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   675篇
  免费   53篇
  国内免费   74篇
化学   572篇
晶体学   2篇
力学   19篇
综合类   1篇
数学   50篇
物理学   158篇
  2023年   9篇
  2022年   4篇
  2021年   14篇
  2020年   12篇
  2019年   25篇
  2018年   13篇
  2017年   10篇
  2016年   17篇
  2015年   34篇
  2014年   38篇
  2013年   27篇
  2012年   48篇
  2011年   45篇
  2010年   32篇
  2009年   20篇
  2008年   39篇
  2007年   49篇
  2006年   48篇
  2005年   45篇
  2004年   33篇
  2003年   26篇
  2002年   24篇
  2001年   27篇
  2000年   16篇
  1999年   14篇
  1998年   13篇
  1997年   8篇
  1996年   5篇
  1995年   12篇
  1994年   8篇
  1993年   8篇
  1992年   6篇
  1991年   4篇
  1990年   10篇
  1989年   10篇
  1988年   6篇
  1987年   6篇
  1986年   3篇
  1985年   4篇
  1984年   6篇
  1983年   4篇
  1982年   4篇
  1981年   4篇
  1980年   4篇
  1979年   2篇
  1978年   1篇
  1977年   2篇
  1976年   1篇
  1974年   1篇
  1971年   1篇
排序方式: 共有802条查询结果,搜索用时 15 毫秒
41.
A new chemical space was generated via C2-functionalization of 3-arylbenzofurans. Mannich reaction of 3-arylbenzofurans with secondary amines and formaldehyde allowed for installation of aminomethyl unit at C2 position of benzofurans. A formyl group at C2 site introduced as a result of Vilsmeier-Haack formylation of 3-arylbenzofurans was employed as a reacting partner for three-component Kabachnik-Fields reaction with various amines and triethyl phosphite to give a wide variety of aminomethylphosphonates. Furthermore, several benzo[d]oxazoles and pyrrolo[1,2-a]quinoxalines were prepared by using the formyl group. Biological screening of the synthesized compounds revealed that the benzofuran bearing a pyrrolo[1,2-a]quinoxaline moiety ( 5b ) most potently inhibited the viability of human blood cancer cells, but not solid tumor cells. Caspase activity assay, analysis of Annexin V-positive cells, and Western blot analysis indicated that 5b -induced death of human lymphoma U937 cells could result from its potential to induce the caspase-dependent apoptotic death of blood cancer cells with inhibition of ERK activation.  相似文献   
42.
Long-chain aliphatic amines such as (S,Z)-heptadec-9-en-7-amine and 9-aminoheptadecane were synthesized from ricinoleic acid and oleic acid, respectively, by whole-cell cascade reactions using the combination of an alcohol dehydrogenase (ADH) from Micrococcus luteus, an engineered amine transaminase from Vibrio fluvialis (Vf-ATA), and a photoactivated decarboxylase from Chlorella variabilis NC64A (Cv-FAP) in a one-pot process. In addition, long chain aliphatic esters such as 10-(heptanoyloxy)dec-8-ene and octylnonanoate were prepared from ricinoleic acid and oleic acid, respectively, by using the combination of the ADH, a Baeyer–Villiger monooxygenase variant from Pseudomonas putida KT2440, and the Cv-FAP. The target compounds were produced at rates of up to 37 U g−1 dry cells with conversions up to 90 %. Therefore, this study contributes to the preparation of industrially relevant long-chain aliphatic chiral amines and esters from renewable fatty acid resources.  相似文献   
43.
The energetic chemical reaction between Zn(NO3)2 and Li is used to create a solid‐state interface between Li metal and Li6.4La3Zr1.4Ta0.6O12 (LLZTO) electrolyte. This interlayer, composed of Zn, ZnLix alloy, Li3N, Li2O, and other species, possesses strong affinities with both Li metal and LLZTO and affords highly efficient conductive pathways for Li+ transport through the interface. The unique structure and properties of the interlayer lead to Li metal anodes with longer cycle life, higher efficiency, and better safety compared to the current best Li metal electrodes operating in liquid electrolytes while retaining comparable capacity, rate, and overpotential. All‐solid‐state Li||Li cells can operate at very demanding current–capacity conditions of 4 mA cm?2–8 mAh cm?2. Thousands of hours of continuous cycling are achieved at Coulombic efficiency >99.5 % without dendrite formation or side reactions with the electrolyte.  相似文献   
44.
