全文获取类型
收费全文 | 3766篇 |
免费 | 86篇 |
国内免费 | 31篇 |
专业分类
化学 | 2988篇 |
晶体学 | 48篇 |
力学 | 57篇 |
数学 | 176篇 |
物理学 | 614篇 |
出版年
2022年 | 22篇 |
2021年 | 29篇 |
2020年 | 37篇 |
2019年 | 41篇 |
2018年 | 23篇 |
2017年 | 33篇 |
2016年 | 44篇 |
2015年 | 66篇 |
2014年 | 78篇 |
2013年 | 266篇 |
2012年 | 168篇 |
2011年 | 231篇 |
2010年 | 131篇 |
2009年 | 108篇 |
2008年 | 196篇 |
2007年 | 200篇 |
2006年 | 223篇 |
2005年 | 210篇 |
2004年 | 186篇 |
2003年 | 199篇 |
2002年 | 197篇 |
2001年 | 50篇 |
2000年 | 54篇 |
1999年 | 58篇 |
1998年 | 42篇 |
1997年 | 38篇 |
1996年 | 55篇 |
1995年 | 51篇 |
1994年 | 43篇 |
1993年 | 39篇 |
1992年 | 30篇 |
1991年 | 27篇 |
1990年 | 31篇 |
1989年 | 35篇 |
1988年 | 35篇 |
1987年 | 26篇 |
1986年 | 25篇 |
1985年 | 47篇 |
1984年 | 46篇 |
1983年 | 27篇 |
1982年 | 55篇 |
1981年 | 40篇 |
1980年 | 54篇 |
1979年 | 58篇 |
1978年 | 41篇 |
1977年 | 29篇 |
1976年 | 23篇 |
1975年 | 23篇 |
1974年 | 25篇 |
1973年 | 18篇 |
排序方式: 共有3883条查询结果,搜索用时 31 毫秒
181.
The INDO calculations were performed on bicyclo[2.1.1]hex-5-yl radical. From these calculations, it was confirmed that the hyperfine coupling constants depend largely on the geometry of the α hydrogen. The localized MO's were obtained from the canonical MO's calculated by using the INDO method. With the use of the localized MO's thus obtained, the variation in the hyperfine coupling constants at the 6exo- and 6endo-protons in this radical was explained in terms of the through-bond and/or the through-space interactions according to the procedure which we proposed previously. That is by the procedure we can selectively pick up a particular interaction between the specified localized MO's. The hyperfine coupling constant in this radical can be expressed by the summation of several interaction terms. The difference in the hyperfine spin coupling constants of the H6exo and H6endo in the radical now concerned has been attempted to explain using MO coefficients of the occupied orbitals. 相似文献
182.
Abstract— Some immunochemical properties of double-stranded DNA irradiated with UV were studied, using a radioimmunoassay with irradiated [3 H]-DNA and experimentally produced antibodies to DNA. Reactivity of antibodies revealed that irradiated DNA contained an immunologically active structure other than the irradiated DNA specific structure, resembling that of thermally denatured DNA. inhibition assay demonstrated that while DNA-antibody binding was effectively inhibited by mixed purine and pyrimidine oligonucleotides, thymine dimer containing pyrimidine oligonucleotides derived from the irradiated DNA showed no appreciable inhibition. The antigenic structure specific for irradiated DNA was found to be thermally labile in low salt medium. Cupric and ferrous ions and cysteine added to the DNA solution inhibited antigenicity formation during irradiation, but these substances exhibited no effect on dimer formation in irradiated frozen thymine solution. Calcium ions and histidine were inert for the former reaction but inhibited the latter effectively. This suggests that different mechanisms are involved in the 2 processes. The immunologically active UV-induced lesions appeared to depend mainly on a conformational structure change of the DNA strands rather than on a single modified base moiety. 相似文献
183.
A new class of deoxyribonucleic acid (DNA)-intercalating antitumor agents, novel 9-anilino-2,3-ethylenedioxyacridines (five compounds) have been synthesized and evaluated for activity against P388 leukemia in vivo. A few of them possessed the same potency of antitumor activity as amsacrine (m-AMSA) which is an important antitumor agent in clinical use. 相似文献
184.
185.
An automatic HPLC system for analyzing nitropolycyclic aromatic hydrocarbons (NPAHs, nitroarenes) in airborne particulates was previously described (Anal. Chim. Acta, 2001, 445, 20). Some problems with this system were that it generated a peak originating from an ascorbic acid solution that elutes at a retention time close to that of 1,6-dinitropyrene (DNP), and that it was able to analyze only 1,3-, 1,6-, 1,8-DNPs and 1-nitropyrene (I-NP). Here, we describe an improved system that effectively removes the interfering peak by introducing an ODS column just after the pump for the ascorbic acid solution, and which is capable of analyzing several additional compounds (2-, 4-NPs, 2-nitrofluorene. 6-nitrochrysene, 7-nitrobenz[a]anthracene, 3-nitroperylene and 6-nitrobenzo[a]pyrene etc.). The improved sensitivities were achieved by concentrating the compounds in a benzene-ethanol extract from airborne particulates, by increasing the loading time of the sample solution from 20 to 38 min, and by increasing the flow rate of an ascorbic acid solution from 1.3 to 1.8 mL/min. 相似文献
186.
