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   772篇
  免费   15篇
  国内免费   135篇
化学   554篇
晶体学   1篇
力学   38篇
数学   1篇
物理学   328篇
  2023年   29篇
  2022年   13篇
  2021年   18篇
  2020年   19篇
  2019年   21篇
  2018年   14篇
  2017年   27篇
  2016年   27篇
  2015年   30篇
  2014年   37篇
  2013年   47篇
  2012年   57篇
  2011年   84篇
  2010年   63篇
  2009年   111篇
  2008年   81篇
  2007年   83篇
  2006年   51篇
  2005年   29篇
  2004年   21篇
  2003年   21篇
  2002年   10篇
  2001年   9篇
  2000年   6篇
  1999年   3篇
  1998年   2篇
  1997年   2篇
  1996年   2篇
  1995年   4篇
  1990年   1篇
排序方式: 共有922条查询结果,搜索用时 15 毫秒
51.
SERS标记纳米粒子用于免疫识别   总被引:3,自引:1,他引:3  
激光拉曼光谱技术近年来已成为研究生物分子结构常用的光谱手段.尤其在研究水溶液中蛋白质的结构和构象方面发挥了重要作用.然而,常规拉曼光谱的信号强度很低,限制了其在各个领域中的应用.表面增强拉曼光谱(SERS)和表面增强共振拉曼光谱(SERRS)技术可使信号增强6~10个数量级,尤其是SERS技术已发展到检测单分子的水平,更为其在生物方面的应用开拓了新的局.  相似文献   
52.
一种具有高效光致变色性能的WO3/ZnO纳米粒子复合体系   总被引:2,自引:0,他引:2  
WO3是一种重要的无机光致变色材料,在大屏幕显示和高密度信息存储等领域中具有广泛的应用前景[1~3].与有机光致变色材料相比,WO3稳定性好、成本低,但其光致变色效率较差.为了提高这类无机材料的变色效率,已经提出了各种解决方案并已取得了许多有意义的结果.例如将光响应材料与WO3复合可以有效地抑制光激发后电子的复合过程,从而提高参与变色过程的光生载流子的数量,改善WO3的光致变色性能.利用金纳米粒子对WO3薄膜进行修饰可以使其变色效率提高近2倍[4],而利用TiO2与WO3溶胶复合则可使变色效率提高近40倍[5].本文报道一种新型的WO3/ZnO纳米粒子复合体系.实验结果表明与WO3相比这种新型纳米粒子复合体系的变色效率可提高200倍以上.  相似文献   
53.
纳米颗粒复合材料增强的葡萄糖生物传感器   总被引:20,自引:1,他引:20  
孟宪伟  唐芳琼  冉均国  苟立 《化学通报》2001,64(6):365-367,364
二氧化硅和金或铂组成的复合纳米颗粒可以大幅度地提高葡萄糖生物传感器的电流响应,其效果明显优于这三种纳米颗粒单独使用时对葡萄糖生物传感器的增强作用。除了具有吸附浓缩效应,吸附定向和量子尺寸颗粒 应外,复合纳米颗粒比单独一种纳米颗粒更易于形成连续势场,降低电子在电极和固定化酶间的迁移阻力,提高电子迁移率,有效地加速了酶的再生过程,因此复合纳米颗粒显著增强了传感器电流响应。  相似文献   
54.
ZnS nanoparticles could be synthesized, when two kinds of Triton X-100/n-C10H21OH/H2O lamellar liquid crystal were mixed, in which Zn(CH3COO)2 and Na2S were dissolved in the solvent layer, respectively. The size of ZnS nanoparticles was about 10 nm and limited by the thickness of the solvent layer of the lamellar liquid crystal. The lubrication properties of the mixed system of Triton X-100/n-C10H21OH/H2O lamellar liquid crystal and ZnS nanoparticles were determined. The results showed that the presence of ZnS nanoparticles could improve the anti-wear ability of the Triton X-100/n-C10H21OH/H2O lamellar liquid crystal and decrease its friction coefficient.  相似文献   
55.
