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   1341篇
  免费   44篇
  国内免费   3篇
化学   887篇
晶体学   5篇
力学   29篇
数学   163篇
物理学   304篇
  2024年   2篇
  2023年   13篇
  2022年   64篇
  2021年   52篇
  2020年   34篇
  2019年   31篇
  2018年   44篇
  2017年   37篇
  2016年   52篇
  2015年   41篇
  2014年   59篇
  2013年   90篇
  2012年   86篇
  2011年   90篇
  2010年   79篇
  2009年   68篇
  2008年   87篇
  2007年   75篇
  2006年   70篇
  2005年   43篇
  2004年   45篇
  2003年   23篇
  2002年   26篇
  2001年   28篇
  2000年   8篇
  1999年   25篇
  1998年   14篇
  1997年   12篇
  1996年   10篇
  1995年   14篇
  1994年   9篇
  1993年   10篇
  1992年   4篇
  1991年   3篇
  1990年   8篇
  1989年   7篇
  1988年   2篇
  1987年   3篇
  1986年   3篇
  1985年   4篇
  1984年   4篇
  1983年   2篇
  1982年   3篇
  1981年   1篇
  1980年   1篇
  1978年   1篇
  1975年   1篇
排序方式: 共有1388条查询结果,搜索用时 15 毫秒
91.
New strategies for the synthesis of perfectly alternating segmented polyimide-polydimethyl siloxane copolymers were developed by utilizing a transimidization method. Imide oligomers endcapped with 2-aminopyrimidine were reacted with aminopropyl terminated (dimethyl siloxane) oligomers to afford perfectly alternating segmented imide siloxane copolymers. The polymerization was conducted in solvents such as chlorobenzene and chlorofrom. High molecular weight, fully imidized perfectly alternating segmented imide siloxane copolymers were obtained within 2 h at temperatures of 60-110°C. The mechanism of the reaction was further elucidated via model compounds and NMR characterization. The block copolymers exhibited two Tgs due to the microphase separation of the polyimide and polysiloxane phases. The Tg of the polyimide phase was a function of the length of the polyimide block. However, partial phase mixing was also evident from the DSC results on the imide siloxane copolymers prepared with low molecular weight polyimide segments. Thermooxidative stability and tensile properties of the perfectly alternating segmented imide siloxane copolymers were found to be principally dependent on the amount of poly (dimethyl siloxane) incorporated in the copolymer and did not correlate with the poly (dimethyl siloxane) or polyimide block lengths. The stress-strain behavior of both solvent cast films or molded films is also reported. © 1994 John Wiley & Sons, Inc.  相似文献   
92.
Solid polymer electrolyte (SPE) systems based on interpenetrating blends of poly(ethylene oxide‐co‐propylene oxide) and poly(methyl methacrylate) host matrices, with lithium perchlorate as guest salt, were prepared. These electrolytes were presented as free‐standing films, and their thermal and electrochemical properties were characterized by conductivity and electrochemical stability measurements. The properties of the interpenetrating blends of poly(ethylene oxide‐co‐propylene oxide) and poly(methyl methacrylate) host matrices as the electrolyte component of a solid‐state electrochromic device are reported and the results obtained suggest that this electrolyte provides an encouraging performance in this application. The most conducting electrolyte composition of this SPE system is the formulation designated as SPE2‐0PC (5.01 × 10?4 S cm?1 at about 57°C). The lowest decomposition temperature was registered with the SPE6‐15PC composition (233°C). The average transmittance in the visible region of the spectrum was above 41% for all the samples analyzed. After coloration the device assembled with 71 wt% PC presented an average transmittance of 15.71% and an optical density at 550 nm of 0.61. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
93.
The first report on the fabrication and application of a nanocomposite containing poly-N-vinyl carbazole (PVK) polymer and graphene oxide (GO) as an antimicrobial film was demonstrated. The antimicrobial film was 90% more effective in preventing bacterial colonization relative to the unmodified surface. More importantly, the nanocomposite thin film showed higher bacterial toxicity than pure GO-modified surface.  相似文献   
94.
