全文获取类型
收费全文 | 1988篇 |
免费 | 40篇 |
国内免费 | 6篇 |
专业分类
化学 | 1391篇 |
晶体学 | 30篇 |
力学 | 44篇 |
数学 | 333篇 |
物理学 | 236篇 |
出版年
2021年 | 16篇 |
2020年 | 24篇 |
2019年 | 21篇 |
2018年 | 13篇 |
2016年 | 23篇 |
2015年 | 27篇 |
2014年 | 35篇 |
2013年 | 70篇 |
2012年 | 62篇 |
2011年 | 96篇 |
2010年 | 42篇 |
2009年 | 44篇 |
2008年 | 84篇 |
2007年 | 95篇 |
2006年 | 82篇 |
2005年 | 67篇 |
2004年 | 69篇 |
2003年 | 75篇 |
2002年 | 63篇 |
2001年 | 26篇 |
2000年 | 18篇 |
1999年 | 16篇 |
1998年 | 23篇 |
1997年 | 27篇 |
1996年 | 42篇 |
1995年 | 32篇 |
1994年 | 25篇 |
1993年 | 25篇 |
1992年 | 26篇 |
1991年 | 16篇 |
1990年 | 20篇 |
1989年 | 25篇 |
1988年 | 19篇 |
1987年 | 28篇 |
1986年 | 20篇 |
1985年 | 43篇 |
1984年 | 38篇 |
1983年 | 36篇 |
1982年 | 38篇 |
1981年 | 31篇 |
1980年 | 15篇 |
1979年 | 29篇 |
1978年 | 40篇 |
1977年 | 33篇 |
1976年 | 35篇 |
1975年 | 37篇 |
1974年 | 26篇 |
1973年 | 22篇 |
1972年 | 14篇 |
1966年 | 16篇 |
排序方式: 共有2034条查询结果,搜索用时 343 毫秒
31.
Anion excess colorless fluorite-type strontium-yttrium chloride has been prepared. Single crystals of the SrY compound exhibit a primitive cubic lattice with a = 6.967(1)Å. Two mutually exclusive structural models for solutions, neither of which is exact, are discussed. The first is a vacancy model in which the extra charge which results from substitution of Y3+ for Sr2+ is balanced by the simultaneous removal of a Sr2+Cl? ion pair. This model requires individual ion sites to be partially occupied and nonequivalent and is strongly suggestive of vacancy ordering. Refinement in space group P1, with sites refined independenty, led to R = 0.1096. The second model describes the structure in terms of a Willis cluster of defects and includes both anion vacancies and interstitial anions. Full-matrix least squares refinement in space group Fm3m, with positions analogous to those in UO2.12 and (Ca,Y)F2.10, converged at R = 0.0633 for the 114 face-centered parent structure reflections whose |F|;2 > σ(F2). This second model is discussed in relation to a probable true solution which involves longrange order. 相似文献
32.
Harry W. Gibson Dennis K. Chesney Frank D. Popp 《Journal of heterocyclic chemistry》1972,9(3):541-544
Treatment of 2-(4-chlorobutanoyl)- and 2-(5-chloropentanoyl)-1, 2-dihydroisoquinaldonitrile with sodium hydride gave rise to tricyclic benzoquinolizone and azepino[1,2-α]isoquinoline derivatives. A similar reaction was observed in the quinoline series. Several reactions of 1,2,3,4-tetrahydro-4-oxo-11bH-benzo[α]quinolizine-11b-carbonitrile are reported. 相似文献
33.
Greenblatt HM Guillou C Guénard D Argaman A Botti S Badet B Thal C Silman I Sussman JL 《Journal of the American Chemical Society》2004,126(47):15405-15411
Bifunctional derivatives of the alkaloid galanthamine, designed to interact with both the active site of the enzyme acetylcholinesterase (AChE) and its peripheral cation binding site, have been assayed with Torpedo californica AChE (TcAChE), and the three-dimensional structures of their complexes with the enzyme have been solved by X-ray crystallography. Differences were noted between the IC(50) values obtained for TcAChE and those for Electrophorus electricus AChE. These differences are ascribed to sequence differences in one or two residues lining the active-site gorge of the enzyme. The binding of one of the inhibitors disrupts the native conformation of one wall of the gorge, formed by the loop Trp279-Phe290. It is proposed that flexibility of this loop may permit the binding of inhibitors such as galanthamine, which are too bulky to penetrate the narrow neck of the gorge formed by Tyr121 and Phe330 as seen in the crystal structure. 相似文献
34.
