全文获取类型
收费全文 | 5351篇 |
免费 | 774篇 |
国内免费 | 330篇 |
专业分类
化学 | 4314篇 |
晶体学 | 21篇 |
力学 | 625篇 |
综合类 | 59篇 |
数学 | 487篇 |
物理学 | 949篇 |
出版年
2024年 | 7篇 |
2023年 | 53篇 |
2022年 | 223篇 |
2021年 | 298篇 |
2020年 | 239篇 |
2019年 | 159篇 |
2018年 | 183篇 |
2017年 | 165篇 |
2016年 | 276篇 |
2015年 | 267篇 |
2014年 | 296篇 |
2013年 | 542篇 |
2012年 | 337篇 |
2011年 | 321篇 |
2010年 | 233篇 |
2009年 | 300篇 |
2008年 | 288篇 |
2007年 | 313篇 |
2006年 | 275篇 |
2005年 | 267篇 |
2004年 | 237篇 |
2003年 | 217篇 |
2002年 | 165篇 |
2001年 | 110篇 |
2000年 | 102篇 |
1999年 | 63篇 |
1998年 | 72篇 |
1997年 | 73篇 |
1996年 | 69篇 |
1995年 | 40篇 |
1994年 | 33篇 |
1993年 | 34篇 |
1992年 | 40篇 |
1991年 | 24篇 |
1990年 | 20篇 |
1989年 | 13篇 |
1988年 | 23篇 |
1987年 | 12篇 |
1986年 | 12篇 |
1985年 | 9篇 |
1984年 | 6篇 |
1982年 | 12篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 8篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有6455条查询结果,搜索用时 15 毫秒
101.
Hedi Hannachi Naoual Anoune Christian Arnaud Pierre Lant ri R mi Longeray Henry Chermette 《Journal of Molecular Structure》1998,434(1-3):183-191
The Baeyer-Villiger reaction of polymethoxybenzaldehydes with peroxysuccinic acid (PSA) is studied theoretically. The semi-empirical SCF-MO/PM3 method has been used to study the reaction and to calculate the energy profiles. In addition, heat of formation computations and bond order analyses of the transition species along the reaction coordinates have been performed and are interpreted qualitatively in terms of electron flow through the system during aryl migration. Our results support the hypothesis that the second step is a concerted reaction. Our data support a definite effect of the substituent on the aryl migration. The theoretical predictions are in good agreement with experimental results. 相似文献
102.
消臭抗菌纤维素纤维的制备、结构和性能 总被引:2,自引:0,他引:2
采用一种制备消臭、抗菌纤维素纤维的新方法,即先将纤维素纤维用多元羧酸进行化学修饰,然后在铜溶液中处理,生成铜螯合纤维素纤维,用红外光谱、电子自旋波谱表征了该纤维的配位结构,消臭和抗菌实验结果显示,这种功能性纤维对硫化氢,氢气、三甲胺的消臭率分别达到100%,92.1%和80.4%,对金黄色葡萄球菌,大肠杆菌和白色念珠菌的抑菌率分别为79.14%,93.59%和82.50%,用X射线衍射,电子自旋波谱分析了该纤维吸附硫化氢,氨气、三甲胺的机理。 相似文献
103.
M. M. Kabachnic E. V. Zobnina V. Yu. Pavlov I. O. Konstantinov G. V. Ponomarev I. P. Beletskaya 《Russian Chemical Bulletin》2005,54(1):262-265
A preparative procedure is proposed for the synthesis of α-aminophosphonates of natural porphyrins by the microwave-assisted Kabachnik—Fields reaction.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 256–259, January, 2005. 相似文献
104.
105.
