全文获取类型
收费全文 | 1862篇 |
免费 | 48篇 |
国内免费 | 15篇 |
专业分类
化学 | 1130篇 |
晶体学 | 20篇 |
力学 | 52篇 |
数学 | 315篇 |
物理学 | 408篇 |
出版年
2023年 | 13篇 |
2022年 | 48篇 |
2021年 | 52篇 |
2020年 | 40篇 |
2019年 | 23篇 |
2018年 | 46篇 |
2017年 | 32篇 |
2016年 | 76篇 |
2015年 | 49篇 |
2014年 | 64篇 |
2013年 | 138篇 |
2012年 | 106篇 |
2011年 | 124篇 |
2010年 | 81篇 |
2009年 | 82篇 |
2008年 | 86篇 |
2007年 | 98篇 |
2006年 | 76篇 |
2005年 | 75篇 |
2004年 | 91篇 |
2003年 | 54篇 |
2002年 | 48篇 |
2001年 | 24篇 |
2000年 | 24篇 |
1999年 | 24篇 |
1998年 | 19篇 |
1997年 | 23篇 |
1996年 | 28篇 |
1995年 | 25篇 |
1994年 | 17篇 |
1993年 | 20篇 |
1992年 | 17篇 |
1991年 | 21篇 |
1990年 | 12篇 |
1989年 | 17篇 |
1988年 | 14篇 |
1987年 | 9篇 |
1986年 | 8篇 |
1985年 | 12篇 |
1984年 | 14篇 |
1983年 | 8篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 12篇 |
1979年 | 7篇 |
1978年 | 8篇 |
1977年 | 11篇 |
1976年 | 4篇 |
1975年 | 5篇 |
1961年 | 4篇 |
排序方式: 共有1925条查询结果,搜索用时 15 毫秒
1.
A Mechanistic Study on the Oxidative Degradation of Dibenzazepine Derivatives by Manganese(III) Complexes in Acidic Sulfate Media
下载免费PDF全文
![点击此处可从《国际化学动力学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The oxidative degradation of tricyclic antidepressants (TCA) was studied in the presence of a large excess of the oxidizing agent manganese(III) and its reduced form manganese(II) sulfate in acidic media. The products were detected and identified using UV–vis, ESI‐MS, IR, and EPR methods. The mechanism of the reaction was studied for the following two classes of TCA: 10,11‐dihydro‐5H‐dibenz[b, f]azepines and dibenz[b, f]azepines. The oxidative degradation between dibenz[b, f]azepines and the manganese(III) ions resulted in the formation of substituted acridine with the same substituent as in the origin dibenz[b, f]azepine derivative. The pseudo–first‐order rate constants (kobs) were determined for the degradation process. The dependences of the observed rate constants on the [MnIII] with a zero intercept were linear. The reaction between 10,11‐dihydro‐5H‐dibenz[b, f]azepines, and the manganese(III) sulfate ion resulted in oxidative dehydrogenation, which proceeded via the formation of the following two intermediates: a free organic radical and a dimer. Further oxidation of the second intermediate led to a positively charged radical dimer as the single final product. Linear dependences of the pseudo–first‐order rate constants (kobs) on the [MnIII] with a zero intercept were established for the degradation of 10,11‐dihydro‐5H‐dibenz[b, f]azepines. The observed rate constants were dependent on the [H+] and independent of the [TCA] within the excess concentration range of the manganese(III) complexes used in the isolation method. The radical product of the degradation of 10,11‐dihydro‐5H‐dibenz[b, f]azepines was not stable in the aqueous solution and was subsequently transformed to a nonradical dimer in the next slower step. The observed rate constants were independent of the [MnIII], independent of the [H+] and increased slightly with increasing TCA concentrations when TCA was used in excess. The mechanistic consequences of all of these results are discussed. 相似文献
2.
Teresa uczak Radosaw Pankiewicz Bogusawa ska Grzegorz Schroeder Maria Betowska-Brzezinska Bogumil Brzezinski 《Journal of Molecular Structure》2006,800(1-3):140-145
Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li+ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods. 相似文献
3.
