首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   488篇
  免费   21篇
  国内免费   4篇
化学   363篇
晶体学   5篇
力学   8篇
数学   53篇
物理学   84篇
  2023年   2篇
  2022年   7篇
  2021年   5篇
  2020年   7篇
  2019年   3篇
  2018年   6篇
  2017年   6篇
  2016年   14篇
  2015年   14篇
  2014年   15篇
  2013年   30篇
  2012年   30篇
  2011年   44篇
  2010年   19篇
  2009年   27篇
  2008年   30篇
  2007年   47篇
  2006年   34篇
  2005年   28篇
  2004年   18篇
  2003年   17篇
  2002年   23篇
  2001年   2篇
  2000年   3篇
  1999年   11篇
  1998年   5篇
  1997年   11篇
  1996年   5篇
  1995年   2篇
  1994年   3篇
  1993年   3篇
  1992年   4篇
  1990年   2篇
  1987年   3篇
  1986年   2篇
  1985年   2篇
  1984年   2篇
  1982年   3篇
  1981年   4篇
  1978年   1篇
  1977年   1篇
  1976年   1篇
  1975年   2篇
  1974年   1篇
  1973年   2篇
  1972年   2篇
  1971年   2篇
  1970年   1篇
  1969年   2篇
  1933年   1篇
排序方式: 共有513条查询结果,搜索用时 734 毫秒
1.
2.
3.
We derive a moderate deviation principle for the lower tail probabilities of the length of a longest increasing subsequence in a random permutation. It refers to the regime between the lower tail large deviation regime and the central limit regime. The present article together with the upper tail moderate deviation principle in Ref. 12 yields a complete picture for the whole moderate deviation regime. Other than in Ref. 12, we can directly apply estimates by Baik, Deift, and Johansson, who obtained a (non-standard) Central Limit Theorem for the same quantity.  相似文献   
4.
Tschmelak J  Proll G  Gauglitz G 《Talanta》2005,65(2):313-323
Certain contaminants at trace concentrations in surface waters can have dramatic effects on the hormonal system of organisms in the aquatic environment. Therefore, immunoanalytical methods at a very low limit of detection (LOD) and a low limit of quantification (LOQ) are becoming more and more important for environmental analysis and especially for monitoring drinking water quality. Environmental monitoring of antibiotics, hormones, endocrine disrupting chemicals, and pesticides in real water samples (e.g. surface, ground or drinking water) with difficult matrices places high demands on chemical analysis. Biosensors have suitable characteristics such as efficiency in allowing very fast, sensitive, and cost-effective detection. Here we describe an assay optimization process with a fully automated immunoassay for estrone which resulted in a LOD below 0.20 ng L−1 and a LOQ below 1.40 ng L−1. In contrast to common analytical methods such as GC-MS or HPLC-MS, the biosensor used requires no sample pre-treatment and pre-concentration. The very low validation parameters for estrone are the result of the continuous optimization of the immunoassay. The basis of our sensitive assay is the antibody with a high affinity constant towards estrone. During the optimization process, we reduced the amount of antibody per sample and improved the chip surface modification. Finally, this proceeding led to a calibration routine with an amount of antibody of only 3.0 ng per sample (sample volume: 1.0 mL). The reduction of the amount of antibody per sample results in better validation parameters (LOD, LOQ, and IC50), but this reduction leads to the current device-related limitation of the River Analyser (RIANA).For some endocrine disrupting compounds, no effect levels (NOELs) in the lower nanogram per liter range are reported. This defines the challenge, which analytical methods have to compete with and our RIANA instrument with its improved sensitivity for the detection of a single hormone in the lower nanogram per liter range is a powerful tool in aquatic analytics in addition to the common analytical methods.  相似文献   
5.
[reaction: see text] A new method to facilitate the separation of diastereomeric syn- and anti-1,3-diols is described. The method relies on the different hydrolysis rates of the corresponding diastereomeric acetonides. Treatment of a dichloromethane solution of syn- and anti-1,3-diol-acetonide with a catalytic amount of diluted aqueous hydrochloric acid leads to the selective cleavage of the anti diastereomer. The resulting anti-1,3-diol can be easily separated from the unchanged syn-1,3-diol-acetonide.  相似文献   
6.
7.
Tetrakis(pentafluorophenyl)tellurium(IV), Te(C6F5)4, was prepared from the reaction of TeCl4 and Mg(C6F5)Br. Crystallization of the crude product from n‐pentane at ?25 °C gave suitable single crystals. The title compound crystallizes in the monoclinic space group P21/c (Z = 8) with two independent molecules per unit cell.  相似文献   
8.
X-ray crystal structures are reported of a free host compound 1, comprising two diphenylmethanol terminal groups attached to a central 9,10-ethynyl substituted anthracene unit, and of three inclusion compounds of a fluoren-9-ol substituted analogous host 2 with acetone, dimethyl sulphoxide (DMSO) and dimethylformamide (DMF) as guest, respectively. Despite the presence of two hydroxyl groups in 1, there is no O–H...O hydrogen bond between the molecules in the guest free crystal – only weaker C–H...O interactions and van der Waals' type connections. In the inclusion compounds of 2, H-bonded 1:2 host–guest associates are formed, where each of the host hydroxyl groups binds to a guest oxygen atom. The orientations of the host–guest connections in these complexes vary, being E for acetone and Z for both DMSO and DMF guests, relative to the host anthracene unit. The DMSO and DMF inclusion compounds of 2 proved to be isostructural.  相似文献   
9.
44 members of thecompound series Ph4−nMRn (M=Si, Ge, Sn, Pb; R=o-, m-, p-Tol; n=0–4) were synthesized (15 newcompounds). The crystal structures of Ph3Sn (o-Tol) and PhSn (o-Tol)3 were determined and compared to 16 known structures. Subject to the distanced (M–C), an interplay between through-space ππ repulsion and πσ attraction leads to either elongated or compressed tetrahedral geometry. 29 Si-, 119 Sn- and 207 Pb-NMR chemical shifts were determined in solution and in the solid state. 73 Ge chemical shifts were measured only in solution. Anupfield or downfield sagging of the chemical shifts along each series is rationalized in terms of a πσcharge transfer which is constrained by torsion of the aromatic groups.  相似文献   
10.
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号