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   368篇
  免费   41篇
  国内免费   49篇
化学   202篇
晶体学   2篇
力学   34篇
综合类   1篇
数学   108篇
物理学   111篇
  2024年   2篇
  2023年   5篇
  2022年   1篇
  2021年   3篇
  2020年   5篇
  2019年   7篇
  2018年   7篇
  2017年   19篇
  2016年   16篇
  2015年   19篇
  2014年   29篇
  2013年   33篇
  2012年   16篇
  2011年   13篇
  2010年   20篇
  2009年   17篇
  2008年   18篇
  2007年   18篇
  2006年   15篇
  2005年   12篇
  2004年   10篇
  2003年   23篇
  2002年   34篇
  2001年   31篇
  2000年   15篇
  1999年   20篇
  1998年   17篇
  1997年   18篇
  1996年   4篇
  1995年   4篇
  1993年   1篇
  1992年   2篇
  1983年   1篇
  1982年   1篇
  1980年   1篇
  1979年   1篇
排序方式: 共有458条查询结果,搜索用时 15 毫秒
91.
A novel non‐enzymatic sensor based on Ag/MnOOH nanocomposites was developed for the detection of hydrogen peroxide (H2O2). The H2O2 sensor was fabricated by immobilizing Ag/MnOOH nanocomposites on a glassy carbon electrode (GCE). The morphology and composition of the sensor surface were characterized using scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, transmission electron microscopy and X‐ray diffraction spectroscopy. The electrochemical investigation of the sensor indicates that it possesses an excellent electrocatalytic property for H2O2, and could detect H2O2 in a linear range from 5.0 µM to 12.8 mM with a detection limit of 1.5 µM at a signal‐to‐noise ratio of 3, a response time of 2 s and a sensitivity of 32.57 µA mM?1 cm?2. Additionally, the sensor exhibits good anti‐interference. The good analytical performance, low cost and straightforward preparation method made this novel electrode material promising for the development of effective non‐enzymatic H2O2 sensor.  相似文献   
92.
Electron density distribution of Di‐2‐pyrazylamine ( Hdpza ) is studied both by single‐crystal X‐ray diffraction method at 100K and theoretical calculation. Structural determination reveals that Hdpza molecules crystalize in a synanti conformation with an intramolecular C? H?N hydrogen bond between two pyrazine rings and then gather together via two intermolecular N? H?N and C? H?N hydrogen interaction and π? π stacking interaction between pyrazine rings. Charge density analysis is made in terms of deformation density (Δπ), Laplacian distribution and topological analysis of total electron density based on multipole model and theoretical calculation. The agreement between experiment and theory is good. The topological properties at bond critical points of C? C and C? N bonds reveal a covalent bond character, and those of intermolecular interactions, such as hydrogen bonds and π? π stacking interactions, reveal a closed‐shell interaction. The potential energy curve of Hdpza molecule shows that the syn‐anti conformation is the most stable one (global minima) than the other two of syn‐syn and anti‐anti conformations.  相似文献   
93.
The formal total synthesis of stevastelins B and B3 ( 2 and 4 , resp.) have been accomplished employing a highly enantiomerically controlled Lewis acid catalyzed non‐aldol approach to obtain the syn aldol product and temperature controlled hydroboration oxidation reaction to construct four consecutive stereogenic centers. The other key reactions include Sharpless asymmetric epoxidation, macrolactonization, and macrolactamization towards building the core skeleton 2 and 4 .  相似文献   
94.
用分子动力学模拟方法,计算了氟代硼酸锂玻璃的电导率.研究的温度范围高于和近于玻璃转变温度,共模拟了七个体系,研究的成分大致覆盖了能形成玻璃的区域.所得极限电导率、活化能以及电导率随温度的变化与实验数据符合得相当好.以往的研究认为快离子传导的典型特征是仅有一种离子发生迁移,我们的模拟表明氟离子对电导也有较大贡献.用活化能数据可顺利解释这个三元系各体系的电导率相对高低问题.  相似文献   
95.
