全文获取类型
收费全文 | 3401篇 |
免费 | 86篇 |
国内免费 | 7篇 |
专业分类
化学 | 2334篇 |
晶体学 | 42篇 |
力学 | 68篇 |
数学 | 356篇 |
物理学 | 694篇 |
出版年
2022年 | 18篇 |
2021年 | 37篇 |
2020年 | 50篇 |
2019年 | 40篇 |
2018年 | 26篇 |
2017年 | 27篇 |
2016年 | 47篇 |
2015年 | 52篇 |
2014年 | 71篇 |
2013年 | 163篇 |
2012年 | 148篇 |
2011年 | 201篇 |
2010年 | 119篇 |
2009年 | 83篇 |
2008年 | 181篇 |
2007年 | 199篇 |
2006年 | 196篇 |
2005年 | 194篇 |
2004年 | 177篇 |
2003年 | 134篇 |
2002年 | 131篇 |
2001年 | 62篇 |
2000年 | 47篇 |
1999年 | 37篇 |
1998年 | 35篇 |
1997年 | 43篇 |
1996年 | 41篇 |
1995年 | 39篇 |
1994年 | 52篇 |
1993年 | 58篇 |
1992年 | 33篇 |
1991年 | 41篇 |
1990年 | 37篇 |
1989年 | 29篇 |
1988年 | 30篇 |
1987年 | 21篇 |
1986年 | 23篇 |
1985年 | 31篇 |
1984年 | 46篇 |
1983年 | 29篇 |
1982年 | 49篇 |
1981年 | 37篇 |
1980年 | 29篇 |
1979年 | 35篇 |
1978年 | 36篇 |
1977年 | 29篇 |
1976年 | 38篇 |
1975年 | 28篇 |
1974年 | 30篇 |
1973年 | 23篇 |
排序方式: 共有3494条查询结果,搜索用时 328 毫秒
51.
The calculation of non-paired spatial orbitals and alternant molecular orbital wavefunctions for the benzyl radical is described. The NPSO and AMO methods give comparable energy lowerings which indicate that they make substantial allowance for electron correlation. The calculated spin densities are not in very good accord with experiment and it is thought that this reflects inadequacies in the integral approximations used. 相似文献
52.
Two approaches for performing competitive binding immunoassays by HPLC and other flow-based systems are the simultaneous and sequential injection methods. Both these techniques make use of a column with a limited amount of antibody, onto which is injected a sample and a fixed amount of a labeled analyte analog. An indirect measure of the unlabeled analyte in the sample is then obtained by looking at the amount of analog in either the nonretained or retained peaks. In the simultaneous injection mode, the sample and labeled analog are applied at the same time to the column, while in the sequential mode the sample is injected first, followed by the analog. This results in a difference in the analytical characteristics of these two approaches. This study used chromatographic theory and previous data obtained for injections of human serum albumin (HSA) onto an anti-HSA antibody column to compare the response, detection limits, range, and sensitivity of these methods. Under equivalent conditions, it was found that the sequential method always provided the best lower limit of detection and sensitivity. However, the simultaneous mode had a broader dynamic range and higher upper limit of detection. From these observations, several guidelines were developed regarding the use and selection of such assays for new applications. 相似文献
53.
Bashall A Bond AD Doyle EL García F Kidd S Lawson GT Parry MC McPartlin M Woods AD Wright DS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(15):3377-3385
Amination of [ClP(micro-NtBu)](2) (1) using NH(3) in THF gives the cyclophospha(III)zane dimer [H(2)NP(micro-NtBu)](2) (2), in good yield. (31)P NMR spectroscopic studies of the reaction of 1 with 2 in THF/Et(3)N show that almost quantitative formation of the cyclic tetramer [[P(micro-NtBu)](2)(micro-NH)](4) (3) occurs. The remarkable selectivity of this reaction can (in part) be attributed to pre-organisation of 1 and 2, which prefer cis arrangements in the solid state and solution. The macrocycle 3 can be isolated in yields of 58-67 % using various reaction scales. The isolation of the major by-product of the reaction (ca. 0.5-1 % of samples of 3), the pentameric, host-guest complex [[P(micro-NtBu)(2)](2)(micro-NH)](5)(HCl).2 THF] (4.2 THF), gives a strong indication of the mechanism involved. In situ (31)P NMR spectroscopic studies support a stepwise condensation mechanism in which Cl(-) ions play an important role in templating and selection of 3 and 4. Amplification of the pentameric arrangement occurs in the presence of excess LiX (X=Cl, Br, I). In addition, the cyclisation reaction is solvent- and anion-dependent. The X-ray structures of 2 and 4.2 THF are reported. 相似文献
54.