Selective production of hydrogen by oxidative steam reforming of methanol (OSRM) was studied over Cu/SiO2 catalyst using fixed bed flow reactor. Textural and structural properties of the catalyst were analyzed by various instrumental methods. TPR analysis illustrates that the reduction temperature peak was observed between 510?K and 532?K at various copper loadings and calcination temperatures and the peaks shifted to higher temperature with increasing copper loading and calcination temperature. The XRD and XPS analysis demonstrates that the copper existed in different oxidation states at different conditions: Cu2O, Cu0, CuO and Cu(OH)2 in uncalcined sample; CuO in calcined sample: Cu2O and metallic Cu after reduction at 600?K and Cu0 and CuO after catalytic test. TEM analysis reveals that at various copper loadings, the copper particle size is in the range between 3.0?nm and 3.8?nm. The Cu particle size after catalytic test increased from 3.6 to 4.8?nm, which is due to the formation of oxides of copper as evidenced from XRD and XPS analysis. The catalytic performance at various Cu loadings shows that with increasing Cu loading from 4.7 to 17.3?wt%, the activity increases and thereafter it decreases. Effect of calcination shows that the sample calcined at 673?K exhibited high activity. The O2/CH3OH and H2O/CH3OH molar ratios play important role in reaction rate and product distribution. The optimum molar ratios of O2/CH3OH and H2O/CH3OH are 0.25 and 0.1, respectively. When the reaction temperature varied from 473 to 548?K, the methanol conversion and H2 production rate are in the range of 21.9–97.5% and 1.2–300.9?mmol?kg?1?s?1, respectively. The CO selectivity is negligible at these temperatures. Under the optimum conditions (17.3?wt%, Cu/SiO2; calcination temperature 673?K; 0.25 O2/CH3OH molar ratio, 0.5 H2O/CH3OH molar ratio and reaction temperature 548?K), the maximum hydrogen yield obtained was 2.45?mol of hydrogen per mole of methanol. The time on stream stability test showed that the Cu/SiO2 catalyst is quite stable for 48?h.  相似文献   
56.
加氢是现代化工产业中的一类主干反应,广泛应用于精细化学品、药物、食品、染料、功能聚合物及香料等制造产业中.高效催化剂的引入使得加氢反应能够在相对温和的条件下还原各类不饱和化合物.金属催化剂在加氢反应中活性高,所需的反应温度较低,适用性广,但是容易和S,N,As和P等元素结合而"中毒"失去反应活性.金属氧化物催化剂和金属硫化物催化剂具有一定的抗毒性,但活性相对较差,通常需要采用高温高压的反应条件,对催化剂本身和反应器的要求较为苛刻.传统催化剂在反应中具有一定的局限性,所以亟需开发新一代高效的加氢催化剂,在保证高活性和高选择性催化效果的同时,降低对能源的消耗和对环境的负面影响.金属有机骨架(MOFs)作为一种新型的多孔材料在过去二十年中受到相当大的关注,并在催化、气体存储和分离、传感器、发光材料和药物输送等众多领域的应用中表现出卓越的性能.利用MOF材料良好的相容性,将MOF和其它功能材料结合形成新的复合材料可以在更大程度上扩大MOF材料的应用领域.与传统的催化剂相比,MOF基材料具有优异的物理化学特性和结构可调性,通过合理的设计能够满足不同的催化加氢过程:(1)MOF基催化剂具有多样且特异性的活性位点.除了组成MOF材料的金属离子/簇和功能有机配体之外,MOF材料可通过封装其他活性物质或者被活性物质包裹等方式引入其他类型的催化位点,进一步扩大MOF基催化剂在不同催化加氢中的适应性.此外,不同的活性位点之间的协同作用又能特异性地促进反应的进行,对提高反应的选择性起到重要的作用.(2)活性位点的尺寸大小和空间分布可以被有效控制.这能影响到催化剂在催化反应过程中的活性和选择性,并且通过MOF材料的限域效应,同时能增强活性位点的稳定性和耐久性.(3)高比表面积能提高MOF基催化剂的催化活性.这种结构特性不仅可以增加MOF基催化剂的活性位点,而且能够吸附反应物和还原剂达到扩大其局部浓度的效果.(4)反应分子的扩散可通过调节MOF基催化剂的结构实现控制.通过调整MOF材料的孔窗口和通道的尺寸,能够改变反应物在催化剂内部的扩散途径,影响底物和活性位点的接触,能进一步影响反应的活性和选择性.本文总结了近几年来MOF基材料在不同的催化加氢反应中的应用,其中包括烯烃、炔烃、芳硝基化合物、肉桂醛、糠醛和苯等化合物的加氢反应.首先介绍了MOF基材料中不同类型的活性位点,除了MOF材料自身的金属离子/簇和功能有机配体外,MOF基复合材料中的金属纳米颗粒?金属硫化物?金属氧化物?均相催化剂等活性位点可以通过封装或包裹的方式引入.在不同加氢反应中,着重介绍了MOF基催化剂中不同类型活性位点的加氢过程中的催化方式、催化剂本身的结构优化及催化剂与反应底物之间的相互作用,以及这些因素之间的协同作用对反应活性和选择性的影响.最后,讨论了MOF基材料在加氢反应中应用存在的问题以及未来发展展望.  相似文献   
57.
