全文获取类型
收费全文 | 4431篇 |
免费 | 260篇 |
国内免费 | 383篇 |
专业分类
化学 | 4273篇 |
晶体学 | 17篇 |
力学 | 18篇 |
综合类 | 16篇 |
数学 | 100篇 |
物理学 | 650篇 |
出版年
2024年 | 10篇 |
2023年 | 119篇 |
2022年 | 91篇 |
2021年 | 161篇 |
2020年 | 130篇 |
2019年 | 159篇 |
2018年 | 110篇 |
2017年 | 141篇 |
2016年 | 156篇 |
2015年 | 141篇 |
2014年 | 188篇 |
2013年 | 282篇 |
2012年 | 208篇 |
2011年 | 259篇 |
2010年 | 234篇 |
2009年 | 296篇 |
2008年 | 242篇 |
2007年 | 276篇 |
2006年 | 292篇 |
2005年 | 296篇 |
2004年 | 295篇 |
2003年 | 137篇 |
2002年 | 90篇 |
2001年 | 92篇 |
2000年 | 95篇 |
1999年 | 78篇 |
1998年 | 72篇 |
1997年 | 60篇 |
1996年 | 57篇 |
1995年 | 48篇 |
1994年 | 38篇 |
1993年 | 33篇 |
1992年 | 29篇 |
1991年 | 28篇 |
1990年 | 30篇 |
1989年 | 14篇 |
1988年 | 17篇 |
1987年 | 16篇 |
1986年 | 14篇 |
1985年 | 5篇 |
1984年 | 12篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 1篇 |
1980年 | 6篇 |
1979年 | 4篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 2篇 |
排序方式: 共有5074条查询结果,搜索用时 31 毫秒
81.
A chiral stationary phase (CSP) based on (-)-(18-crown-6)-2,3,11,12-tetracarboxylic acid was evaluated for the direct resolution of the enantiomers of dipeptides and tripeptides. The type and concentration of the acid and the methanol content were optimized with regard to retention time and resolution using Ala-Phe as model peptide. A mobile phase consisting of 10 mM sulfuric acid in 70% aqueous methanol was applied to the separation of a set of 16 structurally diverse dipeptides and tripeptides. Generally, the configuration of the amino acid at the N-terminus determined the enantiomer elution order. With a few exceptions the LL- and LD-enantiomers interacted stronger with the CSP compared to the corresponding DD- or DL-enantiomers. The experimental conditions also allowed the simultaneous separation of all four stereoisomers of Ala-Phe. Addition of ammonium sulfate generally reduced retention times and enantiomer resolution. Addition of triethylamine as modifier led to an overall increase of the retention times while the resolution did not show a general trend, increasing in the case of Ala-Ala but decreasing in the case of Ala-Phe. 相似文献
82.
Andrea Basso 《Tetrahedron letters》2004,45(3):587-590
Intramolecular Ugi reactions with bicyclic β-amino acids have been performed and the effects of the configuration and N-alkylation have been studied. We have proven that preferential ring contraction or nucleophilic attack by the solvent depend not only on the presence of N-alkylation but also on the relative disposition of the carboxyl group and the amine. Excellent results in terms of stereoselectivity have been obtained in the case of N-alkyl-3-exo-amino-7-oxabicyclo[2.2.1]-2-endo-carboxylic acids. 相似文献
83.
Peroxisomicine A1 is a potentially antineoplastic compound isolated from the seeds of Karwinskia parvifolia. It is considered as a useful chemotype for the preparation of topoisomerase II targeted anticancer cells. Stereochemically, it is characterized by the presence of two stereocenters and a rotationally hindered and thus likewise stereogenic biaryl axis. In this contribution, the absolute configuration of peroxisomicine A1 and its epimer, peroxisomicine A2, was established by means of a five-step degradative procedure giving the respective R- and S-configured methyl 2-(2′-methyl-5′-oxotetrahydrofuryl)acetates. The configuration of the degradation product was obtained by means of optical rotation, 1H NMR analysis using a chiral displacement reagent, and by experimental and quantum chemical circular dichroism (CD) investigations. Based on the results obtained here and considering our previous work on the relative configuration at centers versus axis of these compounds, peroxisomicine A1 resulted to be the P,3S,3′S-isomer and peroxisomicine A2 the P,3R,3′S-isomer. 相似文献
84.
两个新的氢键诱导液晶化合物的合成 总被引:3,自引:0,他引:3
通过4-丁氧基苯甲酸(4BA0与两个手性取代的苯乙烯基吡啶(VSZ及LSZ)间的氢键作用合成了2个新的液晶化合物,用DSC、偏光显微镜研究了其液晶行为,并由红外光谱证实了分子间氢键的存在,形成的复合物4BA-VSZ具有手性近晶C相。 相似文献
85.
