylpent-1-ene (hexamer) gave perfluoro-1-methyl-2-(1-methyl- propyl)-cyclobut-1-ene and perfluoro-2-methyl-3-(1-methylpropyl)-buta- 1,3-diene.These reactions and the structural elucidation of the products will be discussed. 相似文献
78.
Robert Graham 《Zeitschrift für Physik B Condensed Matter》1977,26(3):281-290
A method is given for the derivation of a path integral representation of the Green's function solutionP of equationsP/t=L
P,L being some Liouville operator. The method is applied to general diffusion processes.Feynman's path integral representation of the Schrödinger equation and Stratonovich's path integral representation of multivariate Markovian processes are obtained as special cases if the metric of the general diffusion process is flat. For curved phase spaces our result is a nontrivial generalization and new. New applications e.g. to quantized motion in general relativity, to transport processes in inhomogeneous systems, or to nonlinear non-equilibrium thermodynamics are made possible. We expect applications to be fruitfull in all cases where (continuous) macroscopic transport processes in Riemann geometries have to be considered. 相似文献
79.
80.
Shengfei Jin Hang T. Dang Graham C. Haug Viet D. Nguyen Hadi D. Arman Oleg V. Larionov 《Chemical science》2020,11(34):9101
Construction of C–C bonds at the α-carbon is a challenging but synthetically indispensable approach to α-branched carbonyl motifs that are widely represented among drugs, natural products, and synthetic intermediates. Here, we describe a simple approach to generation of boron enolates in the absence of strong bases that allows for introduction of both α-alkyl and α-aryl groups in a reaction of readily accessible 1,2-dicarbonyls and organoboranes. Obviation of unselective, strongly basic and nucleophilic reagents permits carrying out the reaction in the presence of electrophiles that intercept the intermediate boron enolates, resulting in two new α-C–C bonds in a tricomponent process.α-Branched carboxylic acids and other carbonyls are readily accessed by a metal- and base-free deoxygenative α-alkylation and α-arylation of 1,2-dicarbonyls via boron enolates, resulting in a tricomponent coupling with unconventional electrophiles. 相似文献