全文获取类型
收费全文 | 43276篇 |
免费 | 4590篇 |
国内免费 | 7030篇 |
专业分类
化学 | 30499篇 |
晶体学 | 1333篇 |
力学 | 1376篇 |
综合类 | 381篇 |
数学 | 9555篇 |
物理学 | 11752篇 |
出版年
2024年 | 62篇 |
2023年 | 450篇 |
2022年 | 906篇 |
2021年 | 1042篇 |
2020年 | 1336篇 |
2019年 | 1332篇 |
2018年 | 1123篇 |
2017年 | 1501篇 |
2016年 | 1585篇 |
2015年 | 1394篇 |
2014年 | 1930篇 |
2013年 | 3693篇 |
2012年 | 2364篇 |
2011年 | 2946篇 |
2010年 | 2466篇 |
2009年 | 2911篇 |
2008年 | 3027篇 |
2007年 | 2998篇 |
2006年 | 2796篇 |
2005年 | 2538篇 |
2004年 | 2229篇 |
2003年 | 1934篇 |
2002年 | 1712篇 |
2001年 | 1433篇 |
2000年 | 1355篇 |
1999年 | 1161篇 |
1998年 | 1004篇 |
1997年 | 852篇 |
1996年 | 726篇 |
1995年 | 657篇 |
1994年 | 602篇 |
1993年 | 501篇 |
1992年 | 399篇 |
1991年 | 279篇 |
1990年 | 203篇 |
1989年 | 183篇 |
1988年 | 185篇 |
1987年 | 123篇 |
1986年 | 108篇 |
1985年 | 130篇 |
1984年 | 115篇 |
1983年 | 62篇 |
1982年 | 91篇 |
1981年 | 79篇 |
1980年 | 75篇 |
1979年 | 97篇 |
1978年 | 58篇 |
1977年 | 47篇 |
1976年 | 24篇 |
1974年 | 20篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
During the heating of YBCO a peritectic reaction takes place at 1020C, which can be described by: 2YBa2Cu3O7–xY2BaCuO5+L+(1-2x)/2O2 (1) whereL = 3BaCuO2 +2CuO is a fluid with limited amount of yttrium.It has been reported, that many parameters can influence the reaction. From one side not only the starting size of grains but also the heating rate have an influence on the resulting Y2BaCuO5-phase. From the other side, there is a change of the peritectical temperature caused by changing of the partial pressure of O2 and the presence of parasitic phase.From general kinetic consideration one can draw the conclusion, that different mechanisms (nucleation, phase-boundary reaction and diffusion) can control the reaction.Using DTA/TG measurements, the peritectic reaction has been examined. Classical kinetic methods (Kissinger and Friedman) has been used. The Friedman method has given the dependence of the activation energy from reaction degree. This suggests many steps reactions. The dependence of the DTA-peaks from the heat rate suggest a parallel steps of reaction. This assumption can be motivated by evaluation of free O2, one solid and liquid phase formation. Amount of this phases depends on the heating rate. Additionally X-ray and microscopic methods has been used. In this way was shown, that the perovskit structure is stable up to peritectical temperature and than is dramatically destroyed. From microscopic observations has been got information about shape and size of solid phase and it's creation as a function of temperature, time and starting grain size.
Die Arbeit wurde BMBF gefördert und durch Land NRW unterschtützt. 相似文献
992.
Cyclisation of the title compounds leads to mixtures of the expected 4H-cyclopental[b]pyrrol-4-ones (1), the corresponding 6-ones (3) by a single rearrangement, and the cyclopenta[c]pyrrol-4-ones (4) by a double rearrangement, the proportions depending upon the substituents.The 1H NMR spectra of 2-methyl-4H-cyctopenta[b]thiophen-6-one (3f) shows 6J long range coupling, but this is absent in the corresponding pyrroles (3c,d). The 13C spectra of 1 and 3 cannot be interpreted on the basis of substituent chemical shifts in pyrroles and thiophens, and are clearly -CH = CH-X (X = NMe, NPh, S) bridged derivatives of cyclopent-2-enone. 相似文献
993.
四(2,4—二叔戊基苯氧基)酞菁铜(Ⅱ)的合成及其LB膜 总被引:5,自引:3,他引:5
合成了标题酞菁铜衍生物,并通过元素分析,高压液相色谱,紫外光谱,红外光谱,核磁共振谱,电镜,顺磁共振谱及质谱加以确认。该化合物在稀氯仿溶液和LB膜中各以单,双分子缔合的形式存在。Z型沉积形成的单层LB膜对氨气有很高的灵敏度和选择性。 相似文献
994.