A simple liquid chromatographic method was developed for the separation and quantification of voriconazole and its enantiomer
in drug substance. The separation was achieved on Chiral cel-OD (250 mm × 4.6 mm × 10 μm) using mobile phase consisting of
n-hexane and ethanol in the ratio 9:1 (v/v) with a flow rate of 1.0 mL min−1, at 27 °C column temperature and detection at 254 nm with an injection volume of 20 μL. Ethanol was used as diluent. The
method is capable of detecting the (2S, 3R) enantiomer down to 0.0075% and can quantify down to 0.021% with respect to sample concentration. The method is rapid and
the resolution achieved was about 3.0. This method can be employed for the quantification of (2S, 3R) enantiomer in voriconazole drug substance. 相似文献
86.
Mathis B. Hodge 《Tetrahedron》2004,60(42):9397-9403
The addition of chlorotitanium enolates of N-acetyl isopropyl thiazolidine-2-thione to aldehydes was investigated. The stereoselectivity of the aldol products was controlled by the number of equivalents of base added. The syn aldol product was obtained preferentially when 2 equiv of Lewis acid and 1 equiv of base were employed. The anti aldol product was obtained preferentially when 1 equiv of Lewis acid and 2 equiv of base were employed for unsaturated aldehydes. Unexpected results were found with hindered aldehydes when 2 equiv of base were employed. 相似文献
87.
手性5-l-(艹孟)氧基丁内酯并[3,4-d]-3-取代基-异(口恶)唑啉类化合物的合成 总被引:2,自引:0,他引:2
研究了手性元5-(R)-(l-(艹孟)氧基)-2(5H)-呋喃酮与取代苯甲醛肟以次氯酸钙作为氧化剂进行的区域选择性原位1,3-偶极环加成反应,同步生成两个新的手性中心,得到了一系列光学纯丁内酯并[3,4-d]-3-取代基-异(口恶)唑啉类化合物;应用波谱学手段及X射线单晶衍射法确证了产物的绝对构型,并对产物的核磁共振氢谱规律性加以总结. 相似文献
88.
An efficient method of photoaffinity labeling has been developed based on rationally designed multifunctional photoprobes. Photoaffinity techniques have been used to elucidate the protein structure at the interface of biomolecules by the photochemical labeling of interacting sites. However, the identification of labeled sites within target proteins is often difficult. Novel biotinyl bioprobes bearing a diazirine photophore have contributed significantly to the rapid elucidation of ligand binding sites within proteins, thereby extending conventional photoaffinity methods. This article discusses the synthesis and applications of various photoprobes bearing a biotin, including strategies using cleavable linkages between photophores. The combination of photoaffinity methods with chip technology is also described as a novel entry to rapid affinity-based screening of inhibitors. This review focuses on a rapid and reliable photoaffinity method utilizing diazirine-based multifunctional photoprobes with numerous potential applications in functional proteomics of biomolecular interactions. 相似文献
89.
A chiral base route to a range of highly functionalised amino cyclopentenes has been developed. The key asymmetric step involved the chiral lithium amide base-mediated rearrangement of a protected trans-4-hydroxy cyclopentene oxide to give an allylic alcohol (88% ee). Subsequent Overman rearrangement gave a protected trans-1,2-aminocyclopentenol whereas Mitsunobu substitution with BocNHNs gave a protected cis-amino cyclopentenol. Both are proven intermediates for natural product synthesis. The protected cis-aminocyclopentenol was transformed in a few steps into a precursor of the cyclopentene core of nucleoside Q, a natural product whose deficiency in animals is related to tumour growth. 相似文献
90.
NMR spectroscopy techniques for screening and identifying ligand binding to protein receptors 总被引:9,自引:0,他引:9
Binding events of ligands to receptors are the key for an understanding of biological processes. Gaining insight into protein-protein and protein-ligand interactions in solution has recently become possible on an atomic level by new NMR spectroscopic techniques. These experiments identify binding events either by looking at the resonance signals of the ligand or the protein. Ideally, both techniques together deliver a complete picture of ligand binding to a receptor. The approaches discussed in this review allow screening of compound libraries as well as a detailed identification of the groups involved in the binding events. Also, characterization of the binding strength and kinetics is possible, competitive binding as well as allosteric effects can be identified, and it has even been possible to identify ligand binding to intact viruses and membrane-bound proteins. 相似文献