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   950篇
  免费   127篇
  国内免费   244篇
化学   919篇
晶体学   24篇
力学   19篇
综合类   13篇
数学   71篇
物理学   275篇
  2023年   11篇
  2022年   19篇
  2021年   22篇
  2020年   18篇
  2019年   28篇
  2018年   21篇
  2017年   30篇
  2016年   47篇
  2015年   41篇
  2014年   65篇
  2013年   87篇
  2012年   103篇
  2011年   88篇
  2010年   72篇
  2009年   79篇
  2008年   88篇
  2007年   76篇
  2006年   69篇
  2005年   68篇
  2004年   51篇
  2003年   42篇
  2002年   41篇
  2001年   39篇
  2000年   24篇
  1999年   17篇
  1998年   17篇
  1997年   4篇
  1996年   4篇
  1995年   12篇
  1994年   5篇
  1993年   6篇
  1992年   4篇
  1991年   4篇
  1990年   2篇
  1989年   1篇
  1988年   1篇
  1987年   3篇
  1986年   2篇
  1985年   2篇
  1984年   2篇
  1983年   3篇
  1981年   2篇
  1968年   1篇
排序方式: 共有1321条查询结果,搜索用时 15 毫秒
981.
In weakly acidic buffer medium, vitamin B1 (VB1) interacts with gold nanoparticles to form a binding product, which resulted in a significant enhancement of resonance Rayleigh scattering (RRS) intensity and the appearance of a new RRS spectrum. The maximum RRS peak was at 368 nm, and there are three smaller scattering peaks that were at 284 nm, 440 nm and 495 nm, respectively. The enhanced RRS intensity (ΔI) was directly proportional to the concentration of VB1 in the range of 0–2.8 × 10−7 mol L−1. The method had high sensitivity and its detection limit (3σ) was 0.9 ng mL−1. The optimum conditions and the influencing factors have been investigated. The method had good selectivity, which could be observed from the influence of coexisting substances. A sensitive, simple and fast RRS method for the determination of VB1 with gold nanoparticle probe has been developed. In addition, the reasons for RRS enhancement were discussed.  相似文献   
982.
Yongjin Zou  Lixian Sun  Fen Xu 《Talanta》2007,72(2):437-442
A Prussian Blue (PB)/polyaniline (PANI)/multi-walled carbon nanotubes (MWNTs) composite film was fabricated by step-by-step electrodeposition on glassy carbon electrode (GCE). The electrode prepared exhibits enhanced electrocatalytic behavior and good stability for detection of H2O2 at an applied potential of 0.0 V. The effects of MWNTs thickness, electrodeposition time of PANI and rotating rate on the current response of the composite modified electrode toward H2O2 were optimized to obtain the maximal sensitivity. A linear range from 8 × 10−9 to 5 × 10−6 M for H2O2 detection has been observed at the PB/PANI/MWNTs modified GCE with a correlation coefficient of 0.997. The detection limit is 5 × 10−9 M on signal-to-noise ratio of 3. To the best of our knowledge, this is the lowest detection limit for H2O2 detection. The electrode also shows high sensitivity (526.43 μA μM−1 cm−2) for H2O2 detection which is more than three orders of magnitude higher than the reported.  相似文献   
983.
The ability to vary the temperature of an electrochemical cell provides opportunities to control reaction rates and pathways and to drive processes that are inaccessible at ambient temperature. Here, we explore the effect of temperature on electrochemical etching of Ni–Pt bimetallic nanoparticles. To observe the process at nanoscale resolution we use liquid cell transmission electron microscopy with a modified liquid cell that enables simultaneous heating and biasing. By controlling the cell temperature, we demonstrate that the reaction rate and dissolution potential of the electrochemical Ni etching process can be changed. The in situ measurements suggest that the destabilization of the native nickel oxide layer is the slow step prior to subsequent fast Ni removal in the electrochemical Ni dissolution process. These experiments highlight the importance of in situ structural characterization under electrochemical and thermal conditions as a strategy to provide deeper insights into nanomaterial transformations as a function of temperature and potential.

The combination of electrochemical analysis, temperature control and in situ TEM imaging directly probes the etching of Ni from bimetallic Ni–Pt nanoparticles.  相似文献   
984.
Four new ent‐pimarane diterpenes were isolated from the EtOH extract of Aralia dumetorum, together with three known compounds involving ent‐pimar‐8(14),15‐dien‐19‐oic acid ( 5 ), ent‐pimar‐8(14),15‐dien‐19‐ol ( 6 ), and ent‐kaur‐16‐en‐19‐oic acid ( 7 ). By detailed analyses of the MS, IR, and NMR data, the structures of four new diterpenes were characterized as (5β,9β,10α,13α)‐pimara‐6,8(14),15‐trien‐18‐oic acid ( 1 ), (5β,7β,9β,10α,13α)‐7‐methoxypimara‐8(14),15‐dien‐18‐oic acid ( 2 ), (5β,9β,10α,13α,14β)‐14‐methoxypimara‐7,15‐dien‐18‐oic acid ( 3 ), and (5β,10α,13α,14α)‐14‐hydroxypimara‐7,9(11),15‐trien‐18‐oic acid ( 4 ). The cytotoxic activities of compounds 1  –  7 were assayed in vitro through MTT method.  相似文献   
985.
