全文获取类型
收费全文 | 28556篇 |
免费 | 3914篇 |
国内免费 | 2124篇 |
专业分类
化学 | 5107篇 |
晶体学 | 99篇 |
力学 | 4951篇 |
综合类 | 500篇 |
数学 | 11631篇 |
物理学 | 12306篇 |
出版年
2024年 | 54篇 |
2023年 | 278篇 |
2022年 | 695篇 |
2021年 | 773篇 |
2020年 | 907篇 |
2019年 | 790篇 |
2018年 | 747篇 |
2017年 | 1064篇 |
2016年 | 1238篇 |
2015年 | 893篇 |
2014年 | 1531篇 |
2013年 | 2209篇 |
2012年 | 1606篇 |
2011年 | 1890篇 |
2010年 | 1618篇 |
2009年 | 1920篇 |
2008年 | 1785篇 |
2007年 | 1793篇 |
2006年 | 1510篇 |
2005年 | 1362篇 |
2004年 | 1257篇 |
2003年 | 1070篇 |
2002年 | 1020篇 |
2001年 | 801篇 |
2000年 | 765篇 |
1999年 | 677篇 |
1998年 | 626篇 |
1997年 | 466篇 |
1996年 | 399篇 |
1995年 | 372篇 |
1994年 | 332篇 |
1993年 | 280篇 |
1992年 | 253篇 |
1991年 | 190篇 |
1990年 | 171篇 |
1989年 | 131篇 |
1988年 | 128篇 |
1987年 | 142篇 |
1986年 | 116篇 |
1985年 | 133篇 |
1984年 | 135篇 |
1983年 | 73篇 |
1982年 | 101篇 |
1981年 | 62篇 |
1980年 | 32篇 |
1979年 | 38篇 |
1978年 | 35篇 |
1977年 | 30篇 |
1976年 | 17篇 |
1973年 | 25篇 |
排序方式: 共有10000条查询结果,搜索用时 187 毫秒
961.
Nashaat N. Nassar 《Journal of Dispersion Science and Technology》2013,34(12):1714-1720
Water-in-oil (w/o) microemulsions are very appealing reaction media due to their ability to provide huge surface of contact between water-soluble and oil-soluble reactants. Their application as reaction media, including the preparation of nanoparticles, is, however, limited to water soluble precursors. In this study, we present a first step scheme in a two-step process for the preparation of metal oxide nanoparticles starting from their water-insoluble metal oxide bulk powder. This step involves solubilizing the metal oxide in the water pools of the microemulsion with the aid of a solubilizing agent. The variables affecting the solubilizing capacity of iron and copper oxides, as examples of important metal oxides, in single HCl-containing AOT/water/isooctane microemulsions were investigated. The effect of the following variables on the solubilization capacity is reported, namely, mixing time, surfactant concentration, water to surfactant mole ratio (R), and the nominal concentration of HCl in the water pool. At 300-rpm, time-invariant concentration of the metals in the microemulsions was achieved in about 6 hours. These values were quoted as the solubilization capacity of the metal oxide at the corresponding conditions. Solubilization capacity increased linearly with the surfactant concentration and R, and portrait a power function with the nominal concentration of HCl in the water pool. A mathematical model previously derived to describe nanoparticle uptake by single microemulsion accurately accounted for the effect of the aforementioned variables on the solubilization capacity. 相似文献
962.
H. Bargozin R. A. Hadadhania H. Faraji H. Yousefzadeh 《Journal of Dispersion Science and Technology》2013,34(6):755-764
This study investigated the effect of the orientation of rough nanoparticles on Derjaguin and Landau, Verwey and Overbeek (DLVO) energy interaction. Rippled sphere model was used to survey van der Waals attraction energy and repulsive double-layer interaction energy between nanoparticles. The effect of particle size, asperity size, number of asperities, and concentration was studied for different orientations. Spherical coordinates were used to evaluate the effect of changes in orientation under controlled conditions. Surface element integral method was used to calculate DLVO energy interactions between rough particles at specific orientations. The DLVO energy results show that a change in orientation significantly affected the stability of the nanoparticles. The stability of dispersion varied as the contact surface between nanoparticles changed. 相似文献
963.