A sensitive and reliable method using liquid chromatography-electrospray tandem mass spectrometry has been developed and validated for the trace determination of beta-lactam antibiotics in natural and wastewater matrices. Water samples were enriched by solid-phase extraction. The analytes included amoxicillin (AMOX), ampicillin (AMP), oxacillin (OXA), cloxacillin (CLOX) and cephapirin (CEP). Average recoveries of beta-lactams (BLs) in fortified samples were generally above 75% (except amoxicillin) with the standard deviations lower than 10% in water matrices. Amoxicillin was not quantified due to poor recovery (less than 40%) in the investigated water matrices. Matrix effects were found to be minimal when measuring these compounds in water matrices. The accuracy, within- and between-run precision of the assay fell within acceptable ranges of 15% absolute. The method detection limit (MDL) was estimated to range between 8 and 10 ng/L in surface water, 13 and 18 ng/L in the influent and 8 and 15 ng/L in the effluent from a wastewater treatment plant. A large number of actual water samples were analyzed using this method in order to evaluate the occurrence of the beta-lactams in a river and a wastewater treatment plant in northern Colorado. Most of the samples were negative for all analytes. These compounds were found at 15-17 ng/L in the three influent samples and at 9-11 ng/L in three surface water samples out of a total of 200 samples. This indicates that contamination by beta-lactam antibiotics is of minor importance to the small mixed-watershed.  相似文献   
45.
传统分子筛是以硅氧四面体和铝氧四面体为骨架的微孔晶体材料. 近年来, 以无机-有机结构单元为骨架组成的微孔晶体材料已引起人们的广泛关注[1~19]. 该类材料是由金属离子(或金属氧簇)与有机配体(大多数是芳香多酸和多碱)构成的建筑单元通过共价键或者分子间作用力构成的. 无机-有机杂化晶体材料有多种结构类型, 如1-D, 2-D, 3-D和笼状结构等.  相似文献   
46.
巯基化合物自组装单分子层的研究进展   总被引:20,自引:1,他引:20  
董献堆  陆君涛 《电化学》1995,1(3):248-258
超薄层有机材料的制备与研究 ̄[1]受到人们的广泛关注,有关研究结果和进展正在不断丰富着人类对表面结构与性质关系的理解和认识。与其它制备单分子层的技术相比,自组装技术是一种较新的制备方法,在80年代后期,迅速成为有关学科的研究焦点。采用此技术制备的超薄层体系主要有两类:一类是巯基化合物在金、银、铜、铂表面吸附形成的单层 ̄[2,3],一类是在硅、玻璃、金属氧化物表面通过硅烷化反应形成的单层 ̄[4]。其中,硫醇类分子自组装单层(self-assembledmonolayer,3AM)是被研究得最为广泛和深入的体系。本文主要综述十年来巯基化合物SAM的研究进展。  相似文献   
47.
48.
Cho YS  Kim HY  Cha JH  Pae AN  Koh HY  Choi JH  Chang MH 《Organic letters》2002,4(12):2025-2028
[reaction: see text] Intramolecular Prins-type reactions of compounds having both functionalities of homoallyl alcohol and acetal moiety are described. The intramolecular Prins cyclizations were performed using indium trichloride in chloroform or 25% aqueous THF. Both 9-oxabicyclo[3.3.1]nonane and 3,9-dioxabicyclo[3.3.1]nonane compounds were successfully obtained in moderate yields.  相似文献   
49.
Low tropospheric wind measurement with Mie Doppler Lidar   总被引:3,自引:0,他引:3  
A double edge Mie Doppler lidar at 1064 nm was developed in Hefei, China in 2005 for low tropospheric wind measurement. Intercomparison experiments with a wind profiler and a wiresonde were held. Intercomparisons of concurrent lidar and other instrument observations show good agreement with expected measurement accuracy. The examples of validated lidar wind profiles obtained during these experiments as well as an example of continuous wind observations are presented. The instrument has demonstrated the capability of atmospheric wind field measurement from 0.2 to 5 km altitude, achieving below 2 m/s accuracy with 1 min averaging and 21.2 m vertical resolution.  相似文献   
50.
Beam amplitudes of successive orders diffracted on holographic gratings are calculated and thus nonlinear effects in amplitude, bleached phase and reversal bleached phase holograms are compared. Then values of intermodulation noise are compared for the above three types of Fourier hologram of two circular holes.  相似文献   
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