全文获取类型
收费全文 | 4934篇 |
免费 | 663篇 |
国内免费 | 467篇 |
专业分类
化学 | 2472篇 |
晶体学 | 48篇 |
力学 | 109篇 |
综合类 | 21篇 |
数学 | 279篇 |
物理学 | 1484篇 |
无线电 | 1651篇 |
出版年
2024年 | 15篇 |
2023年 | 44篇 |
2022年 | 107篇 |
2021年 | 109篇 |
2020年 | 161篇 |
2019年 | 126篇 |
2018年 | 150篇 |
2017年 | 158篇 |
2016年 | 229篇 |
2015年 | 216篇 |
2014年 | 345篇 |
2013年 | 357篇 |
2012年 | 264篇 |
2011年 | 345篇 |
2010年 | 267篇 |
2009年 | 296篇 |
2008年 | 312篇 |
2007年 | 305篇 |
2006年 | 317篇 |
2005年 | 244篇 |
2004年 | 264篇 |
2003年 | 228篇 |
2002年 | 171篇 |
2001年 | 137篇 |
2000年 | 119篇 |
1999年 | 135篇 |
1998年 | 82篇 |
1997年 | 99篇 |
1996年 | 68篇 |
1995年 | 63篇 |
1994年 | 61篇 |
1993年 | 38篇 |
1992年 | 39篇 |
1991年 | 29篇 |
1990年 | 19篇 |
1989年 | 17篇 |
1988年 | 22篇 |
1987年 | 20篇 |
1986年 | 9篇 |
1985年 | 13篇 |
1984年 | 26篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有6064条查询结果,搜索用时 15 毫秒
151.
Karen Wright Fernando FormaggioClaudio Toniolo Roland TörökAntal Péter Michel WakselmanJean-Paul Mazaleyrat 《Tetrahedron letters》2003,44(22):4183-4186
Resolution of trans 3-(9-fluorenylmethyloxycarbonylamino)-1-oxyl-2,2,5,5-tetramethylpyrrolidine-4-carboxylic acid (Fmoc-POAC-OH) was quickly achieved upon esterification with (aR)-1,1′-binaphthyl-2,2′-diol, chromatographic separation of the obtained diastereomers, and facile saponification of the aryl ester function with removal of the chiral auxiliary. 相似文献
152.
从光干涉方式,瞳窗关系和光源带宽等基本关系出发,利用空间不变系统理论解析了相移显微干涉检测系统中衍射效应的影响。为了减小横向分辨率对纵向分辨率的影响,利用相关信息提取或数字滤波的方法,获得了纳米分辨率的三维形貌。 相似文献
153.
Roxana Irimescu 《Tetrahedron letters》2004,45(3):523-525
Lipase-catalyzed enantioselective acylation of 1-phenylethylamine and 2-phenyl-1-propylamine was performed by reacting the amines with carboxylic acids in a non-solvent system or in ionic liquids as reaction media. The reaction equilibrium was shifted toward amide synthesis by the removal of formed water under reduced pressure. 相似文献
154.
无烟煤结构的高分辨电镜研究 总被引:1,自引:0,他引:1
镜质组不仅是煤结构变化最具规律性,也是影响煤质的主要微成分。用点分辨率为2.1A的高分辨电镜对几种不同煤化程度的无烟煤大分子结构进行了研究。结果表明:电镜图像直接表征了无烟煤分子的非均匀性孔隙结构。京西煤分子方向化程度强,主要以芳层平行堆或有序化前结构为主;晋城煤方向化程度弱,主要以粒状嵌晶结构为主。高分辨电镜技术是研究煤分子结构和煤化作用实质的有效方法。 相似文献
155.
从自模式曲线分辨到渐进类因子分析法 总被引:1,自引:1,他引:1
本文对自模式曲线分辨法的发展作了简要回顾,其中特别对近来来迅速发展的一类用于色谱波谱联用仪产生的二维分析数据的渐进类分析法作了详尽的讨论。这些新化学计量学方法的涌现,对复杂的未知分析体系的定性定量分析,将带来深刻的变化。 相似文献
156.
