全文获取类型
收费全文 | 6663篇 |
免费 | 1405篇 |
国内免费 | 1456篇 |
专业分类
化学 | 4755篇 |
晶体学 | 138篇 |
力学 | 541篇 |
综合类 | 107篇 |
数学 | 837篇 |
物理学 | 3146篇 |
出版年
2024年 | 8篇 |
2023年 | 101篇 |
2022年 | 190篇 |
2021年 | 164篇 |
2020年 | 249篇 |
2019年 | 239篇 |
2018年 | 241篇 |
2017年 | 221篇 |
2016年 | 337篇 |
2015年 | 375篇 |
2014年 | 444篇 |
2013年 | 584篇 |
2012年 | 603篇 |
2011年 | 644篇 |
2010年 | 552篇 |
2009年 | 505篇 |
2008年 | 557篇 |
2007年 | 498篇 |
2006年 | 516篇 |
2005年 | 456篇 |
2004年 | 347篇 |
2003年 | 294篇 |
2002年 | 273篇 |
2001年 | 238篇 |
2000年 | 176篇 |
1999年 | 126篇 |
1998年 | 84篇 |
1997年 | 77篇 |
1996年 | 83篇 |
1995年 | 49篇 |
1994年 | 51篇 |
1993年 | 39篇 |
1992年 | 38篇 |
1991年 | 34篇 |
1990年 | 28篇 |
1989年 | 29篇 |
1988年 | 14篇 |
1987年 | 13篇 |
1986年 | 18篇 |
1985年 | 13篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1968年 | 1篇 |
1957年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有9524条查询结果,搜索用时 15 毫秒
171.
α-Al2O3纳米粒子对Co-Ni合金异常共沉积电化学行为的影响 总被引:1,自引:0,他引:1
为了研究在电化学复合共沉积过程中,惰性纳米粒子和金属离子、电极表面的相互作用,以及由此产生的对合金电化学共沉积行为的影响.本文从两个吸附过程出发: 电解液中的金属离子和H+在纳米粒子表面的吸附;纳米粒子迁移到阴极表面,在电极表面的吸附.采用Zeta电势和稳态极化以及电化学交流阻抗(EIS)研究了纳米Al2O3粒子和电解液中的金属离子,和电极表面的相互作用,进而分析了纳米粒子对Co2+和Ni2+还原沉积的影响规律.通过对阻抗数据的拟合,讨论了Al2O3纳米粒子对等效电路中各物理参数的影响.在H+和不同金属离子在纳米粒子上发生竞争吸附的基础上,提出了纳米粒子和合金共沉积的可能反应历程. 相似文献
172.
Preparation of conductive polypyrrole (PPy) composites under supercritical carbon dioxide conditions
Electrically conductive composites were prepared via the chemical oxidative polymerization of the pyrrole monomer in polystyrene
(PS) and zinc neutralized sulfonated polystyrene (Zn-SPS) films under supercritical carbon dioxide (SC-CO2) conditions. The strong swelling effect of SC-CO2 made polypyrrole (PPy) particles not only form on the surface, but also become incorporated into the film, resulting in a
homogeneous structure with a relatively higher conductivity. By comparison, the composite prepared in aqueous solutions shows
a skin-core structure and a conductivity of 3 to 4 orders of magnitude lower than that of the former due to the diffusion-controlled
process of the pyrrole monomer. The percolation thresholds of PS/PPy and Zn-SPS/PPy composites were 6.2% and 2.7% of the volume
fraction of PPy, respectively, much lower than the theoretically predicted value of 16%. Moreover, the conductive composites
prepared under SC-CO2 conditions showed higher thermal stability, especially in the high-temperature region.
Translated from Chemical Journal of Chinese Universities, 2006, 27(4): 771–774 (in Chinese) 相似文献
173.
174.
A pressure-filter-template approach was employed to prepare polyelectrolyte nanotubes through layer-by-layer deposition in the alumina template. With the thicker wall, the ordered polymer nanotubes possess a high flexibility. The results demonstrate that the electrostatic interactions of polyelectrolytes play a key role in fabricating water-soluble charged polymer nanotubes. The structure of the polyelectrolyte nanotube was confirmed by SEM, TEM, and UV, respectively. 相似文献
175.
Peng Yang Xuan Wang Bo Li Yixuan Yang Jinfeng Yue Yanrui Suo Huarong Tong Gang He Xiaojie Lu Gong Chen 《Chemical science》2021,12(16):5804
A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. The method exhibits a broad substrate scope for thiols, aryl iodides and amino acid units. Peptide macrocycles of a wide range of size and composition can be readily assembled in high yield from various easily accessible building blocks. This method has been successfully employed to prepare an 8-million-membered tetrameric cyclic peptide DNA-encoded library (DEL). Preliminary screening of the DEL library against protein p300 identified compounds with single digit micromolar inhibition activity.A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. 相似文献
176.
