全文获取类型
收费全文 | 3337篇 |
免费 | 522篇 |
国内免费 | 457篇 |
专业分类
化学 | 2597篇 |
晶体学 | 72篇 |
力学 | 137篇 |
综合类 | 32篇 |
数学 | 433篇 |
物理学 | 1045篇 |
出版年
2024年 | 12篇 |
2023年 | 87篇 |
2022年 | 180篇 |
2021年 | 166篇 |
2020年 | 209篇 |
2019年 | 177篇 |
2018年 | 164篇 |
2017年 | 145篇 |
2016年 | 218篇 |
2015年 | 219篇 |
2014年 | 225篇 |
2013年 | 266篇 |
2012年 | 251篇 |
2011年 | 245篇 |
2010年 | 217篇 |
2009年 | 184篇 |
2008年 | 176篇 |
2007年 | 167篇 |
2006年 | 145篇 |
2005年 | 118篇 |
2004年 | 87篇 |
2003年 | 70篇 |
2002年 | 73篇 |
2001年 | 64篇 |
2000年 | 43篇 |
1999年 | 35篇 |
1998年 | 28篇 |
1997年 | 24篇 |
1996年 | 34篇 |
1995年 | 31篇 |
1994年 | 20篇 |
1993年 | 31篇 |
1992年 | 26篇 |
1991年 | 27篇 |
1990年 | 19篇 |
1989年 | 12篇 |
1988年 | 8篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 7篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 7篇 |
1973年 | 6篇 |
1927年 | 3篇 |
排序方式: 共有4316条查询结果,搜索用时 138 毫秒
31.
The diffusiophoretic motion of a polyelectrolyte molecule or charged floc in an unbounded solution of a symmetrically charged electrolyte with a uniform prescribed concentration gradient is analytically studied. The model used for the particle is a porous sphere in which the density of the hydrodynamic frictional segments, and therefore also that of the fixed charges, is constant. The electrokinetic equations which govern the electrostatic potential profile, the ionic concentration distributions (or electrochemical potential energies), and the fluid velocity field inside and outside the porous particle are linearized by assuming that the system is only slightly distorted from equilibrium. Using a regular perturbation method, these linearized equations are solved for a charged porous sphere with the density of the fixed charges as the small perturbation parameter. An analytical expression for the diffusiophoretic mobility of the charged porous sphere in closed form is obtained from a balance between its electrostatic and hydrodynamic forces. This expression, which is correct to the second order of the fixed charge density of the particle, is valid for arbitrary values of kappaa and lambdaa, where kappa is the reciprocal of the Debye screening length, lambda is the reciprocal of the length characterizing the extent of flow penetration inside the particle, and a is the particle radius. Our result to the first order of the fixed charge density agrees with the corresponding solution for the electrophoretic mobility obtained in the literature. In general, the diffusiophoretic mobility of a porous particle becomes greater as the hindrance to the diffusive transport of the solute species inside the particle is more significant. 相似文献
32.
A highly sensitive and selective catalytic adsorptive cathodic striping procedure for the determination of trace germanium is presented. The method is based on adsorptive accumulation of the Ge(IV)‐gallic acid (GA) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is enhanced catalytically by addition of vanadium(IV)‐EDTA. The optimal experimental conditions include the use of 0.03 mol/L HClO4 (pH1.6), 6.0×10?3 mol/L GA, 3.0×10?3 mol/L V(IV), 4.0×10?3 mol/L EDTA, an accumulation potential of ?0.10 V(vs. Ag/AgCl), an accumulation time of 120 s and a differential pulse potential scan mode. The peak current is proportional to the concentration of Ge(IV) over the range of 3.0×10?11 to 1.0×10?8 mol/L and the detection limit is 2×10?11 mol/L for a 120 s adsorption time. The relative standard deviation at 5.0×10?10 mol/L level is 3.1%. No serious interferences were found. The method was applied to the determination of germanium in ore, mineral water and vegetable samples with satisfactory results. 相似文献
33.
为建立一种快速、简便、灵敏测定葡萄糖酸锌含量的方法,在非离子型表面活性剂聚氧乙烯异辛基苯基醚(TritonX-100)存在下,用2-(3,5-二溴-2-吡啶偶氮)-5-二甲氨基酚(3,5-diBr-DM-PAP)作显色剂,直接光度法测定了葡萄糖酸锌。结果表明,该法显色络合物最大吸收波长为560 nm,线性范围为0~1.5μg.mL-1,表观摩尔吸光系数为1.10×105L.mol-1.cm-1,回收率为98.7%~102.2%,具有操作快速、简便,结果灵敏可靠等优点,应用该法直接测定补锌口服液葡萄糖酸锌含量,结果满意。 相似文献
34.
