全文获取类型
收费全文 | 533篇 |
免费 | 17篇 |
国内免费 | 105篇 |
专业分类
化学 | 564篇 |
晶体学 | 1篇 |
力学 | 4篇 |
物理学 | 86篇 |
出版年
2024年 | 1篇 |
2023年 | 7篇 |
2022年 | 11篇 |
2021年 | 10篇 |
2020年 | 10篇 |
2019年 | 8篇 |
2018年 | 7篇 |
2017年 | 12篇 |
2016年 | 9篇 |
2015年 | 17篇 |
2014年 | 18篇 |
2013年 | 42篇 |
2012年 | 24篇 |
2011年 | 45篇 |
2010年 | 50篇 |
2009年 | 56篇 |
2008年 | 35篇 |
2007年 | 48篇 |
2006年 | 30篇 |
2005年 | 27篇 |
2004年 | 36篇 |
2003年 | 19篇 |
2002年 | 15篇 |
2001年 | 14篇 |
2000年 | 12篇 |
1999年 | 13篇 |
1998年 | 9篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1994年 | 11篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1973年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有655条查询结果,搜索用时 31 毫秒
31.
《Journal of Coordination Chemistry》2012,65(1-4):77-89
Abstract A steric effect in the carbon-skeleton rearrangement catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester]C104, was investigated under electrochemical conditions. The controlled-potential electrolyses of alkyl halides having two carboxylic ester groups of different bulkiness on the same carbon atom, such as 2,2-bis(ethoxycarbonyl)-l-bromopropane, l-bromo-2-tert-butoxycarbonyl-2-ethoxy-carbonylpropane, l-bromo-2-cyclohexyloxycarbonyl-2-ethoxycarbonylpropane, and l-bromo-2-ethoxy-carbonyl-2-phenoxycarbonylpropane, were carried out in N,N-dimethylformamide, as catalyzed by [Cob(II)7C1ester]CIO4, to give the corresponding ester-migrated products in the dark at—1.5 V vs SCE in the presence of acetic acid and at—2.0 V vs SCE without acetic acid. As regards a correlation between bulkiness of an ester group and a migration aptitude, a smaller ester group tends to migrate to the adjacent carbon atom more readily than a larger one. The origin of such a steric effect is discussed with attention to the rate-determining step. 相似文献
32.
以偶氮二异丁腈、十二胺为主要原料,通过Pinner反应制备了一种两端各带有12个碳烷基链的水溶性偶氮引发剂——2,2'-偶氮二异丁基十二脒盐酸盐AIBL.采用核磁氢谱、元素分析及液相色谱对AIBL进行了结构及纯度表征,采用TGA、DSC和紫外分光光度计研究了其热分解现象和热分解动力学,采用表面张力仪对其表面活性进行了测定.结果表明,所合成的引发剂AIBL具有预想的结构和较高的纯度,其热分解反应属于一级反应,热分解活化能为134.80 k J/mol,70℃下水中的半衰期约为4 h;AIBL在水溶液中具有表面活性,其临界胶束浓度为0.13 g/L,对应的表面张力为33.57 m N/m.以丙烯酰胺为单体、AIBL为引发剂制备了水溶性端基疏水聚合物SPAM.采用溴化法研究其转化率,应用乌氏黏度法、零切黏度法以及荧光探针对其缔合作用进行了研究.结果表明,AIBL具有良好的引发丙烯酰胺聚合的能力;相对于不带疏水长链的引发剂所合成的聚合物PAM,SPAM具有明显的疏水缔合效应,这说明AIBL成功地将疏水长链引入到聚合物的端基中,从而形成端基疏水聚合物. 相似文献
33.
A new, simple and low‐cost method for patterning hydrophobic barriers in porous support such as paper by Parafilm® has been introduced. This method is then used for electrochemical paper‐based ammonia sensor construction. Ammonia sensor is based on electrochemical concentration cell which ammonia reaction with electrolyte in halves cell caused in concentration gradient and therefore potential difference dependent on ammonia concentration. The effect of concentrations of the involved chemicals, time periods of the required processes, the presence of Faraday cage as well as the effects of different salts used in the salt bridge on the response of the sensor, were investigated in order to find the optimized conditions. 相似文献
34.
35.
Self-assembling Dimeric and Trimeric Aggregates Based on Solvophobic and Charge-pairing Interactions
Self-assembly processes based on shape complementarity and noncovalent binding interactions are widely recognized as a fundamental principle in nature. Besides charge pairing and hydrogen bonding, hydrophobic interactions play a crucial role in water. Here we report the self-assembly of structurally simple monomers to yield defined dimeric and trimeric aggregates in highly polar media, based on ionic and solvophobic interactions. NMR, mass spectrometry and curve fitting were used to characterize these supramolecular assemblies in water–methanol solutions. 相似文献
36.