Peng S Okeley NM Tsai AL Wu G Kulmacz RJ van der Donk WA 《Journal of the American Chemical Society》2002,124(36):10785-10796
Prostaglandin H synthase (PGHS) catalyzes the conversion of arachidonic acid to prostaglandin G(2) in the cyclooxygenase reaction. The first step of the mechanism has been proposed to involve abstraction of the pro-S hydrogen atom from C13 to generate a pentadienyl radical spanning C11-C15. We report here the synthesis of six site-specifically deuterated arachidonic acids to investigate the structure of the radical intermediate. The preparation of these compounds was achieved using a divergent scheme that involved one advanced intermediate for all targets. The synthetic design introduced the label late in the routes and allowed the utilization of common synthetic intermediates in the preparation of various targets. Both 13(R)- and 13(S)-deuterium-labeled arachidonic acids were synthesized in high enantiomeric purity as deduced from soybean lipoxygenase assays and mass spectrometric analysis of the resulting enzymatic products. Each synthetic compound was reacted under anaerobic conditions with the wide singlet tyrosyl radical of PGHS-2 to generate a radical intermediate that was analyzed by EPR. Deuterium substitution at positions 11, 13(S), and 15 resulted in the loss of one hyperfine interaction, indicating that the protons at these positions interact with the unpaired electron. Simulation of the spectra was achieved with one set of parameters that are consistent with the assignment of a pentadienyl radical. Use of 16-[(2)H(2)]-arachidonic acid indicated that only one of the protons at C16 gives rise to a strong hyperfine interaction. The findings are discussed in the context of two proposed mechanisms for the cyclooxygenase reaction. 相似文献
177.
一类新型的双β-氨基醇的合成及催化硼烷对芳酮的不对称还原反应 总被引:7,自引:0,他引:7
以L-半胱氨酸盐酸盐出发,经与二卤代烷偶联,成酯和格氏反应制得三种双手性β-氨基醇,1,2-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]乙烷(4a),1,3-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]丙烷(4b),1,4-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]丁烷(4c)。将此类双手性β-氨基醇与硼烷在THF溶液中反应,in situ制备双手性恶唑硼烷催化硼烷对芳酮的不对称还原,产物苯乙醇的光学收率达72.8%、α-溴代苯乙醇的光学收率达91.4%。 相似文献
178.
Oligomerization and Polymerization of Ethylene Initiated by a Novel Ni(Ⅱ)-Based Acetyliminopyridine Complexes as Single-Site Catalysts
下载免费PDF全文
![点击此处可从《天然气化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Baojun Zhang Yanji Wang Gang Wang Jun Cao Shukun Sun Lihua Xing Yongcheng Sun Yunguang Han Hebei University of Technology Tianjin China Research Institute of Daqing Petrochemical Company Daqing Heilongjiang China College of Chemical Science Engineering China University of Petroleum Beijing China 《天然气化学杂志》2007,16(1):64-69
Novel Ni(Ⅱ)-based acetyliminopyridine complexes 1b, 2b, 3b (1-3b), which are synthesized from ligands 1a, 2a, 3a (1-3a) and [NiCl2(DME)], are suitable precursors for the catalysts that are necessary for ethylene oligomerization and polymerization reactions, activated by methylaluminoxane (MAO). The MAO-treated 1-3b presents an active catalytic center, which may oligomerize and polymerize ethylene to produce linearα-olefins and polyethylene, respectively. The molecular weight distributions of oligomers that are obtained are in good agreement with the Schulz-Flory rules for oligomers>C4. The activity of 3b-MAO complex is 6.3×107 g/(molNi·h) at 50℃. The activities and molecular weight distributions of oligomers show significant reliance on the structures of catalyst precursors. 相似文献
179.
Chen H Li G Zhang FF Sun L Chen HL Zhang SY 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(12):2767-2774
Time resolved photoacoustic calorimetry (PAC) was applied to a study of the photolysis of a coenzyme B(12) analog 2',5'-dideoxyadenosylcobalamin, which lacks an -OH group at the 2' position of ribofuranose ring. In aqueous solution, we report for the first time the quantum yield Phi(d) (0.25+/-0.02), Co-C bond dissociation energy (BDE; 31.8+/-2.5 kcal mol(-1)) and reaction volume change deltaV(R) (6.5+/-0.5 ml mol(-1)) due to conformation changes of the corrin ring and its side chains accompanying the cleavage of the Co-C bond. These values for the analog are very similar to those for the natural cofactor. Based our results and previous studies, a possible explanation for the similarity in their structure and properties versus the large difference in their enzymatic activity is discussed. 相似文献
180.
细乳液聚合法制备磁性复合微球及其表征 总被引:16,自引:7,他引:16
在制备超细Fe3O4 磁性粒子的基础上 ,以 3种低分子量聚合物Disperbyk 1 0 6、Disperbyk 1 0 8和Disperbyk 1 1 1为Fe3O4 微粒在单体相中的分散稳定剂 ,采用细乳液聚合法制备了平均粒径为 3 40nm的PS Fe3O4 磁性复合微球 .详细研究了分散剂种类对细乳液聚合制备磁性复合微球的影响 ,并采用XRD、TGA和TEM等手段对磁性复合微球的形态、结构及磁响应性等进行了表征 .实验结果证明分散剂的选择对磁性复合微球的成功制备起着至关重要的作用 ,兼具酸性和碱性功能基的分散剂Disperbyk 1 0 6具有更好的分散和稳定效果 .TEM结果表明 ,所制备的复合微球具有一些缺陷 ,而缺陷处往往是Fe3O4 磁性粒子聚集的地方 相似文献