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   2009篇
  免费   84篇
  国内免费   267篇
化学   2212篇
晶体学   13篇
综合类   11篇
物理学   124篇
  2024年   4篇
  2023年   16篇
  2022年   58篇
  2021年   55篇
  2020年   55篇
  2019年   54篇
  2018年   36篇
  2017年   64篇
  2016年   53篇
  2015年   63篇
  2014年   73篇
  2013年   175篇
  2012年   88篇
  2011年   96篇
  2010年   63篇
  2009年   85篇
  2008年   105篇
  2007年   140篇
  2006年   86篇
  2005年   113篇
  2004年   104篇
  2003年   104篇
  2002年   89篇
  2001年   71篇
  2000年   62篇
  1999年   64篇
  1998年   64篇
  1997年   46篇
  1996年   47篇
  1995年   43篇
  1994年   46篇
  1993年   32篇
  1992年   17篇
  1991年   20篇
  1990年   15篇
  1989年   14篇
  1988年   8篇
  1987年   8篇
  1986年   4篇
  1985年   5篇
  1984年   1篇
  1982年   6篇
  1981年   2篇
  1980年   2篇
  1978年   1篇
  1976年   1篇
  1973年   1篇
  1970年   1篇
排序方式: 共有2360条查询结果,搜索用时 15 毫秒
101.
Concanavalin A (Con A) immobilized poly(2-hydroxyethyl methacrylate) (PHEMA) beads were investigated for specific adsorption of yeast invertase from aqueous solutions. PHEMA beads were prepared by a suspension polymerization technique with an average size of 150-200 microm, and activated by epichlorohydrin. Con A was then immobilized by covalent binding onto these beads. The maximum Con A immobilization was found to be 10 mg/g. The invertase-loading capability of the PHEMA/Con A beads was 107 mg/g. The maximum invertase adsorption capacity on the PHEMA/Con A adsorbents was observed at pH 5.0. The values of the Michaelis constant K(m) of invertase were significantly larger upon adsorption, indicating decreased affinity by the enzyme for its substrate, whereas V(max) was smaller for the adsorbed invertase. Adsorption improved the pH stability of the enzyme as well as its temperature stability. Thermal stability was found to increase with adsorption. The adsorbed enzyme activity was found to be quite stable in repeated experiments. Storage stability of adsorbed invertase.  相似文献   
102.
采用silicalite-1对HY型分子筛进行修饰,得到具有核壳结构的复合分子筛HY/silicalite-1。通过X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、N2的吸附-脱附及吡啶吸附红外(Py-FTIR)等手段对不同晶化时间合成的HY/silicalite-1复合分子筛进行了表征,研究了复合分子筛对纤维素水解的催化性能。结果表明,晶化时间直接影响复合分子筛的晶体生长规律和两组分的相对含量,最佳晶化时间为16-24 h,所得到的复合分子筛外貌呈核壳结构,silicalite-1附晶生长在HY型分子筛的表面;随着晶化时间的延长,复合分子筛的表面由胶浊状变为光滑,最终变为鳞片状;其B酸量先减少后增加,而L酸量则先增加后减少。其中,晶化时间为24 h的HY/silicalite-1复合分子筛B酸量最大,L酸量最小,对纤维素水解反应具有良好的催化性能,葡萄糖收率由HY型分子筛催化获得的28.0%大幅提高至45.8%。  相似文献   
103.
The structure of polynuclear PdII hydroxocomplexes (PHC) formed as a result of alkaline hydrolysis of PdII chloride complexes was studied by EXAFS, SAXS, and TEM methods. It is established that in aqueous solutions a hydroxocomplex particle is a filament curled into a ball containing about 100 Pd atoms. The filament consists of planar coordination squares of PdO4 units linkedvia one or two oxygen bridges of different geometry. Aging of samples results in an increase in the number of single bridging ligands and a decrease in the diameter of particles. Interatomic distances around palladium atoms were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimlcheskaya, No. 10, pp. 1901–1905, October, 1995.  相似文献   
104.