The relevance of metal interactions with azides has led us to the study of the complexation of some transition metals, nickel and cobalt, by azidoacetone by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of NiCl(2) and CoCl(2) , in methanol/water. Nickel was electrosprayed with other counter ion, bromide (Br), as well as other solvent (ethanol/water). For nickel and cobalt, the complexes detected were single positively charged, with various stoichiometries, some resulted from the fragmentation of the ligand, the loss of N(2) being quite common. The most abundant species were [Ni(II)Az(2)X](+) where X = Cl, Br and Az = azidoacetone. Some of the complexes showed solvation with the solvent components. Metal reduction was observed in complexes where a radical was lost, resulting from the homolytic cleavage of a metal coordination bond. Collision-induced dissociation (CID) experiments followed by tandem mass spectrometry (MS-MS) analysis were not absolutely conclusive about the coordination site. However, terminal ions of the fragmentation routes were explained by a gas-phase mechanism proposed where a C-C bond was activated and the metal inserted subsequently. Density functional theory calculations provided structures for some complexes. In [Ni(II)Az(2)X](+) species, one azidoacetone ligand is monodentate and the dominant binding location is the alkylated nitrogen and not the carbonyl group. The other azidoacetone ligand is bidentate showing coordination through alkylated nitrogen and the carbonyl group. These are also the preferential binding sites for the most stable isomer of [Ni(II)AzX](+) species.  相似文献   
95.
Deacidification of vegetable oils can be performed using liquid–liquid extraction as an alternative method to the classical chemical and physical refining processes. This paper reports experimental data for systems containing refined babassu oil, lauric acid, ethanol, and water at 303.2 K with different water mass fractions in the alcoholic solvent (0, 0.0557, 0.1045, 0.2029, and 0.2972). The dilution of solvent with water reduced the distribution coefficient values, which indicates a reduction in the loss of neutral oil. The experimental data were used to adjust the NRTL equation parameters. The global deviation between the observed and the estimated compositions was 0.0085, indicating that the model can accurately predict the behavior of the compounds at different levels of solvent hydration.  相似文献   
96.
97.
98.
Immobilization of quantum dots (QDs) onto solid supports could improve their applicability in the development of sensing platforms and solid‐phase reactors by allowing the implementation of reusable surfaces and the execution of repetitive procedures. As the reactivity of QDs relies mostly on their surface chemistry, immobilization could also limit the disruption of solution stability that could prevent stable measurements. Herein, distinct strategies to immobilize QDs onto porous aminated supports, such as physical adsorption and the establishment of chemical linking, were evaluated. This work explores the influence of QD capping and size, concentration, pH, and contact time between the support and the QDs. Maximum QD retention was obtained for physical adsorption assays. Freundlich and Langmuir isotherms were used to analyze the equilibrium data. Gibbs free energy, enthalpy, and entropy were calculated and the stability of immobilized QDs was confirmed.  相似文献   
99.
100.
An extracellular β-glucanase secreted by Kluyveromyces marxianus was identified for the first time. The optimal conditions for the production of this enzyme were evaluated by response surface methodology. The optimal conditions to produce β-glucanase were a glucose concentration of 4 % (w/v), a pH of 5.5, and an incubation temperature of 35 °C. Response surface methodology was also used to determine the pH and temperature required for the optimal enzymatic activity. The highest enzyme activity was obtained at a pH of 5.5 and a temperature of 55 °C. Furthermore, the enzyme was partially purified and sequenced, and its specificity for different substrates was evaluated. The results suggest that the enzyme is an endo-β-1,3(4)-glucanase. After optimizing the conditions for β-glucanase production, the culture supernatant was found to be effective in digesting the cell wall of the yeast Saccharomyces cerevisiae, showing the great potential of β-glucanase in the biotechnological production of soluble β-glucan.  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