964.
J. J. Ge G. C. Zhang P. Jiang L. Wang H. H. Pei X. L. Liu 《Journal of Dispersion Science and Technology》2013,34(2):278-286
Alkali and alkali/surfactant displacing agents are designed for two kinds of heavy oil. Results of emulsifying capacity, dynamic interfacial tension (IFT) and water-wet core flooding tests show that, although alkaline/surfactant systems exhibit better capacity in emulsification and IFT reduction, oil recovery values of alkaline/surfactant flooding are lower than those of alkaline flooding. Glass-etched micromodel tests further demonstrate that, when alkaline solution penetrates into the oil phase, water streams break into ganglia coating oil film. Water ganglia may be entrapped by narrow throats, consequently presenting a water-oil alternating slug flow. Similar water ganglia also appears in alkaline/surfactant flooding, however, water channeling along the pore surface occurs subsequently, resulting in its relatively lower oil recovery. 相似文献
965.
生物油模型化合物催化裂化制备芳香烃的实验研究 总被引:1,自引:0,他引:1
通过HZSM-5分子筛催化剂对生物油典型模型化合物(乙酸、愈创木酚、正庚烷和环己烷等)在550℃进行了催化裂化反应,研究模型化合物催化裂化特性和反应机理以及催化剂性质。结果表明,正庚烷和环己烷裂化产物主要是芳香烃(53%和91%,均为积分面积分数),对于此类不含氧的模型化合物,催化裂化反应过程更容易进行;随着催化剂用量的增加,可以有效增加乙酸裂化产物中芳香烃含量(12%到90%,均为积分面积分数);愈创木酚结构比较复杂,HZSM-5催化剂主要脱除了甲氧基,催化剂用量的增加可以使芳香烃类稳定物质更容易形成。 相似文献
966.
对神东上湾煤(SDR)及其岩相分离所得惰质组富集物(SDI)分别进行核磁(13C-NMR)、红外光谱(FT-IR)和X射线光电子能谱(XPS)表征,得到煤结构单元信息,与元素分析数据相结合构建了SDR和SDI的结构模型,用ACD/CNMR predictor软件计算结构模型的 13C化学位移。结果表明,SDR芳香结构主要是缩合程度为2的萘,SDI主要是菲和萘,SDI较SDR结构芳香度较高,两个结构中氧主要以羰基氧和羟基氧的形式存在,氮主要以吡咯和吡啶形式存在,两个结构模型计算得到核磁谱图与实验谱图吻合较好,结构式分别为C181H136N2O24和C186H148N2O22。 相似文献
967.
内蒙五牧场矿区号煤层原煤大分子结构特征及其形成机制 《燃料化学学报》2013,41(11):1294-1302
在对内蒙古自治区呼伦贝尔市伊敏盆地五牧场区11号煤层原煤工业分析、元素分析、13C-NMR、FT-IR、XPS等分析基础上,获得了煤大分子结构中碳骨架信息、脂肪结构以及含氧官能团类型及比例、氮原子的存在形式和比例等结构信息。以此为基础,构建了煤的大分子结构模型,并应用 13C-NMR预测软件ACD/CNMR predictor 对其进行了修正, 获得与实验核磁共振谱图吻合较好的大分子结构模型。大分子结构的芳香结构单元以苯、萘、蒽、菲为芳香结构单元,数量分别是1、2、2、1,醚键、氢化芳环以及邻位亚甲基作为连接芳香结构的主要桥键;氧原子以酚羟基、羰基、羧基的形式存在,数量分别是7、3、2;氮原子分别以吡啶和吡咯的形式存在,甲基和脂肪短链分布在芳香单元的边缘。与相邻矿区的褐煤及相近变质程度的神东长焰煤的比较发现,其形成机制主要是在高温低压环境下,热演化过程中快速失去各种含氧官能团,导致短链脂肪类物质的形成,而低压环境则有利于热演化过程中形成的各种小分子物质逸散导致自由基的缩聚,形成较大的芳香结构单元,但是直链脂肪类物质的存在具有位阻效应,不利于芳香结构单元的定向排列,导致所谓的"化学成分成熟超前于其结构成熟"现象。 相似文献
968.
