全文获取类型
收费全文 | 66750篇 |
免费 | 5947篇 |
国内免费 | 11967篇 |
专业分类
化学 | 47911篇 |
晶体学 | 1894篇 |
力学 | 697篇 |
综合类 | 435篇 |
数学 | 3316篇 |
物理学 | 13347篇 |
综合类 | 17064篇 |
出版年
2024年 | 187篇 |
2023年 | 1047篇 |
2022年 | 1988篇 |
2021年 | 1998篇 |
2020年 | 2059篇 |
2019年 | 1891篇 |
2018年 | 1584篇 |
2017年 | 2045篇 |
2016年 | 2235篇 |
2015年 | 2092篇 |
2014年 | 2856篇 |
2013年 | 5285篇 |
2012年 | 4181篇 |
2011年 | 4489篇 |
2010年 | 3873篇 |
2009年 | 4574篇 |
2008年 | 4411篇 |
2007年 | 4798篇 |
2006年 | 4473篇 |
2005年 | 3888篇 |
2004年 | 3671篇 |
2003年 | 3142篇 |
2002年 | 2572篇 |
2001年 | 2104篇 |
2000年 | 1968篇 |
1999年 | 1694篇 |
1998年 | 1314篇 |
1997年 | 1199篇 |
1996年 | 1023篇 |
1995年 | 1008篇 |
1994年 | 894篇 |
1993年 | 744篇 |
1992年 | 710篇 |
1991年 | 560篇 |
1990年 | 404篇 |
1989年 | 347篇 |
1988年 | 283篇 |
1987年 | 191篇 |
1986年 | 132篇 |
1985年 | 119篇 |
1984年 | 96篇 |
1983年 | 37篇 |
1982年 | 66篇 |
1981年 | 92篇 |
1980年 | 66篇 |
1979年 | 67篇 |
1978年 | 46篇 |
1977年 | 50篇 |
1976年 | 30篇 |
1973年 | 33篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
131.
132.
Pedro lvarez‐Boo Jos Sergio Casas Alfonso Castieiras María Delfina Couce Eduardo Freijanes Eva Novoa Jos Sordo 《应用有机金属化学》2003,17(9):725-729
Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe2Cl2(PMP)] and [SnMe2Br2(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (1H, 13C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
133.
在氨性溶液中,光照射对ZnTPPS的形成影响很大。光-极谱试验表明:光电流(i_p)与浓度(c)间有以下的关系:对Zn(NH_3)_4~(2+),i_p∝C_((Zn)(NH_3)_4)~(2+)_~(1/2),对H_2TPPS,i_p∝C_(H_2TPPS),ZnTPPS络合物还原波的i_p不明显。本文对其差异性和光电流产生的原因做了初步探讨。 相似文献
134.
四苯基卟啉蒽醌化合物与钴(Ⅱ)配位反应动力学 总被引:1,自引:0,他引:1
用光度法研究了5-[p-(β-蒽醌酰亚胺)甲氧基]-10,15,20-对甲基四苯基卟啉(H2TPP)在DMF溶剂中与金属钴(Ⅱ)离子配位反应的动力学以及镉(Ⅱ)离子对该反应的催化作用,提出了反应机理,并研究了温度对反应动力学参数的影响,求得基元反应的活化参数△rHm^≠、△rSm^≠及平衡步的△rHm^θ、△rSm^θ. 相似文献
135.
杨青 《高校应用数学学报(A辑)》2002,17(3):353-362
热传导型半导体器件的瞬时状态由四个方程的非线性偏微分方程组的初边值问题所决定,其中电子位势方程是椭圆型的,电子和空穴浓度方程是对流扩散型的,温度方程为热传导型的。本文提出解这类问题的特征变网格有限元法,并进行了理论分析,在一定条件下,得到了某种意义下的最佳L^2误差估计结果。 相似文献
136.
In this article, a kind of auxiliary design BSA* for constructing BSAs is introduced and studied. Two powerful recursive constructions on BSAs from 3‐IGDDs and BSA*s are exploited. Finally, the necessary and sufficient conditions for the existence of a BSA(v, 3, λ; α) with α = 2, 3 are established. © 2006 Wiley Periodicals, Inc. J Combin Designs 15: 61–76, 2007 相似文献
137.
