全文获取类型
收费全文 | 2098篇 |
免费 | 177篇 |
国内免费 | 8篇 |
专业分类
化学 | 1744篇 |
晶体学 | 22篇 |
力学 | 16篇 |
数学 | 107篇 |
物理学 | 394篇 |
出版年
2023年 | 23篇 |
2022年 | 28篇 |
2021年 | 38篇 |
2020年 | 63篇 |
2019年 | 78篇 |
2018年 | 43篇 |
2017年 | 29篇 |
2016年 | 109篇 |
2015年 | 91篇 |
2014年 | 94篇 |
2013年 | 108篇 |
2012年 | 201篇 |
2011年 | 231篇 |
2010年 | 88篇 |
2009年 | 76篇 |
2008年 | 138篇 |
2007年 | 118篇 |
2006年 | 117篇 |
2005年 | 89篇 |
2004年 | 82篇 |
2003年 | 46篇 |
2002年 | 42篇 |
2001年 | 19篇 |
2000年 | 21篇 |
1999年 | 10篇 |
1998年 | 13篇 |
1997年 | 8篇 |
1996年 | 8篇 |
1995年 | 13篇 |
1994年 | 16篇 |
1993年 | 6篇 |
1992年 | 9篇 |
1991年 | 7篇 |
1990年 | 14篇 |
1989年 | 9篇 |
1988年 | 12篇 |
1987年 | 14篇 |
1986年 | 18篇 |
1985年 | 22篇 |
1984年 | 22篇 |
1983年 | 7篇 |
1982年 | 13篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1978年 | 13篇 |
1976年 | 5篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1973年 | 13篇 |
排序方式: 共有2283条查询结果,搜索用时 31 毫秒
21.
We achieved the total synthesis of the histone deacetylase inhibitor spiruchostatin A, as the prelude to the preparation of a combinatorial library of its analogues. Two key reactions were an asymmetric acetate aldol reaction using a Zr-enolate and macrolactonization using the Shiina method. 相似文献
22.
Hidetake Sakuraba Toshimori Nakai Yoshio Tanaka 《Journal of inclusion phenomena and macrocyclic chemistry》1984,2(3-4):829-839
Asymmetric halogenation and hydrohalogenation oftrans-cinnamic acid have been achieved in the microcrystals of cyclodextrin complexes. The bromination of the organic acid in the cavity of -cyclodextrin gave theerythro-dibromide in 40 % optical yield which was much larger than that from the resolution treatment of the racemic dibromide with -cyclodextrin and the absolute configuration was opposite in sign. The asymmetric induction in the gas-solid reaction was not due to optical resolution but to the reaction itself which was influenced by the chiral frame of cyclodextrin. The reaction shows the molecular size effect that the acid in the cavity of -cyclodextrin reacted with smaller hydrogen bromide but did not with larger bromine and chlorine. In contrast, the guest molecule in the wider cavity of -cyclodextrin reacted with bromine and chlorine as well as hydrogen bromide. The stereospecificities of the gas-solid halogenations of the acid in -cyclodextrin were similar to those of the both reactions in the solid state and in carbon tetrachloride solution without -cyclodextrin: bromination of the acid yieldederythro-2, 3-dibromo-3-phenylpropionic acid stereospecifically in 100 % in three different conditions, but chlorination gave an excess ofthreo-2, 3-dichloro-3-phenylpropionic acid to theerythro-isomer in 7287 % yields. 相似文献
23.
The deterioration of zinc, zinc—calcium and manganese phosphate coatings and oxalate coatings on steel on heating was investigated by conversion electron Mössbauer spectrometry. and the chemical change of the coatings was analysed on the basis of the thermal characteristics of Zn3(PO4)2·4H2O, Zn2Fe(PO4)4·4H2O, CaZn2(PO4)2·2H2O, Fe3(PO4)2·8H2O. (Mn, Fe)5H2(PO4)4·4H2O and FeC2O4·2H2O. The steel substrate beneath the coatings influenced the thermal decomposition and evaporation of coating materials under the various heating atmospheres. The heat resistance of these coatings and the state of the substrate were also investigated. 相似文献
24.
Preparation of Sr2CeO4:Eu3+,Dy3+ white luminescence phosphor particles and thin films by using an emulsion liquid membrane system 总被引:3,自引:0,他引:3
Sr(2)CeO(4) and Sr(2)CeO(4):Eu(3+),Dy(3+) phosphor particles and thin films were prepared by using an emulsion liquid membrane (ELM, water-in-oil-in-water (W/O/W) emulsion) system, containing VA-10 (2-methyl-2-ethylheptanoic acid) as extractant (cation carrier). A two-step extraction enabled efficient extraction for Sr(3+) and rare earth ions, and the resulting precursor metal oxalate particles produced in the internal water phase of the ELM system were about 60 nm in diameter. Calcination of the oxalate particles in air gave submicrometer-sized Sr(2)CeO(4) and Sr(2)CeO(4):Eu(3+),Dy(3+) particles, which showed blue and white luminescence, respectively, by UV excitation. Blue and white luminescence phosphor thin films were also prepared by soaking alumina substrates into the W/O emulsion containing precursor oxalate particles, followed by calcination in air. 相似文献
25.
