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   1808篇
  免费   149篇
  国内免费   2篇
化学   1491篇
晶体学   24篇
力学   22篇
数学   166篇
物理学   256篇
  2023年   29篇
  2022年   34篇
  2021年   44篇
  2020年   75篇
  2019年   77篇
  2018年   59篇
  2017年   29篇
  2016年   82篇
  2015年   86篇
  2014年   86篇
  2013年   118篇
  2012年   143篇
  2011年   160篇
  2010年   80篇
  2009年   61篇
  2008年   101篇
  2007年   96篇
  2006年   75篇
  2005年   71篇
  2004年   40篇
  2003年   36篇
  2002年   34篇
  2001年   20篇
  2000年   27篇
  1999年   14篇
  1998年   15篇
  1997年   12篇
  1996年   7篇
  1995年   14篇
  1994年   16篇
  1993年   16篇
  1991年   11篇
  1990年   7篇
  1988年   6篇
  1987年   5篇
  1986年   6篇
  1981年   8篇
  1980年   7篇
  1978年   8篇
  1977年   7篇
  1976年   5篇
  1971年   6篇
  1970年   6篇
  1969年   9篇
  1968年   8篇
  1963年   6篇
  1962年   8篇
  1961年   11篇
  1958年   8篇
  1955年   5篇
排序方式: 共有1959条查询结果,搜索用时 9 毫秒
71.
Sol/gel-derived silica gel was prepared at room temperature from tetraethyl orthosilicate precursor. The extracts of Terminalia chebula (Haritoki) were entrapped into the porous silica gel. Fourier transform infrared analysis revealed the proper adsorption of herbal values in the nanopores of the silica gel. Porosity was estimated by transmission electron microscope studies. The release kinetics of the extract in both 0.1 N HCl, pH 1.2, and Phosphate-buffer saline (PBS), pH 7.2, were determined using UV–Vis spectroscopy. Different dissolution models were applied to release data in order to evaluate the release mechanisms and kinetics. Biphasic release patterns were found in every formulation for both the buffer systems. The kinetics followed a zero-order equation for first 4 h and a Higuchi expression in a subsequent timeline in the case of 0.1 N HCl. In the case of PBS, the formulations showed best linearity with a first-order equation followed by Higuchi’s model. The sustained release of the extract predominantly followed diffusion and super case II transport mechanism. The release value was always above the minimum inhibitory concentration.  相似文献   
72.
73.
74.
75.
The content of tenuazonic acid in human urine was determined by a stable isotope dilution assay (SIDA) that was recently developed for the analysis of food commodities and extensively re-validated for urine matrix in this study. Linearity of the response curve was proven between molar ratios n(labeled standard)/n(analyte) of 0.02–100. The limits of detection and determination were 0.2 and 0.6 μg/L, respectively. The mean recovery of the stable isotope dilution assay was 102?±?3 % in the range between 1.0 and 100 μg/L. Interassay precision was 6.7 % (relative standard deviation of three triplicate analyses of a human urine sample during 3 weeks). The method was applied to two studies dealing with urinary excretion of tenuazonic acid: In the first study, tenuazonic acid was quantified in the 24-h urine of six volunteers from Germany (three female, three male) in a concentration range of 1.3–17.3 μg/L or 2.3–10.3 ng/mg?1 creatinine, respectively. In the second study, two volunteers (one female, one male) ingested 30 μg tenuazonic acid by consumption of naturally contaminated whole meal sorghum infant cereals and tomato juice, respectively. The urinary excretion of the ingested tenuazonic acid was 54–81 % after 6 h, depending on matrix and volunteer. After 24 h, 87–93 % of the ingested amount of tenuazonic acid was excreted, but the fate of the remaining about 10 % is open. Thus, it is not possible to exclude potential health hazards for the consumer, completely.
Figure
Urinary excretion of tenuazonic acid (TA) by two volunteers (A and B) after ingestion of sorghum infant cereals [1] and tomato juice [2]  相似文献   
76.