By using an oligopeptide chain as a functional linker and introducing coumarin 2 and coumarin 343 at the chain ends, an effective photo-induced energy transfer system was constructed and energy transfer from coumarin 2 to coumarin 343 was switched on and off by a solvent-induced helix-coil secondary transition of the oligopeptide chain. 相似文献
187.
Belik AA Azuma M Matsuo A Whangbo MH Koo HJ Kikuchi J Kaji T Okubo S Ohta H Kindo K Takano M 《Inorganic chemistry》2005,44(19):6632-6640
SrCu2(PO4)2 was prepared by the solid-state method at 1153 K. Its structure was solved by direct methods in the space group Pccn (No. 56) with Z = 8 from synchrotron X-ray powder diffraction data measured at room temperature. Structure parameters were then refined by the Rietveld method to obtain the lattice parameters, a = 7.94217(8) A, b = 15.36918(14) A, and c = 10.37036(10) A. SrCu2(PO4)2 presents a new structure type and is built up from Sr2O16 and Cu1Cu2O8 units with Cu1...Cu2 = 3.256 A. The magnetic properties of SrCu2(PO4)2 were investigated by magnetic susceptibility, magnetization up to 65 T, Cu nuclear quadrupole resonance (NQR), electron-spin resonance, and specific heat measurements. With spin-dimer analysis, it was shown that the two strongest spin-exchange interactions between Cu sites result from the Cu1-O...O-Cu2 and Cu2-O...O-Cu2 super-superexchange paths with Cu1...Cu2 = 5.861 A and Cu2...Cu2 = 5.251 A, and the superexchange associated with the structural dimer Cu1Cu2O8 is negligible. The magnetic susceptibility data were analyzed in terms of a linear four-spin cluster model, Cu1-Cu2-Cu2-Cu1 with -2J(1)/kB = 82.4 K for Cu1-Cu2 and -2J(2)/k(B) = 59 K for Cu2-Cu2. A spin gap deduced from this model (Delta/kB = 63 K) is in agreement with that obtained from the Cu NQR data (Delta/kB = 65 K). A one-half magnetization plateau was observed between approximately 50 and 63 T at 1.3 K. Specific heat data show that SrCu2(PO4)2 does not undergo a long-range magnetic ordering down to 0.45 K. SrCu2(PO4)2 melts incongruently at 1189 K. We also report its vibrational properties studied with Raman spectroscopy. 相似文献
188.
Ayae Sugawara Akira Oichi Hiroko Suzuki Yuzo Shigesato Toshihiro Kogure Takashi Kato 《Journal of polymer science. Part A, Polymer chemistry》2006,44(17):5153-5160
Assembled structures of calcium carbonate (CaCO3) nanocrystals have been examined for polymer/CaCO3 thin-film composites synthesized through a self-organization process inspired by biomineralization. For the crystallization of CaCO3, a thin-film matrix of chitosan has been used as a polymeric substrate. When the matrix is immersed into a supersaturated aqueous solution of CaCO3 containing 1.4 × 10−3 wt % poly(aspartate) (PAsp), thin-film crystals of CaCO3 are formed spontaneously. Three kinds of disklike films have been observed under a polarizing optical microscope. Electron diffraction analyses of each film have revealed that one is aragonite, displaying radial orientation of the c axes, and the others are vaterite, exhibiting different orientations. Detailed observation by scanning electron microscopy has clarified that these films are assemblies of crystalline particles 10–20 nm in size. The thin-film composites have been obtained over a PAsp concentration range of 4.4 × 10−4 to 1.0 × 10−2 wt %. Vaterite formation becomes dominant when the concentration of PAsp is increased. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5153–5160, 2006 相似文献
189.
Kondo M Irie Y Shimizu Y Miyazawa M Kawaguchi H Nakamura A Naito T Maeda K Uchida F 《Inorganic chemistry》2004,43(20):6139-6141
Reversible construction of a nanoporous framework from a nonporous framework has been found in the zinc(II) coordination polymer with 4,4'-oxybis(benzoate) (oba). [Zn(2)(oba)(2)(dmf)(2)].2DMF (1), which has 1 nm scale channels, transforms to the nonporous coordination polymer [Zn(oba)(H(2)O)] (2) with the loss of the open framework. Compound 2 on treatment with DMF reversibly yields nanoporous compound 1. 相似文献
190.
Akira Hirota Masahira Nakagawa Heiichi Sakai Akira Isogai Kazuo Furihata Haruo Seto 《Tetrahedron letters》1985,26(32):3845-3848
Feeding experiments with [2-3H3]acetate and [2-13C2H3]acetate in Thom No. 14 indicated that the hydrogen at C-2 in terrecyclic acid A is incorporated without migration from the precursor acetic acid; the results favour our group's earlier speculation for the cyclization to the tricyclic skeleton in the biosynthetic scheme. 相似文献