Pengchong Li Zhi Shang Kejian Cui Huan Zhang Zhi Qiao Caizhen Zhu Ning Zhao Jian Xu 《中国化学快报》2019,30(1):157-159
Polystyrene (PS) fibers with core-shell structure were prepared by coaxial electrostatic spinning using liquid epoxy or curing agent as the core and PS solution as the shell. Scratch self-healing coatings were realized by using the healant-loaded core-shell fibers in the matrix. 相似文献
35.
淫羊藿根与叶活性成分的分析和比较 总被引:8,自引:0,他引:8
采用细胞膜色谱法(CMC)筛选,并结合离体药理实验确定主要活性成分,利用高效液相色谱法分析比较了淫羊藿根与叶中的活性成分及其差异性.色谱条件为Kromasil ODS 柱(150 mm× 4.6 mm.I.D )流动相甲醇-水(70:30,V:V);检测波长270nm。筛选发现淫羊藿根中的两个有效成分YYH-214和YYH-216对血管有较强的舒张作用,表明活性成分在CMC模型体系中的保留特性与药理作用之间存在良好的相关性。在此色谱条件下淫羊藿叶未检测到这两种活性成分. 相似文献
36.
Two New C—21 Steroidal Glycosides from Cynanchum aurichulatum 总被引:2,自引:0,他引:2
Two new C-21 steroidal glycosides, cynanauriculoside I and cynanauriculoside Ⅱ, were isolated from the roots of Cynanchum aurichulatum. Their structures were established using spectroscopic methods including one and two-dimensional NMR. 相似文献
37.
38.
The efficient utilization of carbon dioxide (CO2) as a C1 feedstock is of great significance for green and sustainable development. Therefore, the efficient chemical conversion of CO2 into value-added products has recently attracted a lot of research attention in recent years. The transformation of CO2 generally requires high-energy substrates, specific catalysts, and harsh reaction conditions due to its high thermodynamic stability and kinetic inertness. Consequently, several efforts have been dedicated toward the development of high-performance catalysts and new reaction routes for CO2 conversion over the last few decades. To date, many routes of convert CO2 into value-added chemicals have been proposed, together with the development of heterogeneous and homogeneous catalysts. Among the advanced catalysts reported to date, ionic liquids (ILs) have been widely investigated and show great potential for the efficient, selective, and economical conversion of CO2 into highly valuable products under mild conditions, even under ambient conditions. Some task-specific ILs have been designed with unique functional groups (e.g., —OH, —SO3H, —NH2, —COOH, and —C≡N), which can act as the solvent, absorbent, activating agent, catalyst, or cocatalyst to realize the transformation of CO2 under metal-free and mild conditions. In addition, a variety of catalytic systems composed of ILs and metal catalysts have also been reported for the transformation of CO2, in which the combination of the IL and metal catalyst is responsible for CO2 conversion with high efficiency. In this review article, we summarize the recent advances in IL-mediated CO2 transformation into chemicals prepared via C—O, C—N, C—S, C—H, and C—C bond forming processes. ILs that can chemically capture CO2 with high capacity are first introduced, which can activate CO2 via the formation of IL-based carbonates or carbamates, thus realizing the transformation of CO2 under metal-free and mild conditions. Recent progress in IL-mediated CO2 transformations to form carbonates and various kinds of N- and S-containing compounds (e.g., oxazolidinones, ureas, benzimidazolones, formamides, methylamines, benzothiazoles, and other chemicals) as well as CO2 hydrogenation to give formic acid, methane, acetic acid, low-carbon alcohols, and hydrocarbons has been summarized in this review with a focus on the reaction routes, catalytic systems, and reaction mechanism. In these reactions, ILs can simultaneously activate the substrate via strong H-bonding in addition to activating CO2, and the cooperative effects among the ionic and molecular species and metal catalysts accomplish the reactions of CO2 with various kinds of substrates to afford a wide range of value-added chemicals. Finally, the shortcomings and perspectives of ILs are discussed. In short, IL-mediated CO2 transformations provide green and effective routes for the synthesis of high-value chemicals, which may have great potential for a wide range of applications. 相似文献
39.
40.
Shu Ping XU* Huan Wen CHEN Ai Min YU Qin Han JIN Hua Ying LIAO Changchun R&D Center for Analytical Instruments Department of Chemistry Jilin University Changchun Key Laboratory for Supramolecular Structure Spectroscopy of Ministr 《中国化学快报》2002,13(7):660-661
In recent years, the determination of Cr (VI) has attracted great attention because of its toxicity to human, plants and animals1-5. Usually, in the industrial waste water, the concentration of Cr (VI) is relatively high and should be determined frequently. So, an accurate, quick, and convenient method for the measurement of Cr (VI) in environmental water, as well as in river, lake, sea and tap water, is of great importance. The method for determination of Cr (VI) by diphenylcarbazine … 相似文献