全文获取类型
收费全文 | 933篇 |
免费 | 35篇 |
国内免费 | 5篇 |
专业分类
化学 | 618篇 |
晶体学 | 11篇 |
力学 | 29篇 |
数学 | 109篇 |
物理学 | 206篇 |
出版年
2023年 | 11篇 |
2022年 | 12篇 |
2021年 | 51篇 |
2020年 | 22篇 |
2019年 | 33篇 |
2018年 | 52篇 |
2017年 | 33篇 |
2016年 | 43篇 |
2015年 | 37篇 |
2014年 | 34篇 |
2013年 | 73篇 |
2012年 | 73篇 |
2011年 | 76篇 |
2010年 | 49篇 |
2009年 | 31篇 |
2008年 | 63篇 |
2007年 | 63篇 |
2006年 | 45篇 |
2005年 | 41篇 |
2004年 | 37篇 |
2003年 | 34篇 |
2002年 | 18篇 |
2001年 | 10篇 |
2000年 | 2篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1984年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1977年 | 4篇 |
排序方式: 共有973条查询结果,搜索用时 346 毫秒
11.
Sergei D. Kirik Julia N. Zaitseva Igor S. Yakimov Nikolay N. Golovnev 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(11):i159-i160
Lithium sodium aluminium fluoride was obtained as a white powder by melting a stoichiometric mixture of AlF3, NaF and LiF at 1223 K, and then cooling to 923 K and sintering at this temperature for 4 h. The ab initio crystal structure determination was carried out using X‐ray powder diffraction techniques. The monoclinic structure of LiNa2AlF6 can be related to cubic elpasolite. The Li and Al atoms lie on inversion centres. The main octahedral AlF6 structural elements are not deformed, but are rotated slightly with respect to the unit‐cell axes. The Li atoms have octahedral coordinations, whereas the Na atoms have cubo‐octahedral coordinations. The Na coordination polyhedron is distorted in comparison with that of elpasolite. 相似文献
12.
Roman L. Antipin Elena K. Beloglazkina Nikolay V. Zyk Nikolay S. Zefirov 《Tetrahedron letters》2007,48(4):729-731
Arylselenenation of conjugated and non-conjugated dienes by arylselenenamides in the presence of phosphorus(V) oxyhalides has been studied. Reactions with conjugated dienes lead to 1,4-adducts whilst only addition to double bonds takes place in reactions with non-conjugated dienes. 相似文献
13.
A new procedure for the preparation of high aspect ratio Au nanowires utilizing gold electroless reduction in the hexagonally ordered, thiol-modified nanosized channels of the SBA-15 material is reported. Two different Au precursors were adsorbed onto pedant thiol groups, covalently bonded to the mesoporous silica surface, and used as seeds to grow extended Au nanostructures by treatment in Au electroless reduction bath. It is shown that the dimensions and the assembly of the Au seeds are important parameters for the subsequent electroless reduction process. The [AuCl4]- ions complexed to the TOAB molecules assembled on the thiol-modified mesoporous surface of the SBA-15 material are suitable precursors for the subsequent gold electroless reduction. The resulting structures are several micrometer long Au nanowires with uniform diameters of about 5 nm, having large single-crystalline domains. The TEM results clearly show that the growth of the Au nanowires is templated by the channel structure of the SBA-15 material. 相似文献
14.
Yulu Yang Mingguang Wu Xingwang Zhu Hui Xu Si Ma Yongfeng Zhi Hong Xia Xiaoming Liu Jun Pan Jie-Yinn Tang Siang-Piao Chai Leonardo Palmisano Francesco Parrino Junli Liu Jianzhong Ma Ze-Lin Wang Ling Tan Yu-Fei Zhao Yu-Fei Song Pardeep Singh Pankaj Raizada Deli Jiang Di Li R. A. Geioushy Jizhen Ma Jintao Zhang Song Hu Rongjuan Feng Gang Liu Minghua Liu Zhenhua Li Mingfei Shao Neng Li Jiahe Peng Wee-Jun Ong Nikolay Kornienko Zhenyu Xing Xiujun Fan Jianmin Ma 《中国化学快报》1990,30(12):2065-2088
This roadmap demonstrates a series of two-dimensional nanomaterials, such as graphene, black phosphorus, oxides, layered double hydroxides, chalcogenides, bismuth-based layered compounds, MXenes, metal organic frameworks, covalent organic frameworks, and others, for environmental catalysis. 相似文献
15.
Nikolay Tyutyulkov Ivo Kanev Oskar Polansky Jürgen Fabian 《Theoretical chemistry accounts》1977,46(3):191-203
The analysis of experimental data for singlet transitions (E
n) of even polyenes (I), cations (II) and anions (III) of odd polyenes show that for infinite chains E
(I)/E
(II)=E
(I)/E
(III) = 2:1. It is shown that the energy gap is equal for the three systems. In cases (II) and (III) there is a level (NBMO) in the gap which is vacant in (II) and occupied in (III). That is why the first optical transition in (II) and (III) depends on the semiwidth of the gap. 相似文献
16.
Maria Atanassova Victoria Lachkova Nikolay Vassilev Sabi Varbanov Ivan Dukov 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):173-179
The synergistic solvent extraction of five selected lanthanoid ions (La3+, Nd3+, Eu3+, Ho3+ and Lu3+) with a 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone(HP) and the 5,11,17,23-tert-butyl-25,26,27,28-tetrakis(dimethylphosphinoylmethoxy)calix[4]arene, (S) in CHCl3 has been studied. It was found that in presence of this phosphorus-containing calix[4]arene the lanthanoids have been extracted
as LnP3 · S. On the basis of the experimental data, the values of the equilibrium constants have been calculated. The influence of
the synergistic agent on the extraction process has been discussed. A synergistic effect of almost three orders of magnitude
occurs in the extraction of Ln(III) with mixture of HP and S. The values of the separation factors (S.F.) between the adjacent
elements have been evaluated.
