全文获取类型
收费全文 | 2208篇 |
免费 | 83篇 |
国内免费 | 7篇 |
专业分类
化学 | 1616篇 |
晶体学 | 7篇 |
力学 | 51篇 |
数学 | 300篇 |
物理学 | 324篇 |
出版年
2023年 | 18篇 |
2022年 | 28篇 |
2021年 | 47篇 |
2020年 | 54篇 |
2019年 | 39篇 |
2018年 | 17篇 |
2017年 | 32篇 |
2016年 | 63篇 |
2015年 | 59篇 |
2014年 | 54篇 |
2013年 | 88篇 |
2012年 | 112篇 |
2011年 | 148篇 |
2010年 | 73篇 |
2009年 | 66篇 |
2008年 | 127篇 |
2007年 | 129篇 |
2006年 | 100篇 |
2005年 | 107篇 |
2004年 | 74篇 |
2003年 | 80篇 |
2002年 | 87篇 |
2001年 | 30篇 |
2000年 | 23篇 |
1999年 | 15篇 |
1998年 | 18篇 |
1997年 | 20篇 |
1996年 | 50篇 |
1995年 | 33篇 |
1994年 | 31篇 |
1993年 | 19篇 |
1992年 | 30篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 18篇 |
1987年 | 11篇 |
1986年 | 11篇 |
1985年 | 18篇 |
1984年 | 12篇 |
1983年 | 10篇 |
1982年 | 18篇 |
1981年 | 10篇 |
1980年 | 11篇 |
1979年 | 11篇 |
1977年 | 18篇 |
1976年 | 11篇 |
1974年 | 11篇 |
1973年 | 12篇 |
1967年 | 8篇 |
1884年 | 7篇 |
排序方式: 共有2298条查询结果,搜索用时 93 毫秒
41.
42.
43.
44.
45.
The X-ray structures of 4,10-di-tert-butyl-5,9-diisopropyl-4,5,9,10-tetraazatetracyclo[6.2.2.2(3,6)]tetradecane (s4iPr) and its 4,9-di-tert-butyl-5,10-diisopropyl isomer (a4iPr) are reported. Both compounds are in conformations having their in-N-alkyl groups (directed toward the central CH-CH bond of the molecule) anti to each other, as expected from previous work. The principal feature of interest is that one in-isopropyl group in each compound is in an eclipsed conformation, NN,C(alpha)Me twist angle -0.5(5) degrees for s4iPr and -6.4(4) degrees for a4iPr. Low energy (somewhat less) eclipsed in-isopropyl conformations are predicted by both molecular mechanics (MM2) and semiempirical quantum mechanical (AM1) calculations. The asymmetry of the potentially C(2) symmetric a4iPr because the two in-isopropyl groups are in different rotamers is apparently not a result of crystal packing forces, because a conformation with different isopropyl rotamers is the more stable one by at least 1.0 kcal/mol in solution, determined by (13)C-NMR spectroscopy. This result is not predicted by either calculation method. The "monomer", 2-tert-butyl-3-isopropyl-2,3-diazabicyclo[2.2.2]octane (3), proves to be a poor model for the conformations of 4iPr. 相似文献
46.
Garner DK Fitch SB McAlexander LH Bezold LM Arif AM Berreau LM 《Journal of the American Chemical Society》2002,124(34):9970-9971
The synthesis and properties of mononuclear zinc methoxide ([(ebnpa)Zn-OCH3]ClO4) (1) and hydroxide ([(ebnpa)Zn-OH]ClO4) (2) complexes of a new mixed nitrogen/sulfur ligand (ebnpa = N-2-(ethylthio)ethyl-N,N-bis(6-neopentylamino-2-pyridylmethyl)amine) are reported. The structures of 1 and 2 were determined by X-ray diffraction. Each possesses a single zinc-coordinated anion (methoxide or hydroxide) and exhibits an overall trigonal bipyramidal geometry. Structural and spectroscopic studies indicate the presence of two hydrogen-bonding interactions involving the oxygen atom of the zinc-bound anion in each complex. Treatment of [(ebnpa)Zn-OH]ClO4 with CH3OH results in the formation of an equilibrium mixture of 1 and 2. 1H NMR spectroscopic methods were used to examine the equilibrium as a function of temperature, yielding KMe (304 K) = 0.30(8), DeltaHMe = -0.9(1) kcal/mol, and DeltaSMe = -5(1) eu. The negative enthalpy indicates that spontaneous zinc alkoxide formation from a hydroxide precursor occurs in this system at low temperature. Using the experimentally determined DeltaHMe value, we found the homolytic Zn-O bond dissociation energy (BDE) in the Zn-OCH3 unit to be approximately -14 kcal/mol relative to the Zn-O BDE in the Zn-OH unit. 相似文献
47.
