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   1013篇
  免费   51篇
  国内免费   23篇
化学   900篇
晶体学   4篇
力学   25篇
数学   67篇
物理学   91篇
  2024年   4篇
  2023年   8篇
  2022年   33篇
  2021年   37篇
  2020年   67篇
  2019年   57篇
  2018年   81篇
  2017年   40篇
  2016年   74篇
  2015年   58篇
  2014年   73篇
  2013年   136篇
  2012年   74篇
  2011年   82篇
  2010年   57篇
  2009年   51篇
  2008年   48篇
  2007年   36篇
  2006年   10篇
  2005年   14篇
  2004年   7篇
  2003年   8篇
  2002年   8篇
  2001年   4篇
  2000年   2篇
  1999年   2篇
  1997年   1篇
  1996年   1篇
  1994年   1篇
  1991年   1篇
  1988年   2篇
  1986年   1篇
  1985年   4篇
  1982年   1篇
  1980年   1篇
  1976年   2篇
  1974年   1篇
排序方式: 共有1087条查询结果,搜索用时 15 毫秒
81.
Chemical speciation (extraction of elemental information and identification of molecular environment for an analyte in a complex sample) has been a long sought after goal for analytical chemists. Recently, because of successful developments in more sensitive element-specific detectors and gentle separation schemes, which preserve the true chemical information in a real sample, routine speciation experiments are becoming a common occurrence in the scientific literature. For many reasons, the combination of capillary electrophoresis (for separation of different chemical species) with inductively coupled plasma mass spectrometry (for element and isotope specific detection) has emerged as the method of choice for these analyses. In this article the basic principles of capillary electrophoresis inductively coupled plasma mass spectrometry are discussed. Design consideration for instrument interface, anticipated difficulties with speciation experiments and applications for specific matrices and analytes are also presented in this article.  相似文献   
82.
The effect of aqueous solutions of selected ionic liquids solutions on Ideonella sakaiensis PETase with bis(2-hydroxyethyl) terephthalate (BHET) substrate were studied by means of molecular dynamics simulations in order to identify the possible effect of ionic liquids on the structure and dynamics of enzymatic Polyethylene terephthalate (PET) hydrolysis. The use of specific ionic liquids can potentially enhance the enzymatic hydrolyses of PET where these ionic liquids are known to partially dissolve PET. The aqueous solution of cholinium phosphate were found to have the smallest effect of the structure of PETase, and its interaction with (BHET) as substrate was comparable to that with the pure water. Thus, the cholinium phosphate was identified as possible candidate as ionic liquid co-solvent to study the enzymatic hydrolyses of PET.  相似文献   
83.
A straightforward and modular preparative approach to 1,3,5-triaroylbenzene-based functionalized cyclophane ring systems has been developed. The key cyclophane-forming macrocyclization reaction was accomplished during the course of a regioselective cross-benzannulation between bis(aryl ethynyl) ketone and enaminone reactants. Macrocyclic products with ring sizes ranging from 18- to 22-membered were successfully constructed. The composition of the tether connecting the two aryl ethynyl ketone fragments can be easily varied; consequently, this method is suitable for construction of a diverse range of structurally distinct cyclophane products. To illustrate this feature, cyclophanes possessing xylyl, alkyl, di(ethylene triamine), and di(ethylene oxy) bridging units were synthesized in isolated yields of 11-46%. Three new cyclophanes (calixarene-like macrocyles 8 and 9, as well as crownophane 18) were structurally characterized by X-ray diffractometry.  相似文献   
84.
In this study a sunlight-induced method for rapid synthesis of silver nanoparticles using an ethanol extract of Andrachnea chordifolia is described. The silver nitrate solutions (1 mM) containing the ethanol extract of Andrachnea chordifolia were irradiated by both sunlight radiation and by sunlight radiation passed through different colored filters (red, yellow or green). The smallest size of silver nanoparticles was obtained when a silver ion solution was irradiated for 5 minutes by direct sunlight radiation. Further examination of the shape and size and of the surface chemistry of these biogenic silver nanoparticles, which were prepared under sunlight radiation, was carried out using transmission electron microscopy and infrared spectroscopy, respectively. Transmission electron microscopy images show spherical particles with an average size of 3.4 nm. Hydroxyl residues were also detected on the surface of these biogenic silver nanoparticles fabricated using plant extract of Andrachnea chordifolia under sunlight radiation. Our study on the reduction of silver ions by this plant extract in darkness shows that the synthesis process can take place under dark conditions at much longer incubations (48 hours). Larger silver polydispersed nanoparticles ranging in size from 3 to 30 nm were obtained when the silver ions were treated with the ethanol extract of Andrachnea chordifolia under dark conditions for 48 hours.  相似文献   
85.