Martin A. Bos Bertus Dunnewind Ton van Vliet 《Colloids and surfaces. B, Biointerfaces》2003,31(1-4):95-105
Interfacial rheological properties and their suitability for foam production and stability of two vegetable proteins were studied and compared to β-casein. Proteins used ranged from flexible to rigid/globular in the order of β-casein, gliadin and soy glycinin. Experiments were performed at pH 6.7. Network forming properties were characterised by the surface dilational modulus (determined with the ring trough) and the critical falling film length (Lstill) at which a stagnant protein film will break. Gliadin had the highest dilational modulus, followed by glycinin and β-casein, whereas glycinin formed the strongest film against fracture in the overflowing cylinder. The rate of decrease in the surface tension was studied at the air–water (Wilhelmy plate method) and the oil–water interface (bursting membrane) and the dynamic surface tension during compression and expansion in the caterpillar. Gliadin had the lowest equilibrium interfacial tensions and β-casein the lowest dynamic surface tension during expansion. Hardly any foam could be formed at a concentration of 0.1 g/l by shaking. At a concentration of 1.4 g/l most foam was formed by β-casein, followed by gliadin and glycinin. It seems that in the first place the rate of adsorption is important for foam formation. For the vegetable proteins, adsorption was slow. This resulted in lower foamability, especially for glycinin. 相似文献
138.
自由电子激光振荡器的二维数值模拟 总被引:2,自引:2,他引:0
在柱二维坐标系中,用数值计算方法求解了摇摆器内电子模拟方程组、光场方程组和无源区(不含摇摆器区)经非自适应方法变换后的无源旁轴波动方程并设计了相应的程序R_2D。用该程序计算的数值结果表明,在有源条件下二维数值模拟结果与高斯光束近似下的数值模拟结果符合较好;取完全相同的计算条件R-2D程序与洛斯阿拉莫斯实验室(LANL)的FELEX程序的计算结果符合较好;初步认为LANL实验数据的物理图象合理,数值结果基本可信;最后给出北京自由电子激光器(BFEL)的一些物理数据。 相似文献
139.
L. J. Yamí n S. E. Blanco J. M. Luco F. H. Ferretti 《Journal of Molecular Structure》1997,390(1-3):209-215
The isomerization mechanism of 2′(OH)chalcone (1) in flavanone (2) was studied. The calculations were performed with the semiempirical method AM1, using totally optimized molecular geometries. A 6-step mechanism including several equilibrium states was proposed. It was concluded that: (a) At the conformational equilibrium of 1 there could be 43.9% of s-cis conformer; (b) The acid dissociation of 1 trans-s-trans is considerable; (c) The EE, ΔHf and net charges show that the rotation of ring A of 1 and the formation of ring C of 2 occurs without greater impairments; (d) Although the keto structure is the most stable one, the enolate of 2 is present in the reaction medium; (e) The conversion of enol of 2 in the keto form would be the limiting step of the analyzed isomerization rate. 相似文献
140.
This Review discusses the synthesis and characterization by our Group of new antibiotics belonging to the class of penicillins, cephalosporins and rifamycins with ferrocenyl and 1, 1′-ferrocenilene residues in the molecule. As reactants for 6-aminopenicillanic acid (6-APA) and 7-aminocephalosporanic acid (7-ACA) the following were used: 1, 1-bis(chlorocarbonyl)ferrocene, ferrocenyl sulfochloride, 1, 1′-ferrocenylenedisulfochloride and thioglycolic acids S-modified with ferrocene. In the synthesis of rifamycins, the hydrazides of the thioglycolic acids, S-modified with ferrocene, were employed as nucleophilic agents. The synthesized intermediates were characterized by elemental analysis, TLC, IR, UV and 1H NMR spectra. The characterization of new antibiotics was made by TLC, IR and UV spectral analysis. Biological activity was tested on Gram-negative and Gram-positive bacteria. Good activity is reported towards Gram-positive bacteria in the case of derivatives containing residues of thioglycolic acid S-modified with ferrocene, the antibacterial activity being similar to that of amoxicillin, carbenicillin and cephalothin. All compounds are inactive towards Gram-negative bacteria. 相似文献