全文获取类型
收费全文 | 7901篇 |
免费 | 494篇 |
国内免费 | 25篇 |
专业分类
化学 | 5814篇 |
晶体学 | 71篇 |
力学 | 104篇 |
数学 | 901篇 |
物理学 | 1530篇 |
出版年
2023年 | 61篇 |
2022年 | 71篇 |
2021年 | 117篇 |
2020年 | 212篇 |
2019年 | 214篇 |
2018年 | 82篇 |
2017年 | 111篇 |
2016年 | 306篇 |
2015年 | 292篇 |
2014年 | 330篇 |
2013年 | 381篇 |
2012年 | 534篇 |
2011年 | 576篇 |
2010年 | 325篇 |
2009年 | 292篇 |
2008年 | 446篇 |
2007年 | 431篇 |
2006年 | 378篇 |
2005年 | 321篇 |
2004年 | 315篇 |
2003年 | 233篇 |
2002年 | 261篇 |
2001年 | 147篇 |
2000年 | 124篇 |
1999年 | 107篇 |
1998年 | 97篇 |
1997年 | 114篇 |
1996年 | 103篇 |
1995年 | 103篇 |
1994年 | 126篇 |
1993年 | 82篇 |
1992年 | 72篇 |
1991年 | 77篇 |
1990年 | 69篇 |
1989年 | 62篇 |
1988年 | 71篇 |
1987年 | 69篇 |
1986年 | 36篇 |
1985年 | 50篇 |
1984年 | 42篇 |
1983年 | 38篇 |
1982年 | 34篇 |
1981年 | 53篇 |
1980年 | 48篇 |
1979年 | 39篇 |
1978年 | 38篇 |
1977年 | 27篇 |
1976年 | 27篇 |
1975年 | 22篇 |
1974年 | 17篇 |
排序方式: 共有8420条查询结果,搜索用时 15 毫秒
71.
Summary The capillary gas chromatographic retention behavior of -pinene and tricyclene has been investigated on stationary phases of different polarities. On all but one of the columns employed, tricyclene eluted before -pinene; only permethylated -cyclodextrins dissolved in moderately polar polisiloxanes gave a reversed elution order. The intermolecular interactions which caused the unexpected retention behavior were investigated in detail, applying methods of computer simulation. To achieve this, we have developed a calculation algorithm on the basis of molecular mechanical optimizations and programmed it in a macro. This makes it possible to systematically investigate a given configuration space in which all the possible interactions can take place. It was shown that permethylated -cyclodextrin as host molecule for both guest molecules offers an optimum cavity size. As a result the number of energetically favorable contacts between host and guest molecules as well as the strength of the interactions in this stationary phase were larger. As a consequence the elution order, normally only influenced by the vapor pressure of the compounds at a given temperature, was changed. Nonspecific interactions played an especially important role for these kinds of substances. 相似文献
72.
Summary The application of capillary SFC for SIMDIST investigations of paraffins and waxes is reported. Pressure, density and temperature of the mobile phase are optimized to obtain high chromatographic resolution of complex mixtures of industrial products. Isothermal linear pressure programming and asymptotic pressure and density programming are used in the range from 15 to 35 MPa in the isothermic mode above 100°C. SFC chromatograms of natural and synthetic paraffins, microcrystalline wax and candle wax are compared. The retention behaviour of paraffin mixtures and waxes has been investigated on methyl/phenyl and biphenyl capillary columns. The polarity of the stationary phases influences the absolute retention time more than it influences the chromatographic resolution. 相似文献
73.
The equilibrium phase behavior of a binary mixture of charged colloids and neutral, nonadsorbing polymers is studied within free-volume theory. A model mixture of charged hard-sphere macroions and ideal, coarse-grained, effective-sphere polymers is mapped first onto a binary hard-sphere mixture with nonadditive diameters and then onto an effective Asakura-Oosawa model [S. Asakura and F. Oosawa, J. Chem. Phys. 22, 1255 (1954)]. The effective model is defined by a single dimensionless parameter-the ratio of the polymer diameter to the effective colloid diameter. For high salt-to-counterion concentration ratios, a free-volume approximation for the free energy is used to compute the fluid phase diagram, which describes demixing into colloid-rich (liquid) and colloid-poor (vapor) phases. Increasing the range of electrostatic interactions shifts the demixing binodal toward higher polymer concentration, stabilizing the mixture. The enhanced stability is attributed to a weakening of polymer depletion-induced attraction between electrostatically repelling macroions. Comparison with predictions of density-functional theory reveals a corresponding increase in the liquid-vapor interfacial tension. The predicted trends in phase stability are consistent with observed behavior of protein-polysaccharide mixtures in food colloids. 相似文献
74.