UV cured transparent films containing non‐aqueous conductive microgels coated with poly(aniline)/dodecyl benzenesulfonic acid(DBSA) were obtained. The conductive microgels were prepared by interface polymerization of aniline/DBSA in the presence of non‐aqueous polymeric microgels. The electrical conductivity and the particle size of the prepared conductive microgel were 0.5 S/cm and 58 nm, respectively. The prepared conductive microgels were easily blended with a UV curable coating formulation, and then were cured to make highly optically transparent films. For the UV cured film containing about 35 wt% of the conductive microgels, a surface resistance in the range of 107 to 108 Ω/square was obtained. In a polar cosolvent, such as NMP and m‐cresol, the critical volume was shifted to the lower range, with a value of 10 wt%. The UV cured films containing the conductive microgels exhibited good electrical stability against the thermal aging and humidity. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   
96.
Voltammetry of microparticles is applied to the identification of lead corrosion products by means of an essentially non‐invasive ‘one‐touch’ technique based on the use of graphite pencil. This methodology permits the mechanical attachment of few nanograms of sample from the surface of lead archaeological artefacts to a paraffin‐impregnated graphite electrode, which, upon immersion in aqueous electrolytes, provides distinctive voltammetric responses for litharge and cotunnite‐ anglesite‐, cerusite‐based corrosion products. The reported method is applied to the identification of corrosion products in archaeological lead pieces from different Iberian sites in Valencia (Spain).  相似文献   
97.
基于密度泛函理论(DFT)设计了一种新型的由4个咔唑组成的类芴风车格(GZP)的有机半导体材料, 研究了其结构特点及热力学和电子性质. 结果表明, GZP分为船式和椅式2种构象, 且船式构象GZP1(0 kJ/mol)比椅式构象GZP2(122.88 kJ/mol)稳定; GZP1构象的内孔径为0.298 nm, 外孔径为1.079 nm; GZP1的内重组能非常低, 空穴和电子重组能分别为0.089和0.106 eV, 可作为潜在的电荷传输材料.  相似文献   
98.
The concept of biocompatibility with reference to chromatographic stationary phases for separation of biomolecules (including proteins and peptides) is introduced. Biocompatible is a characteristic that indicates resistance to nonspecific adsorption of biomolecules and preservation of their structures and biochemical functions. Two types of biocompatible polymeric monoliths [i. e., polyacrylamide‐ and poly(meth)acrylate‐based monoliths] used for protein and peptide separations are reviewed in detail, with emphasis on size exclusion, ion exchange, and hydrophobic interaction chromatographic modes. Biocompatible monoliths for enzyme reactors are also included. The two main synthetic approaches to produce biocompatible monoliths are summarized, i. e., surface modification of a monolith that is not inherently biocompatible and direct copolymerization of hydrophilic monomers to form a biocompatible monolith directly. Integration of polyethylene glycol into the poly(meth)acrylate monolith network is becoming popular for reduction of non‐specific protein interactions.  相似文献   
99.
A novel flower like 3D nickel/manganese dioxide (Ni/MnO2) nanocomposite was synthesized by a kind of simple electrochemical method and the formation mechanism of flower like structure was also researched. In addition, morphology and composition of the nanocomposite were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), and X‐ray photoelectron spectroscopy (XPS). Then the Ni/MnO2 nanocomposites were applied to fabricate electrochemical non‐enzymatic glucose sensor. The electrochemical investigation for the sensor indicated that it possessed an excellent electrocatalytic property for glucose, and could applied to the quantification of glucose with a linear range from 2.5×10?7 to 3.5×10?3 M, a sensitivity of 1.04 mA mM?1 cm?2, and a detection limit of 1×10?7 M (S/N=3). The proposed sensor also presented attractive features such as interference‐free, and long‐term stability. The present study provided a general platform for the one‐step synthesis of nanomaterials with novel structure and can be extended to other optical, electronic and magnetic nanocompounds.  相似文献   
100.
观察了经腹腔注射低剂量三氯化钐(0.05mg/kg)对链脲佐菌素引志的非胰岛素依赖型糖尿病(NDIDDM)大鼠胰岛形态和功能的影响。结果表明,三氯化钐治疗组糖耐量改善、血清胰岛水平长高、血清胰镐血糖素水平降低、平均单个胰岛面积和胰岛β细胞数量明显增多,肝细胞内糖原含量增多。提示低剂量三氯化钐对实验性NIDDM大鼠有一定的治疗作用。  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