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   11715篇
  免费   2189篇
  国内免费   1408篇
化学   8094篇
晶体学   163篇
力学   821篇
综合类   118篇
数学   1270篇
物理学   4846篇
  2024年   6篇
  2023年   286篇
  2022年   321篇
  2021年   473篇
  2020年   504篇
  2019年   513篇
  2018年   423篇
  2017年   389篇
  2016年   620篇
  2015年   574篇
  2014年   691篇
  2013年   831篇
  2012年   1075篇
  2011年   1058篇
  2010年   827篇
  2009年   758篇
  2008年   737篇
  2007年   650篇
  2006年   672篇
  2005年   585篇
  2004年   384篇
  2003年   313篇
  2002年   315篇
  2001年   233篇
  2000年   218篇
  1999年   231篇
  1998年   181篇
  1997年   208篇
  1996年   186篇
  1995年   168篇
  1994年   142篇
  1993年   110篇
  1992年   91篇
  1991年   82篇
  1990年   81篇
  1989年   73篇
  1988年   61篇
  1987年   33篇
  1986年   46篇
  1985年   34篇
  1984年   20篇
  1983年   15篇
  1982年   15篇
  1981年   7篇
  1980年   9篇
  1975年   7篇
  1973年   4篇
  1972年   7篇
  1965年   6篇
  1964年   5篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
A competitor‐switched electrochemical sensor based on a generic displacement strategy was designed for DNA detection. In this strategy, an unmodified single‐stranded DNA (cDNA) completely complementary to the target DNA served as the molecular recognition element, while a hairpin DNA (hDNA) labeled with a ferrocene (Fc) and a thiol group at its terminals served as both the competitor element and the probe. This electrochemical sensor was fabricated by self‐assembling a dsDNA onto a gold electrode surface. The dsDNA was pre‐formed through the hybridization of Fc‐labeled hDNA and cDNA with their part complementary sequences. Initially, the labeled ferrocene in the dsDNA was far from surface of the electrode, the electrochemical sensor exhibited a "switch‐off" mode due to unfavorable electron transfer of Fc label. However, in the presence of target DNA, cDNA was released from hDNA by target DNA, the hairpin‐open hDNA restored its original hairpin structure and the ferrocene approached onto the electrode surface, thus the electrochemical sensor exhibited a "switch‐on" mode accompanying with a change in the current response. The experimental results showed that as low as 4.4×10−10 mol/L target DNA could be distinguishingly detected, and this method had obvious advantages such as facile operation, low cost and reagentless procedure.  相似文献   
992.
Sulfur doped ZnO/TiO2 nanocomposite photocatalysts were synthesized by a facile sol‐gel method. The structure and properties of catalysts were characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), UV‐vis diffusive reflectance spectroscopy (DRS) and N2 desorption‐adsorption isotherm. The XRD study showed that TiO2 was anatase phase and there was no obvious difference in crystal composition of various S‐ZnO/TiO2. The XPS study showed that the Zn element exists as ZnO and S atoms form SO2?4. The prepared samples had mesoporosity revealed by N2 desorption‐adsorption isotherm result. The degradation of Rhodamine B dye under visible light irradiation was chosen as probe reaction to evaluate the photocatalytic activity of the ZnO/TiO2 nanocomposite. The commercial TiO2 photocatalyst (Degussa P25) was taken as standard photocatalyst to contrast the prepared different photocatalyst in current work. The improvement of the photocatalytic activity of S‐ZnO/TiO2 composite photocatalyst can be attributed to the suitable energetic positions between ZnO and TiO2, the acidity site caused by sulfur doping and the enlargement of the specific area. S‐3.0ZnO/TiO2 exhibited the highest photocatalytic activity under visible light irradiation after Zn amount was optimized, which was 2.6 times higher than P25.  相似文献   
993.
4‐Amino‐5‐nitro‐1,2,3‐triazole (ANTZ) and its derivatives, such as 2‐(4‐amino‐5‐nitro‐1,2,3‐trazole‐1‐yl)‐1,3,5‐trinitrobenzene (T‐ANTZ) and 4‐amino‐5‐nitro‐1,2,3‐triazole (M‐ANTZ), were synthesized and characterized, whose structures were confirmed by IR, NMR and elemental analysis. The thermal behaviors of ANTZ, T‐ANTZ and M‐ANTZ were studied by the methods of DSC and TG‐DTG, and the results showed that there is an obvious melting process of ANTZ with melting point of 278.38°C, while there is no melting process in the thermal behavior of T‐ANTZ and M‐ANTZ (the derivatives of ATNZ).  相似文献   
994.
