全文获取类型
收费全文 | 2591篇 |
免费 | 87篇 |
国内免费 | 363篇 |
专业分类
化学 | 2582篇 |
晶体学 | 20篇 |
力学 | 4篇 |
综合类 | 13篇 |
数学 | 106篇 |
物理学 | 316篇 |
出版年
2024年 | 4篇 |
2023年 | 77篇 |
2022年 | 55篇 |
2021年 | 72篇 |
2020年 | 103篇 |
2019年 | 84篇 |
2018年 | 94篇 |
2017年 | 135篇 |
2016年 | 135篇 |
2015年 | 82篇 |
2014年 | 151篇 |
2013年 | 463篇 |
2012年 | 253篇 |
2011年 | 155篇 |
2010年 | 132篇 |
2009年 | 137篇 |
2008年 | 142篇 |
2007年 | 150篇 |
2006年 | 142篇 |
2005年 | 124篇 |
2004年 | 128篇 |
2003年 | 79篇 |
2002年 | 18篇 |
2001年 | 11篇 |
2000年 | 7篇 |
1999年 | 13篇 |
1998年 | 12篇 |
1997年 | 11篇 |
1996年 | 8篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 6篇 |
1991年 | 12篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1984年 | 3篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有3041条查询结果,搜索用时 15 毫秒
111.
Taishi Nakanishi Dr. Jun Kikuchi Dr. Atsushi Kaga Prof. Dr. Shunsuke Chiba Prof. Dr. Masahiro Terada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(37):8230-8234
A catalytic enantioselective synthesis of β-amino secondary amides was achieved using vinyl azides as the enamine-type nucleophile and chiral N-Tf phosphoramide as the chiral Brønsted acid catalyst through a five-step sequential transformation in one pot. The established sequential transformation involves an enantioselective [4+2] cycloaddition reaction of vinyl azides with N-acyl imines as the key stereo-determining step that is efficiently accelerated by a chiral N-Tf phosphoramide catalyst in a highly enantioselective manner in most cases. Further generation of the iminodiazonium ion intermediate through ring opening of the cycloaddition product and subsequent skeletal rearrangement involving Schmidt-type 1,2-aryl group migration followed by recyclization of the resulting nitrilium ion were also initiated by the same acid catalyst. Final acid hydrolysis of the recyclized products in the same pot gave rise to enantioenriched β-amino amides through C−C bond formation at the α-position of the secondary amides. 相似文献
112.
113.
本文采用超声法制备了柚皮素(NAR)与β-环糊精(βCD)的包合物.粉末-X射线衍射(XRD)和红外吸收光谱(IR)测定均表明形成的包合物具有不同于主客体的新的结构性质.1H NMR与ROESY核磁共振(NMR)实验表明NAR以苯环端从βCD的宽口端进入,并形成稳定的超分子包合物.量子化学计算分析NAR/βCD包合物的形成过程表明,驱动力源于焓驱动与氢键弱相互作用力;能隙和结合能分析得到的最优包合模式与NMR研究结果一致;ONIOM分层计算验证了上述结果.分子对接模拟出的最优包合模式也与量子化学计算、NMR的分析结果吻合.本文获取了清晰的NAR/βCD包合物构型及其形成机理,为该超分子药物的定量构效关系研究提供了理论参考. 相似文献
114.
Herein, two unit of β-cyclodextrin linked by thiomethylene bridge was synthesized and employed as a novel efficient supramolecular host for the synthesis of biologically active chromenones templates via three-component single-pot reaction. A possible reaction mechanism through molecular complexation is suggested based on 2D ROESY NMR spectroscopic analysis. Moreover, the catalyst could be easily recycled, while a 94% yield and 89% rate of catalyst recovery could be achieved after four cycles of catalyst recycling. Environmentally benign reaction conditions, excellent yields, and avoidance of organic solvent and conventional isolation as well as purification are the noteworthy credits of this developed protocol. 相似文献
115.
