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   619篇
  免费   17篇
  国内免费   138篇
化学   719篇
晶体学   1篇
力学   3篇
综合类   1篇
物理学   50篇
  2023年   21篇
  2022年   10篇
  2021年   7篇
  2020年   21篇
  2019年   18篇
  2018年   14篇
  2017年   22篇
  2016年   13篇
  2015年   11篇
  2014年   19篇
  2013年   64篇
  2012年   32篇
  2011年   40篇
  2010年   27篇
  2009年   40篇
  2008年   48篇
  2007年   51篇
  2006年   57篇
  2005年   39篇
  2004年   42篇
  2003年   18篇
  2002年   21篇
  2001年   17篇
  2000年   17篇
  1999年   20篇
  1998年   15篇
  1997年   11篇
  1996年   9篇
  1995年   14篇
  1994年   11篇
  1993年   6篇
  1992年   5篇
  1991年   1篇
  1990年   3篇
  1989年   3篇
  1988年   2篇
  1987年   3篇
  1986年   1篇
  1979年   1篇
排序方式: 共有774条查询结果,搜索用时 375 毫秒
1.
In this study, parenchyma cellulose, which was extracted from maize stalk pith as an abundant source of agricultural residues, was applied for preparing cellulose nanoparticles (CNPs) via an ultrasound-assisted etherification and a subsequent sonication process. The ultrasonic-assisted treatment greatly improved the modification of the pith cellulose with glycidyltrimethylammonium chloride, leading to a partial increase in the dissolubility of the as-obtained product and thus disintegration of sheet-like cellulose into nanoparticles. While the formation of CNPs by ultrasonication was largely dependent on the cellulose consistency in the cationic-modified system. Under the condition of 25% cellulose consistency, the longer sono-treated duration yielded a more stable and dispersible suspension of CNP due to its higher zeta potential. Degree of substitution and FT-IR analyses indicated that quaternary ammonium salts were grafted onto hydroxyl groups of cellulose chain. SEM and TEM images exhibited the CNP to have spherical morphology with an average dimeter from 15 to 55 nm. XRD investigation revealed that CNPs consisted mainly of a crystalline cellulose Ι structure, and they had a lower crystallinity than the starting cellulose. Moreover, thermogravimetric results illustrated the thermal resistance of the CNPs was lower than the pith cellulose. The optimal CNP with highly cationic charges, good stability and acceptable thermostability might be considered as one of the alternatively renewable reinforcement additives for nanocomposite production.  相似文献   
2.
Summary The solubility parameters of cationic surfactants were obtained using the inverse gas chromatographic technique. The surfactants didodecyl dimethyl ammonium bromide, dioctadecyl dimethyl ammonium bromide and dodecyl pyridinium chloride were used as stationary phase and retention data of different probe solutes were measured at different temperatures. The results were analysed by the combination of Flory-Huggins and Hildebrand theories, and the solubility parameters of the surfactants were obtained in a range of temperatures between 80–120°C.  相似文献   
3.
小分子硫原子团簇正离子的结构稳定性   总被引:1,自引:0,他引:1       下载免费PDF全文
用分子图形软件设计出 4 9种硫原子团簇Sn+ (n =3~ 13)的结构 ,使用B3LYP密度泛函进行几何构型优化和振动频率计算 ,根据分子的总能量得出最稳定的同分异构体 .在硫原子团簇正离子中 ,大部分原子为二配位成键 .带有一、三配位的原子结构的总能量较高 .部分最稳定硫原子团簇正离子的构型与最稳定的中性硫原子团簇的构型完全不同 .  相似文献   
4.
The cationic azo-surfactants possessing different spacers and tail alkyl chain lengths have been synthesized by azocoupling ofp-alkylaniline orop-ethoxyaniline with phenol, followed by alkylation and quaternalization with dibromoalkane and trimethylamine, respectively. These surfactants showed a good solubility in water. A reversibletrans-cis isomerization of the azosurfactants by photoirradiation was assessed by UV-Vis absorption spectra. Due to a difference in HLB between thetrans- andcis-surfactants, the observed critical micelle concentration (CMC) values and the electric conductivity of the surfactant solution at above the CMC were significantly affected by the photoinducedtrans-cis isomerization. The azo-surfactants bearing moderate alkyl chain lengths such as surfactants 6 (R2=C2H4, R3=C4H9) and 9 (R2=C4H8, R3=C2H5) were found to be effective to achieve large CMC changes (3.6 mmol/L for 6 and 5.9 mmol/L for 9) by UV-light irradiation. The replacement of the tail chain species also affected the photoresponsive function. The surfactant 12, possessingp-ethoxy group as the tail chain, was found to form a stable micelle aggregation as compared with the structurally related surfactant 10 having ethyl unit as its tail group, but it exhibited a large CMC change (5.3 mmol/L) by UV-light irradiation.  相似文献   
5.
