全文获取类型
收费全文 | 638篇 |
免费 | 10篇 |
国内免费 | 1篇 |
专业分类
化学 | 369篇 |
晶体学 | 6篇 |
力学 | 35篇 |
数学 | 57篇 |
物理学 | 182篇 |
出版年
2023年 | 3篇 |
2022年 | 10篇 |
2021年 | 22篇 |
2020年 | 21篇 |
2019年 | 13篇 |
2018年 | 16篇 |
2017年 | 22篇 |
2016年 | 22篇 |
2015年 | 14篇 |
2014年 | 25篇 |
2013年 | 48篇 |
2012年 | 43篇 |
2011年 | 58篇 |
2010年 | 24篇 |
2009年 | 30篇 |
2008年 | 33篇 |
2007年 | 39篇 |
2006年 | 23篇 |
2005年 | 25篇 |
2004年 | 17篇 |
2003年 | 14篇 |
2002年 | 12篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1999年 | 8篇 |
1998年 | 3篇 |
1997年 | 6篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1984年 | 6篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 2篇 |
1978年 | 6篇 |
1977年 | 2篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1971年 | 1篇 |
1970年 | 2篇 |
1969年 | 2篇 |
排序方式: 共有649条查询结果,搜索用时 15 毫秒
1.
2.
A direct, versatile method for the determination of ethyl glucuronide (EtG), a biomarker of ethanol consumption, in urine has been developed using reversed-phase liquid chromatography with pulsed electrochemical detection (PED). EtG and methyl glucuronide (MetG), which serves as an internal standard, are readily separated using a mobile phase consisting of 1% acetic acid/acetonitrile (98/2, v/v). Post-column addition of NaOH allows for the detection of all glucuronides using PED at a gold working electrode. Upon optimization, EtG was found to have a limit of detection of 0.03 μg/mL (7 pmol; 50 μL injection volume) and repeatability at the limit of quantitation of 1.7%R.S.D. (relative standard deviation). Solid-phase extraction (SPE) using an aminopropyl phase was used to remove interferents in urine samples prior to their analysis. Compound recovery following SPE was approximately 50 ± 2%. The forensic utility of this method was further validated by the analysis of 29 post-mortem urine specimens, whose results agreed strongly with certified determinations. 相似文献
3.
Malhotra E. Kaushik N. K. Sodhi G. S. 《Journal of Thermal Analysis and Calorimetry》2002,68(1):215-222
A number of ionic chelate complexes of maltol(A) and hafnium(IV) the type[(η5−C5H5)2HfL]+[MCl3]− (B) [HL=maltol; M=Zn(II), Cd(II), Hg(II), Cu(II)]have been synthesized and characterized by spectral studies (IR, UV, 1H NMR and 13C NMR). The stoichiometry of the complexes has been confirmed by conductance measurements. Thermogravimetric (TG) and differential
thermal analytical (DTA) studies have been carried out for these complexes and from TG curves, the order, apparent activation
energy and apparent activation entropy of the thermal decomposition reactions have been elucidated .The order in each case
has been determined to be one and the degree of spontaneity and lability have been inferred from the apparent activation energy
and entropy, respectively. Thermal parameters have been correlated with some structural aspects of the complexes concerned.
From differential thermal analysis curves, the heat of reaction has been calculated.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
4.
The various thermodynamic parameters for the periodate oxidation of six anilines, viz. aniline, p-chloroaniline, p-ethoxyaniline, o- and p-methoxyanilines and p-methylaniline have been reported and discussed. The validity of the isokinetic relationship and various linear free energy relationships (LFERs) have been tested and discussed. An attempt has been made to correlate these findings with the mechanism operative in these reactions. 相似文献
5.
Kundu S Pal A Ghosh SK Nath S Panigrahi S Praharaj S Pal T 《Inorganic chemistry》2004,43(18):5489-5491
Ligands with a beta-diketone skeleton have been employed for the first time as reductant to produce ligand stabilized gold nanoparticles of different shapes from aqueous HAuCl(4) solution. Evolution of stable gold nanoparticles follows first order (k approximately equal to 10(-2) min(-1)) kinetics with respect to Au(0) concentration. Growth of particles of different shapes (spherical or triangular or hexagonal) goes hand in hand under the influence of different beta-diketones, which have excellent capping and reducing properties. Chlorine insertion was observed to take place in the beta-diketone skeleton. 相似文献
6.
Singha K Roy A Dutta PK Tripathi S Sahabuddin S Achari B Mandal SB 《The Journal of organic chemistry》2004,69(19):6507-6510
A simple synthesis of chiral spironucleosides and spirobisnucleosides is described. Intramolecular 1,3-dipolar nitrone cycloaddition reaction of d-glucose-derived precursors having olefin at C-3 and nitrone at C-5, C-1, or C-2 (in nor-series) furnished bisisoxazolidinospirocycles 4-7, 11, and 12 in good yields. Reductive ring opening of the isoxazolidine moieties in 4-6 followed by construction of a nucleoside base upon the generated amino groups smoothly yielded spirobisnucleosides 17 and 18 and spironucleosides 20 and 21. 相似文献
7.
8.
Recently, we have developed a fast approach to calculate NMR chemical shifts using the divide and conquer method at the semiempirical level. To demonstrate the utility of this approach for characterizing protein-ligand interactions, we used the deviation of calculated chemical shift perturbations from experiment to determine the orientation of a ligand (GPI-1046) in the binding pocket of the FK506 binding protein (FKBP12). Moreover, we were able to select the native state of the ligand from a collection of decoy poses. A key hydrogen bond between O1 and HN in Ile56 was also identified. Our results suggest that ligand-induced chemical shift perturbations can be used to refine protein/ligand structures. 相似文献
9.
Treatment of pyrimethamine with blood plasma in vitro yields a metabolite which is also produced when the drug is administered through intravenous injection in the rat. A thin layer liquid chromatographic method for quantitative and qualitative determination of pyrimethamine and its metabolite in plasma and biological tissues is described. 相似文献
10.
Raha K van der Vaart AJ Riley KE Peters MB Westerhoff LM Kim H Merz KM 《Journal of the American Chemical Society》2005,127(18):6583-6594
Pairwise decomposition of the interaction energy between molecules is shown to be a powerful tool that can increase our understanding of macromolecular recognition processes. Herein we calculate the pairwise decomposition of the interaction energy between the protein human carbonic anhydrase II (HCAII) and the fluorine-substituted ligand N-(4-sulfamylbenzoyl)benzylamine (SBB) using semiempirical quantum mechanics based methods. We dissect the interaction between the ligand and the protein by dividing the ligand and the protein into subsystems to understand the structure-activity relationships as a result of fluorine substitution. In particular, the off-diagonal elements of the Fock matrix that is composed of the interaction between the ionic core and the valence electrons and the exchange energy between the subsystems or atoms of interest is examined in detail. Our analysis reveals that the fluorine-substituted benzylamine group of SBB does not directly affect the binding energy. Rather, we find that the strength of the interaction between Thr199 of HCAII and the sulfamylbenzoyl group of SBB affects the binding affinity between the protein and the ligand. These observations underline the importance of the sulfonamide group in binding affinity as shown by previous experiments (Maren, T. H.; Wiley: C. E. J. Med. Chem. 1968, 11, 228-232). Moreover, our calculations qualitatively agree with the structural aspects of these protein-ligand complexes as determined by X-ray crystallography. 相似文献