全文获取类型
收费全文 | 7165篇 |
免费 | 754篇 |
国内免费 | 1243篇 |
专业分类
化学 | 7280篇 |
晶体学 | 56篇 |
力学 | 45篇 |
综合类 | 84篇 |
数学 | 245篇 |
物理学 | 1452篇 |
出版年
2024年 | 13篇 |
2023年 | 81篇 |
2022年 | 186篇 |
2021年 | 266篇 |
2020年 | 343篇 |
2019年 | 209篇 |
2018年 | 236篇 |
2017年 | 240篇 |
2016年 | 317篇 |
2015年 | 293篇 |
2014年 | 414篇 |
2013年 | 604篇 |
2012年 | 402篇 |
2011年 | 428篇 |
2010年 | 379篇 |
2009年 | 457篇 |
2008年 | 435篇 |
2007年 | 462篇 |
2006年 | 490篇 |
2005年 | 458篇 |
2004年 | 445篇 |
2003年 | 390篇 |
2002年 | 218篇 |
2001年 | 213篇 |
2000年 | 203篇 |
1999年 | 176篇 |
1998年 | 163篇 |
1997年 | 123篇 |
1996年 | 99篇 |
1995年 | 110篇 |
1994年 | 74篇 |
1993年 | 56篇 |
1992年 | 33篇 |
1991年 | 27篇 |
1990年 | 24篇 |
1989年 | 22篇 |
1988年 | 17篇 |
1987年 | 9篇 |
1986年 | 9篇 |
1985年 | 14篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1969年 | 1篇 |
排序方式: 共有9162条查询结果,搜索用时 15 毫秒
51.
Tali Menahem Yitzhak Mastai 《Journal of polymer science. Part A, Polymer chemistry》2006,44(9):3009-3017
A series of chiral polymers based on poly(N‐acryl) amino acids was synthesized using a convergent synthetic approach. These chiral polymers have been used as chiral additives to induce enantioselective crystallization of racemic or conglomerate amino acids in solutions. These polymeric additives showed strong capabilities to enhance highly enantioselective resolution during the crystallization of amino acids. In addition, these polymers caused unusual modifications of amino acid crystal morphologies. Furthermore, spherical microparticles of those same chiral polymers were also shown active in similar chiral discriminations during amino acid crystallizations occurring on microparticle surfaces. Our study demonstrates the high potential of chiral polymers and microparticles to resolve amino acids throughout crystallization processes. High enantiomeric excesses in one targeted enantiomer of amino acids can also be maximized via time‐dependent kinetic control of crystallizations. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3009–3017, 2006 相似文献
52.
53.
We present a new algorithm for the identification of ring pairs in Cherenkov detectors. The approach combines linear regression methods for the construction of an appropriate reference quantity, methods from statistics for the evaluation of hypotheses and Monte Carlo simulation runs for the tuning of threshold levels. 相似文献
54.
55.
Takuji Hirose Kumiko Naito Megumi Nakahara Hiroaki Shitara Yoshio Aoki Hiroyuki Nohira Bruce W. Baldwin 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(1-2):87-93
Two Kemp's acid diamides were synthesized and applied to chiral amine recognition using 1H NMR analysis. One derivative based on 1-(1-naphthyl)ethylamine had good chiral recognition of six amines and was useful to determine the optical purity for three amines, i.e., methylbenzylamine, 1-(1-naphthyl)ethylamine and 1- henylpropylamine,however, the cyclohexylethylamine derivative showed little discrimination for the amines studied. Together with the results for alkylamines, it was shown that aromatic structure was important for aromatic shielding anisotropy and –– interactions between host and guest. The structure of the 1-(1-naphthyl)ethylamine derivative in solution was also considered based on 1H NMR data and computer simulation. 相似文献
56.
Summary Chiral recognition of many enantiomeric solutes by a chiral amide stationary phase is based mainly on hydrogen bonding. A
chiral-recognition-factor CHI is proposed, given by the difference of the enthalpy change in the enantiomer discrimination,
standardized with respect to the specific interaction of the solutes with the diamide core of the stationary phase. The r?le
of the entropy part is also discussed. By extrapolation of the retention behaviour to elevated temperature, peak inversion
of enantiomers is predicted.
Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984 相似文献
57.
手性配体立体选择性萃取分离扁桃酸对映体 总被引:6,自引:0,他引:6
Based on chiral ligand exchange, the distribution behavior of mandelic acid enantiomers in the two-phase system containing copper ion(Ⅱ)(Cu2+) and N-n-dedecane-L-hydroxyproline (L), was studied. At different pH, the partition of Cu2+ in the two-phase system containing N-n-dedecane-L-hydroxyproline, was investigated. The formation constant of binary cpmplex(Li2Cu) was obtained by regression. The influence of pH, concentrations of Cu2+ and chiral ligand, and solvents on partition coefficients(K) and separation factor(α), was discussed. The experimental results show that Li forms more stable ternary complex with D-mandelic acid than with L- mandelic acid. There is a large influence of pH on K and α. At low pH values (<3.5), formation of binary complexes is thermodynamically unfavourable. K and α are best when pH values are above 3.5 and the molar ratio of chiral ligand to Cu2+ is 2∶1. At the same time, solvents influence K and α very much. 相似文献
58.
59.
顺式-二(乙二胺)二硝基合钴(Ⅲ)苹果酸盐的晶体结构及手性识别 总被引:2,自引:1,他引:2
合成了标题化合物,并用X-射线衍射法确定了该分子的晶体结构。化合物Δ(λλ),Λ(δδ)-cis-[Co(en)2(NO2)2]2d,l-C4H4O5,Co2C12N12O13H22,Mr=657.94.晶体属单斜晶系,空间群为P21/c,晶胞参数:a=13.969(4),b=6.440(1),c=14.408(4)A,β=94.37(1)°,V=1292.3A3,Z=2,Dc=1.69g/cm3,μ=105.833cm-1,F(000)=668.最终偏离因子R=0.066,Rw=0.085。结构分析表明晶体存在无序现象,其阴离子C4H4O52-有两种排列方式。R-构型和S-构型的几率各为50%,手性识别是通过Δ构型的阳离子与阴离子R-构型C原子上羟基氧形成氢键相互作用;Λ构型的阳离子与阴离子S-构型C原子上羟基氧形成氢键相互作用而实现的。 相似文献
60.
In recent years, the synthesis of chiral tetrahedral clusters has been studied extensively and various types are accessible , which are a kind of organometallic compounds with greatly growing interest due to their potential application to asymmetric reaction catalysts. As an efficient 相似文献