A monolithic C18-bonded silica rod column (Merck Chromolith) was compared to particle-based C18 and amide C16 sorbents in the HPLC separation of eight microcystins and nodularin-R. Two gradient mobile phases of aqueous trifluoroacetic acid modified with acetonitrile or methanol, different flow-rates and different gradient lengths were tested. The performance of the Chromolith column measured as the resolution of some microcystin pairs, the selectivity, efficiency (peak width) and peak asymmetry equalled, or exceeded, the performance of traditional particle-based columns. The Chromolith column allowed a shortening of the total analysis time to 4.3 min with a flow-rate 4 ml min(-1). 相似文献
48.
T. Bücherl M. Eschler A. Gruner N. Palibroda E. Wolff 《Journal of separation science》1994,17(11):765-769
An integral restrictor interface with jet separator for coupling capillary column supercritical fluid extraction – supercritical fluid chromatography with high resolution mass spectrometry (SFE-SFC-MS) has been built and used for the analysis of a fatty acid ester, and of polymer additives with a wide range of masses. The mobile phase used was supercritical carbon dioxide; a flame ionization detector (FID) was used in parallel with the mass spectrometer. Different SFC-MS interface operating conditions, e.g. temperature, restrictor position, flow rate, and sample transfer conditions were optimized to obtain good sensitivity and separation for these applications. In addition, the sensitivity of measurements performed with the direct insertion probe and by SFC-MS interface have been compared. 相似文献
49.
Jaan A. Pesti Jill A. Downard Mark D. Lauritsen Goss S. Kauffman Walter M. Bryant George F. Huhn John F. Arnett Robert E. Yule James Segretario Kimberly A. Nelson Edward F. Gorko Gary O. Page Lisa M. Lloyd Richard E. Olson Christopher S. Bamum Joseph J. Mrowca 《Journal of heterocyclic chemistry》1998,35(1):249-255
The methanesulfonates of (α-(4-chlorophenyl)-α-[1-(2-chlorophenyl)ethenyl]-1H-1,2,4-triazole-1-ethanol and α-[1-(2-chlorophenyl)ethenyl]-α-(2,4-difluorophenyl)-1H-1,2,4-triazole-1-ethanol ( 1a, b ) are orally effective α-styryl carbinol derivatives developed for the treatment and prevention of systemic fungal infections. Practical new processes amenable for the large-scale production of these compounds are described. Of note is the selection of dichlorostyrene as a convenient precursor of the styryl portion, modification of a sensitive Grignard addition into a realistic preparative reaction and the use of 1,2,4-triazole simultaneously as a base transfer agent and nucleophile. 相似文献
50.
Binary polymer brushes grafted to Si wafers were prepared from hydrophilic and hydrophobic polymer components, which allow switching the surface properties (as revealed by contact angles) by exposure to varying solvents. The hydrophilic component was poly-2-vinylpyridine; the hydrophobic component was a copolymer of styrene and 2-(4-vinylphenyl)indene containing the photodimerizable phenylindene chromophore. The brushes were prepared via thermal and via photochemical grafting-to methods, which led to distinct layer thicknesses. Structural patterns differing in surface properties were produced and fixed via crosslinking the hydrophobic component by 2pi+2pi photodimerization of phenylindene moieties. The patterns were visually observable. 相似文献