K. E. Collins M. L. M. M. Granja R. G. Pereira Filho T. A. Anazawa I. C. S. F. Jardim 《Chromatographia》1997,45(1):99-103
Summary Poly(methyloctylsiloxane) (PMOS), sorbed into the pores of HPLC silica particles by solvent evaporation, can function as a
useful stationary phase for reversed-phase chromatography. The present work addresses the question of how the PMOS is distributed
in the pores. Measurements of the surface area (BET, N2) of a series of partially loaded samples (0–40% PMOS, m/m) using a typical batch of HPLC silica (10 μm irregular particles
with 6 nm pores) show that the specific surface area of the samples decreases linearly with the specific loading (mass of
PMOS per gram of silica). This result is not consistent with a “film” model in which the PMOS is deposited uniformly on the
pore walls, but is consistent with a model in which long segmented “plugs” of PMOS are deposited within the pore system.
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996 相似文献
55.
A preconcentration procedure was established for sulphate determination in rain waters at the mg/l level, employing a small column packed with the AG1-X8 (200-400 mesh) anionic resin inserted into a flow injection system. Sulphate determination was performed by using the turbidimetric method based on reaction with barium. For concentrations within 0.10 and 2.0 MgSO(2-)(4)/l, a throughput of 50 determinations/hr was achieved, and the relative standard deviation of results was better than 2%. 相似文献
56.
Brian F.G. Johnson Jack Lewis William J.H Nelson Maria D. Vargas Dario Braga Mary McPartlin 《Journal of organometallic chemistry》1983,246(2):c69-c73
The high nuclearity mixed metal cluster monoanions [Os10C(CO)24Cu(NCMe)]? (I) and [Os10C(CO)24AuPPh3]? (II) have been obtained by reaction of the carbido-dianion [Os10C(CO)24]2? (III) with one equivalent of [Cu(NCMe)4] [BF4] and Ph3PAuCl, respectively, in CH2Cl2. X-ray analysis of the [PPh3Me]+ salts of I and II show that the Cu and Au ligands have added to capping tetrahedra of the dianion III in μ3- and μ2-bridging positions, respectively. 相似文献
57.
Carbon dioxide emulsion assisted loading of polymer microspheres toward sustained release materials 总被引:2,自引:0,他引:2
Baker GA Campbell ML Yates MZ McCleskey TM 《Langmuir : the ACS journal of surfaces and colloids》2005,21(9):3730-3732
An organic solvent-free method for encapsulating progesterone at high loadings within micron-sized inert latex polymer beads is reported. This approach makes use of a polymeric surfactant to emulsify carbon dioxide into an aqueous latex suspension. In this way, preformed approximately 4 microm polystyrene (PS) microparticles surface-grafted with poly(N-vinylpyrrolidone) (PVP) were plasticized and swollen followed by rapid partitioning of progesterone into the polymer matrix. The as-prepared polystyrene beads incorporated over 10% progesterone by weight while maintaining their initial size and morphological uniformity. Dissolution experiments were also carried out to obtain the release profile of progesterone entrapped within the PVP/PS particles. 相似文献
58.
Cappa CD Smith JD Wilson KR Messer BM Gilles MK Cohen RC Saykally RJ 《The journal of physical chemistry. B》2005,109(15):7046-7052
Measurements of the oxygen K-edge X-ray absorption spectrum (XAS) of aqueous sodium halide solutions demonstrate that ions significantly perturb the electronic structure of adjacent water molecules. The addition of halide salts to water engenders an increase in the preedge intensity and a decrease in the postedge intensity of the XAS, analogous to those observed when increasing the temperature of pure water. The main-edge feature exhibits unique behavior and becomes more intense when salt is added. Density functional theory calculations of the XAS indicate that the observed red shift of the water transitions as a function of salt concentration arises from a strong, direct perturbation of the unoccupied molecular orbitals on water by anions, and does not require significant distortion of the hydrogen bond network beyond the first solvation shell. This contrasts the temperature-dependent spectral variations, which result primarily from intensity changes of specific transitions due to geometric rearrangement of the hydrogen bond network. 相似文献
59.
Bao Shan Huang Mary Jane Lauzon James C. Parham 《Journal of heterocyclic chemistry》1979,16(4):811-813
Alkylation of 4(5)-nitroimidazole-5(4)-sulfonamide with benzyl bromide occurred on both ring nitrogens. The structures of the products could be assigned by comparison of the chemical shifts of the sulfonamide hydrogens in the nmr spectra with those of the isomeric methyl derivatives, which were prepared by differing routes. Uv and nmr spectral data are reported for a number of bromo-, nitro-, mercapto-, sulfamyl- and amino- substituted imidazoles as well as for both of the isomeric methylated derivatives of the series. 相似文献
60.
This review covers recent progress in polyelectrolyte multilayer (PEM) coatings applied to analytical separations using open-tubular capillary electrochromatography (OT-CEC). The simple preparation procedure involved in the PEM approach has provided some attractive features over other modes of capillary electrophoresis-based separations including packed column capillary electrochromatography (PC-CEC) and micellar electrokinetic chromatography (MEKC). PEM coatings have been used to alleviate the adsorption of basic analytes, to improve separations, and to improve the stability of the electroosmotic flow. Fundamental aspects of PEM coatings on surfaces and analytical separation platforms are briefly outlined in this review. In addition, applications of PEM coatings to fused-silica capillaries or microchip separation devices for the separation of small achiral or chiral analytes, as well as large biomolecules, are discussed. 相似文献