全文获取类型
收费全文 | 15295篇 |
免费 | 1139篇 |
国内免费 | 1310篇 |
专业分类
化学 | 16294篇 |
晶体学 | 257篇 |
力学 | 24篇 |
综合类 | 55篇 |
数学 | 156篇 |
物理学 | 958篇 |
出版年
2024年 | 8篇 |
2023年 | 122篇 |
2022年 | 222篇 |
2021年 | 375篇 |
2020年 | 536篇 |
2019年 | 441篇 |
2018年 | 349篇 |
2017年 | 372篇 |
2016年 | 487篇 |
2015年 | 405篇 |
2014年 | 500篇 |
2013年 | 1034篇 |
2012年 | 1555篇 |
2011年 | 688篇 |
2010年 | 593篇 |
2009年 | 784篇 |
2008年 | 881篇 |
2007年 | 1024篇 |
2006年 | 836篇 |
2005年 | 791篇 |
2004年 | 733篇 |
2003年 | 666篇 |
2002年 | 513篇 |
2001年 | 438篇 |
2000年 | 445篇 |
1999年 | 383篇 |
1998年 | 331篇 |
1997年 | 344篇 |
1996年 | 354篇 |
1995年 | 349篇 |
1994年 | 242篇 |
1993年 | 197篇 |
1992年 | 168篇 |
1991年 | 116篇 |
1990年 | 71篇 |
1989年 | 53篇 |
1988年 | 55篇 |
1987年 | 46篇 |
1986年 | 41篇 |
1985年 | 33篇 |
1984年 | 35篇 |
1983年 | 13篇 |
1982年 | 27篇 |
1981年 | 15篇 |
1980年 | 19篇 |
1979年 | 15篇 |
1978年 | 9篇 |
1977年 | 7篇 |
1975年 | 4篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
101.
B. G. Ershov A. F. Seliverstov N. L. Sukhov G. L. Bykov 《Russian Chemical Bulletin》1992,41(10):1805-1809
The sorption of Cu2+ ions by chitin and chitosan from aqueous solutions has been investigated, as well as the molecular structure of the complexes formed. The static exchange capacities have been determined, equal to 3.5 and 0.25 mmole/g for chitosan and chitin, respectively, and the partition coefficients (5000 and 70 g/ml). It has been shown that in complex formation a bond with the amino group is formed as the result of the substitution of a proton in the latter. The EPR spectra of these complexes have been obtained and their radiospectroscopic parameters determined (g
= 2.334,g
= 2.054,A = 0.0156 cm–1, andB = 0.0028 cm–1 for chitin, andg
= 2.231,g
= 2.048,A = 0.0192 cm–1, andB = 0.0025 cm–1 for chitosan). For chitosan the ligands are two nitrogen atoms of the amino groups and two oxygen atoms of the hydroxyl groups in the position C3 of adjacent glucosamine rings; for chitin, the oxygen atoms of the acetyl groups take part in addition in the complex formation. The analysis of the radiospectroscopic parameters and their comparison with published data lead to the conclusion that the Cu2+ complex with chitosan has a tetragonal symmetry, while the complex with chitin most probably has an octahedral structure.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2305–2311, October, 1992. 相似文献
102.
本文通过异氰酸酰化反应合成了含有脲基的苯乙炔新型配体及以它作为辅助配体的4′-(对甲基苯基)-6-苯基-2,2′-二联吡啶铂(II)络合物,初步研究了铂(II)络合物的光物理性质,发现由于脲基的存在,当浓度大于3.32×10-5mol/L时铂(II)络合物能够发生分子间簇集. 相似文献
103.
Hydrothermal Synthesis and Structure of a Copper(II) Complex, [Cu(4,4''''bpy)(H_2O)_3]SO_42H_2O 总被引:1,自引:0,他引:1
1 INTRODUCTION Recently, there has been increasing interest in crystal engineering of supramolecular architectures by means of covalent bonding, hydrogen bonding or other weak intermolecular interactions[1, 2], which reflect their potential applications in host-guest che- mistry, catalysis and function materials[3~5]. The construction of such materials is mainly provided by geometry of transition metal extending through rigid ligands. The oxidation state and coordination predisposition … 相似文献
104.
O. N. Babkina O. M. Chukanova E. E. Faingol"d N. M. Bravaya 《Russian Chemical Bulletin》2004,53(4):785-790
Quantitative characteristics of changes in the energy of charge transfer from -bonded ligands to metal are presented for the series of structurally similar ansa-metallocene complexes of IVB Group elements. The changes are caused by the solvation effect, replacement of -bonded chlorine ligands by methyl groups and of bridging ethylene groups by dimethylsilylene moieties, introduction of the methyl substituent into position 2 and phenyl substituent into position 4 of the indenyl system, variation of the transition metal in metallocene, and formation of complexes with polymethylalumoxane (MAO) at different AlMAO/Zr ratios. These effects are found to be additive. 相似文献
105.
106.