Trace analysis of rapamycin in human blood by micellar electrokinetic chromatography 总被引:1,自引:0,他引:1
A capillary electrophoretic method with UV detection at 278 nm has been developed for analysis of the immunosuppressant rapamycin (sirolimus) in human blood at low microgram per liter levels. Separation has been achieved in an acidic carrier electrolyte containing sodium dodecylsulfate and 30% (v/v) acetonitrile. For sample clean-up and preconcentration, an off-line solid-phase extraction step using a silica-based reversed-phase material and an on-capillary focussing technique were employed. The latter allows the injection of increased sample volumes without excessive band broadening. Although this new method is less sensitive than existing liquid chromatographic procedures combined with mass spectrometry, it is fully suited to routine analysis of rapamycin in blood from patients treated with this drug. Last but not least the low costs make it an attractive alternative to established methods. 相似文献
75.
Horn M Ihringer J Glink PT Stoddart JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4046-4054
A template-directed dynamic clipping procedure has generated a library of nine [2]rotaxanes that have been formed from three dialkylammonium salts-acting as the dumbbell-shaped components-and three dynamic, imino bond-containing, [24]crown-8-like macrocycles-acting as the ring-shaped components-which are themselves assembled from three dialdehydes and one diamine. The rates of formation of these [2]rotaxanes differ dramatically, from minutes to days depending on the choice of dialkylammonium ion and dialdehyde, as do their thermodynamic stabilities. Generally, [2]rotaxanes formed by using 2,6-diformylpyridine as the dialdehyde component, or bis(3,5-bis(trifluoromethyl)benzyl)ammonium hexafluorophosphate as the dumbbell-shaped component, assembled the most rapidly. Those rotaxanes containing this particular electron-deficient dumbbell-shaped unit, or 2,5-diformylfuran units in the macroring, were the most stable thermodynamically. The relative thermodynamic stabilities of all nine of the [2]rotaxanes were determined by competition experiments that were monitored by (1)H NMR spectroscopy. 相似文献
76.
A. Weisz E. Iberkleid A. Mandelbaum W. Blum W. J. Richter 《Journal of mass spectrometry : JMS》1987,22(1):3-5
Low energy CID mass spectra of m/z 173, C8H13O4+, obtained from the diethyl ester of cis,syn,cis-l,2,3,3a,4,5,5a,6,7,8-decahydroindacene-4,5-dicarboxylic acid and cis,syn,cis-l,2,3,4,5,6,7,8,8a,9,10,10a-dodecahydrophenanthrene-9,10-dicarboxylic acid indicate they have the structure of protonated diethyl maleate. This finding together with previous deuterium labelling results suggest that the formation of this ion from both precursors takes place by migration of a hydrogen atom from an allylic δ-position followed by the concerted cleavage of two allylic C? C bonds in analogy to the ground state retro-Diels–Alder fragmentation. 相似文献
77.
78.
Klein SR Himel TM Abrams G Amidei D Baden AR Barklow T Boyarski AM Boyer J Burchat PR Burke DL Butler F Dorfan JM Feldman GJ Gidal G Gladney L Gold MS Goldhaber G Golding L Haggerty J Hanson G Hayes K Herrup D Hollebeek RJ Innes WR Jaros JA Juricic I Kadyk JA Karlen D Lankford AJ Larsen RR LeClaire BW Levi M Lockyer NS Lüth V Matteuzzi C Nelson ME Ong RA Perl ML Petersen A Richter B Riles K Rowson PC Schaad T Schellman H Schmidke WB Sheldon PD Trilling GH de la Vaissiere C Wood DR Yelton JM 《Physical review letters》1987,58(7):644-647
79.
The phase-conjugate reflectivity obtainable by degenerate four-wave mixing in silicon at a 1.06 m is calculated including free-carrier absorption. A maximum reflectivity of more than 100% is possible. The dependence of the reflectivity on the signal and pump energy densities up to 70 mJ/cm2 is measured and found to agree with theory. The wave-front-correction property of DFWM is demonstrated with a lens in the signal beam. 相似文献
80.
Gidal G Boyer J Butler F Cords D Abrams GS Amidei D Baden AR Barklow T Boyarski AM Burchat P Burke DL Dorfan JM Feldman GJ Gladney L Gold MS Goldhaber G Golding LJ Haggerty J Hanson G Hayes K Herrup D Hollebeek RJ Innes WR Jaros JA Juricic I Kadyk JA Karlen D Klein SR Lankford AJ Larsen RR LeClaire BW Levi ME Lockyer NS Lüth V Matteuzzi C Nelson ME Ong RA Perl ML Richter B Riles K Rowson PC Schaad T Schellman H Schmidke WB Sheldon PD Trilling GH de la Vaissière C Wood DR Yelton JM Zaiser C 《Physical review letters》1987,59(18):2016-2019