995.
本文以Triton X-100/C10H21OH/H2O体系层状溶致液晶为模板,Ca(NO3)2和(NH4)2HPO4为反应物,在一定的pH条件下,通过三元相图确定了层状液晶单相区域,并合成了羟基磷灰石(HA)纳米颗粒。用傅立叶红外光谱(FTIR),X射线衍射(XRD)和透射电子显微镜(TEM)对产物进行了表征。并考察了不同助表面活性剂浓度和不同表面活性剂浓度对产物的形貌和尺寸的影响。结果表明所制备的HA纳米颗粒平均直径为8~10nm、长度在100nm左右,呈针状。助表面活性剂浓度对HA形貌及尺寸影响不大,但是在一定范围内改变表面活性剂浓度可以起到调控HA纳米颗粒形貌和尺寸的作用。  相似文献   
996.
化学振荡反应是一类典型的非线性现象[1-5],研究各种因素对化学振荡反应的动力学控制问题在生物和化学应用中有重要的意义[6,7].生物体系中化学振荡反应实际上是产生于溶胶中(包括高分子溶液和表面活性剂溶液)[8],因此,要模拟生物体系的化学振荡就不能不考虑溶胶对振荡反应的影响.  相似文献   
997.
建立了蔬菜和食用菌中19种氨基甲酸酯农药残留的液相色谱串联质谱(UPLC-MS/MS)确证方法.实验方法采用丙酮和乙腈混合溶液提取,凝胶渗透色谱净化,经浓缩后由HPLC-MS/MS测定.实验结果表明:方法定性定量准确,灵敏度高,满足了国内外限量要求,具有较好的推广价值.回收率为70.1%~95.7%,RSD为1.63%~13.83%,方法最低检出限0.01 mg/kg.  相似文献   
998.
在水热条件下合成了一例新型的多金属氧酸盐二聚物,[Ni(enMe)2]4{[Ni(enMe)2][Ni(enMe)2(H2O)]2[Mo8ⅥV6ⅣO38(VⅤO4)]2}.8H2O(1)(enMe=1,2-丙二胺),利用元素分析、红外光谱分析、粉末X射线衍射、热重分析和单晶X射线衍射表征了其结构。结果表明,化合物(1)属于单斜晶系,P2(1)/n空间群.晶胞参数为a=1.9685(4)nm,b=1.3549(3)nm,c=2.7039(5)nm,α=90°,β=93.94(3)°,γ=90°,V=7.195(2)nm3,Z=4,Dc=2.390g/cm3,Mr=2588.4,μ=3.195mm-1,F(000)=5012,最终R1=0.0743,wR2=0.1861.与此同时,(1)是第一个具有二帽-Keggin型钼钒氧簇的二聚体,它由过渡金属部分[Ni(enMe)2(H2O)]22+连接形成{[Ni(enMe)2][Ni(enMe)2(H2O)]2[Mo8ⅥV6ⅣO38(VⅤO4)]2}8-二聚阴离子.  相似文献   
999.
采用量子化学密度泛函理论(DFT)B3LYP/6-31G(d)方法,对4,1,6-MC2B10H1213顶点金属碳硼烷几何构型进行优化,结合有限场(FF)方法计算了它们的极化率和二阶非线性光学(NLO)系数.结果表明,十个13顶点金属碳硼烷分子中1a~6a的二阶NLO系数与其构型纵向扩张呈现相同的规律.分子的前线分子轨道能级差越小,其二阶NLO系数越大.对于不同自旋态的同种金属碳硼烷分子,其偶极矩值为高自旋态大于相应的低自旋态,极化率和二阶NLO系数与自旋多重度没有一致的对应规律,自旋多重度对NLO性质影响不大.  相似文献   
1000.
The dispersion of Nafion ionomer particles and Pt/C catalyst aggregates in liquid media was studied using both ultra-small-angle X-ray scattering (USAXS) and cryogenic TEM. A systematic approach was taken to study first the dispersion of each component (i.e., ionomer particles and Pt/C aggregates), then the combination of the components, and last the catalyst ink. Multiple-level curve fitting was used to extract the particle size, size distribution, and geometry of the Pt/C aggregates and the Nafion particles in liquid media from the scattering data. The results suggest that the particle size, size distribution, and geometry are not uniform throughout the systems but rather vary significantly. It was found that the interaction of each component (i.e., the Nafion ionomer particles and the Pt/C aggregates) occurs in the dispersion. Cryogenic TEM was used to observe the size and geometry of the particles in liquid directly and to validate the scattering results. The TEM results showed excellent agreement.  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