The acid-catalysed esterification of myristic acid with isopropanol was studied by using near-infrared spectroscopy (NIR) in combination with soft-modeling curve resolution (MCR) methodology with a view to establishing the effect of experimental variables on the reaction kinetics. The reaction was conducted at temperatures above the boiling point of the alcohol, with continuous addition of an isopropanol/water mixture to the reactor. Spectral and concentration profiles were determined by applying soft-modeling curve resolution methodology to a column-wise augmented data matrix containing the spectra for the pure components. MCR profiles were compared with reference values and found to depart from then by less than 3% as %RSE for concentrations and to exhibit correlation above 0.999 for spectra.The reaction kinetics as estimated from the concentration profiles was found to be pseudo-first-order. Also, the pseudo-first-order rate constant was found to depend on the flow-rate of the isopropanol/water mixture and its water content; although the constant decreased with increase in the proportion of water, a content of ca. 15% could be used without important retarding effects on the kinetics. The proposed NIR-MCR method allows the rate constant and the influence of the initial water content to be determined with a view to minimizing consumption of the raw materials and optimizing the experimental conditions. 相似文献
157.
Karel Strnský Tom Jursík Antonín Vítek Jií Skoepa 《Journal of separation science》1992,15(11):730-740
A method has been developed for calculating more accurate and reproducible equivalent chain length (ECL) values of 33 straight-chain fatty acids (FA), with various positions and numbers of cis double bonds, chromatographed on DB-Wax and DB-1 columns. The dependence of ECL values on the position and the number of double bonds is described, as is a method of utilizing these relationships for the characterization of FA by gas chromatography. 相似文献
158.
The condensation of 2′-formylbiphenyl-2-carboxylic acid 4 with (S)-valinol proceeds under kinetic control to give a major product, (4bR,7S,aS)-6,7-dihydro-7-isopropyldibenz[c,e]oxazolo[3,2-a]azepin-9(4bH)-one 6a (84%), in which the biaryl axis has the (S)-configuration. Heating 6a at 140°C with a catalytic amount of acid gives rise to an equilibrium dominated by the diastereoisomeric (4bS,7S)-lactam 6b (6a:6b ratio 27:73), in which the biaryl unit has the (R)-configuration. The structures of both lactams were established by X-ray crystallography; no other diastereoisomers were obtained. 相似文献
159.
Narotham V. Maddireddy Himanshu M. Godbole Girij P. Singh Suvarna G. Kini Gautham G. Shenoy 《合成通讯》2020,50(18):2810-2818
AbstractAn efficient asymmetric oxidation of sulfides was achieved using (R)-6,6'-dibromo-BINOL as chiral ligand in combination with Ti(OiPr)4 using 70% aqueous tertiary butyl hydroperoxide as oxidant. The resulting sulfoxides had high enantiopurities and good yields. A range of aryl alkyl and aryl benzyl sulfides were oxidized to the corresponding sulfoxides with 78–95% ee in 72–80% yields. 相似文献
160.
《Arabian Journal of Chemistry》2020,13(1):1198-1228
Vanadate and vanadium compounds exist in many environmental, biological and clinical matrices, and despite the need only limited progress has been made on the analysis of vanadium compounds. The vanadium coordination chemistry of different oxidation states is known, and the result of the characterization and speciation analysis depends on the subsequent chemistry and the methods of analysis. Many studies have used a range of methods for the characterization and determination of metal ions in a variety of materials. One successful technique is high performance liquid chromatography (HPLC) that has been used mainly for measuring total vanadium level and metal speciation. Some cases have been reported where complexes of different oxidation states of vanadium have been separated by HPLC. Specifically reversed phase (RP) HPLC has frequently been used for the measurement of vanadium. Other HPLC methods such as normal phase, anion-exchange, cation-exchange, size exclusion and other RP-HPLC modes such as, ion-pair and micellar have been used to separate selected vanadium compounds. We will present a review that summarizes and critically analyzes the reported methods for analysis of vanadium salts and vanadium compounds in different sample matrices. We will compare various HPLC methods and modes including sample preparation, chelating reagents, mobile phase and detection methods. The comparison will allow us to identify the best analytical HPLC method and mode for measuring vanadium levels and what information such methods provide with regard to speciation and quantitation of the vanadium compounds. 相似文献