A short and efficient enantioselective synthesis of natural product (S)-3-hydroxypiperidine has been achieved starting from commercially available raw materials employing two catalytic routes: (i) cocatalyzed hydrolytic kinetic resolution (HKR) of racemic methyl-3-(oxiran-2-yl)propanoate; (ii) proline-catalyzed α-aminooxylation followed by Horner–Wardsworth–Emmons olefination in high enantiomeric purity (97% ee) and high overall yield (38%).  相似文献   
77.
Artificial implants and biomaterials lack the natural defense system of our body and, thus, have to be protected from bacterial adhesion and biofilm formation. In addition to the increasing number of implanted objects, the resistance of bacteria is also an important problem. Silver ions are well‐known for their antimicrobial properties, yet not a lot is known about their mode of action. Silver is expected to interact on many levels, thus the development of silver resistance is very difficult. Nevertheless, some bacteria are able to resist silver, even at higher concentrations. One such defense mechanism of bacteria against heavy‐metal intoxication includes an efflux system. SilE, a periplasmic silver‐binding protein that is involved in this defense mechanism, has been shown to possess numerous histidine functions, which strongly bind to silver atoms, as demonstrated by ourselves previously. Herein, we address the question of how histidine binds to silver ions as a function of pH value. This property is important because the local proton concentration in cells varies. Thus, we solved the crystal structures of histidine–silver complexes at different pH values and also investigated the influence of the amino‐acid configuration. These results were completed by DFT calculations on the binding strength and packing effects and led to the development of a model for the mode of action of SilE.  相似文献   
78.
Versatile ruthenium(II) complexes allow for site‐selective C H oxygenations with weakly‐coordinating aldehydes. The challenging C H functionalizations proceed with high chemoselectivity by rate‐determining C H metalation. The new method features an ample substrate scope, which sets the stage for the step‐economical preparation of various bioactive heterocycles.  相似文献   
79.
N,N-Dimethylaminoalkyl chalcogenolate Pd(II) complexes [PdCl(ENMe2)]n has been investigated as a moisture/air-stable and robust catalyst for Sonogashira cross-coupling reaction in the absence of copper and phosphine ligand. The dimeric palladium(II) complex of selenium containing ligand shows the best catalytic activity as compared with monomeric and trimeric complexes. The variety of functional groups are tolerated under optimized catalytic systems and provide excellent yields of the products.  相似文献   
80.
Sequential reaction of a multisite LH4 ligand {2‐[2‐hydroxy‐3‐(hydroxymethyl)‐5‐methylbenzylideneamino]‐2‐methylpropane‐1,3‐diol} with appropriate lanthanide salts followed by the addition of Ni(NO3)2 ? 6 H2O in a 4:1:2 stoichiometric ratio in the presence of triethylamine afforded four heterobimetallic trinuclear complexes [Ni2Gd(LH3)4] ? 3 NO3 ? 3 MeOH ? H2O ? CH3CN ( 1 ), [Ni2Tb(LH3)4] ? 3 NO3 ? 3 MeOH ? CH3CN ( 2 ), [Ni2Dy(LH3)4] ? 3 NO3 ? 3 MeOH ? H2O ? CH3CN ( 3 ), and [Ni2Ho(LH3)4] ? 3 NO3 ? 3 MeOH ? H2O ? CH3CN ( 4 ). Complexes 1 – 4 possess linear trimetallic cores with a central lanthanide ion. Magnetic studies revealed a predominant ferromagnetic interaction between the Ni and Ln centers. Alternating current susceptibility measurements of complex 3 showed a small frequency dependence of the out‐of‐phase signal, χ′′M , under zero direct current field, but without achieving a net maximum above 2 K. Magnetic studies on 1 revealed that it has a significant magnetocaloric effect.  相似文献   
[首页] « 上一页 [3] [4] [5] [6] [7] 8 [9] [10] [11] [12] [13] 下一页 » 末  页»
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