全文获取类型
收费全文 | 3612篇 |
免费 | 96篇 |
国内免费 | 22篇 |
专业分类
化学 | 2594篇 |
晶体学 | 30篇 |
力学 | 94篇 |
数学 | 486篇 |
物理学 | 526篇 |
出版年
2022年 | 18篇 |
2021年 | 27篇 |
2020年 | 33篇 |
2019年 | 37篇 |
2018年 | 28篇 |
2017年 | 30篇 |
2016年 | 64篇 |
2015年 | 57篇 |
2014年 | 62篇 |
2013年 | 185篇 |
2012年 | 175篇 |
2011年 | 216篇 |
2010年 | 103篇 |
2009年 | 82篇 |
2008年 | 211篇 |
2007年 | 216篇 |
2006年 | 191篇 |
2005年 | 179篇 |
2004年 | 184篇 |
2003年 | 144篇 |
2002年 | 136篇 |
2001年 | 39篇 |
2000年 | 36篇 |
1999年 | 37篇 |
1998年 | 39篇 |
1997年 | 45篇 |
1996年 | 57篇 |
1995年 | 52篇 |
1994年 | 54篇 |
1993年 | 42篇 |
1992年 | 34篇 |
1991年 | 34篇 |
1990年 | 43篇 |
1989年 | 34篇 |
1988年 | 45篇 |
1987年 | 45篇 |
1986年 | 41篇 |
1985年 | 76篇 |
1984年 | 54篇 |
1983年 | 54篇 |
1982年 | 66篇 |
1981年 | 56篇 |
1980年 | 61篇 |
1979年 | 41篇 |
1978年 | 36篇 |
1977年 | 40篇 |
1976年 | 25篇 |
1975年 | 27篇 |
1974年 | 34篇 |
1973年 | 32篇 |
排序方式: 共有3730条查询结果,搜索用时 10 毫秒
81.
Aihara H Alston-Garnjost M Bakken JA Barbaro-Galtieri A Barnes AV Barnett BA Bengtsson H Blumenfeld BJ Bross AD Buchanan CD Chamberlain O Chien C Clark AR Cordier A Dahl OI Day CT Derby KA Eberhard PH Fancher DL Fujii H Fujii T Gabioud B Gary JW Gorn W Hadley NJ Hauptman JM Hofmann W Huth JE Hylen J Kamae T Kaye HS Kenney RW Kerth LT Koda RI Kofler RR Kwong KK Layter JG Lindsey CS Loken SC Lu X Lynch GR Madansky L Madaras RJ Maruyama K Marx JN Matthews JA Melnikoff SO Moses W Nemethy P 《Physical review letters》1985,54(4):270-273
82.
Rick Gussio Sovitj Pou Jih-Hsiang Chen Gary W. Smythers 《Journal of computer-aided molecular design》1992,6(2):149-158
Summary Thirteen 4,5-epoxymorphinan agonists with established analgesic action were docked into an Asp-Lys-His-Phe pseudoreceptor complex under a range of distance-dependent dielectric conditions. The number of compounds with potential energies of the docked complexes that agreed in rank order with corresponding analgesic potencies was determined for each condition. Two dielectric conditions, n-decane (1.991) and ethanol (24.3), enabled the greatest number of compounds to relate to their pseudoreceptors with each having 9 and 8 successes respectively. Both of these conditions demonstrated unique influences on the types of structures that were successfully docked. For example, the morphine stereoisomer -isomorphine, the geometric isomer B/C trans-morphine, and the 8-position-substituted -isomorphine were successes in the n-decane condition, whereas the ethanol condition produced the substituted codeine derivatives dihydroco-deinone and dihydroxycodeinone. These findings emphasize the importance of dielectric influence when developing force-field modeled quantitative structure-activity relationships for a closely related homologous series. 相似文献
83.
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
84.
Gary M. Coppola 《Journal of heterocyclic chemistry》1979,16(5):897-901
Novel fused tricyclic phosphorus heterocycles 9 and 11 and the tetracycle 15 were synthesized by cyclization of 1-haloalkyl (or 3-haloalkyl)-2,3-dihydro-1,3,2-benzodiazaphosphorin-4(1H)one 2-oxides with sodium hydride. Some spectral data of the products are also discussed. 相似文献
85.
86.