Boris S. Krumgalz Rita Pogorelsky Kenneth S. Pitzer 《Journal of solution chemistry》1995,24(10):1025-1038
The ion interaction approach developed by Pitzer was used for the prediction of volumetric properties of mixed electrolyte solutions at 25°C based on parameters calculated from experimental data for single-solute electrolyte solutions. Such an approach was shown to be especially effective for application to the calculation of volumetric properties of natural hypersaline brines and of industrial electrolyte solutions of large complexity. The use of the latest recommended sets of volumetric ion interaction parameters for single electrolyte solutions and symmetrical mixing parameters for Na–K–Cl ion combinations considerably improved the precision of the density calculations of highly concentrated mixed electrolyte solutions and of various natural waters. 相似文献
106.
Tonino CarusoAldo Spinella 《Tetrahedron》2003,59(39):7787-7790
An improved methodology for the preparation of copper(I) alkynides has been developed using cesium carbonate as base. In the presence of cesium carbonate and CuI various 1-alkynes were converted smoothly to the corresponding copper alkynides which in situ reacted with propargylic halides in order to synthesize skipped diynes. 相似文献
107.
Marimganti S Yasmeen S Fischer D Maier ME 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6687-6700
The synthesis of the omega-amino acid 4 is described utilizing a two-dimensional synthesis strategy combined with an enzymatic differentiation of homotopic ester groups. The amino acid 4 features two non-bonded interactions that result in conformational constraints on a cyclic construct. This amino acid was incorporated into the four macrolactams 17, 22, 31, and 37. The ring in 17 and 22 is 18-membered, whereas 31 and 37 have a 19-membered ring. The pairs with the same ring size differ in a N-methyl group. For the larger macrolactams (31 and 37) conformational analysis showed that the macrocyclic rings are somewhat more rigid than in the natural lead, the depsipeptide jasplakinolide. Nevertheless, their conformations are comparable to the natural product. There are no intramolecular hydrogen bonds, neither is the cis-rotamer populated in the N-methyl compound 37. Due to the increased flexibility of the smaller macrolactams 17 and 22 and signal overlap, a distinct solution structure could not be obtained for these compounds. The amino acid 4 should be useful for restricting the conformation of other small peptides. 相似文献
108.
R. Pikl U. Posset S. Möller R. Lankat W. Malisch W. Kiefer 《Vibrational Spectroscopy》1996,10(2):161-167
In order to examine the influence of the transition metal on the metal-silyl fragment MSiH3 and the metal-silicon bond, polarized Raman spectra of the complexes (C5R5)(CO)2FeSiH3 R = H (Cp) (1a), Me (Cp*) (1b)], (C5H5)(CO)(PPh3)FeSiH3 (1c), (C5Me5)(CO)2RuSiH3 (2), (C5R5)(CO)2(PMc3)MoSiH3 [R = H (3a), Me (3b)], and (C5R5)(CO)2(PMe3)WSiH3 [R = H(4a), Me (4b)] have been recorded. The spectral data have been evaluated and interpreted on the basis of a normal coordinate analysis of the MSiH3 core and the derived force constants and potential energy distributions were compared to results obtained for analogous halogen derivatives in the series XSiH3 [X = Br (5), I (6)]. 相似文献
109.
本文综述了利用分子对称性简化天然有机产物合成设计的策略,讨论了具有下述四种对称性的分子的合成:一、对称中心和旋转对称轴;二、对称平面;三、潜在的对称性;四、局部的对称性。 相似文献
110.
A. A. Bogdanov Yu. V. Kosmotynskaya K. I. Yakovlev N. A. Kas’yanenko 《Journal of Structural Chemistry》2006,47(1):178-185
A comparison has been made of conformational changes in the DNA molecule during its interaction in solution with different binuclear coordination compounds of platinum [Pt(NH3)2Cl-R-Pt(NH3)2Cl]Cl2 in cis and trans conformations, which contain cytosine, pyrazine, and carboxypyrazine as the common ligand (R). The influence of concentration of the components, and in particular, of ionic strength of the solution on the complexation process was studied. The influence of the nature of the common ligand, and of cis and trans conformations of coordination compounds on the character of their interaction with DNA was considered. A comparison was made between the structures of DNA complexes with mono-and binuclear compounds with the same set of ligands in the platinum coordination sphere. 相似文献