全文获取类型
收费全文 | 2467篇 |
免费 | 133篇 |
国内免费 | 226篇 |
专业分类
化学 | 2064篇 |
晶体学 | 84篇 |
力学 | 50篇 |
综合类 | 14篇 |
数学 | 227篇 |
物理学 | 387篇 |
出版年
2023年 | 34篇 |
2022年 | 31篇 |
2021年 | 67篇 |
2020年 | 70篇 |
2019年 | 66篇 |
2018年 | 73篇 |
2017年 | 77篇 |
2016年 | 61篇 |
2015年 | 77篇 |
2014年 | 99篇 |
2013年 | 170篇 |
2012年 | 206篇 |
2011年 | 151篇 |
2010年 | 104篇 |
2009年 | 135篇 |
2008年 | 136篇 |
2007年 | 143篇 |
2006年 | 138篇 |
2005年 | 131篇 |
2004年 | 130篇 |
2003年 | 89篇 |
2002年 | 83篇 |
2001年 | 55篇 |
2000年 | 51篇 |
1999年 | 52篇 |
1998年 | 44篇 |
1997年 | 33篇 |
1996年 | 55篇 |
1995年 | 27篇 |
1994年 | 32篇 |
1993年 | 36篇 |
1992年 | 24篇 |
1991年 | 18篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 9篇 |
1987年 | 10篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 9篇 |
1983年 | 3篇 |
1982年 | 7篇 |
1981年 | 14篇 |
1980年 | 9篇 |
1979年 | 4篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1975年 | 6篇 |
1974年 | 6篇 |
1973年 | 3篇 |
排序方式: 共有2826条查询结果,搜索用时 312 毫秒
41.
Alternative Ligands. XXII. Rhodium(I) complexes with Donor/Acceptor Ligands of the Typs Me2PCH2CH2SiXnMe3?n(X = F, Cl, OMe) Donor/acceptor ligand of the type Me2PCH2SiXnMe3?n react with [Rh(CO)2Cl]2 ( 1 ) to give the mononuclear complexes RhCl(CO)(PMe2CH2CH2SiXnMe3?n)2 ( 2-6 , Table 1) with planar geometry of the donor atoms, one exception being Me2PCH2CH2CH2SiCl3, yielding the crystalline RhIII-complex RhCl2(CO)(PMe2CH2CH2SiCl2)(PMe2CH2CH2SiCl3) ( 7 ) by oxidative addition of one of the SiCl bonds to the Rh1 precursor. Structures with Rh → Si interaction between the basic central atoms and the acceptor group SiXnMe3?n could be detected in the isolated products neither spectroscopically nor by X-ray diffraction of the two representatives RhCl(CO)(PMe2CH2CH2SiF3)2 ( 2 ) and RhCl(CO)[PMe2CH2CH2siF3]2 ( 2 ) and RhCl(CO) [PMe2CH2CH2Si(OMe3]2 ( 6 ). The presence of such acid/base adducts in the reaction mixture is indicated for the more acidic acceptor groups SiXnMe3?n byvco values near 1990cm?1, (see Table 3). The complex RhCl(CO)PMe3)(PMe2CH2CH2SiF3 ( 8 ) is obtained by the reaction of RhCl(CO)(PMe3)2 ( 9 ) with Me2PCH2SiF3 and has been identified spectroscopically in a mixture with 2 and 9 . 相似文献
42.
From phasebarograms it is possible to construct phase diagrams. We show on example of the system Bi/Se/O how follow ternary sections from the total pressure measurements in equilibrium and how we can attribute the barogram of the ternary region Bi2Se3/Bi2O2Se/Se to the binary system Bi2Se3/Se. The knowledge of the ternary system Bi/Se/I and its coexistent pressure courses allow to followT-p-x conditions for the chemical transport of phases from this system. 相似文献
43.
