全文获取类型
收费全文 | 572篇 |
免费 | 29篇 |
国内免费 | 7篇 |
专业分类
化学 | 435篇 |
力学 | 5篇 |
数学 | 89篇 |
物理学 | 79篇 |
出版年
2023年 | 6篇 |
2022年 | 8篇 |
2021年 | 17篇 |
2020年 | 8篇 |
2019年 | 19篇 |
2018年 | 11篇 |
2017年 | 5篇 |
2016年 | 25篇 |
2015年 | 12篇 |
2014年 | 18篇 |
2013年 | 25篇 |
2012年 | 27篇 |
2011年 | 39篇 |
2010年 | 20篇 |
2009年 | 20篇 |
2008年 | 39篇 |
2007年 | 37篇 |
2006年 | 43篇 |
2005年 | 27篇 |
2004年 | 33篇 |
2003年 | 19篇 |
2002年 | 28篇 |
2001年 | 10篇 |
2000年 | 6篇 |
1999年 | 1篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 6篇 |
1994年 | 7篇 |
1993年 | 10篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 7篇 |
1984年 | 7篇 |
1983年 | 1篇 |
1982年 | 5篇 |
1981年 | 6篇 |
1980年 | 1篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 2篇 |
排序方式: 共有608条查询结果,搜索用时 15 毫秒
1.
Jeroen J. L. M. Cornelissen W. Sander Graswinckel Alan E. Rowan Nico A. J. M. Sommerdijk Roeland J. M. Nolte 《Journal of polymer science. Part A, Polymer chemistry》2003,41(11):1725-1736
The conformational properties of polymers derived from isocyanodipeptides have been investigated with a combination of model calculations, X‐ray diffraction, and circular dichroism spectroscopy. Depending on the configuration of the side chains, defined arrays of hydrogen bonds along the polymeric backbone are formed. This leads to a well‐defined conformation as, for example, expressed in the formation of lyotropic liquid‐crystalline phases and increased helical stability. Upon the disruption of the hydrogen bonds by a strong acid, a less well‐defined macromolecular conformation is observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1725–1736, 2003 相似文献
2.
José L. Ló pez Nico M. Temme 《Transactions of the American Mathematical Society》2004,356(11):4323-4342
Taylor expansions of analytic functions are considered with respect to several points, allowing confluence of any of them. Cauchy-type formulas are given for coefficients and remainders in the expansions, and the regions of convergence are indicated. It is explained how these expansions can be used in deriving uniform asymptotic expansions of integrals. The method is also used for obtaining Laurent expansions in several points as well as Taylor-Laurent expansions.
3.
4.
The ligand‐exchange mechanism of solvated Be2+ cations has been studied by means of DFT calculations (RB3LYP/6‐311+G**). Ligand exchange around [BeL4]2+, where L=H2O, NH3, CO2, formaldehyde (H2CO), HCN, N2, and CO, was found to follow an associative interchange (Ia) process in all cases. The size of the activation barrier is almost independent of the type of donor atom, and depends mainly on the hybridization undergone by the donor atom. This, in turn, suggests that steric effects play a major role in solvent‐ and ligand‐exchange reactions in Be2+ systems. 相似文献
5.
6.
Floris P. J. T. Rutjes Henk Hiemstra Hendrik H. Mooiweer W. Nico Speckamp 《Tetrahedron letters》1988,29(52):6975-6978
Acid catalyzed cyclization of methoxymethyl substituted acyclic hydrazides 4 provides cyclic hydrazides 5 in moderate to good yields through the intermediacy of N,N′-di(methoxycarbonyl)hydrazinium intermediates. 相似文献
7.