Chun H Dybtsev DN Kim H Kim K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(12):3521-3529
A systematic modulation of organic ligands connecting dinuclear paddle-wheel motifs leads to a series of isomorphous metal-organic porous materials that have a three-dimensional connectivity and interconnected pores. Aromatic dicarboxylates such as 1,4-benzenedicarboxylate (1,4-bdc), tetramethylterephthalate (tmbdc), 1,4-naphthalenedicarboxylate (1,4-ndc), tetrafluoroterephthalate (tfbdc), or 2,6-naphthalenedicarboxylate (2,6-ndc) are linear linkers that form two-dimensional layers, and diamine ligands, 4-diazabicyclo[2.2.2]octane (dabco) or 4,4'-dipyridyl (bpy), coordinate at both sides of Zn(2) paddle-wheel units to bridge the layers vertically. The resulting open frameworks [Zn(2)(1,4-bdc)(2)(dabco)] (1), [Zn(2)(1,4-bdc)(tmbdc)(dabco)] (2), [Zn(2)(tmbdc)(2)(dabco)] (3), [Zn(2)(1,4-ndc)(2)(dabco)] (4), [Zn(2)(tfbdc)(2)(dabco)] (5), and [Zn(2)(tmbdc)(2)(bpy)] (8) possess varying size of pores and free apertures originating from the side groups of the 1,4-bdc derivatives. [Zn(2)(1,4-bdc)(2)(bpy)] (6) and [Zn(2)(2,6-ndc)(2)(bpy)] (7) have two- and threefold interpenetrating structures, respectively. The non-interpenetrating frameworks (1-5 and 8) possess surface areas in the range of 1450-2090 m(2)g(-1) and hydrogen sorption capacities of 1.7-2.1 wt % at 78 K and 1 atm. A detailed analysis of the sorption data in conjunction with structural similarities and differences concludes that porous materials with straight channels and large openings do not perform better than those with wavy channels and small openings in terms of hydrogen storage through physisorption. 相似文献
107.
Shvalagin V. V. Stroyuk A. L. Kuchmii S. Ya. 《Theoretical and Experimental Chemistry》2004,40(3):149-153
The photoreduction of Cu2+ at the surface of ZnO nanoparticles and ZnO/Ag nanostructures was investigated. The spectral characteristics of the obtained ZnO/Cu and ZnO/Ag/Cu composites were studied in relation to the reaction conditions. It was shown that the ZnO/Ag nanoparticles have higher photocatalytic activity in the reduction of Cu2+ ions than the individual ZnO particles. 相似文献
108.
Yingjin liu Naoto Horiuchi Yoshimi Sueishi Shunzo Yamamoto 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(3-4):233-239
The kinetics of the hydride transfer reaction between Methylene Blue (MB+) and 1-benzyl-1,4-dihydronicotinamide (BNAH) were studied in 10% ethanol-90% water mixed solvents containing β- and γ-cyclodextrins (β-CD and γ-CD). The pseudo-first order rate constant shows kinetic saturation at high initial concentration of BNAH. This indicates the formation of a complex between MB+ and BNAH. The reaction was suppressed by addition of β-CD, but enhanced by addition of γ-CD. MB+ and BNAH were separately accommodated within the β-CD cavity and the cavity walls may protect the activity site of the reactants. On the other hand, in the MB+-BNAH-γ-CD system, the inclusion of the complex between MB+ and BNAH with γ-CD occurred. This effect of γ-CD can distinguish between the productive and non-productive nature of the complex. 相似文献
109.
含铜三元类水滑石化合物的合成及其性质 总被引:11,自引:0,他引:11
以Cu(NO3)2,Zn(NO3)2和Al(NO3)3为原料,以NaOH为沉淀剂,利用共沉淀法合成了含铜三元类水滑石化合物CuZnAl-HTLcs.从不同Cu/Zn/Al比的混合原料溶液的滴定曲线入手,详细探讨了溶液pH值、原料加入方式、组分配比及水热处理条件对类水滑石合成的影响,利用XRD,ICP及比表面积测定对合成物进行了表征,并以苯酚羟基化为探针反应评价了催化剂的催化性能.结果表明,在体系pH=5.0~6.2,(Cu+Zn)/Al摩尔比=2.0,Cu/Zn摩尔比≤1.0及室温条件下共沉淀后,于100℃水热处理3h,即可得到晶相单一和结晶度高的CuZnAl-HTLcs.变化pH法合成的样品的相对结晶度为100%,低过饱和法为76.5%,高过饱和法为75.9%.合成的CuZnAl-HTLcs中Cu2+的含量均比原料液中Cu2+的含量有所增加,这可能是由于在pH=5.8时Cu2+对Al(OH)3的同晶取代能力比Zn2+强.随着CuZnAl-HTLcs中Cu含量的增加,催化剂对苯酚羟化反应的催化活性逐渐增大. 相似文献
110.
Synthesis and Characterization of Novel Orange-emitting Iridium(Ⅲ) Complexes with Diphenylquinoline Ligands Containing Fluorinated Substituent 总被引:1,自引:0,他引:1
Xiao Wei ZHANG Chu Luo YANG Zhong An LI Lin Na ZHU Jin Gui QIN Jia GAO Dong Ge MA 《中国化学快报》2006,17(3):411-414
Three new cyclometalated iridium(m) complexes based on ligands of diphenylquinoline with fluorinated subsfituents were prepared, and characterized by elemental analysis (EA), ^1H NMR, and mass spectroscopy (MS). The photophysical and electrophosphorescent properties of the complexes were briefly discussed. 相似文献