Mercury Compounds with Cyancarbanions. II Synthesis and Crystal Structure of Dimercury(I)-bis(1,1,3,3-tetracyanpropenide) The structure of dimercury(I)-bis(1,1,3,3-tetracyanpropenide), Hg2(tcp)2, has been determined by single-crystal X-ray diffraction methods. The crystals are monoclinic, space group P 21/n. The unit cell dimensions are: a = 9.9193(3) Å, b = 5.6912(6) Å, c = 13.3806(4), β = 92.544(4)° and Z = 2. The mercury atoms in the centrosymmetric cation are three-coordinate with Hg? Hg 2.503, Hg? N 2.207, 2.207, 2.560 Å. tcp behaves as a bidentate ligand forming infinite chains running parallel to the a-axis. 相似文献
44.
火焰原子吸收光谱法测定天然水中微量铁的形态 总被引:3,自引:1,他引:3
研究了用抗坏血酸为还原剂,使二价铁离子与邻菲啰啉(phen)形成螯合物,用硝基苯萃取,火焰原子吸收光谱法测定有机相中的铁。方法检出限为1.7ng·ml~(-1),回收率为98.0%~109.6%,线性范围为0~10.0μg·ml~(-1)(原水相),线性相关系数为0.9994。测定结果与ICP-AES法结果对照相对误差小于9.46%。 相似文献
45.
Trigonal Planar CuX3-Groups in Cu2Mo6X14, X = Cl, Br, I Cu2Mo6Cl14 (I), Cu2Mo6Br14 (II) and Cu2Mo6I14 (III) were synthesized by thermal treatment of corresponding mixtures of copper(I) and molybdenum(II) halides. The crystal structures were determined by single crystal X-ray analyses. I and II show isotypism, cubic, Pn3 (no. 201, sec. setting), Z = 4, I: a = 12.772(3) Å, II: a = 13.350(2) Å. III shows a new structural type, orthorhombic, Pbca (No. 61), Z = 4, a = 16.058(3) Å, b = 10.643(2) Å, c = 16.963(3) Å. Trigonal planar CuX3 units were found in I? III. Structural behaviour relations are discussed, especially with regard to ionic conductivity. 相似文献
46.
HUA Er-BingCoordination Chemistry Institute State Key Laboratory of Coordination Chemistry Nanjing University Nanjing Jiangsu ChinaYANG Pin LI Qing-Shan YANG Bin-ShengInstitute of Molecular Science Shanxi University Taiyuan Shanxi China 《中国化学》1996,14(4):297-302
The effect of Cu2+ on the triple-stranded helical structure of poly(A:2I) was studied by means of circular dichroism spectral method with the help of ultraviolet spectral and ethidium bromide fluorescence probe methods. It was found that Cu2+ destabilizes the structure of the triple helix poly(A:2I) and induces its structural transformations, meanwhile, the transformations can be partially reversed by a higher NaCl concentration. The structural transformations may be expressed by the following scheme: poly(A:2I) - poly(A:I) + poly(I)- poly(A) + 2poly(I) 相似文献
47.
M. G. El-Shaarawy 《Journal of Thermal Analysis and Calorimetry》1998,53(1):247-254
The crystallization kinetics of the γ-irradiated and the unirradiated glass Ag7I4VO4 was studied dynamically by means of DTA,
and isothermally via electrical conductivity measurements. The influence of doping with alkali metal ions (Li+, Na+, K+, Rb+
or Cs+) on the crystallization process in the glass was also investigated. The results showed that the rate of crystallization
depends on the nature of the added metal ion and on the crystallization growth mechanism. The latter is a two-dimensional
process for both the pure and the alkali metal-doped glasses. The effects of irradiation and additive ions on the crystallization
process are discussed.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
48.