On the basis of the IR and NMR spectra the stoichiometry and the structure of the solid complexes of Eu(III) with HP and Eu(III)
with HP and S were proposed. 相似文献
17.
The relationship of the microstructure of supercooled, highly viscous glycerol to the temperature dependence of its density, thermal expansion coefficient, and shear viscosity are discussed. The character of this temperature dependence at the transition from low viscosity state to the solid amorphous state (solidified state without nuclei) is described with help of function psi, which can be interpreted as the effective number of degrees of freedom responsible for the change of viscosity of glycerol over a broad range; these degrees of freedom are those related to the alpha-relaxation process. It is shown that the change in effective activation energy of the viscosity is completely determined by the parameter psi. The change in the shear viscosity of glycerol due to the influence of the solid-phase nuclei is considered. It is shown that the introduction of the parameter phi, equal to the specific volume occupied by the nuclei of the solid phase, together with psi provides a natural explanation of the temperature dependence of density and thermal expansion coefficients of glycerol in its liquid, solid amorphous, glassy, and crystal states. The peculiarities of the temperature dependence of phi(T) and psi(T) for glycerol and o-terphenyl are compared. 相似文献
18.
Backinowsky LV Abronina PI Shashkov AS Grachev AA Kochetkov NK Nepogodiev SA Stoddart JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(19):4412-4423
Glycosylation of sugar trityl ethers with sugar 1,2-O-(1-cyano)ethylidene derivatives (the trityl-cyanoethylidene condensation) has been applied to the synthesis of highly branched (dendritic) mannooligosaccharides incorporating a Manalpha1-->3(Manalpha1-->6)Man structural motif. The convergent synthetic strategy used to assemble these oligosaccharides was based on the use of glycosyl acceptors and/or a glycosyl donor already bearing this structural motif. The former were represented by mono- and ditrityl ethers of ManalphaOMe, Manalpha1-->3ManalphaOMe, and Manalpha1-->3(Manalpha1-->6)ManalphaX, where X=OMe or SEt. The pivotal glycosyl donor was the peracetylated 1,2-O-(1-cyano)ethylidene-3,6-di-O-(alpha-D-mannopyranosyl)-beta-D-mannopyranose (1), prepared by orthogonal Helferich glycosylation of the known 1,2-O-(1-cyano)ethylidene-beta-D-mannopyranose with tetra-O-acetyl-alpha-D-mannopyranosyl bromide followed by O-acetylation. Glycosylation of acetates of methyl 6-O-trityl-alpha-D-mannopyranoside and methyl 3,6-di-O-trityl-alpha-D-mannopyranoside with one equivalent of the donor 1 gave rise to the isomeric tetrasaccharide derivatives, Manalpha1-->3(Manalpha1-->6)Manalpha1-->6ManalphaOMe and Manalpha1-->3(Manalpha1-->6)Manalpha1-->3ManalphaOMe, respectively. The latter derivative was further mannosylated at the remaining 6-O-trityl acceptor site to give the protected pentasaccharide Manalpha1-->3(Manalpha1-->6)Manalpha1-->3(Manalpha1-->6)ManalphaOMe. The isomeric pentasaccharide, Manalpha1-->3(Manalpha1-->6)Manalpha1-->6(Manalpha1-->3)ManalphaOMe, was prepared by reaction of 1 with the 6-O-trityl derivative of (Manalpha1-->3)ManalphaOMe. In a similar fashion, 6'- and 6"-O-trityl derivatives of the branched trisaccharide Manalpha1-->3(Manalpha1-->6)ManalphaOMe served as precursors for two isomeric mannohexaosides. The 3,6-di-O-trityl ether of ManalphaOMe and the 6',6"-di-O-trityl ether of Manalpha1-->3(Manalpha1-->6)ManalphaX (X=OMe or SEt) were efficiently bis-glycosylated with the donor 1 to give the corresponding protected mannoheptaoside and mannononaoside. The yields of these glycosylations with the donor 1 ranged from 50 to 66 %. Final deprotection of all the oligosaccharides was straightforward and afforded the target products in high yields. Both the acylated and deprotected products were characterized, and the intersaccharide connectivities were elucidated by extensive one- and two-dimensional NMR spectroscopy. The described blockwise convergent approach allows assembly of a variety of 3,6-branched mannooligosaccharides. 相似文献
19.
Nikolay T. Tzvetkov 《Tetrahedron letters》2005,46(45):7751-7755
Bicyclic cyclopentafuranols were formed by photoinitiated radical cyclization of allyl- and propinyloxymethyl substituted cyclopentanones with high regioselectivity. The irradiations were carried out at a wavelength of 300 nm in aprotic solvents such as benzene and acetonitrile. We could also show that reductive photoinduced electron transfer (PET) of the propynyloxymethyl substituted cyclopentanone 5 does not lead to any cyclization. The starting materials were synthesized in good yields following known procedures. 相似文献
20.
E. V. Alekseev S. S. Nosov E. V. Suleimanov N. G. Chernorukov E. V. Chuprunov 《Journal of Structural Chemistry》2003,44(3):506-510
The crystal structure of HAsUO6 4H2O was solved at 295 K by X-ray analysis. Reasons for structural changes due to temperature variation are analyzed. 相似文献