全文获取类型
收费全文 | 1459篇 |
免费 | 86篇 |
国内免费 | 142篇 |
专业分类
化学 | 1032篇 |
晶体学 | 6篇 |
力学 | 177篇 |
综合类 | 3篇 |
数学 | 67篇 |
物理学 | 402篇 |
出版年
2024年 | 1篇 |
2023年 | 20篇 |
2022年 | 21篇 |
2021年 | 47篇 |
2020年 | 59篇 |
2019年 | 80篇 |
2018年 | 49篇 |
2017年 | 51篇 |
2016年 | 45篇 |
2015年 | 50篇 |
2014年 | 75篇 |
2013年 | 93篇 |
2012年 | 77篇 |
2011年 | 84篇 |
2010年 | 91篇 |
2009年 | 102篇 |
2008年 | 85篇 |
2007年 | 88篇 |
2006年 | 70篇 |
2005年 | 71篇 |
2004年 | 74篇 |
2003年 | 45篇 |
2002年 | 39篇 |
2001年 | 26篇 |
2000年 | 30篇 |
1999年 | 16篇 |
1998年 | 21篇 |
1997年 | 35篇 |
1996年 | 20篇 |
1995年 | 19篇 |
1994年 | 16篇 |
1993年 | 13篇 |
1992年 | 10篇 |
1991年 | 13篇 |
1990年 | 10篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 8篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有1687条查询结果,搜索用时 78 毫秒
31.
Delatour T 《Analytical and bioanalytical chemistry》2004,380(3):515-523
Liquid chromatography–tandem mass spectrometry (LC-MS/MS) is a versatile coupling system which combines both selectivity and sensitivity and certainty. Hence, it is generally considered as the most reliable technique to quantify chemical compounds in complex matrices. In the present paper, we evaluate the performance of LC-MS/MS methods for the quantification of 3-nitrotyrosine in human urine in order to point out its dependence on the design of the quantification method, and emphasize the role of matrix effects in the performance. We compare external and internal calibrations, isotope dilution and isotopomer-based exact matching. The role of both sample preparation and multiple transitions monitoring is particularly addressed. 相似文献
32.
The densities of ethanol and ethanol–water mixtures were measured with a vibrating tube densimeter at 25.0, 50.0 and 75.0 °C in the pressure range from 0.10 to 40.00 MPa. Densities were correlated using an empirical model. Partial molar volumes, excess molar volumes, isothermal compressibilities, cubic expansion coefficients and internal pressures were calculated from obtained densities. This study reports the dependence of densities, partial molar volumes, excess molar volumes, isothermal compressibilities, cubic expansion coefficients and internal pressures on composition, temperature and pressure. 相似文献
33.
从甲基弯菌M ethylosinus trichosporium IMV3011的膜中分离出颗粒性甲烷单加氧酶(Particulate MMO,Pmmo)t和NADH脱氢酶,只有当两者同时存在,并添加去垢剂解离膜组分时,NDAH才能为pMMO提供还原当量,对苯二酚能够在整细胞和膜水平代替NADH作为PMMO的电子供体,对于纯化的PMMO,对苯二分配仍是有效的电子供体,而NADH却是无效的电子供体。在NADH脱氢酶存在下,NADH可将对苯醌还原为对苯二酚,纯化过程中,采用对苯二酚作为PMMO活性分析时的电子供体,不必共纯化NADH脱氢酶,且有利于对PMMO活性中心进行深入研究。 相似文献
34.
吡咯烷二硫代氨基甲酸铵-Ni(Ⅱ)快速共沉淀分离富集和原子吸收光谱法测定痕量铜、铅和镉 总被引:1,自引:0,他引:1
研究了用吡咯烷二硫代氨基甲酸铵(APDC)为沉淀剂,以Ni(Ⅱ)为载体离子的共沉淀体系快速共沉淀分离富集铜、铅和镉,并用火焰原子吸收光谱(FAAS)测定的方法。通常情况下,内标元素和载体离子选择不同的元素,本文尝试将Ni既作为载体又作为内标元素。实验证明,该体系在pH=3.0的条件下,能够定量共沉淀试样中的铜、铅和镉。当试液为100 mL时,铜、铅、镉的检出限分别为9.7×10-3、3.3×10-2,1.01×10-3μg.mL-1,加标回收率为95.8%~101.8%,取得了较为满意的结果。本法只需快速收集部分沉淀,与传统的共沉淀方法比较,具有快速、简便、重现性好的优点。 相似文献
35.
ICP-AES中内标法的应用研究 Ⅲ.用内标法校正基体干扰 总被引:1,自引:0,他引:1
通过观测基体对分析元素发射强度的干扰情况,分析干扰机制,从而确定用来校正基体干扰的内标元素与分析元素的匹配条件。实验结果表明,只要选择合适的内标元素,可以校正基体干扰。 相似文献
36.
Several novel substituted bis(2‐pyridylimino)isoindolato (BPI) cobalt(II) and iron(II) complexes [M(BPI)(OAc)(H2O)] (M = Co: 1 ‐ 6, Fe: 7) have been synthesized by reaction of bis(2‐pyridylimino)isoindole derivatives with the corresponding metal(II) acetates. Reaction of 1‐6 with 1.5 ‐ 2 molar equivalents of t‐BuOOH gave the corresponding alkylperoxocobalt(III) complexes [Co(BPI)(OAc)(OOtBu)] (10 ‐ 15). Using an aqueous solution of t‐BuOOH (70 %), cyclohexene was selectively catalytically oxidized to the dialkylperoxide cyclohex‐2‐ene‐1‐t‐butylperoxide. 相似文献
37.
38.
Vojinović K McLachlan LJ Hinchley SL Rankin DW Mitzel NW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):3033-3042
The simple silylhydrazines F(3)SiN(Me)NMe(2) (1), F(2)Si(N(Me)NMe(2))(2) (2), and F(3)SiN(SiMe(3))NMe(2) (3) have been prepared by reaction of SiF(4) with LiN(Me)NMe(2) and LiN(SiMe(3))NMe(2), while F(3)SiN(SnMe(3))NMe(2) (4) was prepared from SiF(4) and (Me(3)Sn)(2)NNMe(2) (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy ((1)H, (13)C, (14/15)N, (19)F, (29)Si, (119)Sn), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules 1 and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311+G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si.N beta-donor-acceptor bonds between the SiF(3) and geminal NMe(2) groups in silylhydrazines. The strength of these non-classical Si.N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si.N distances are (crystal/gas): 1 104.2(1)/106.5(4) degrees, 2.438(1)/2.510(6) A; 3 83.6(1)/84.9(4) degrees, 2.102(1)/2.135(9) A; 4 89.6(1) degrees, 2.204(2) A. 相似文献
39.
A new method for the synthesis of azo Schiff an base ligand in which the azo and azomethine groups are coordination sites was developed through a Schiff base precursor. The precursor, N-4-methoxybenzylidene-3-hydroxyphenylamine (SB) derived from 3-aminophenol was regioselectively coupled with a diazonium ion para to the hydroxyl group of the amine component of the Schiff base. The para selectivity was controlled by the directing effect of the hydroxyl group. The ligand and its nickel(Ⅱ) complex were characterized by elemental analyses, IR and UV-Vis spectroscopy. The analytical and spectral data supported the mononuclear formulation of the complex with metal to ligand ratio (M : L = 1 : 2) and suggested a square planar geometry for the complex. 相似文献
40.