Yu. A. Zolotarev E. V. Laskatelev V. S. Kozik E. M. Dorokhova S. G. Rozenberg Yu. A. Borisov N. F. Myasoedov 《Russian Chemical Bulletin》1997,46(10):1726-1729
The solid-phase catalytic hydrogenation of (R-4tert-butoxy-Δ1-pyrroline-2-carboxylic) acid under the action of hydrogen spillover was studied. The reaction proceeds stereoselectively
with the predominant formation of thel-amino acid. The configuration of the asymmetric center formed is determined by that of the asymmetric C(4) atom. The major
portion of the isotope label is incorporated into the allylic C(3) and C(5) positions, and the β-H atoms are more mobile.
Using quantum-chemical calculations, the geometric structure of thel-hydroxyproline molecule was calculated, and the spin-spin coupling constants for this tritium-labeled amino acid were determined.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1820–1823, October, 1997. 相似文献
995.
用密度泛函理论(DFT)在B3LYP/6鄄31G(d,p)的计算水平上研究了离子液中1鄄乙基鄄3鄄甲基咪唑阳离子(EMIM )的4鄄H和5鄄H原子催化丁烯双键异构反应的可能途径,优化了反应体系的平衡态和过渡态的几何构型,分析了反应过程中键参数的变化,通过振动分析对平衡态和过渡态进行了验证.计算结果表明,离子液中的EMIM 首先通过4鄄H和5鄄H原子吸附丁烯,进而催化丁烯的双键异构反应,EMIM 的4鄄H和5鄄H催化1鄄丁烯异构为2鄄丁烯的正反应活化能分别为204.2和207.3kJ·mol-1,逆反应活化能约为220.9和223.8kJ·mol-1,反应为基元反应. 相似文献
996.
Layer-by-layer fluorescent conjugated polyelectrolyte films have been studied. The photoluminescence of conjugate polyelectrolytes was observed to be highly tunable during this film assembly process. Efficient photoinduced electron transfer from thus prepared highly luminescent film to a natural electron-transfer protein cytochrome c has also been observed. 相似文献
997.
Liqing Wu 《Analytica chimica acta》2003,482(2):175-181
In this report, with semi-empirical quantum method, we have studied the conformation and energy of supermolecule composed of picolinamide and its positional isomers with methacrylic acid. We tried to explore the reason why picolinamide was not likely to show imprinting effect when using methacrylic acid as functional monomer in our previous work. In order to produce imprinting effect, which was not achieved based on hydrogen bonding interaction, we have synthesized a molecular-imprinted polymer (MIP) based on copper ion coordination in prepolymerization. The complex in prepolymerization was composed of copper(II), acetate, picolinamide and 4-vinylpyridine (4-Vpy). Suprisingly, the MIP had high selectivity to picolinamide-copper acetate complex, and changes of either copper ion, picolinamide or acetate would result in decrease in the imprinting effect. This is also the first example where the high selective recognition of the MIP to its template was achieved mainly by inhibiting the binding of non-template rather than enhancing the binding of the template. And this report can be also looked upon as a first step towards the solution to the problem of imprinting of template that contains intramolecular hydrogen bond. 相似文献
998.
A possible approximation of the enthalpy of formation of C,H,N,O-containing compounds by trigonometric Fourier series has been shown.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1389–1390, August, 1994. 相似文献
999.
Adsorption of water vapor by granular polymer based on dibenzo-18-crown-6 and containing potassium nitrate or potassium picrate
in the polymer phase was studied by the isopiestic method at 298 K. The adsorption of water vapor is described by isotherms
corresponding (according to BDDT classification) to polymolecular absorption with a high adsorptive potential. In terms of
the Aranovich model of polymolecular absorption, the monolayer capacity and differential heat of adsorption were calculated,
and the stoichiometry of hydration of the potassium nitrate and potassium picrate complexes with immobilized crown ether was
estimated.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1940–1942, October, 1998. 相似文献
1000.
LI Chun-Bao Chen Yi LI Song-Lin ZHANG Wen-Qin CUI Yi JI Xiu-Jie ZHENG Peng-Wu 《结构化学》2002,21(5):470-472
1 INTRODUCTION (9S,13R,14S)-7,8-Didehydro-3,7-dimethoxy-4-hydroxy-17-methylmorphinan-6-one I is an impor- tant natural product that was used to ease pain, decrease blood pressure and diminish inflammation. In order to study the stereochemistry of the reduction of I with potassium boronhydride, the crystal structure of the title compound II was determined by X-ray diffraction method. 2 EXPERIMENTAL 2. 1 Instrument The melting point was measured on a Yanagimoto MP-500 apparatus… 相似文献