In this investigation, a facile sonochemical route has been developed for the preparation of silver vanadium oxide (SVO) micro/nanorods by using silver salicylate and ammonium metavanadate as silver and vanadate precursor, respectively. Here, silver salicylate, [Ag(HSal)], is introduced as a new silver precursor to fabricate AgVO3 nanorods. The effect of numerous solvents and surfactants on the morphology and sonochemical formation mechanism of AgVO3 nanorods was studied. AgVO3 nanorods were characterized by SEM and TEM images, XRD patterns, FT-IR, XPS, and EDS spectroscopy. SEM, TEM, and XRD results showed that AgO nanoparticles were formed onto AgVO3 nanorods in the presence of ethanol, cyclohexanol, dimethylsulfoxide (DMSO), and acetone. By using polyethylene glycol (PEG-6000) and N,N-dimethylformamide (DMF) as organic additives, the thickness of AgVO3 nanorods decreased.  相似文献   
86.
A PVC membrane electrode based on a cadmium–salen (N,N′-bis-salicylidene-1,2ethylenediamine) complex as an anion carrier is described. The electrode has an anti-Hofmeister selectivity sequence with a preference for thiocyanate at pH 1.5–11.0. It has a linear response to thiocyanate from 1.0 × 10–6 to 1.0 × 10–1 mol L–1 with a slope of 59.1 ± 0.2 mV per decade, and a detection limit of 7 × 10–7 mol L–1. This electrode has high selectivity for thiocyanate relative to many common organic and inorganic anions. The proposed sensor has a fast response time of approximately 15 s. It was applied to the determination of thiocyanate in a milk sample. Received: 1 December 2000 / Revised: 19 April 2001 / Accepted: 30 April 2001  相似文献   
87.
A new PVC membrane coated graphite electrode for cesium ion based on 4′,4″(5′)di–tert-butyl di-benzo-18-crown-6 (DTBDB18C6) as ionophore was prepared. The electrode shows a near Nernstian response of 57.0 ± 1.8 mV decade?1 over a wide activity range of 6.0 × 10?6–1.0 × 10?1 mol L?1 with a limit of detection 4.0 × 10?6 mol L?1. The proposed electrode is suitable for use in aqueous solution in the pH range of 3.0–9.5. It has a fast response time of 10 s and can be used for at least 1 month without any considerable divergence in potential. The selectivity coefficients for Cs+ ion with respect to ammonium, alkali, alkaline earth and some selected transition metal ions were determined and showed a superior selectivity over Li+, Na+ and alkaline earth metal ions. The new electrode was applied for determination of Cs+ in spiked tap water. The electrode was also used as indicator electrode in potentiometric titration of Cs+ with sodium tetraphenyl borate.  相似文献   
88.
A new type of potentiometric sensor based on a recently constructed carbon ionic liquid electrode (CILE) is described. Two kinds of ionic liquids, i.e., N‐octylpyridinium hexafluorophosphate (OPFP) and 1‐butyl‐3‐methylimidazoluim hexafluorophosphate (BMFP) were tested as binder for construction of the carbon composite electrode. The characteristics of these electrodes as potentiometric sensors were evaluated and compared with those of the traditional carbon paste electrode (CPE). The results indicate that potentiometric sensors constructed with ionic liquid show an increase in performance in terms of Nernstian slope, selectivity, response time, and response stability compared to CPE.  相似文献   
89.
Research on Chemical Intermediates - The synthesis of 4-Aryl-(3,5-dimethyl-1,4,7,8-tetrahydro-dipyrazolo[3,4b:4′,3′e]pyridine derivatives was accomplished using Fe3O4@SiO2@(BuSO3H)3...  相似文献   
90.
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