A new ferroelectric liquid crystal, 1-ethylpropyl (S)-2-[2-fluoro-4-(4′-decyloxybiphenylcarbonyloxy) benzoyloxy] propanoate, F, was synthesized and mixed with an achiral swallow-tailed material, 2-propylpentyl 4-(4′-nonyloxybiphenyl-4-carbonyloxy) benzoate,P, for the preparation of binary mixtures for the study. The binary mixtures gave a phase sequence SmA* -SmC* -SmX*. The electro-optic response of the mixtures in the ferroelectric SmC* phase was investigated. V-shaped switching was observed as the amount of the achiral swallow-tailed material became greater than 20 wt %. This result suggests that thresholdless, V-shaped switching in ferroelectric liquid crystal mixtures can be achieved by mixing a ferroelectric liquid crystal with an achiral swallow-tailed compound. 相似文献
969.
B. W. Bailey J. M. Rankin R. Weinbloom 《International journal of environmental analytical chemistry》2013,93(1):3-9
The use of ternary complexes in the determination of anionic surfactants has been investigated and an analytical method using linear alkyl sulfonates as a test substance has been developed. The method involves the formation of the chloroform-extractable bisphenanthroline Cu(II)-linear alkyl sulfonate (LAS) complex and the subsequent equilibration of the extract with erythrosine to form the extractable bisphenanthroline Cu(II)-erythrosine complex. In the equilibration step erythrosine displaces LAS quantitatively, allowing the determination of the LAS originally present by measuring the absorbance of the extracted bisphenanthroline-Cu(II)-erythrosine complex. Results are reported of studies made to determine the optimum analytical conditions, the sensitivity, and the precision for the method described. 相似文献
970.
Dipl.‐Ing. Birgit Wilding Dr. Margit Winkler Dr. Barbara Petschacher Dr. Regina Kratzer Dr. Sigrid Egger Dr. Georg Steinkellner Dr. Andrzej Lyskowski Prof. Bernd Nidetzky Prof. Karl Gruber Prof. Norbert Klempier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):7007-7012
Nitrile reductase QueF catalyzes the reduction of 2‐amino‐5‐cyanopyrrolo[2,3‐d]pyrimidin‐4‐one (preQ0) to 2‐amino‐5‐aminomethylpyrrolo[2,3‐d]pyrimidin‐4‐one (preQ1) in the biosynthetic pathway of the hypermodified nucleoside queuosine. It is the only enzyme known to catalyze a reduction of a nitrile to its corresponding primary amine and could therefore expand the toolbox of biocatalytic reactions of nitriles. To evaluate this new oxidoreductase for application in biocatalytic reactions, investigation of its substrate scope is prerequisite. We report here an investigation of the active site binding properties and the substrate scope of nitrile reductase QueF from Escherichia coli. Screenings with simple nitrile structures revealed high substrate specificity. Consequently, binding interactions of the substrate to the active site were identified based on a new homology model of E. coli QueF and modeled complex structures of the natural and non‐natural substrates. Various structural analogues of the natural substrate preQ0 were synthesized and screened with wild‐type QueF from E. coli and several active site mutants. Two amino acid residues Cys190 and Asp197 were shown to play an essential role in the catalytic mechanism. Three non‐natural substrates were identified and compared to the natural substrate regarding their specific activities by using wild‐type and mutant nitrile reductase. 相似文献