全文获取类型
收费全文 | 3160篇 |
免费 | 326篇 |
国内免费 | 134篇 |
专业分类
化学 | 1529篇 |
晶体学 | 19篇 |
力学 | 253篇 |
综合类 | 59篇 |
数学 | 978篇 |
物理学 | 782篇 |
出版年
2024年 | 4篇 |
2023年 | 45篇 |
2022年 | 202篇 |
2021年 | 234篇 |
2020年 | 123篇 |
2019年 | 78篇 |
2018年 | 61篇 |
2017年 | 106篇 |
2016年 | 132篇 |
2015年 | 74篇 |
2014年 | 123篇 |
2013年 | 184篇 |
2012年 | 167篇 |
2011年 | 194篇 |
2010年 | 135篇 |
2009年 | 196篇 |
2008年 | 153篇 |
2007年 | 202篇 |
2006年 | 149篇 |
2005年 | 131篇 |
2004年 | 130篇 |
2003年 | 117篇 |
2002年 | 95篇 |
2001年 | 66篇 |
2000年 | 69篇 |
1999年 | 77篇 |
1998年 | 45篇 |
1997年 | 38篇 |
1996年 | 34篇 |
1995年 | 35篇 |
1994年 | 29篇 |
1993年 | 32篇 |
1992年 | 19篇 |
1991年 | 23篇 |
1990年 | 14篇 |
1989年 | 13篇 |
1988年 | 12篇 |
1987年 | 15篇 |
1986年 | 15篇 |
1985年 | 9篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1959年 | 2篇 |
1957年 | 2篇 |
排序方式: 共有3620条查询结果,搜索用时 15 毫秒
111.
Summary We have investigated to which extent retention data, acquired on single capillary columns, can be used for predicting retention factors in a coupled column system. For this purpose we utilized a model mixture of 18 lipid components with widely different vapor pressures and polarities. The sample was chromatographed on two columns, SB-biphenyl-30 (70% methyl-30% biphenylpolysiloxane) and SB-cyanopropyl-50 (50% methyl-50% cyanopropylsiloxane). Experimental retention factors, acquired in coupled column systems with two columns connected in different order, were thus compared with values calculated from runs on each single column. The agreement between calculated and experimental values generally was better than 5% without any pressure drop correction.To study the possibility of predicting retention behavior in a wide pressure range from a limited number of experiments, we also investigated the relation between solute retention and mobile phase density. We found that all data could be fitted to second order equations, which gives the possibility to optimize the resolution with respect to pressure from a limited number of runs at different pressures. 相似文献
112.
19F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo6Br Cl )F ]2?, n = 0 – 8 The complete system of the innersphere mixed clusters (Mo6BrCl)4+ is formed by exchange of innersphere bound Cli against outersphere bound Bra on tempering the solid [(Mo6Cl)Br] at 500°C for 16 h. After conversion with conc. HCl into (H3O)2[(Mo6BrCl)Cl] and precipitation of the outer Cla with AgBF4 in ethanol, treatment with tetrabutylammonium(TBA)fluoride yields (TBA)2 [(Mo6BrCl)F], a mixture of 22 different species. According to the sets of chemical equivalent fluorine atoms in total 55 19F nmr signals are expected, which are really observed in the high resolution 1D-19F-nmr spectrum. Using increments of chemical shifts, peak intensities and multiplet structures as well as the 2D-19F/19F-COSY spectrum the complete and unambiguous assignment of all resonances is achieved. From the measured integral intensities the distribution of the different compounds is determined, revealing statistical formation of the geometrical isomers. 相似文献
113.
《Tetrahedron letters》2005,46(16):2771-2774
Treatment of 3β-acetoxy-5-bromo-6β,19-epoxy-5α-androstan-17-one with Ac2O and BF3·OEt2, produced the cleavage of the epoxy moiety and migration of the bromine atom to afford 3β,19-diacetoxy-6α-bromo-5-hydroxy-5β-androst-17-one in high yield. 相似文献
114.
Efforts to develop a database of quadratic force fields for organic molecules are described. The database is based on systematic ab initio calculations, scaled to reproduce the experimentally observed frequencies. The choice of the theoretical method, the basis sets, geometries, internal coordinates and the scaling procedure are discussed. A key point in the procedure is the automatic generation of the internal valence coordinates. This is also very advantageous for geometry optimization. The database should permit the prediction of vibrational frequencies for most organic molecules to 10–20 cm−1, together with semiquantitative intensities. The accuracy is sufficient to identify unknown compounds from a list of reasonable candidates. 相似文献
115.
To evaluate the reactivity of new difluroroaromatic compounds in nucleophilic substitution, the positive charges on carbon
atoms of C−F bonds were calculated using the quantum-chemical semiempirical PM3 method. A correlation between the charges
calculated and the chemical shifts in the19F NMR spectra was established.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 623–625, April, 1998. 相似文献
116.
117.
对中段多脉冲机动突防弹道的设计问题进行了研究。采用的原理与方法有别于成熟的航天器多脉冲变轨,而是基于路径规划的思想对弹道设计问题简化。考虑敌方防御系统延迟,改进多脉冲点火模型,并基于变射面的思想对关机点参数进行了设计及优化。然后,从使敌方预测误差最大的角度提出评价函数,并利用遗传算法进行优化。最后,给出了一种同时满足导弹机动突防与打击精度要求的多脉冲弹道设计方法。从模型的可行性,方法的有效性、灵活性、迭代效率及精度等方面进行了仿真验证分析。在PC机仿真中,20 s内就设计出一条保证打击精度的中段突防弹道。结果表明,建立的模型是可行的,提出的突防弹道设计方法是快速有效的。 相似文献
118.
Metal‐pernitride compounds belong to a class of chemical systems in which both the complex ions and the non‐bonding electrons may play roles in the formation of their modified crystalline structures. To investigate this issue, the energy landscapes of pernitrides of metals with different maximum valence (M=Ca, Sr, Ba, La, and Ti) were globally explored on the ab initio level at standard and high pressures, thereby yielding possible (meta)stable modifications in these systems together with information on how the landscape changed as function of the valence of the metal cation. For all of the systems in which no compounds had been synthesized so far, we predicted the existence of kinetically stable modifications that should, in principle, be experimentally accessible. In particular, TiN2 should crystallize in a new structure type, TiN2‐I. 相似文献
119.
120.
Sergey S. Golotvin Rostislav Pol Ryan R. Sasaki Asya Nikitina Philip Keyes 《Magnetic resonance in chemistry : MRC》2012,50(6):429-435
Automated structure verification using 1H NMR data or a combination of 1H and heteronuclear single‐quantum correlation (HSQC) data is gaining more interest as a routine application for qualitative evaluation of large compound libraries produced by synthetic chemistry. The goal of this automated software method is to identify a manageable subset of compounds and data that require human review. In practice, the automated method will flag structure and data combinations that exhibit some inconsistency (i.e. strange chemical shifts, conflicts in multiplicity, or overestimated and underestimated integration values) and validate those that appear consistent. One drawback of this approach is that no automated system can guarantee that all passing structures are indeed correct structures. The major reason for this is that approaches using only 1H or even 1H and HSQC spectra often do not provide sufficient information to properly distinguish between similar structures. Therefore, current implementations of automated structure verification systems allow, in principle, false positive results. Presented in this work is a method that greatly reduces the probability of an automated validation system passing incorrect structures (i.e. false positives). This novel method was applied to automatically validate 127 non‐proprietary compounds from several commercial sources. Presented also is the impact of this approach on false positive and false negative results. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献