Magnetic nanoparticles differing by their size have been synthesized to use them for multiparametric testing, based on their differing magnetic properties. The nanoparticle has two essential roles: to act as a probe owing to its specific magnetic properties and to carry on its surface precursor groups for the covalent coupling of biological recognition molecules, such as antibodies, nucleic acids. A totally unique, newly patented, method has been used to characterize magnetic signatures using the MIAplex technology. The MIAplex reader, developed by Magnisense, measures the non-linear response of the magnetic labels when they are exposed to a multi-frequency alternating magnetic field. This specific signature based on d2B(H)/dH2 was correlated to other more conventional magnetic detection methods (superconducting quantum interference devices (SQUID) and Mössbauer).  相似文献   
58.
易国斌 《高分子科学》2017,35(5):623-630
In this paper,microphase behavior of an ABC triblock copolymer,polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide),namely PS-b-P2VP-b-PEO,was systematically studied during spin-coating and solvent vapor annealing based on various parameters,including the types of the solvent,spin speed and thickness.The morphological features and the microdomain location of the different blocks were characterized by atomic force microscope (AFM) and high resolution transmission electron microscopy (HRTEM).With increasing thickness,the order-order transition from nanopores array to the pattern of nanostripes was observed due to microdomain coarsening.These processes of pattern transformation were based on the selectivity of toluene for different blocks and on the contact time between solvent molecules and the three blocks.This work provides different templates for preparation of gold nanoparticle array on silicon wafer,which can be adopted as an active surface-enhanced Raman scattering (SERS) substrate for poly(3-hexylthiophene) (P3HT).  相似文献   
59.
In this work, Mn0.7Zn0.3Fe2O4 and Ni0.7Zn0.3Fe2O4 nanoparticles with super-paramagnetic properties and size distribution from 10 to 52 nm were investigated. These particles were produced by a low-temperature solid-state reaction method without the ball-milling process. The size and morphology of the nanocrystallites were determined by X-ray diffraction, transmission electron microscopy and scanning tunneling microscopy methods. Magnetic measurements such as alternating gradient field magnetometers were used to justify the super-paramagnetic properties of these nanoparticles. Their microwave absorption in the range of 8-18 GHz was studied by a vector network analyzer. Responses of the device under tests were studied. Also, the percentage of the resin, the size and thickness of the mount were determined. The band width of 2.3 GHz was obtained with reflection-loss/written-loss of −16 dB around 10.4 GHz.  相似文献   
60.
Gold-coated iron oxide nanoparticle Hepatitis B virus (HBV) DNA probes were prepared, and their application for HBV DNA measurement was studied. Gold-coated iron oxide nanoparticles were prepared by the citrate reduction of tetra-chloroauric acid in the presence of iron oxide nanoparticles which were added as seeds. With a fluorescence-based method, the maximal surface coverage of hexaethiol 30-mer oligonucleotides and the maximal percentage of hybridization strands on gold-coated iron oxide nanoparticles were (120 ± 8) oligonucleotides per nanoparticle, and (14 ± 2%), respectively, which were comparable with those of (132 ± 10) and (22 ± 3%) in Au nanoparticle groups. Large network aggregates were formed when gold-coated iron oxide nanoparticle HBV DNA gene probe was applied to detect HBV DNA molecules as evidenced by transmission electron microscopy and the high specificity was verified by blot hybridization. Our results further suggested that detecting DNA with iron oxide nanoparticles and magnetic separator was feasible and might be an alternative effective method.  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