The halohydrin reaction of chiral N-enoyl-2-oxazolidinones 1 by halogen (Br2/I2) and water were efficiently carried out in aqueous organic solvent promoted by silver(I) with high anti- and regioselectivity and moderate to good diastereoselectivities. The alkenoyl, cinnamoyl and electron-deficient cinnamoyl substrates smoothly underwent bromohydrin reaction in aqueous acetone but no iodohydrin reaction, where as electron-rich cinnamoyl substrates preferred to undergo iodohydrin reaction in aqueous acetone with moderate diastereoselectivity and enhanced diastereoselectivity was observed in aqueous THF. 相似文献
49.
Matthias Weil 《Journal of solid state chemistry》2003,172(1):35-44
Mercury(I) selenite(IV) is polymorphic and crystallizes at least in three modifications, named α-, β-and γ-Hg2SeO3. Polycrystalline β-Hg2SeO3 was prepared by precipitation of a concentrated mercurous nitrate solution with selenous acid. Hydrothermal treatment of the colorless β-Hg2SeO3 powder in demineralized water at 250°C (10 days) yields light-yellow single crystals of α-Hg2SeO3 which show the highest density of the three modifications. Colorless needle-shaped single crystals of β-Hg2SeO3 and very few single crystals of γ-Hg2SeO3 co-crystallize from strongly diluted Hg2(NO3)2 and H2SeO3 solutions and were grown by a diffusion technique. All crystal structures were solved and refined from single crystal diffractometer data sets and are based on Hg22+ dumbbells and trigonal pyramidal SeO32− anions as the main building units. A common structural feature of all modifications is the formation of open channels extending parallel to the shortest crystallographic axis. The non-bonding orbitals of the SeIV atoms are stereochemically active and protrude into the channels. Upon heating in an open system under N2 atmosphere, both α- and β-Hg2SeO3 decompose in a well-separated three-step mechanism. The first step (T > 250°C) involves disproportionation into elementary mercury and α-HgSeO3 which at ca. 400°C subsequently transforms into β-HgSeO3. The second step between T = 400 and 500°C is accompanied by a loss of Hg and SeO2 and the formation of the basic salt Hg3SeO6. In the third step, at temperatures between T = 500° and 600°C, this material decomposes completely. Upon heating in a closed system (sealed silica capillaries), β-Hg2SeO3 transforms between 320-340°C into the more dense α-Hg2SeO3 which on further heating likewise converts into elementary mercury and β-HgSeO3. 相似文献
50.
Qing‐Xiang Liu Feng‐Bo Xu Qing‐Shan Li Xian‐Shun Zeng Xue‐Bing Leng Zheng‐Zhi Zhang 《中国化学》2002,20(9):878-883
Dinuclear silver (I) six‐membered ring complex [Ag2 (bta)2 ‐(hmbta)2] (ClO4)2 (3) has been synthesized by the reaction of benzotriazole (bta) (1) and 1‐hydroxymethyl benzotriazole (hmbta) (2) with Ag (CH3CN)4ClO4. The structures of compound 2 and Complex 3 have been studied by single crystal X‐ray diffraction analysis. The change of luminescent intensity of 1, 2 and 3 was reported. Compound 2 crystallizes in the monoclinic system with space group P2 (1)/c, a = 0.7655 (10) nm, b = 1.0126 (14) nm, c =0.9502 (13) nm, β = 95.07 (2)°, V = 0.7337 (17) nm3 and Z = 4. Complex 3 crystallizes in the triclinic system with space group P1, a = 0.73611 (18) nm, b = 0.9152 (2) nm, c = 1.2277 (3) nm, β = 87.170 (5)°, V = 0.8221 (3) nm3 and Z = 1. The main structural feature of complex 3 is a symmetric dinuclear six‐membered ring formed by two silver (I) atoms and four N‐atoms from two benzotriazoles. The second structural feature of complex 3 is the τ‐τ stacking interaction between two adjacent molecular planes, which forms the two‐dimentional layer structure. Besides, compared with 2, the luminescent intensity of complex 3 shows a remarkable enhancement. 相似文献