全文获取类型
收费全文 | 323篇 |
免费 | 21篇 |
国内免费 | 17篇 |
专业分类
化学 | 349篇 |
晶体学 | 2篇 |
物理学 | 10篇 |
出版年
2023年 | 3篇 |
2022年 | 10篇 |
2021年 | 16篇 |
2020年 | 11篇 |
2019年 | 17篇 |
2018年 | 17篇 |
2017年 | 12篇 |
2016年 | 9篇 |
2015年 | 9篇 |
2014年 | 14篇 |
2013年 | 11篇 |
2012年 | 16篇 |
2011年 | 15篇 |
2010年 | 20篇 |
2009年 | 12篇 |
2008年 | 15篇 |
2007年 | 18篇 |
2006年 | 14篇 |
2005年 | 6篇 |
2004年 | 11篇 |
2003年 | 8篇 |
2002年 | 8篇 |
2001年 | 2篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 7篇 |
1997年 | 7篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 7篇 |
1993年 | 3篇 |
1992年 | 7篇 |
1991年 | 6篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 6篇 |
1986年 | 1篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有361条查询结果,搜索用时 109 毫秒
21.
Narayanan Balaji Bhavesh Babulal Gabani Umesh Todmal Suresh P. Sulochana Neeraj Kumar Saini Rajesh Chandran Ramesh Mullangi 《Biomedical chromatography : BMC》2019,33(3)
We developed and validated a simple, sensitive, selective and reliable LC–ESI‐MS/MS method for direct quantitation of dropropizine enantiomers namely levodropropizine (LDP) and dextrodropropizine (DDP) in rat plasma without the need for derivatization as per regulatory guidelines. Dropropizine enantiomers and carbamazepine (internal standard) were extracted from 50 μL rat plasma using ethyl acetate. LDP and DDP resolved with good baseline separation (Rs = 4.45) on a Chiralpak IG‐3 column. The mobile phase consisted of methanol with 0.05% diethylamine pumped at a flow rate of 0.5 mL/min. Detection and quantitation were done in multiple reaction monitoring mode following the transitions m/z 237 → 160 and 237 → 194 for dropropizine enantiomers and the internal standard, respectively, in the positive ionization mode. The proposed method provided accurate and reproducible results over the linearity range of 3.23–2022 ng/mL for each enantiomer. The intra‐ and inter‐day precisions were in the ranges of 3.38–13.6 and 5.11–13.8 for LDP and 4.19–11.8 and 8.89–10.1 for DDP. Both LDP and DDP were found to be stable under different stability conditions. The method was successfully used in a stereoselective pharmacokinetic study of dropropizine enantiomers in rats following oral administration of racemate dropropizine at 100 mg/kg. The pharmacokinetic results indicate that the disposition of dropropizine enantiomers is not stereoselective and chiral inversion does not occur in rats. 相似文献
22.
《中国化学会会志》2017,64(9):1058-1064
To reveal the nature of the interaction of the optical isomers of propranolol with the surface of carbon paste electrodes modified by uracil, we performed a combined computational and experimental study. Our study comprised the different modes of complexation between propranolol and uracil molecules covering the carbon paste electrode within two approaches: molecular dynamics simulation (MD ) and quantum mechanics (QM) modeling. A graphene layer was used as a model of the carbon paste electrode. The computations showed that uracil modification of the carbon paste electrode surface enhanced the selectivity toward the D‐isomer of propranolol as compared to the unmodified case. These theoretical results agree with our voltammetric measurements. 相似文献
23.
Valery Kukhar Vladimir Solodenko Vadim Soloshonok Tamara Kasheva 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):529-532
Abstract Synthesis of enantiomeric amino phosphonic acids APA is described by using chiral auxiliary reagent or enzymatic resolution of racemic mixtures of APA phenacyl derivatives. Peptides with APA residue were obtained by application of trimethylsilyl derivatives or condensation in the presence of enzyme-papain 相似文献
24.
基于单级手性萃取数学模型和质量守恒定律,建立了多级离心手性萃取数学模型,设计了多级离心萃取数学模型程序,并对多级离心萃取分离苯基琥珀酸(PSA)对映体进行了模拟.模拟了相比、萃取剂浓度、对映体浓度、进料位置和萃取级数等工艺参数对萃取效果(产物纯度和产率)的影响.模拟结果表明,考察的工艺参数共同影响萃取相和萃余相的产物纯度及产率;采用中间位置进料和较大的W/F相比有利于对称分离.实验发现:采用中间位置进料,10级离心萃取后萃取相中苯基琥珀酸的光学纯度ee(对映体过量)达到56%以上.模拟结果还表明,采用26级离心萃取器,中间进料,逆流分级萃取,萃取相及萃余相中的光学纯度ee都能达到98%以上. 相似文献
25.
Akkirala Venkat Narsaiah 《合成通讯》2013,43(13):1897-1901
Enantiomerically pure (S)‐RO363 was synthesized by using (R,R) Salen Co(III) complex for the resolution of terminal epoxide. The hydrolytic kinetic resolution process was carried out at room temperature in excellent enantioselectivity. The method can be applied for large‐scale preparation of (S) RO363. 相似文献
26.