Barnes JH Schilling GD Stone SF Sperline RP Denton MB Young ET Barinaga CJ Koppenaal DW Hieftje GM 《Analytical and bioanalytical chemistry》2004,380(2):227-234
The use of a separation step, such as liquid chromatography, prior to inductively coupled plasma mass spectrometry (ICP–MS) has become a common tool for highly selective and sensitive analyses. This type of coupling has several benefits including the ability to perform speciation analysis or to remove isobaric interferences. Several limitations of conventional instruments result from the necessity to scan or pulse the mass spectrometer to obtain a complete mass spectrum. When the instrument is operated in such a non-continuous manner, duty cycle is reduced, resulting in poorer absolute limits of detection. Additionally, with scanning instruments, spectral skew can be introduced into the measurement, limiting quantitation accuracy. To address these shortcomings, a high-performance liquid chromatograph has been coupled to an ICP–MS capable of continuous sample introduction and simultaneous multimass detection. These features have been realized with a novel detector array, the focal plane camera. Instrument performance has been tested for both speciation analysis and for the elimination of isobaric interferences. Absolute limits of detection in the sub picogram to tens of picograms regime are obtainable, while the added mass dimension introduced by simultaneous detection dramatically increases chromatographic peak capacity. 相似文献
87.
Dombrowski GW Dinnocenzo JP Zielinski PA Farid S Wosinska ZM Gould IR 《The Journal of organic chemistry》2005,70(10):3791-3800
[reaction: see text] Deprotonation of the radical cations of aromatic amines, such as anilines, generally occurs much more slowly than other fragmentation reactions. Here we report a stereoelectronic effect involving twisting of the anilino group out of the plane of the benzene ring that results in a significantly increased rate of reactivity toward deprotonation. Quantitative studies of the rate constants for deprotonation as a function of aniline radical cation pKa (Br?nsted plots) demonstrate that the effect is not simply due to a change in the reaction thermodynamics. By combining this stereoelectronic effect with covalent attachment of carboxylate as a base, aniline radical cations that undergo unimolecular deprotonation with rate constants as high as 10(8) s(-1), even in unfavorable protic media, are described. 相似文献
88.
Antoine R Broyer M Dugourd P Breaux G Hagemeister FC Pippen D Hudgins RR Jarrold MF 《Journal of the American Chemical Society》2003,125(30):8996-8997
Molecular beam electric deflection measurements have been used to determine electric susceptibilities for small unsolvated alanine-based peptides. The electric susceptibility provides information about the charge distribution within the peptide and can be used to distinguish between zwitterionic and canonical forms. Measured electric susceptibilities for WAn peptides (n = 1-5) are similar to those for capped Ac-WAn-NH2 peptides (which cannot form zwitterions). Susceptibilities calculated using a simulated tempering-based approach are substantially larger for the zwitterionic form than for the canonical form. The measured susceptibilities are in good agreement with those calculated for the canonical form. For the larger peptides, the lowest potential energy structure found in the simulations is hairpin-like, while the lowest free energy structure found at room temperature is extended. The zwitterionic form is constrained by intramolecular interactions which make it entropically unfavorable. 相似文献
89.
N,N'-Dimethylthiourea and 3,4,5,6-tetrahydro-2-pyrimidinethiol were allowed to react with 2-chloro-nicotinonitrile ( 1 ) and their products investigated by standard methods and by carbon-13 nmr. In both instances, displacement of the chlorine occurred by nitrogen not the sulfur of the thioureas. Secondary cyclizations occurred by attack of nitrogen on the nitrile to furnish 3a , and by sulfur on the nitrile to give 4b , a new ring system. Tricyclic 4b was hydrolyzed in dilute acid to give 5 , or alkylated with methyl iodide in the presence of sodium hydride to give the ring opened product 6 . 相似文献
90.
Gary Paul Rabold 《Journal of polymer science. Part A, Polymer chemistry》1969,7(5):1187-1201
The interaction of sodium dodecyl sulfate (NaDS) with styrene—butadiene latexes was investigated by application of the recently developed spin-probe technique. It is possible by this method to detect the presence of micelles in a latex reasonably quantitatively. The effective surface area occupied per molecule of soap was calculated to be 53 Å2. Differences in purity can readily be detected for several NaDS samples. The less pure samples show a lower critical micelle concentration (CMC) and a significantly more ordered micelle structure. The addition of hexane to NaDS solutions above the CMC leads to a greater immobilization of the spin probe. This is interpreted as reflecting a tighter packing of the soap molecules. The addition of ethanol, acetic acid, and acrylic acid leads to a looser association of the probe with the micelles. The micelles catalyze the decomposition of the nitroxide probe in the presence of organic acids. The aggregation of sodium deoxycholate was also conveniently followed by the spin-probe method. 相似文献