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   2025篇
  免费   380篇
  国内免费   238篇
化学   1456篇
晶体学   28篇
力学   195篇
综合类   6篇
数学   280篇
物理学   678篇
  2024年   10篇
  2023年   46篇
  2022年   66篇
  2021年   75篇
  2020年   99篇
  2019年   66篇
  2018年   89篇
  2017年   74篇
  2016年   103篇
  2015年   127篇
  2014年   129篇
  2013年   168篇
  2012年   165篇
  2011年   174篇
  2010年   128篇
  2009年   110篇
  2008年   113篇
  2007年   114篇
  2006年   99篇
  2005年   75篇
  2004年   61篇
  2003年   52篇
  2002年   74篇
  2001年   66篇
  2000年   50篇
  1999年   44篇
  1998年   44篇
  1997年   33篇
  1996年   34篇
  1995年   21篇
  1994年   19篇
  1993年   18篇
  1992年   18篇
  1991年   17篇
  1990年   14篇
  1989年   3篇
  1988年   2篇
  1987年   4篇
  1986年   5篇
  1985年   6篇
  1984年   7篇
  1983年   3篇
  1982年   3篇
  1981年   3篇
  1975年   1篇
  1974年   2篇
  1973年   2篇
  1964年   1篇
  1957年   1篇
  1936年   1篇
排序方式: 共有2643条查询结果,搜索用时 578 毫秒
41.
Previous work has shown that glucose oxidase can be immobilized on platinum to give an electrode that responds potentiometrically to glucose over the clinically useful range of about 10-250 mg glucose/100 mL. The present studies were carried out with electrochemically pretreated platinum and with gold or porous graphite substituted for the platinum support. The presence of the enzyme gave a significantly enhanced potentiometric response over that obtained with the bare support for both the pretreated platinum and the porous graphite, but not with gold. However, with platinum the potentiometric response became more negative with increasing glucose concentration. With porous graphite, the potential changed in the positive direction as the glucose concentration was increased. Hysteresis was demonstrated for the platinum-enzyme electrode. Mass transfer measurements with a rotating ring-disc electrode (RRDE) showed measurable diffusional resistances to the transport of a model electroactive compound (potassium ferrocyanide) through a matrix of immobilized enzyme attached to the disc of the RRDE. These results are part of a larger study to define the source of the potentiometric response by examining the roles of the support and the mass transfer resistances through the immobilized enzyme matrix.  相似文献   
42.
Liao W  Shang Q  Yu G  Li D 《Talanta》2002,57(6):6184-1092
Phase behavior of the extraction system, Cyanex 923–heptane/H2SO4–H2O has been studied. The third phase appeared at different aqueous H2SO4 concentration with varying initial Cyanex 923 concentration and temperature affects its appearance. Almost all of H2SO4 and H2O are extracted into the middle phase. The H2SO4 concentration in the third phase increases with the increasing aqueous acid concentration (CH2SO4,b) while the water content first increases and then reaches a constant value at CH2SO4,b=11.3 mol l−1. In the region of CH2SO4,b higher than 5.2 mol l−1, the composition of the middle phase is only related to the equilibrium concentration of H2SO4 in the bottom phase. H2SO4 and H2O are transferred into the middle phase mainly by their coordination with Cyanex 923 when CH2SO4,b is less than 11.3 mol l−1. When CH2SO4,b is higher than 11.3 mol l−1, excess H2SO4 is solubilized into the polar layer of the aggregates. In the region considered, the extracted complex changes from C923 · H2SO4 to C923 · H2SO4 · H2O and then to C923 · (H2SO4)2 · H2O.  相似文献   
43.
本文应用CNDO方法研究了H_2CO在Ni(110)面上的分解反应。证明了金属镍使H_2CO对称禁阻的热分解反应变成了对称允许反应; 讨论了H_2CO在Ni(110)面上的各种吸附模型; 论证了卧式多中心吸附作为H_2CO分解的中间步骤。  相似文献   
44.
Thin PVA/cobalt acetate composite fibers were prepared by using sol-gel processing and electrospinning technique.After calcination of the above precursor fibers,Co3O4 nanofibers with a diameter of 50-150 nm could be successfully obtained.The fibers were characterized by SEM,FT-IR,WAXD,respectively.  相似文献   
45.
Shang  Ao  Luo  Siwei  Zhang  Jianquan  Zhao  Heng  Xia  Xinxin  Pan  Mingao  Li  Chao  Chen  Yuzhong  Yi  Jicheng  Lu  Xinhui  Ma  Wei  Yan  He  Hu  Huawei 《中国科学:化学(英文版)》2022,65(9):1758-1766