Enhancement of enantioselectivity in chiral capillary electrophoresis using hydroxypropyl‐beta‐cyclodextrin as chiral selector under molecular crowding conditions induced by dextran or dextrin
下载免费PDF全文
![点击此处可从《Electrophoresis》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Molecular crowding is a new approach to enhance the retention properties and selectivity of molecularly imprinted polymers. In this work, this concept was first applied to chiral CE to enhance its enantioselectivity. A model system, enantioseparation of salbutamol using hydroxypropyl‐beta‐cyclodextrin as chiral selector in the presence of dextran or dextrin as crowding‐inducing agents, was chosen to demonstrate its potency. Some parameters, especially the concentration of crowding‐inducing agents and cyclodextrins were investigated intensively. Moreover, based on fluorescence spectroscopy and affinity CE, it was found that the presence of crowding‐inducing agents could promote the association of enantiomers with cyclodextrins and intensify the interacting differences of two enantiomers with cyclodextrins. As a result, the essential concentration of cyclodextrins to make the enantiomers reach baseline separation was significantly decreased with the aid of molecular crowding. This study shows that molecular crowding is an effective strategy to enhance the enantioselectivity of cyclodextrin in chiral CE. 相似文献
27.
Friederike A. Sandbaumhüter Claudia Gittel M. Paula Larenza-Menzies Regula Theurillat Wolfgang Thormann Christina Braun 《Electrophoresis》2021,42(17-18):1826-1831
The enantioselectivity of the pharmacokinetics of methadone was investigated in anesthetized Shetland ponies after a single intravenous (0.5 mg/kg methadone hydrochloride; n = 6) or constant rate infusion (0.25 mg/kg bolus followed by 0.25 mg/kg/h methadone hydrochloride; n = 3) administration of racemic methadone. Plasma concentrations of l -methadone and d -methadone and their major metabolites, l - and d -2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), respectively, were analyzed by CE with highly sulfated γ-cyclodextrin as chiral selector and electrokinetic analyte injection from liquid/liquid extracts prepared at alkaline pH. In both trials, the d -methadone concentrations were lower than those of l -methadone and the d -EDDP levels were lower than those of L-EDDP. For the case of a single intravenous bolus injection, the plasma concentration versus time profile of methadone enantiomers was analyzed with a two-compartment pharmacokinetic model. l -methadone showed a slower elimination rate constant, a lower body clearance, and a smaller steady-state volume of distribution than d -methadone. d -methadone and d -EDDP were eliminated faster than their respective l -enantiomers. This is the first study that outlines that the disposition of racemic methadone administered to anesthetized equines is enantioselective. 相似文献
28.
Functionalized Graphene as a Gatekeeper for Chiral Molecules: An Alternative Concept for Chiral Separation
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Andreas W. Hauser Narbe Mardirossian Julien A. Panetier Martin Head‐Gordon Alexis T. Bell Peter Schwerdtfeger 《Angewandte Chemie (International ed. in English)》2014,53(37):9957-9960
We propose a new method of chiral separation using functionalized nanoporous graphene as an example. Computational simulations based on density functional theory show that the attachment of a suitable chiral “bouncer” molecule to the pore rim prevents the passage of the undesired enantiomer while letting its mirror image through. 相似文献
29.
Guo‐Feng Liu Prof. Di Zhang Prof. Chuan‐Liang Feng 《Angewandte Chemie (International ed. in English)》2014,53(30):7789-7793
In the three‐dimensional (3D) extracellular matrix (ECM), the influence of nanofiber chirality on cell behavior is very important; the helical nanofibrous structure is closely related to the relevant biological events. Herein, we describe the use of the two enantiomers of a 1,4‐benzenedicarboxamide phenylalanine derivative as supramolecular gelators to investigate the influence of the chirality of nanofibers on cell adhesion and proliferation in three dimensions. It was found that left‐handed helical nanofibers can increase cell adhesion and proliferation, whereas right‐handed nanofibers have the opposite effect. These effects are ascribed to the mediation of the stereospecific interaction between chiral nanofibers and fibronectin. The results stress the crucial role of the chirality of nanofibers on cell‐adhesion and cell‐proliferation behavior in 3D environments. 相似文献
30.
Ann Gogolashvili Lali Chankvetadze Nino Takaishvili Antonio Salgado Bezhan Chankvetadze 《Electrophoresis》2020,41(12):1023-1030
The major goal of this study was to determine the affinity pattern of the terbutaline (TB) enantiomers toward α-, β-, γ-, and heptakis(2,3-di-O-acetyl)-β-cyclodextrins and using NMR spectroscopy for the understanding of the fine mechanisms of interaction between the cyclodextrins (CD) and TB enantiomers. It was shown once again that CE in combination with NMR spectroscopy represents a sensitive tool to study the affinity patterns and structure of CD complexes with chiral guests. Opposite affinity patterns of TB enantiomers toward native α- and β-CDs were associated with significant differences between the structure of the related complexes in solution. In particular, the complex between TB enantiomers and α-CD was of the external type, whereas an inclusion complex was formed between TB enantiomers and β-CD. One of the possible structures of the complex between TB and heptakis(2,3-di-O-acetyl)-β-CD (HDA-β-CD) was quite similar to that of TB and β-CD, although the chiral recognition pattern and enantioselectivity of TB complexation with these two CDs were very different. 相似文献