全文获取类型
收费全文 | 1320篇 |
免费 | 81篇 |
国内免费 | 243篇 |
专业分类
化学 | 1396篇 |
晶体学 | 73篇 |
力学 | 7篇 |
综合类 | 20篇 |
数学 | 2篇 |
物理学 | 146篇 |
出版年
2024年 | 2篇 |
2023年 | 9篇 |
2022年 | 17篇 |
2021年 | 37篇 |
2020年 | 59篇 |
2019年 | 32篇 |
2018年 | 29篇 |
2017年 | 38篇 |
2016年 | 41篇 |
2015年 | 41篇 |
2014年 | 57篇 |
2013年 | 147篇 |
2012年 | 90篇 |
2011年 | 53篇 |
2010年 | 49篇 |
2009年 | 61篇 |
2008年 | 61篇 |
2007年 | 85篇 |
2006年 | 72篇 |
2005年 | 65篇 |
2004年 | 55篇 |
2003年 | 75篇 |
2002年 | 58篇 |
2001年 | 54篇 |
2000年 | 37篇 |
1999年 | 40篇 |
1998年 | 35篇 |
1997年 | 25篇 |
1996年 | 36篇 |
1995年 | 27篇 |
1994年 | 14篇 |
1993年 | 21篇 |
1992年 | 28篇 |
1991年 | 16篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 12篇 |
1987年 | 7篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 6篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
排序方式: 共有1644条查询结果,搜索用时 427 毫秒
81.
Abdelfetah Mounir Mohamed El Guendouzi Abderrahim Dinane 《Journal of solution chemistry》2002,31(10):793-799
Ternary aqueous solutions of MgSO4 and K2SO4 have been studied by the hygrometric method at 25°C. The relative humidity of this system is measured at total molalities from 0.35 mol-kg–1 to about saturation for three ionic-strength fractions (y = 0.25, 0.50, and 0.80 of MgSO4. The data allow calculation of water activities and osmotic coefficients. From these measurements, the Pitzer ionic mixing parameters are determined and used to predict the solute activity coefficients in the mixture. The results are used to calculate the excess Gibbs energy at total molalities for ionic-strength fraction y. 相似文献
82.
对KNO,/MCM-48用于丙醇和碳酸二甲酯进行酯交换合成碳酸二丙酯的催化性能进行了考察.用X射线衍射(XRD)、红外光谱(IR)和X射线荧光法研究了催化剂的结构特征和表面性质.XRD结果表明,随着K负载量的增加,载体特征峰强度逐渐减弱,但仍保留MCM-48的晶体结构.随着焙烧温度的升高,KNO3逐渐分解成K2O.分别考察了活性组分负载量、焙烧温度、焙烧时间和催化剂的用量以及反应时间对反应的影响.结果表明,KNO3/MCM-48催化剂对碳酸二丙酯的合成具有很高的催化活性.在反应温度363K,反应时间6h,催化剂用量5%,丙醇与碳酸二甲酯摩尔比为4的条件下,碳酸二甲酯的转化率可达99.9%,产物碳酸二丙酯选择性93.4%,产率93.3%. 相似文献
83.
E. V. Alekseev E. V. Suleimanov E. V. Chuprunov G. K. Fukin L. G. Alekseeva 《Journal of Structural Chemistry》2005,46(5):936-940
The crystal structure of KAsUO6·3H2O was solved at 100 K and 293 K. KAsUO6·3H2O at T = 100 K: tetragonal, P4/ncc, a = 7.2037(6) Å, c = 17.811(2) Å; Z = 4, R1 = 0.0263, wR2 = 0.0546, for 618 independent reflections; at T = 293 K: tetragonal, P4/ncc, a = 7.1600(4) Å, c = 17.746(1) Å; Z = 4, R1 = 0.0263, wR2 = 0.0433 for 427 independent reflections. The results of X-ray analysis are compared with our previous data on heat capacity of this compound, and changes that take place in the structure at elevated temperature are considered. 相似文献
84.
V. M. Zainullina V. L. Volkov N. V. Podvalnaya A. L. Ivanovskii 《Journal of Structural Chemistry》2005,46(2):340-342
The calculations of the electronic structure of layered polyvanadate K2V3O8 were made employing the spin-polarized tight-binding LMTO method. Calculated magnetic moment for K4V6O16 compound phase equals 1.97 μB. V-O interactions were established to be dominating in the chemical bonding generation in this polyvanadate according to the estimated crystal orbital overlap population. The covalent bonds V(2)-V(2) in V(2)2O7 groups and electron density localization on vanadium atoms in isolated pyramids V(1)O5 were found. 相似文献
85.