Saalfrank RW Deutscher C Maid H Ako AM Sperner S Nakajima T Bauer W Hampel F Hess BA van Eikema Hommes NJ Puchta R Heinemann FW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(8):1899-1905
In the reaction of the N-substituted diethanolamines (H(2)L(1-3)) (1-3) with calcium hydride followed by addition of iron(III) or indium(III) chloride, the iron wheels [Fe(6)Cl(6)(L(1))(6)] (4) and [Fe(6)Cl(6)(L(2))(6)] (6) or indium wheels [In(6)Cl(6)(L(1))(6)] (5), [In(6)Cl(6)(L(2))(6)] (8) and [In(6)Cl(6)(L(3))(6)] (9) were formed in excellent yields. Exchange of the chloride ions of 6 by thiocyanate ions afforded [Fe(6)(SCN)(6)(L(2))(6)] (7). Whereas the structures of 4, 5 and 7 were determined unequivocally by single-crystal X-ray analyses, complexes 8 and 9 were characterised by NMR spectroscopy. Contrary to what is normally presumed, the scaffolds of six-membered metallic wheels are not generally rigid, but rather undergo nondissociative topomerisation processes. This was shown by variable temperature (VT) (1)H NMR spectroscopy for the indium wheel [In(6)Cl(6)(L(1))(6)] (5) and is highlighted for the enantiotopomerisation of one indium centre [ 1/6[S(6)-5]<==>[1/6[S(6)-5']]. The self-assembly of metallic wheels, starting from diethanolamine dendrons, is an efficient strategy for the convergent synthesis of metallodendrimers. 相似文献
8.
Abdurashitov JN Gavrin VN Girin SV Gorbachev VV Ibragimova TV Kalikhov AV Khairnasov NG Knodel TV Kornoukhov VN Mirmov IN Shikhin AA Veretenkin EP Vermul VM Yants VE Zatsepin GT Bowles TJ Nico JS Teasdale WA Wark DL Cherry ML Karaulov VN Levitin VL Maev VI Nazarenko PI Shkol'nik VS Skorikov NV Cleveland BT Daily T Davis R Lande K Lee CK Wildenhain PW Khomyakov YS Zvonarev AV Elliott SR Wilkerson JF 《Physical review letters》1996,77(23):4708-4711
9.
Donners JJ Heywood BR Meijer EW Nolte RJ Sommerdijk NA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2561-2567
Poly(propylene imine) dendrimers that are modified with long alkyl chains self-assemble to form well-defined aggregates. The geometry and surface chemistry of the dendrimer assemblies can be varied through the addition of surfactants. These dendrimer/surfactant aggregates can be tuned to template the formation of the different phases of calcium carbonate. The use of octadecylamine results in the formation of polyhedral aggregates that become embedded within an amorphous calcium carbonate phase that persists in competition with the thermodynamic product, calcite. In combination with hexadecyltrimethylammonium bromide, small spherical aggregates are formed that induce the formation of vaterite. The use of the negatively charged surfactant SDS results in growth retardation by the Ca(2+)-induced agglomeration of dendrimer/surfactant aggregates into giant spherical particles. Eventually these particles become overgrown by rhombohedral calcite. 相似文献
10.
Spehar AM Koster S Linder V Kulmala S de Rooij NF Verpoorte E Sigrist H Thormann W 《Electrophoresis》2003,24(21):3674-3678
This paper characterizes the basic electrokinetic phenomena occurring within native poly(dimethylsiloxane) (PDMS) microchannels. Using simple buffers and current measurements, current density and electroosmosis data were determined in trapezoidal, reversibly sealed PDMS/PDMS and hybrid PDMS/glass channels with a cross-sectional area of 1035.5 microm(2) and about 6 cm length. This data was then compared to that obtained in an air-thermostated 50 microm inner diameter (1963.5 microm(2) cross-sectional area) fused-silica (FS) capillary of 70 cm length. Having a pH 7.8 buffer with an ionic strength (I) of 90 mM, Ohms's law was observed in the microchannels with electric field strengths of up to about 420 V/cm, which is about twice as high as for the FS capillary. The electroosmotic mobility (micro(EO)) in PDMS and FS is shown to exhibit the same general dependences on I and pH. For all configurations tested, the experimentally determined micro(EO) values were found to correlate well with the relationship micro(EO) = a + b log(I), where a and b are coefficients that are determined via nonlinear regression analysis. Electroosmotic fluid pumping in native PDMS also follows a pH dependence that can be estimated with a model based upon the ionization of silanol. Compared to FS, however, the magnitude of the electroosmotic flow in native PDMS is 50-70% smaller over the entire pH range and is difficult to maintain at acidic pH values. Thus, the origin of the negative charge at the inner wall of PDMS, glass, and FS appears to be similar but the density is lower for PDMS than for glass and FS. 相似文献