A hybrid approach combining energy density analysis with the interaction energy decomposition method
We propose a new analysis technique for characterizing molecular interactions that combines an energy decomposition scheme, such as the Kitaura-Morokuma decomposition method, with energy density analysis, which partitions the total energy of the system into atomic contributions. The combined scheme, termed Interaction-EDA, enables us to estimate the local contribution of interaction energy components, such as electrostatic, exchange, polarization, and charge transfer. The evaluation of the local interaction energy is rather important in large systems. For a numerical assessment, the Interaction-EDA method is applied to the process of CO adsorption on Si(100) - (2 x 1) surface. 相似文献
26.
Sasaki M Kawanishi E Nakai Y Matsumoto T Yamaguchi K Takeda K 《The Journal of organic chemistry》2003,68(24):9330-9339
Metalated O-silyl cyanohydrins of beta-silyl-alpha,beta-epoxyaldehyde have been found to serve as functionalized homoenolate equivalents by a tandem sequence involving base-promoted ring opening of the epoxide, Brook rearrangement, and alkylation of the resulting allylic anion. On the basis of mechanistic studies involving competitive experiments using the diastereomeric cyanohydrins, we propose a reaction pathway involving a silicate intermediate 36 formed by a concerted process via an anti-opening of the epoxide followed by the formation of an O-Si bond. 相似文献
27.
Yusuke Kaminaga Takahiro Yamada Hisanori Yamane 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(7):i57-i58
A new quaternary oxide, calcium yttrium stannate, Ca0.8Y2.4Sn0.8O6, is isostructural with Mg3TeO6 (trigonal, R). The empirical formula can be expressed as (Ca0.2667Y0.7333)6(Y0.4Sn0.6)SnO12. The Ca/Y site has a distorted coordination octahedron of O atoms, with Ca/Y—O distances ranging from 2.227 (3) to 2.350 (3) Å, while the octahedra of O atoms that coordinate to the Sn and Y/Sn sites are nearly regular, with an Sn—O distance of 2.066 (2) Å and a Y/Sn—O distance of 2.147 (3) Å. 相似文献
28.
Bo Jiang Hui Song Yunqing Kang Shengyao Wang Qi Wang Xin Zhou Kenya Kani Yanna Guo Jinhua Ye Hexing Li Yoshio Sakka Joel Henzie Yamauchi Yusuke 《Chemical science》2020,11(3):791
Generating high surface area mesoporous transition metal boride is interesting because the incorporation of boron atoms generates lattice distortions that lead to the formation of amorphous metal boride with unique properties in catalysis. Here we report the first synthesis of mesoporous cobalt boron amorphous alloy colloidal particles using a soft template-directed assembly approach. Dual reducing agents are used to precisely control the chemical reduction process of mesoporous cobalt boron nanospheres. The Earth-abundance of cobalt boride combined with the high surface area and mesoporous nanoarchitecture enables solar-energy efficient photothermal conversion of CO2 into CO compared to non-porous cobalt boron alloys and commercial cobalt catalysts.Generating high surface area mesoporous transition metal boride is challenging but interesting because incorporation of boron atoms can generate lattice distortion to form amorphous metal boride which has unique properties in catalysis. 相似文献
29.
Complexes of the type (n-C
n
H2n
+1NH3)2SnX6 (0n 4 and X=Cl or Br) have been investigated with a variety of physico-chemical techniques. The structural phase transitions were found in some of these complexes. The temperature dependence of the Mössbauer spectral absorption area for (C2H5NH3)2SnCl6 and (C2H5NH3)2SnBr6 changed sharply at phase transition temperatures. The temperature dependences for (n-C4H9NH3)2SnCl6 and (n-C4H9NH3)2SnBr6 decreased gradually with an increase in temperature. The correlation between the temperature dependence of the spectral absorption area and the motion of n-C
n
H2n+1NH3
+ ions is discussed. 相似文献
30.
Wataru Ueda Damian Vitry Tomokazu Kato Nobufumi Watanabe Yusuke Endo 《Research on Chemical Intermediates》2006,32(3-4):217-233
Mo-V-O-based complex metal oxide catalysts were synthesized hydrothermally for the first time, characterized structurally and tested in the selective oxidation of propane to acrylic acid, and the results obtained were compared on the basis of catalyst crystal structures in order to clarify key aspects of alkane selective oxidation over multifunctional metal oxide catalysts. The catalysts tested were black solids of rod-shaped crystals, which had a layer structure in the direction of fiber axis and various high dimensional arrangements of metal octahedra in the cross-section plane. A strong dependency on the octahedra arrangements and a facet dependency were observed, and the roles of metal elements in the course of selective oxidation of propane were clarified by comparing the catalytic performance of various Mo-V-O-based catalysts. We discuss the multi-functional character derived from high dimensional structures of the catalysts and mechanism of the selective oxidation of propane. 相似文献