氟钽酸钾中碳存在形式的探讨 总被引:2,自引:0,他引:2
本文从氟钽酸钾(K2TaF6)的生产工艺论述了有机物存在于D2TaF6的可能性。通过K2TaF6低温通氧燃烧前后测定碳的结果比较,以及X射线能谱仪表面分析结果,证实了碳的来源是残留的有机萃取剂。 相似文献
86.
A simple, rapid and specific chemiluminescence (CL) method for the determination of glutathione has been developed. The method
is based on the enhanced CL of the reaction between Ru(phen)3
2+ (phen = 1,10-phenanthroline) and KMnO4 by glutathione in HCl medium. Under the optimum conditions, the response is linearly proportional to the concentration of
glutathione between 1.5 × 10−7 and 1.0 × 10−5 mol L−1. The dection limit for glutathione (5.8 × 10−8 mol L−1) is about 10 and 200 times better than those of the spectrophotometric method using Ellman regent and the Lucigenin – CL
method, respectively. The final procedure allows the determination of glutathione in human serum with recoveries of 92%–108%.
A satisfactory agreement was obtained with a mean relative difference of 2.5% compared to the HPLC method. 相似文献
87.
A novel bimetallic porphyrin complex salt, {[MnTPP(CH3OH)2]3Fe(CN)6}·13H2O (TPP = tetraphenylporphyrin), has been synthesized and structurally characterized by X-ray diffraction analysis. The crystal is of trigonal, space group R-3 with a = b = 31.0618(10), c = 11.8366(8) (A), Z = 3, V = 9890.3(8) (A)3, C144H134FeMn3N18O19, Mr = 2641.36, Dc = 1.330 g/cm3, μ(MoΚα) = 0.463 mm-1, F(000) = 4131, R = 0.0525 and wR = 0.1382 for 3045 observed reflections (I > 2((I)). The title complex is composed of one [Fe(CN)6]3- anion, three [MnTPP(CH3OH)2] cations and thirteen water molecules, which are connected by multiform hydrogen bonds leading to a 3D supramolecular network structure. 相似文献
88.
By means of the addition of Ba into the Bi-Ca-Sr-Cu-O 2122 system, a series of Bi2CaSr2-xBaxCu2O8+δ (0 ≤ × ≤ 2) quinary metal oxides were prepared by the citrate route and by the conventional powder reaction method. The samples prepared by the former method have better properties than the latter. It was found that 5 was not equal to zero for all of them and that it increased with decreasing Tc. Two phases were indentified in the oxides containing all five metal elements. One is the Bi-Ca-Sr-Cu-O 2122 phase, the other is a new insulating phase which probably contains Bi-Ca-Ba-Cu-O with undetermined stoichiometry. Superconductivity was found in those samples for which × ≤ 1.50 with their Tc onsets between 93–78 K by resistivity measurements. Superconductivity decreased monotonically with increasing x. However, residual resistance was found in those samples for which 1.00 ≤ × ≤ 1.50, The Meissner effect appears in the samples where × ≤ 1.00 with Tc onsets between 88–80 K. For x = 1.75 and 2.00, the samples were semiconductors with resistivities of 6.66 × 102 and 6.96 × 103 Ω cm at 290 K, and activation energies of 0.109, and 0.298 eV, respectively. 相似文献
89.
Solid electrolytes in the systems K3 – 3x
Me
x
PO4 (Me = Sc, Y, In, La, Nd, Gd, Tb) are synthesized. Their phase composition and the temperature and concentration dependences of their electroconductivity are studied. In all the systems there form solid solutions based on K3PO4, which have a high potassium cation conductance. The latter is due to the formation of potassium vacancies at substitutions 3K+ Me3+ and, at lower temperatures, to stabilization of a high-temperature -modification of potassium orthophosphate. The electroconductivity of synthesized solid solutions, which equals (4–7) × 10–3 and 10–1 S cm–1 at 300 and 700°C, is similar to that of solid electrolytes K3 – x
P1 – x
E
x
VIO4 and K3 – 4x
E
x
IVPO4. 相似文献
90.
The crucial factor of the reaction of 2,6-di-tert-butylphenol with alkali hydroxides is temperature, depending on which two types of potassium or sodium 2,6-di-tert-butylphenoxides are formed. These types exhibit different catalytic activity in the alkylation of 2,6-di-tert-butylphenol with methyl acrylate. More active forms of 2,6-But
2C6H3OK or 2,6-But
2C6H3ONa are synthesized at temperatures higher than 160 °C and are predominantly the monomers, which dimerize on cooling. The
data of 1H NMR, electronic, and IR spectra for the corresponding forms of 2,6-But
2C6H3OK and 2,6-But
2C6H3ONa isolated in the individual state are in agreement with cyclohexadienone structure. In DMSO or DMF, the dimeric forms of
2,6-di-tert-butylphenoxides react with methyl acrylate to form methyl 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate in 64–92% yield.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2138–2143, December, 2006. 相似文献