全文获取类型
收费全文 | 6001篇 |
免费 | 438篇 |
国内免费 | 15篇 |
专业分类
化学 | 4806篇 |
晶体学 | 36篇 |
力学 | 69篇 |
数学 | 697篇 |
物理学 | 846篇 |
出版年
2023年 | 57篇 |
2022年 | 62篇 |
2021年 | 107篇 |
2020年 | 197篇 |
2019年 | 187篇 |
2018年 | 77篇 |
2017年 | 98篇 |
2016年 | 266篇 |
2015年 | 251篇 |
2014年 | 300篇 |
2013年 | 326篇 |
2012年 | 466篇 |
2011年 | 498篇 |
2010年 | 289篇 |
2009年 | 240篇 |
2008年 | 373篇 |
2007年 | 352篇 |
2006年 | 319篇 |
2005年 | 258篇 |
2004年 | 243篇 |
2003年 | 199篇 |
2002年 | 193篇 |
2001年 | 107篇 |
2000年 | 85篇 |
1999年 | 75篇 |
1998年 | 69篇 |
1997年 | 79篇 |
1996年 | 66篇 |
1995年 | 73篇 |
1994年 | 87篇 |
1993年 | 51篇 |
1992年 | 48篇 |
1991年 | 43篇 |
1990年 | 33篇 |
1989年 | 44篇 |
1988年 | 27篇 |
1987年 | 24篇 |
1986年 | 17篇 |
1985年 | 11篇 |
1984年 | 13篇 |
1983年 | 8篇 |
1982年 | 9篇 |
1981年 | 15篇 |
1980年 | 19篇 |
1979年 | 12篇 |
1978年 | 16篇 |
1977年 | 13篇 |
1976年 | 7篇 |
1961年 | 10篇 |
1959年 | 9篇 |
排序方式: 共有6454条查询结果,搜索用时 15 毫秒
51.
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
52.
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
53.
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
54.
55.
56.
The tetraphosphides (tBu3Si)3P4M3 (M = Li, Na) and (tBu2PhSi)3P4Na3 have been synthesized in high yield from the reaction of 3 equivalents of the silanides tBu3SiM (M = Li, Na) and tBu2PhSiNa with P4 in benzene. (tBu3Si)3P4M3 (M = Li, Na) are transformed into the unsaturated triphosphides (tBu3Si)2P3M (M = Li, Na) and tBu3SiPM2 in tetrahydrofuran at ambient temperature. 相似文献
57.
Matthias Westerhausen Alexander N. Kneifel Peter Mayer Heinrich Nth 《无机化学与普通化学杂志》2004,630(12):2013-2021
Synthesis and Molekular Structures of N‐substituted Diethylgallium‐2‐pyridylmethylamides (2‐Pyridylmethyl)(tert‐butyldimethylsilyl)amine ( 1a ) and (2‐pyridylmethyl)‐di(tert‐butyl)silylamine ( 1b ) form with triethylgallane the corresponding red adducts 2a and 2b via an additional nitrogen‐gallium bond. These oily compounds decompose during distillation. Heating under reflux in toluene leads to the elimination of ethane and the formation of the red oils of [(2‐pyridylmethyl)(tert‐butyldimethylsilyl)amido]diethylgallane ( 3a ) and [(2‐pyridylmethyl)‐di(tert‐butyl)silylamido]diethylgallane ( 3b ). In order to investigate the thermal stability solvent‐free 3a is heated up to 400 °C. The elimination of ethane is observed again and the C‐C coupling product N, N′‐Bis(diethylgallyl)‐1, 2‐dipyridyl‐1, 2‐bis(tert‐butyldimethylsilyl)amido]ethan ( 4 ) is found in the residue. Substitution of the silyl substituents by another 2‐pyridylmethyl group and the reaction of this bis(2‐pyridylmethyl)amine with GaEt3 yield triethylgallane‐diethylgallium‐bis(2‐pyridylmethyl)amide ( 5 ). The metalation product adds immediately another equivalent of triethylgallane regardless of the stoichiometry. The reaction of GaEt3 with 2‐pyridylmethanol gives quantitatively colorless 2‐pyridylmethanolato diethylgallane ( 6 ). 相似文献
58.
In the presence of [Ru(terpyridine)(2,6‐pyridinedicarboxylate)], aliphatic and benzylic alcohols are oxidized to the corresponding aldehydes or ketones with high selectivity by using hydrogen peroxide as the oxidant. There is no need for the addition of co‐catalysts or organic solvents. By applying an optimized reaction protocol, high catalyst productivity (turnover number>10 000) and activity (turnover frequency up to 14 800 h?1) has been achieved. 相似文献
59.
Zusammenfassung Leitfähigkeitsmessungen an Et4NCl-Lösungen zeigen die Gültigkeit derBjerrumschen Theorie in PhPOCl2; die Dissoziationskonstante beträgt 1,5·10–2. FeCl3 verhält sich nicht wie eine Ionenverbindung, doch ähnlich wie in POCl3. Zur Verfolgung von Ionenreaktionen wurden konduktometrische Titrationen ausgeführt. ZnCl2 und AlCl3 geben 2 Chloridionen, BCl3, TiCl4, SnCl4 und PCl5 je 1 Chloridion an die Akzeptoren FeCl3 oder SbCl5, ab. In Gegenwart von polaren Chloriden nehmen BCl3, AlCl3, FeCl3, PCl5 und SbCl5 je 1 Chloridion, ZnCl2, TiCl4 und SnCl4 je nach Angebot 1 oder 2 Chloridionen auf. Sowohl die Chlorometallate, als auch die Chloroniumverbindungen sind im gleichen Ausmaß wie Et4NCl ionisiert.Mit 4 Abbildungen2. Mitt.:M. Baaz, V. Gutmann, M. Y. A. Talaat undT. S. West, Mh. Chem.92, 150 (1961).Herrn Prof. Dr.L. F. Audrieth zum 60. Geburtstag gewidmet. 相似文献
60.
Sabine Strohschein Matthias Pursch Heidrun Händel K. Albert 《Analytical and bioanalytical chemistry》1997,357(5):498-502
The separation of cis/trans isomers of β-carotene has been performed with a C30 stationary phase employing 1H NMR spectroscopy as an on-line detection technique. 1D as well as 2D NMR spectra have been recorded in the stopped-flow
mode for the predominant chromatographic peaks. Structural assignment of the five identified isomers was performed via comparison
of simulated 1D 1H NMR spectra on the basis of the structures of β-carotene cis/trans isomers with the experimental data, and also by the analysis of the proton-proton connectivities in the 2D NMR spectra of
three isomers with the highest concentration. The chromatographic retention behaviour of the isomers agreed well with previously
reported data. The advantage of the applied hyphenated coupling technique compared to conventional off-line techniques lies
in the fact that chromatographic separation and NMR detection are performed in a closed system, so that reisomerization of
the separated compounds is inhibited.
Received: 29 May 1996 / Revised: 1 July 1996 / Accepted: 4 July 1996 相似文献