Egbert Müller Judith Vajda Djuro Josic Tim Schröder Romain Dabre Tim Frey 《Journal of separation science》2013,36(8):1327-1334
An essential part of the modulation of protein‐binding capacity in hydrophobic interaction chromatography is the buffer‐salt system. Besides using “single” electrolytes, multicomponent electrolyte mixtures may be used as an additional tool. Both the protein solubility and the binding capacity depend on the position of a salt in the so‐called Hofmeister series. Specific interactions are observed for an individual protein‐salt combination. For salt mixtures, selectivity, recovery, and binding capacity do not behave like for the single salts that are positioned in between the two mixed components in the Hofmeister series, as the continuous correlation would suggest. Thus, finding strategies for mixed salts could potentially lead to improved capacities in hydrophobic interaction chromatography. Mixtures of ammonium sulfate, sodium citrate, sodium sulfate, sodium chloride, sodium acetate, and glycine were used to investigate the binding capacities for lysozyme and a monoclonal antibody on various hydrophobic resins. Resin capacity for two investigated proteins increases when mixtures consisting of a chaotropic and a kosmotropic salt are applied. It seems to be related to the rather basic isoelectric points of the proteins. 相似文献
37.
Yuanzhong Yang Maria T. Matyska Reinhard I. Boysen Joseph J. Pesek Milton T. W. Hearn 《Journal of separation science》2013,36(7):1209-1216
In this study, the retention behavior of selected hydrophobic and polar bases on a minimally modified silica hydride phase was investigated. From these results and the associated retention plots, significant differences in the chromatographic dependencies of these two classes of basic compounds were evident. The polar bases exhibited strong retention with mobile phases of high organic solvent content, but displayed weak retention with mobile phases of high water content. In contrast, the hydrophobic bases showed “U‐shape” retention dependencies, indicative of the interplay of both RP and normal‐phase retention characteristics. These studies have demonstrated that hydrophobic and polar bases can be simultaneously separated on the same column either under typical RP‐like or aqueous normal‐phase‐like conditions, respectively, with distinctive selectivity. Finally, the effects of temperature on the RP and aqueous normal phase modality of separations with these analytes were investigated, where discrete changes in retention behavior were also observed. 相似文献
38.
Fátima Milhano Santos Augusto Quaresma Pedro Rui Filipe Soares Rita Martins Maria João Bonifácio João António Queiroz Luís António Passarinha 《Journal of separation science》2013,36(11):1693-1702
Despite of membrane catechol‐O‐methyltransferase (MBCOMT, EC 2.1.1.6) physiological importance on catecholamines’ O‐methylation, no studies allowed their total isolation. Therefore, for the first time, we compare the performance of three hydrophobic adsorbents (butyl‐, epoxy‐, and octyl‐Sepharose) in purification of recombinant human COMT (hMBCOMT) from crude Brevibacillus choshinensis cell lysates to develop a sustainable chromatographic process. Hydrophobic matrices were evaluated in terms of selectivity and hMBCOMT's binding and elution conditions. Results show that hMBCOMT's adsorption was promoted on octyl and butyl at ≤375 mM NaH2PO4, while on epoxy higher concentrations (>850 mM) were required. Additionally, hMBCOMT's elution was promoted on epoxy, butyl, and octyl using respectively 0.1–0.5, 0.25–1, and 1% of Triton X‐100. On butyl media, a stepwise strategy using 375 and 0 mM NaH2PO4, followed by three elution steps at 0.25, 0.7 and 1% Triton X‐100, allowed selective hMBCOMT isolation. In conclusion, significant amounts of MBCOMT were purified with high selectivity on a single chromatography procedure, despite its elution occurs on multiple peaks. Although successful applications of hydrophobic interaction chromatography in purification of membrane proteins are uncommon, we proved that traditional hydrophobic matrices can open a promising unexplored field to fulfill specific requirements for kinetic and pharmacological trials. 相似文献
39.
40.
Vipul Gupta Joshua A. Tuscano Naomi R. Romriell Robert C. Davis Matthew R. Linford 《Surface and interface analysis : SIA》2014,46(2):106-108
An important aspect of the robustness of an electronic device is its ability to resist water, fingerprints, dirt, and smudges that may compromise its ability to function and/or the information within it. Here, we report a chemical analysis by ToF‐SIMS, wetting, and XPS of the surfaces in a commercially available Apple iPod nano (8GB, MC525LL/A), which showed good resistance to its environment. This analysis reveals that the front panel (touchscreen) of the device is coated with a low free energy fluorinated polymer that may consist of short segments of a fluorinated hydrocarbon connected through ether linkages. No other part of the device appears to have this hydrophobic coating. A plasma treatment of the device leads to a deterioration of its performance. This work demonstrates how different analytical techniques can complement each other and contribute to a better understanding of a surface or a material. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献