On interpolatory divergence-free wavelets 总被引:1,自引:0,他引:1
We construct interpolating divergence-free multiwavelets based on cubic Hermite splines. We give characterizations of the relevant function spaces and indicate their use for analyzing experimental data of incompressible flow fields. We also show that the standard interpolatory wavelets, based on the Deslauriers-Dubuc interpolatory scheme or on interpolatory splines, cannot be used to construct compactly supported divergence-free interpolatory wavelets.
4.
5.
J. Urban H. Sack-Kongehl K. Weiss 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1996,36(1):73-83
Structure and reactivity with oxigen of Cu clusters in the size range of 4.5±2.5 nm created by the inert gas aggregation technique were studied by HREM. The pure Cu clusters investigated under clean conditions show the structures of MTP's with a small lattice dilatation of the (111) plane of 1.25%. For icosahedral and decahedral particles this dilatation corresponds to a splitting of the nearest neighbour distance showing two different values, i.e. dilatation of 2.2% and contraction of 2.8% for the two edges of the deformed tetrahedral subunits, respectively. Oxidation at room temperature and air pressure of 1 bar only begins after a few minutes of exposure to air, after having undergone creation of probably non-stoichiometric intermediate states in the cuprite Cu2O structure with the bulk values of the bond lengths. 相似文献
6.
7.
In this Note we first introduce the concept of pullback asymptotic compactness. Next, we establish a result ensuring the existence of a pullback attractor for a non-autonomous dynamical system under the general assumptions of pullback asymptotic compactness and the existence of a pullback absorbing family of sets. Finally, we prove the existence of a pullback attractor for a non-autonomous 2D Navier–Stokes model in an unbounded domain, a case in which the theory of uniform attractors does not work since the non-autonomous term is quite general. To cite this article: T. Caraballo et al., C. R. Acad. Sci. Paris, Ser. I 342 (2006). 相似文献
8.
Stanis aw Urban Maria Massalska-Arod
Albert Wü rflinger Roman D browski 《Liquid crystals》2003,30(3):313-318
The pressure-temperature ( p - T ) phase diagrams for four smectogenic members of the 4'-alkyl-4-cyanobiphenyl homologous series ( n CB, n =9, 10, 11 and 12) over the temperature range 320-410 K and pressure range 0.1-300 MPa (3 kbar) were constructed using DTA. At 1 atm 9CB exhibits nematic and smectic A d phases, while the other members show only the smectic A d phase. However, at elevated pressures the clearing line splits in the case of 10CB and 11CB which indicates the induction of a nematic phase. It was found that the triple point, where the isotropic, nematic and smectic phases coexist, is strongly shifted to higher pressures with increasing chain length. This was interpreted as being caused by a loss of the rod-like shape of the molecules containing longer alkyl tails which explore a range of conformations. The slope of the clearing line, d T /d p , depends strongly on the length of the alkyl chain for the n CB series, but does not show a step-wise change between the nematogenic and smectogenic members. 相似文献
9.
Let Hn be an n-dimensional Haar subspace of
and let Hn−1 be a Haar subspace of Hn of dimension n−1. In this note we show (Theorem 6) that if the norm of a minimal projection from Hn onto Hn−1 is greater than 1, then this projection is an interpolating projection. This is a surprising result in comparison with Cheney and Morris (J. Reine Angew. Math. 270 (1974) 61 (see also (Lecture Notes in Mathematics, Vol. 1449, Springer, Berlin, Heilderberg, New York, 1990, Corollary III.2.12, p. 104) which shows that there is no interpolating minimal projection from C[a,b] onto the space of polynomials of degree n, (n2). Moreover, this minimal projection is unique (Theorem 9). In particular, Theorem 6 holds for polynomial spaces, generalizing a result of Prophet [(J. Approx. Theory 85 (1996) 27), Theorem 2.1]. 相似文献
10.
Grzegorz M. Salamończyk 《Tetrahedron letters》2003,44(40):7449-7453
An efficient synthesis of antiviral dendritic prodrug candidates, water-soluble, polyanionic conjugates of 1st and 2nd generation thiophosphate dendrimers with acyclovir, is described. 相似文献