全文获取类型
收费全文 | 17024篇 |
免费 | 1276篇 |
国内免费 | 818篇 |
专业分类
化学 | 16718篇 |
晶体学 | 365篇 |
力学 | 28篇 |
综合类 | 26篇 |
数学 | 54篇 |
物理学 | 1927篇 |
出版年
2024年 | 19篇 |
2023年 | 181篇 |
2022年 | 576篇 |
2021年 | 517篇 |
2020年 | 511篇 |
2019年 | 414篇 |
2018年 | 322篇 |
2017年 | 318篇 |
2016年 | 592篇 |
2015年 | 596篇 |
2014年 | 630篇 |
2013年 | 1296篇 |
2012年 | 789篇 |
2011年 | 721篇 |
2010年 | 810篇 |
2009年 | 815篇 |
2008年 | 821篇 |
2007年 | 870篇 |
2006年 | 832篇 |
2005年 | 778篇 |
2004年 | 832篇 |
2003年 | 725篇 |
2002年 | 1454篇 |
2001年 | 427篇 |
2000年 | 361篇 |
1999年 | 349篇 |
1998年 | 332篇 |
1997年 | 245篇 |
1996年 | 440篇 |
1995年 | 414篇 |
1994年 | 163篇 |
1993年 | 124篇 |
1992年 | 138篇 |
1991年 | 93篇 |
1990年 | 61篇 |
1989年 | 73篇 |
1988年 | 74篇 |
1987年 | 40篇 |
1986年 | 44篇 |
1985年 | 56篇 |
1984年 | 41篇 |
1983年 | 27篇 |
1982年 | 22篇 |
1981年 | 19篇 |
1980年 | 14篇 |
1979年 | 13篇 |
1978年 | 14篇 |
1975年 | 7篇 |
1971年 | 48篇 |
1970年 | 25篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
41.
R. B. King 《Russian Chemical Bulletin》1993,42(11):1772-1781
Reactions of disodium tetracarbonylferrate, Na2Fe(CO)4, with sterically hindered dialkylaminodichlorophosphines, R2NPCl2 (R2N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R2NP)2COFe2(CO)6 as the major products. The phosphorus-bridging carbonyl group in (i-Pr2NP)2COFe2(CO)6 has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993. 相似文献
42.
43.
Jörg Teichgräber 《Journal of organometallic chemistry》2005,690(23):5255-5263
The synthesis, characterization, and thermal decomposition behavior of dicopper(I) oxalato complexes L4Cu2(C2O4) (L = CNtBu (2a), CNCMe2CH2tBu (2b), CNC6H3Me2-2,6 (2c)) is reported. 2c can be prepared in a straightforward manner by the reaction of stoichiometric amounts of Cu2O and oxalic acid with four equivalents of CNC6H3Me2-2,6, while those complexes with aliphatic isocyanides are better prepared from a copper(I) oxalato complex with alkine capping ligands (Me3SiCCSiMe3)2Cu2(C2O4) (1) via ligand exchange. Crystallographic and spectroscopic evidence for 2a-c confirms the anticipated dinuclear structure with the oxalate in a μ-1,2,3,4 bridging mode and an essentially σ-character of the terminal isocyanides. In solid form the complexes are stable at room temperature and can be handled in air for some time. Their decomposition was studied by thermal gravimetric analysis coupled with mass spectrometry, and the degradation pathway was shown to depend on the type of isocyanide capping ligand. Decomposition of 2a,b takes place between 150 and 200 °C to give CuCN in a clean process that involves isobutene elimination from the terminal ligands, with elimination of (CN)2 and conversion to elemental copper at higher temperatures. Heating of 2c leads to CuO (and then to Cu2O) via release of the intact isocyanide, CO2, and CO in a well-behaved thermal process around 200-280 °C. 相似文献
44.
Indoles undergo smooth alkylation with cyclopropyl ketones in the presence of the CeCl3·7H2O/LiI reagent system in refluxing acetonitrile under neutral conditions to produce the corresponding C-3 substituted indole derivatives in good to high yields and with high selectivity. The use of CeCl3·7H2O/LiI makes this method simple, convenient, and cost-effective. 相似文献
45.
高含量钒的钼钒磷杂多化合物的合成和性质研究 总被引:2,自引:0,他引:2
本工作改进了文献[4]报导的几种原料同时混合、加热煮沸合成的方法采用分步加入原料,控制反应温度、多次重结晶的方法合成了6、7、8个钒原子取代的钼钒磷杂多酸铵;并以铵盐为原料,用离子交换、冷冻分离和真空抽吸相结合的提纯方法制备了未见文献报导的相应的固体杂多酸;H5[PMo5V7O37.5]·xH2O,H6[PMo4V8O37.5]·xH2O。通过元素组成分析确定了它们的组成。这些杂多酸在水溶液、非水溶液中的电位滴定表明,杂多阴离子在分解前没有发生自电离、水解等情况,它们在水溶液中是稳定的。酸的碱度分别为5、5、6。通过纸上色谱实验,讨论了杂多酸的分解过程。由热重分析和溶解性实验得到它们的分解温度,本文还讨论了这些化合物的红外、紫外光谱,x光粉末衍射及极谱性质。光谱结果表明,它们可能具有Keggin结构,由导数脉冲极谱得到它们的峰电位。 相似文献
46.
47.
Elimination of matrix effects for headspace solid-phase microextraction of important volatile compounds in red wine using a novel coating 总被引:2,自引:0,他引:2
In this paper, hydroxy-terminated silicone oil-butyl methacrylate-divinylbenzene (OH-TSO-BMA-DVB) copolymer was first synthesized and used as stationary phase with the aid of γ-methacryloxypropyltrimethoxylsilane (KH-570) as bridge in solid-phase microextraction (SPME) using sol–gel method and cross-linking technique. It has high extraction efficiency for both polar alcohols and fatty acids and nonpolar esters in comparison with commercial PDMS, PDMS-DVB and PA fibers. A simple and sensitive headspace SPME-gas chromatography (HS-SPME-GC) method using the novel fiber was presented for the simultaneous analysis of both polar alcohols and fatty acids and nonpolar esters in wine. To check the matrix effects, various model wine matrices, including distilled water; 11.5% ethanol/water (v/v) solution; a concentrated synthetic wine; a ‘volatile-free’ wine and a real wine were investigated in detail. Matrix effects were compensated for by using internal standard method and selecting the ‘volatile-free’ wine as working standard. The method presented in this study showed satisfactory linearity, precision, detection limits and accuracy. The recoveries obtained ranged from 85.87 to 104.2%, and the relative standard deviation values were below 9%. The results obtained indicated that the present method is a validated and accurate procedure for the simultaneous determination of both polar and nonpolar aroma compounds in wine. 相似文献
48.
Solvent-free organic reactions have been attracting great interest of chemists due to the elimination of the usage of harmful organic solvents,low costs,and simplicity in the procedure1.Solvent-free mechanochemical reactions of fullerenes were explored and are significant for the reactions of fullerenes because the low solubility of fullerenes in common organic solvents requires large quantity of organic solvents and some novel fullerene reactions could only occur in the solid-state reaction2.… 相似文献
49.
50.