Rasha Abdelmawla Ghazala Azza El Medney Anisa Meleis Passant Mohie El dien Hend Samir 《Biomedical chromatography : BMC》2020,34(3):e4743
Lipotoxicity is defined as deposition of excess fat associated with an inflammatory response. Metabolomic analysis of fatty acids (FAs) can be a marker of silent inflammation. ω3-Enriched diet, celecoxib, and safranal may have a protective anti-inflammatory role. In this work, total FAs extracted from red blood cells and arachidonic acid-to-eicosapentaenoic acid (AA-to-EPA) ratios were assessed using GC–MS assay in single-ion monitoring mode. The study was conducted on 64 male rats divided into eight groups: I, controls; II, rats received high-fat diet (HFD), III, rats received ω-6-enriched HFD; IV, rats received ω-3-enriched HFD; V, rats received celecoxib with HFD; VI, rats received safranal with HFD; VII and VIII, rats received celecoxib and safranal with ω-3 HFD, respectively. GC–MS Gas chromatography Mass spectrometry was performed for analysis of fatty acid methyl ester. Enzyme-linked immunosorbent assay was used to analyze serum interleukin-6 (IL-6) and transforming growth factor-beta 1 (TGF-β1) concentrations. A statistically significant decrease of AA-to-EPA ratio was observed in group VII when compared with the groups receiving HFDs. This group also showed the lowest serum IL-6 level and highest TGF-β1 level. In conclusion, ω3-enriched diet along with drugs (e.g. celecoxib) and herbal medications (e.g. safranal) may have an anti-inflammatory effect in lipotoxicity. GC–MS with single-ion monitoring is valid for the analysis of FAs. 相似文献
116.
A convenient and efficient reductive amination for the preparation of chiral β-amino amides is developed utilizing microwave heating. A variety of chiral β-keto amides react with ammonium acetate and sodium cyanoborohydride to afford the desired functionalized amines in good yields. This improved procedure takes advantage of microwave heating to significantly accelerate the reaction and offers a convenient and effective method to access some interesting molecules containing primary amine functionalities. 相似文献
117.
Lynn Vanhaecke Lieven Van MeulebroekNathalie De Clercq Julie Vanden Bussche 《Analytica chimica acta》2013
A prominent trend which has been observed in recent years in the analysis of veterinary drugs and growth-promoting agents is the shift from target-oriented procedures, mainly based on liquid chromatography coupled to triple-quadrupole mass spectrometry (LC-QqQ-MS), towards accurate mass full scan MS (such as time of flight (ToF) and Fourier Transform (FT) Orbitrap MS). In this study the applicability of high resolution single-stage-Orbitrap-MS for confirmatory analysis of growth-promoting agents in meat was compared to that of a QqQ-MS. Validation according to CD 2002/657/EC demonstrated that steroid analysis based on Orbitrap MS, operating at a resolution of 50,000 FWHM, is indeed capable to compete with QqQ-MS in terms of selectivity/specificity, while providing excellent linearity (for most compounds >0.99) but somewhat inferior sensitivity. Indeed, CCαs reached from 0.04–0.88 μg kg−1 for the 34 anabolic steroids upon MS/MS detection, while upon Orbitrap MS detection a range of 0.07–2.50 μg kg−1 was observed. Using QqQ-MS adequate precision was obtained since relative standard deviations, associated with the repeatability and intra-laboratory reproducibility, were below 20%. In the case of Orbitrap MS, for some compounds (i.e. some estrogens) this threshold was exceeded and thus poor precision was observed, which is possibly caused by the lack in sensitivity. Overall, it may be concluded that Orbitrap-MS offers an adequate performance in terms of linearity and precision but lacks in sensitivity for some of the compounds. 相似文献
118.
THE REACTIONS OF N3P3CL6 AND RELATED COMPOUNDS WITH DIFUNCTIONAL REAGENTS. COMPARISONS AND CONTRASTS
Abdulla H. Alkubaisi W. Francis Deutsch Michael B. Hursthouse Harold G. Parkes Leylacaron S. Shaw Robert A. Shaw 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):229-237
Abstract The reactions of N3P3Cl6 with a variety of difunctional reagents are discussed. NMR spectroscopic and X-ray crystallographic investigations are presented. 相似文献
119.
Mitsuhiro Yoshimatsu Fumihiro Hatanaka 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):1007-1010
Abstract β-Ethoxy-α-phenyltellanylvinyl lithiums were successfully generated in situ from phenyltellanylacetaldehyde diethyl acetal with lithium 2,2,6,6-tetrame-thylpiperidide (LTMP) and underwent methylation or nucleophilic addition with aldehydes and ketones. The successive dehydration of the allylic alcohols with trimethylsilyl trifluoromethanesulfonate (TMSOTf) gave α-phenyltellanyl α,β-unsaturated aldehydes, which transformed to some useful compounds. 相似文献
120.
Paulo R. Olivato Mirta G. Mondino Giuseppe Distefano Maurizio Dal Colle Gabriella Bombieri Antonio Del Pra 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):443-444
ABSTRACT. The analysis of the carbonyl I.R. band and the U.V. phoelectron spectroscopic data along with the ab-initio calculations and X-ray diffraction of α-(methylsulfinyl)- and α-(phenylsulfinyl)-acetophenones indicated the predominance of the cis rotamers over the qauche ones. 相似文献