考虑到人眼视觉关注特性在视频质量评价(VQA)中所具有的重要作用,提出了一种结合人眼视觉关注特性的视频质量评价方法。首先利用三维Sobel算子以及恰可察觉失真模型得到全局显著图,对全局显著图的每个显著像素点构建结构张量来求取一帧的全局质量;然后利用视频运动信息以及人眼中心关注特性求得局部显著图来进行感知加权,得到一帧的局部质量;最后均衡局部与全局质量得到视频中一帧的质量,并采用机器学习的方法获得时域加权模型,对视频帧进行加权,从而得到客观视频质量评价值。在LIVE视频数据库上进行性能测试,得到PLCC(Pearson Linear Correlation Coefficient)为0.827,SROCC(Spearman Rank Order Correlation Coefficient)为0.802,与已有相关算法相比,所提出的VQA方法的评价结果更接近人眼的主观感知。  相似文献   
986.
A high performance liquid chromatography method using an efficient extraction method was developed for the determination of astaxanthin in eight kinds of animal feed. The chromatographic separation was achieved using a C18 reversed-phase column, using methanol and acetonitrile as the mobile phases with a flow rate of 1 mL/min. The feeds containing astaxanthin were first treated with maxatase, to cause enzymatic hydrolysis, and then extracted with dichloromethane. The optimized method produced recoveries of between 82.4% and 100% for all eight kinds of feed, and the coefficients of variation were lower than 4.28%. The limit of detection, defined as the concentration that gave a signal-to-noise ratio of 3, for astaxanthin was estimated to be 0.1 µg/g. The limit of quantification, defined as the lowest spiked concentration that gave an appropriate level of precision and accuracy, was 0.3 µg/g. Finally, the method developed was used to determine astaxanthin in real, commercially sourced, feed samples. The method met the requirements for the determination of astaxanthin in feed, providing satisfactory recoveries of 70–110%.  相似文献   
987.
A new polyhydroxysterol, (22E)-24-methylenecholestane-22-ene-3β,5α,6β-triol (1), together with four known analogues (25) were isolated from the South China Sea soft coral Sinularia sp. Their structures were elucidated by spectroscopic analyses and comparison with previously reported data. All these compounds exhibited cytotoxic effect against both HepG2 and HeLa cell lines with IC50 values ranging from 8.36 to 37.30 μM. Preliminary structure–activity relationship study identified that the presence of double bonds in the side chains of these polyhydroxysterols significantly reduced the biological effect obtained.  相似文献   
988.
The direct mixing of CoCl2, sodium 2,6‐pyridinedicarboxylate (Na2(2,6‐pda)), KSCN, and 1,2‐bis(4‐pyridyl)ethane (bpye) in water at the ambient temperature afforded purple crystals readily. The crystal structure, as determined by X‐ray diffraction crystallography, consists of discrete inorganic [Co23‐2,6‐pda)2(μ‐SCN)2(H2O)2] and organic bpye molecules. Adjacent dicobalt molecules are connected via intermolecular hydrogen bonds, to form one‐dimensional hydrophobic channels in the solid state, which serve as a host framework to incarcerate bpye guests inside. Every organic molecule attaches to four adjacent inorganic species via arene‐arene interactions. The facile approach in assembling the dicobalt and bpye molecules together into an inorganic clathrate is demonstrated.  相似文献   
989.
Density functional theory has been used to study the Fe‐catalyzed cyclopropanation of Fe‐carbene complexes with ethene. All the intermediates and transition states were optimized completely at the B3LYP/6‐31+G(d,p) level. Calculation results confirm that the cyclopropanation of Fe‐carbene complexes with ethene involves the two reaction paths I and II . In the reaction path I , the double bond of ethene attacks directly on the carbene carbon of Fe‐carbene complexes to generate the cyclopropane. In the reaction path II , ethene substitution for PMe3 or CO in the Fe‐carbene complexes leads to the complexes M2 ; and the attack of one carbon of ethene on the carbene carbon results in the complexes M3 with a Fe? C? C? C four‐membered ring, and then generates the cyclopropane via the elimination reaction. For Fe‐carbene complexes A , C , D , E , and H , the main reaction mode is the reaction path I ; for Fe‐carbene complexes B , F , and G , the main reaction mode is the reaction path II . © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008  相似文献   
990.
A series of nitrogen mustard derivatives were synthesized by chloroform reaction and coupling reaction using DCC/ HOBT as promoting additives. The structure of compound was confirmed by 1H NMR, 31P NMR, MS and IR. The data show that the nitrogen mustard with tripolypyrrole as the linker inhibits all the four tested cells and has the highest activity.  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