Side-chain engineering has been demonstrated as an effective method for fine-tuning the optical, electrical, and morphological properties of organic semiconductors toward efficient organic solar cells (OSCs). In this work, three isomeric non-fullerene small molecule acceptors (SMAs), named BTP-4F-T2C8, BTP-4F-T2EH and BTP-4F-T3EH, with linear and branched alkyl chains substituted on the α or β positions of thiophene as the side chains, were synthesized and systematically investigated. The results demonstrate that the size and substitution position of alkyl side chains can greatly affect the electronic properties, molecular packing as well as crystallinity of the SMAs. After blending with donor polymer D18-Cl, the prominent device performance of 18.25% was achieved by the BTP-4F-T3EH-based solar cells, which is higher than those of the BTP-4F-T2EH-based (17.41%) and BTP-4F-T2C8-based (15.92%) ones. The enhanced performance of the BTP-4F-T3EH-based devices is attributed to its stronger crystallinity, higher electron mobility, suppressed biomolecular recombination, and the appropriate intermolecular interaction with the donor polymer. This work reveals that the side chain isomerization strategy can be a practical way in tuning the molecular packing and blend morphology for improving the performance of organic solar cells.

  相似文献   
46.
铜(Ⅱ)和锌(Ⅱ)分别在0.1mol/LKH_2PO_4-Na_2HPO_4缓冲溶液(pH6.5)和0.25mol/LNH_4Cl溶液中,与氟哌酸形成良好的络合吸附波,峰电位分别为-0.26V和-1.28V(vs;SCE);络合比分别为1:3和1:2;峰电流与铜(Ⅱ)和锌(Ⅱ)的浓度均在4.0×10 ̄(-7)~5.0×10 ̄(-6)mol/L范围内呈线性关系,检测限分别为7.0×10 ̄(-8)和5.0×10 ̄(-8)mol/L。用线性扫描和循环伏安法等手段研究体系的行为,表明均具吸附性,而铜(Ⅱ)-氟哌酸体系属络合物中铜(Ⅱ)的两电子还原的可逆过程。  相似文献   
47.
The synthesis and anion binding properties of new ruthenium(II) and cobalt(II) phenanthroline complexes, containing two amide subunits are described. Evidence for anion binding in dimethyl sulfoxide (DMSO) solution was obtained from u.v.–vis titration experiments. Results indicated that these receptors showed strong affinity for F and AcO, and showed weak affinity for OH and H2PO 4 , and showed no affinity for Cl, Br, I. These receptors interacted with various anions examined through hydrogen-bond formation.  相似文献   
48.
Acetylcholinesterase (AChE) is an extremely critical hydrolase tightly associated with neurological diseases. Currently, developing specific substrates for imaging AChE activity still remains a great challenge due to the interference from butyrylcholinesterase (BChE) and carboxylesterase (CE). Herein, we propose an approach to designing specific substrates for AChE detection by combining dimethylcarbamate choline with a self-immolative scaffold. The representative P10 can effectively eliminate the interference from CE and BChE. The high specificity of P10 has been proved via imaging AChE activity in cells. Moreover, P10 can also be used to successfully map AChE activity in different regions of a normal mouse brain, which may provide important data for AChE evaluation in clinical studies. Such a rational and effective approach can also provide a solid basis for designing probes with different properties to study AChE in biosystems and another way to design specific substrates for other enzymes.

In this work, a new approach was developed for designing the representative P10 with high selectivity and sensitivity for imaging AChE activity in the cells and normal mouse brain.  相似文献   
49.
50.
高质量AlPO4-5分子筛单晶的螯合剂法合成与表征   总被引:1,自引:0,他引:1  
考察了几种螯合剂对AlPO4-5分子筛单晶合成的影响,结果表明,用邻苯二酚,乙酰丙酮,水杨醛为螯合剂可以得到高质量的,尺寸较大的分子筛单晶,其作用机理可能与它们加入到分子筛合成体系中,改变了溶胶中铝的配位数或产生了铝的螯合物有关。  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