《Electroanalysis》2006,18(22):2218-2224
This article deals with the development of a method for the determination of osmium at a carbon paste electrode (CPE) modified with cationic surfactants of the quaternary ammonium salt type; namely, cetyltrimethylammonium bromide (CTAB) and 1‐(ethoxycarbonyl)‐pentadecyltrimethyl‐ammonium bromide (Septonex); both being added in situ and serving for preconcentration of osmium via its hexachloroosmate(IV) anion. The proper electrochemical detection was performed by cathodic scanning in the differential pulse voltammetric mode. Optimization studies concerning important experimental parameters also included a specially performed potentiometric titration, helping to define the actual stoichiometry for the ion‐pairing process, the main principle and driving force of the accumulation step. In a chloride/acetate buffer based supporting medium and with Septonex as the modifier of choice, the reduction signal for osmium was found to be proportional to the Os(IV) concentration in a range from 5×10?9 to 5×10?7 mol L?1 with a limit of detection close to 5×10?9 mol L?1 (with preconcentration for 60 s). The method capable to determine Os(IV) in the presence of both Pt(IV) and Ir(III) was tested on model solutions as well as with real sample of industrial waste water (spiked with the analyte); both yielding the recovery rates within 88–99%.  相似文献   
6.
高分子阳离子絮凝剂用于炼油废水处理研究   总被引:15,自引:0,他引:15  
用聚二甲基二烯丙基氯化铵型高分子阳离子絮凝剂处理炼油废水考察了险油和化学耗氧量的动态变化规律。对产生的浮渣性质及滤饼的成份进行了研究。并且与聚合铝的处理效果进行对照。研究结果表明,HCA除油和化学耗管氧量的性能优于PAC,HCA产生的浮渣是PAC的三分之一,而浮渣中的含油量则是PAC的三倍。  相似文献   
7.
阳、阴、非离子表面活性剂胶束对酯碱性水解的影响   总被引:13,自引:0,他引:13  
应用紫外分光光度法和热动力学方法研究了芳香酸酯和正脂肪酸酯在表面活性剂DTAB、TTAB、CTAB、SDS、Brij35、TritonX-100胶束中的碱性水解反应。阳、阴、非离子表面活性剂胶束对酯的碱性水解均有禁阻作用。讨论了胶束对酯碱性水解禁阻作用的原因。  相似文献   
8.
Two esters of chlorin e6 have been synthesized by esterification with aminoalcohols via the formation of acid chloride using oxalyl chloride and converted to the corresponding cationic water-soluble esters of chlorin e6. The visible absorption and circular dichroism spectra have revealed that these two cationic chlorin e6 esters synthesized are readily soluble in water as a monomer.  相似文献   
9.
It is of a great challenge to develop semiconductor photocatalysts with potential possibilities to simultaneously enhance photocatalytic efficiency and inhibit generation of toxic intermediates.In this study,we developed a facile method to induce the La doping and cationic vacancie(V(Zn))on ZnO for the highly efficient complete NO oxidation.The photocatalytic NO removal efficiency increases from 36.2%to 53,6%.Most importantly,a significant suppressed NO2 production also has been realized.According to the DFT calculations,ESR spectra and in situ FTIR spectra,the introduction of La^3+induce the redistribution of charge carriers in La-ZnO,which promote the production of·O2^- and lead to the formation of V(Zn)for the formation of·OH,contributing to the complete oxidation of NO to nitrate.Besides,the conversion pathway of photocatalytic NO oxidation has been elaborated,This work paves a new way to simultaneously realize the photocatalytic pollutants removal and the inhibition of toxic intermediates generation for efficient and safe air purification.  相似文献   
10.
The interaction of carbenium ion pairs with silica is studied by means of UV-spectroscopy, electrokinetic and adsorption measurements using triphenylmethyl derivatives, (RC6H4)3CX, (X=F, Cl, Br, SCN, OH; R=Cl, I, H, CH3, C(CH3)3, OCH3, N(CH3)2) in interaction with silica particles suspended in 1,2-dichloroethane. The adsorption of triarylmethyl-halides onto silica is accompanied by the heterolytic dissociation of the tertiary carbonhalogen bond. The degree of ionization depends on the basicity of the counter anion and acidity of the cation, respectively. The influences of both concentration and structure of triarylmethyl halides on the zeta-potential are discussed with regard to steric and electronic factor. The zeta-potential values of the adsorbates decrease significantly, as compared with the free silica surface, from a certain triarylmethyl halide concentration where ionization takes place, to a constant level which is characteristic of the carbenium ion pair. These constant zeta-potential values of the adsorbates depend on the basicity of the counter ion and the p Hammett constants of the ring substitutents, with exclusion of sterically hindered substituents and salt derivatives, e.g., crystal violet and malachite green.  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