全文获取类型
收费全文 | 34726篇 |
免费 | 4045篇 |
国内免费 | 3213篇 |
专业分类
化学 | 28777篇 |
晶体学 | 802篇 |
力学 | 1170篇 |
综合类 | 108篇 |
数学 | 755篇 |
物理学 | 10372篇 |
出版年
2024年 | 86篇 |
2023年 | 365篇 |
2022年 | 1247篇 |
2021年 | 1182篇 |
2020年 | 1435篇 |
2019年 | 1043篇 |
2018年 | 861篇 |
2017年 | 961篇 |
2016年 | 1476篇 |
2015年 | 1236篇 |
2014年 | 1433篇 |
2013年 | 2782篇 |
2012年 | 2151篇 |
2011年 | 1894篇 |
2010年 | 1700篇 |
2009年 | 2045篇 |
2008年 | 2172篇 |
2007年 | 2446篇 |
2006年 | 2202篇 |
2005年 | 1774篇 |
2004年 | 1754篇 |
2003年 | 1488篇 |
2002年 | 1141篇 |
2001年 | 907篇 |
2000年 | 869篇 |
1999年 | 826篇 |
1998年 | 769篇 |
1997年 | 546篇 |
1996年 | 532篇 |
1995年 | 511篇 |
1994年 | 437篇 |
1993年 | 327篇 |
1992年 | 276篇 |
1991年 | 188篇 |
1990年 | 151篇 |
1989年 | 130篇 |
1988年 | 102篇 |
1987年 | 70篇 |
1986年 | 80篇 |
1985年 | 87篇 |
1984年 | 71篇 |
1983年 | 19篇 |
1982年 | 34篇 |
1981年 | 40篇 |
1980年 | 28篇 |
1979年 | 27篇 |
1978年 | 16篇 |
1977年 | 17篇 |
1976年 | 11篇 |
1975年 | 13篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
Tikhonova I. A. Shubina E. S. Dolgushin F. M. Tugashov K. I. Teplitskaya L. N. Filin A. M. Sivaev I. B. Petrovskii P. V. Furin G. G. Bregadze V. I. Epstein L. M. Shur V. B. 《Russian Chemical Bulletin》2003,52(3):594-600
The reaction of cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4Hg)3 (1) with the polyhedral [B12H11SCN]2– anion in THF at 20 °C affords the {[(o-C6F4Hg)3](B12H11SCN)}2– (4) and {[(o-C6F4Hg)3]2(B12H11SCN)}2– (5) complexes. Complex 5 was isolated as the tetrabutylammonium salt. X-ray diffraction analysis showed that this complex has a bent-sandwich structure in which the [B12H11SCN]2– anion is located between the planes of two molecules 1 and is coordinated to both these molecules through B—H—Hg bridges and S—Hg bonds. The stability constants of complexes 4 and 5 in THF (20 °C), which were determined from the IR spectroscopic data, are 16 L mol–1 and 992 L2 mol–2, respectively. 相似文献
972.
On dehydration of La[Co(CN)6]·5H2O, the color of the complex, changes from white to pale blue at around 230°C. Heating the pale blue specimen, the color changes
to deep blue at around 290°C. This deep blue specimen is easily rehydrated to a pink one. As reported previously, in the pale
blue specimen, Co3+ ions are situated in the center of the D4h crystal field formed by six CN- ions.
The deep blue specimen is due to the presence of [Co(CN)4]2- ions in which Co2+ was situated in a Td coordination field formed by four CN- ions and the Co-C bond length is 1.67 Ĺ. The pink species corresponded to trans-[Co(CN)4(H2O)2]2- and the bond lengths of Co-C and Co-O are 1.89 and 1.85 Ĺ, respectively.
The Raman spectra of the complex observed at 25°C displays two bands at 2157 and 2176 cm-1 associated with the vibration of C-N bond, and the band of 2157 cm-1 was split into two bands, 2150 and 2156 cm-1, at around 100°C. When the complex was heated to around 230°C, three new bands were observed at 2103, 2116 and 2141 cm-1.
The bands of 2103 and 2116 cm-1 were assigned to the stretching vibration of C=N bonding to Co2+. The band of 2141 cm-1 was assigned to the stretching vibration of the inverted CN- as follows: Co-C=N-La→Co-N=C-La. The activation energy for the inversion of CN- was estimated as 67 kJ mol-1.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
973.
Bredikhin A. A. Lazarev S. N. Bredikhina Z. A. Savel"ev D. V. Vandyukova I. I. Gubaidullin A. T. Litvinov I. A. 《Russian Chemical Bulletin》2003,52(4):846-852
Crystalline specimens of homochiral and racemic glycidyl p-toluenesulfonate were studied by IR spectroscopy, differential scanning calorimetry, and X-ray diffraction analysis. The melting phase diagram of glycidyl p-toluenesulfonate was constructed. The stacking effect in the crystals of the racemic sulfonate is responsible for a more dense molecular packing, with the result that a heterochiral type of crystallization becomes more favorable. 相似文献
974.
975.
