全文获取类型
收费全文 | 15827篇 |
免费 | 1403篇 |
国内免费 | 727篇 |
专业分类
化学 | 15721篇 |
晶体学 | 353篇 |
力学 | 24篇 |
综合类 | 13篇 |
数学 | 4篇 |
物理学 | 1842篇 |
出版年
2024年 | 11篇 |
2023年 | 151篇 |
2022年 | 197篇 |
2021年 | 495篇 |
2020年 | 517篇 |
2019年 | 380篇 |
2018年 | 331篇 |
2017年 | 298篇 |
2016年 | 588篇 |
2015年 | 568篇 |
2014年 | 619篇 |
2013年 | 1213篇 |
2012年 | 756篇 |
2011年 | 680篇 |
2010年 | 765篇 |
2009年 | 772篇 |
2008年 | 804篇 |
2007年 | 839篇 |
2006年 | 801篇 |
2005年 | 751篇 |
2004年 | 796篇 |
2003年 | 712篇 |
2002年 | 1435篇 |
2001年 | 400篇 |
2000年 | 347篇 |
1999年 | 343篇 |
1998年 | 313篇 |
1997年 | 231篇 |
1996年 | 431篇 |
1995年 | 398篇 |
1994年 | 154篇 |
1993年 | 120篇 |
1992年 | 133篇 |
1991年 | 83篇 |
1990年 | 55篇 |
1989年 | 69篇 |
1988年 | 71篇 |
1987年 | 37篇 |
1986年 | 41篇 |
1985年 | 57篇 |
1984年 | 40篇 |
1983年 | 24篇 |
1982年 | 22篇 |
1981年 | 19篇 |
1980年 | 15篇 |
1979年 | 11篇 |
1978年 | 13篇 |
1975年 | 7篇 |
1972年 | 6篇 |
1969年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 751 毫秒
81.
人工神经网络方法预测气相色谱保留值 总被引:8,自引:2,他引:8
本文运用一典型的人工神经网络模型-“反向传播“模型的改进形式,研究了诱导效应指数I,摩尔折射度Ro,疏水亲脂参数IgP,以及分子联通性指数与气象色谱保留行为的关系,实现了对色谱保留植的预测。神经网络预测模型的最大相对误差不超过8.7%。结果表明,该方法性能良好,可望成为色谱保留值预测的有效手段。 相似文献
82.
蛋白质—四氯苯醌荷移反应的分光光度研究 总被引:5,自引:0,他引:5
本文用分光光度法研究了蛋白质—四氯苯醌荷移反应。通过对影响反应各因素的研究,确立了以四氯苯醌形成荷移络合物的方法测定蛋白质的最佳条件,测定了最大结合数及反应平衡常数。 相似文献
83.
84.
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
85.
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
86.
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
87.
Hubert HuppertzRolf-Dieter Hoffmann Rainer Pöttgen 《Journal of solid state chemistry》2002,169(2):155-159
EuPd0.72In1.28 and EuPt0.56In1.44 were prepared under multianvil high-pressure (10.5 GPa) high-temperature (1500 and 1400 K) conditions from the precursor compounds EuPdIn and EuPtIn. They were investigated by X-ray diffraction on both powders and single crystals: MgZn2-type, space group P63/mmc, a=578.7(1) pm, c=944.9(3) pm, wR2=0.0734, 263 F2 values for EuPd0.72In1.28 and a=591.1(2) pm, c=933.8(2) pm, wR2=0.0853, 151 F2 values for EuPt0.56In1.44 with 13 variable parameters per refinement. Both structures are built up from face- and corner-sharing tetrahedra of palladium (platinum) and indium atoms. The europium cations are located in cavities within the three-dimensional [Pd0.72In1.28] and [Pt0.56In1.44] networks. The 2a and 6 h positions of the tetrahedral networks show mixed Pd/In and Pt/In occupancy in EuPd0.72In1.28 and EuPt0.56In1.44, respectively. The crystal chemistry of these indides is briefly discussed. 相似文献
88.
89.
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
90.
化学计量学在有机物电分析化学中的应用 总被引:1,自引:0,他引:1
化学计量学在有机物电分析化学中的应用日益广泛,并发挥重要的作用。本文就化学计量学方法在色素、抗氧化剂、维生素、氨基酸、环境污染物、农药及药物等电分析化学方面的应用作一综述。引用参考文献58篇。 相似文献