Prasad V. S. Ika Harry L. Frisch Kurt C. Frisch 《Journal of polymer science. Part A, Polymer chemistry》1985,23(4):1163-1173
The synthesis of crosslinked polydiacetylenes and its two-component interpenetrating polymer networks (IPNs) was carried out utilizing its polar and flexible substituent groups. Polydiacetylenes were crosslinked by the formation of allophanate linkages utilizing urethane groups in the substituent groups of the polydiacetylenes. Elemental analysis, DSC, TMA, solvent resistance, and IR spectra are presented as evidence for the formation of crosslinked polydiacetylenes. IPNs of polydiacetylenes and an epoxy resin (diglycidyl ether of bisphenol A) were synthesized by using simultaneous and sequential methods of synthesis. A study of phase morphology of the simultaneous and sequential IPNs was carried out using electron microscopy, TMA, and DSC. 相似文献
35.
A high resolution mass spectrometric read-out system for a vacuum fusion apparatus is described. Rapid analyses are possible and the rate at which various gases are evolved can be monitored. Gas mixture assays are accomplished by scanning the nominal mass 28 peak. Serial measurements of CO+, N2+ and C2H4+ are made. Thus detection and measurement of evolved hydrocarbons are possible. The results for silver and tin from a conventional vacuum fusion apparatus and the mass spectrometer apparatus are compared. 相似文献
36.
On Ternary Chalcogenides. XXIV. The Structure of TlGaSe2 TlGaSe2 is monoclinic with a = 10.772(3), b = 10.771(5), c = 15.636(8) Å, ß = 100.6(3)°, Z = 16, space group Cc. The refinement yielded an R value of 0.082 for 1366 unique observed reflections (MoKα). The compound crystallizes with a layer structure with two anion layers perpendicular to c* in the unit cell. The structural motive of the layers are large corner-linked Ga4Se10- tetraeder consisting of four corner-linked GaSe4 tetrahedra. Two adjacent layers are turned relative to each other by 90°. They are kept together by Tl1+ ions, which are situated on straight lines parallel to the edges of the Ga4Se10 groups. They are surrounded by six selenium atoms forming trigonal-prismatic TlSe6 polyhedra. 42 screw-axes within the layers are the reason for a strongly pronounced pseudo tetragonal symmetry. Different possibilities of stacking cause a onedimensional disorder along the c* direction. The relations between the TlGaSe2 type and the TlSe type and also the high-pressure modifications of some compounds with the TlGaSe2 structure are discussed. 相似文献
37.
Harry R. Chobanian Ping Liu Marc D. Chioda Yan Guo Linus S. Lin 《Tetrahedron letters》2007,48(7):1213-1216
We report an expedient method for the heteroarylation of acetone under tin-free conditions. The coupling is performed using the commercially available enol silane of acetone (2-trimethylsilyloxypropene) and a corresponding aryl bromide, chloride or triflate under microwave-assisted conditions, with tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) or palladium acetate (Pd(OAc)2) and 2-(2′,6′-dimethoxybiphenyl)dicyclohexylphosphine (S-Phos) as the catalyst system. 相似文献
38.
The fluoride ion effect in the reactions of enolic systems with singlet oxygen has been investigated. β-Dicarbonyl compounds yielded 1,2,3-tricarbonyl derivatives, some of which underwent further hydration, whereas α-diketones suffered oxidative decarboxylation to give open-chain aldehydo-acids or keto-acids. 相似文献
39.
Eneyskaya EV Ivanen DR Shabalin KA Kulminskaya AA Backinowsky LV Brumer Iii H Neustroev KN 《Organic & biomolecular chemistry》2005,3(1):146-151
Transglycosylation catalyzed by a beta-D-xylosidase from Aspergillus sp. was used to synthesize a set of 4-methylumbelliferyl (MU) beta-1-->4-D-xylooligosides having the common structure [beta-D-Xyl-(1-->4)]2-5-beta-D-Xyl-MU. MU xylobioside synthesized chemically by the condensation of protected MU beta-D-xylopyranoside with ethyl 2,3,4-tri-O-acetyl-1-thio-beta-D-xylopyranoside was used as a substrate for transglycosylation with the beta-D-xylosidase from Aspergillus sp. to produce higher MU xylooligosides. The structures of oligosaccharides obtained were established by 1H and 13C NMR spectroscopy and electrospray tandem mass spectrometry. MU beta-D-xylooligosides synthesized were tested as fluorogenic substrates for the GH-10 family beta-D-xylanase from Aspergillus orizae and the GH-11 family beta-D-xylanase I from Trichoderma reesei. Both xylanases released the aglycone from MU xylobioside and the corresponding trioside. With substrates having d.p. 4 and 5, the enzymes manifested endolytic activities, splitting off MU, MUX, and MUX2 primarily. 相似文献
40.
Stern HA 《Journal of computational chemistry》2004,25(5):749-761
We review principles of non-Hamiltonian statistical mechanics and present a new set of equations and integration algorithm for isothermal-isobaric dynamics. The chief advantage of the present scheme is that it is somewhat simpler than previous methods. We perform numerical simulations to test the accuracy of the algorithm and compare its stability to that of a "gold standard," a symplectic integrator for Hamiltonian dynamics of the same system. The stability of the isothermal-isobaric algorithm is comparable to the stability of the symplectic integrator. 相似文献