Joseph T. Perryman Forrest P. Hyler Jessica C. Ortiz-Rodríguez Apurva Mehta Ambarish R. Kulkarni 《Journal of Coordination Chemistry》2019,72(8):1322-1335
AbstractThe electronic structures of S and Mo as well as the local coordination of Mo are investigated as a function of metal promotion Chevrel-phase (CP) sulfides. We observe the effect of metal promoter-induced electron donation into the stoichiometric range MxMo6S8 (M?=?Fe, Ni, Cu; x?=?0–2) through analysis of X-ray absorption near-edge structure regions. We further observe the effect of this promotion on the bonding environment of Mo6 metal centers through extended X-ray absorption fine structure analysis. We monitor expansion and contraction of Mo6 octahedra with and without metal promotion, as has been predicted by Hückel molecular orbital theory. We further observe a marked tunability in the electronic structure of sulfur upon charge transfer between promoting species and Mo6S8 units. Average Mo6 octahedron Mo–Mo bond contraction from 2.76 Å to as short as 2.69 Å was observed upon incorporation of metal promoters, while intercluster separation displays a pronounced increase for promoter-host lattices compared to un-promoted Mo6S8. To corroborate spectroscopically observed phenomena, we performed computational analyses of spin-polarized densities of state for the CP materials investigated herein, where a detectable increase in sulfur-based frontier orbital population is observed in accordance with experimentally validated orbital filling. 相似文献
976.
977.
Cryogels have been demonstrated to be efficient when applied for protein isolation. Owing to their macroporous structure, cryogels can also be used for treating particle‐containing material, e.g. cell homogenates. Another challenging development in protein purification technology is the use of molecularly imprinted polymers (MIPs). These MIPs are robust and can be used repeatedly. The paper presents a new technology that combine the formation of cryogel beads concomitantly with making imprints of a protein. Protein A was chosen as the print molecule which was also be the target in the purification step. The present paper describes a new method to produce protein‐imprinted cryogel beads. The protein‐imprinted material was characterized and the separation properties were evaluated with regard to both the target protein and whole cells with target protein exposed on the cell surface. The maximum protein A adsorption was 18.1 mg/g of wet cryogel beads. The selectivity coefficient of protein A‐imprinted cryogel beads for protein A was 5.44 and 12.56 times greater than for the Fc fragment of IgG and protein G, respectively. 相似文献
978.
Lemi Türker 《无机化学与普通化学杂志》2019,645(18-19):1118-1126
Polynitrogen compounds, are rare molecules having only nitrogen atoms. In recent years, they have been considered as promising candidates of clean (green) high energy density materials. They possess high energy content and their sole decomposition product is N2. Presently some prismatic polynitrogen structures (N6 – N14) are considered within the limitations of density functional theory at the levels of B3LYP/6‐311++G(d,p) and B3LYP/cc‐PVTZ. The calculations reveal that they are all highly endothermic but stable. Certain quantum chemical properties, IR and UV/Vis spectra are reported. Homolytic bond cleavage of top rings are considered. Then, the transition state and activation energies, and also homolytic bond dissociation energies for the top rings have been calculated at the level of UB3LYP/6‐311++G(d,p). Also NICS(0) values have been calculated at the level of B3LYP/6‐311++G(d,p). The results indicate that N6 and N10 have aromatic and nonaromatic top (and also base) rings, respectively. All the rest of the structures have antiaromatic rings (all the structures have antiaromatic N4 rings). 相似文献
979.
Sugam Kharel Kyle J. Cluff Nattamai Bhuvanesh John A. Gladysz Janet Blümel 《化学:亚洲杂志》2019,14(15):2704-2711
The three secondary phosphine oxides [CH2=CH(CH2)4]2HPO ( 1 ), [CH2=CH(CH2)5]2HPO ( 2 ), and [CH2=CH(CH2)6]2HPO ( 3 ), and two diphosphine dioxides, {[CH2=CH(CH2)6]2PO(CH2)7}2 ( 4 ) and {[CH2=CH(CH2)6]2PO(CH2)4}2 ( 5 ), incorporating long methylene chains, are described. The single crystal X‐ray structures of 1 , 2 , and 5 have been determined. The phosphine oxides 3 , 4 , and 5 have been adsorbed on silica in submonolayer quantities to give 3 a – 5 a . The 1H, 13C, and 31P solid‐state NMR spectra of polycrystalline 3 – 5 have been analyzed and compared with those of 3 a – 5 a . The changes of the solid‐state NMR characteristics upon adsorption and the surface mobilities of the phosphine oxides are discussed. 相似文献
980.
Hongjuan Chen Peng Fan Xingxin Tu Hui Min Xianyong Yu Xiaofang Li Ju‐Lan Zeng Shaowei Zhang Peng Cheng 《化学:亚洲杂志》2019,14(20):3611-3619
The hydrothermal reaction of Zn2+ ions with a mixture of two ligands, Hcptpy and H3btc (Hcptpy=4‐(4‐carboxyphenyl)‐2,2′:4′,4′′‐terpyridine; H3btc=1,3,5‐benzenetricarboxylic acid), led to the formation of a 3D metal–organic framework (MOF) with 1D channels, [Zn2(cptpy)(btc)(H2O)]n ( 1 ), which was structurally characterized by using single‐crystal X‐ray diffraction (SXRD). In MOF 1 , two independent Zn2+ ions were interconnected by btc3? ligands to form a 1D chain, whilst adjacent Zn2+ ions were alternately bridged by cptpy? ligands to generate a 2D sheet, which was further linked by 1D chains to form a 3D framework with a new (3,3,4,4)‐connected topology. Furthermore, compound 1 also exhibited excellent stability towards air and water and, more importantly, luminescence experiments indicated that it could serve as a probe for the sensitive detection of paraquat (PAQ) and Fe3+ ions in aqueous solution. 相似文献