Xylan is the major component of hemicellulose, which consists of up to one-third of the lignocellulosic biomass. When the zinc chloride solution was used as a pretreatment agent to facilitate cellulose hydrolysis, hemicellulose was hydrolyzed during the pretreatment stage. In this study, xylan was used as a model to study the hydrolysis of hemicellulose in zinc chloride solution. The degradation of xylose that is released from xylan was reduced by the formation of zinc-xylose complex. The xylose yield was >90% (w/w) at 70°C. The yield and rate of hydrolysis were a function of temperature and the concentration of zinc chloride. The ratio of zinc chloride can be decreased from 9 to 1.3 (w/w). At this ratio, 76% of xylose yield was obtained. When wheat straw was pretreated with a concentrated zinc chloride solution, the hemicellulose hydrolysate contained only xylose and trace amounts of arabinose and oligosaccharides. With this approach, the hemicellulose hydrolysate can be separated from cellulose residue, which would be hydrolyzed subsequently to glucose by acid or enzymes to produce glucose. This production scheme provided a method to produce glucose and xylose in different streams, which can be fermented in separated fermenters.  相似文献   
105.
自从1972年Field等据丙二酸为底物的Belousov-Zhabotinskii(BZ)反应提出T著名的FKN机理以来,人们发现了许多与生化过程有关的化学振荡体系并应用于临床实践.机体在新陈代谢过程中,糖元的糖酵解反应是以糖类为基础的复杂化学振荡,考虑到代谢过程,糖类分解有许多中间物的振荡.  相似文献   
106.
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   
107.
19F and 31P NMR spectroscopy were used to study the kinetics of the hydrolysis of LiPF6 in the homogenous solvent system propylene carbonate (PC)—dimethyl carbonate (DMC)—H2O. It was found that the main products of the hydrolysis are HF, LiPO2F2 and Li2PO3F. The content of POF3 and PF5 was negligibly low. We set up a hypothesis that the main factor determining the rate of the process is the so-called ‘secondary’ catalytic effect, caused by solvated H+ ions.  相似文献   
108.
In this paper we report the first synthesis of isoxazolidine and isoxazoline-POSS macromers by 1,3-dipolar cycloaddition reactions of vinyl- and styryl-POSS with N-methyl-C-ethoxycarbonylnitrone and ethoxycarbonyl nitrile oxide, promoted by microwave irradiation. The nature of the resulting cycloadducts has been determined by NOE experiments and supported by computational studies at PM3 and DFT B3LYP/6-31G* levels.  相似文献   
109.
The 1,3-dipolar cycloaddition reaction of meso-tetraaryl porphyrin with 2,6-dichlorobenzonitrile oxide yielded novel isoxazoline-fused chlorins and two stereoisometric bacteriochlorins. The crystal structure of bacteriochlorin was characterized by X-ray diffraction.  相似文献   
110.
Heterometal materials based on glycidoxypropyltrialkoxysilane and titaniumalkoxide are used for optical applications and require a high homogeneity on the molecular level. The presence of heterometal titanosiloxanes, their distribution and hydrolytic stability should influence the homogeneity of these materials. 29Si and 17O NMR spectroscopy has been used to investigate sols with molar ratios Si : Ti = 1 and H2O : OR (H) = 0.5 – 2.0 and their gels after heat treatment at 130°C. The presence of Si—O—Ti bonds in sols with a low water content (H < 0.2) and in the corresponding gels was identified by the high-field shift of the 29Si NMR signals of T1 and T2 units of up to 2–3 ppm compared to corresponding signals of homo-condensed Si—O—Si bonds. The existence of Si—O—Ti bonds in the sols is supported by 17O NMR spectra which show a characteristic signal around 340 ppm. A cleavage of the Si—O—Ti bonds occurs with increasing water/OR ratio in the sols. The cleavage of the heterometal bonds and the building up of homo-condensed species leads to a separation into areas with predominantly Ti—O—Ti and Si—O—Si bonds resulting in a decreased molecular homogeneity of the materials.  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