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   169篇
  免费   73篇
  国内免费   138篇
化学   257篇
晶体学   2篇
力学   1篇
数学   3篇
物理学   117篇
  2023年   2篇
  2022年   4篇
  2021年   8篇
  2020年   8篇
  2019年   9篇
  2018年   10篇
  2017年   12篇
  2016年   13篇
  2015年   18篇
  2014年   18篇
  2013年   36篇
  2012年   30篇
  2011年   32篇
  2010年   31篇
  2009年   20篇
  2008年   16篇
  2007年   25篇
  2006年   25篇
  2005年   17篇
  2004年   10篇
  2003年   7篇
  2002年   4篇
  2001年   5篇
  2000年   6篇
  1999年   4篇
  1998年   6篇
  1997年   1篇
  1996年   2篇
  1994年   1篇
排序方式: 共有380条查询结果,搜索用时 15 毫秒
1.
An effcient multiparty quantum secret sharing scheme is proposed with Greenberger-Horne-Zeilinger (GHZ) states following some ideas in quantum dense coding. The agents take the single-photon measurements on the photons received for eavesdropping check and exploit the four local unitary operations Ⅰ, σx, σx and iσy to code their message. This scheme has the advantage of high capacity as each GHZ state can carry two bits of information. The parties do not need to announce the measuring bases for almost all the photons, which will reduce the classical information exchanged largely. The intrinsic efficiency for qubits and the total effciency both approach the maximal values.  相似文献   
2.
反胶束笼对纳米氯化银反应性能的微环境限定   总被引:4,自引:0,他引:4  
研究了反映束中直径为10 ̄17nm的AgCl微料与亚甲基蓝之间的作用,比较了阴离子型和非离子型表面活性剂组成的反胶束微环境的影响,讨论了亚甲基蓝在粒子上的吸附,二聚体形成的钠米AgCl粒子对亚甲基蓝荧光猝灭机制。  相似文献   
3.
The synthesis of a fluorous diol 4 bearing a perfluorodecyl chain was described. A series of boronic acid were attached to 4 by esterification. The purification of the products was fulfilled by facile filtration instead of expensive and environmental troublesome fluorous liquid-liquid extraction. The Suzuki cross-coupling reactions of the formed fluorous boronates 5 underwent smoothly and the fluorous diol 4 was recycled in good yields.  相似文献   
4.
Hong-Yuan Luo  Chun-Yan Li 《Talanta》2007,72(2):575-581
The design and synthesis of a porphyrin-appended terpyridine, 5-(4-([2,2′:6′,2″]-terpyridin-4-yl-carboxyamidyl)phenyl)-10,15,20-triphenylporphyrin (H2TPPTPy) and its application as potential fluoroionophore for recognition of metal ions are reported. For preparation of the fluoroionophore, a novel simple strategy with improved total yield has been applied for the synthesis of 2,2′:6′,2″-terpyridine-4′-carboxylic acid as a ligand. H2TPPTPy shows chelation-enhanced fluorescence effect with cadmium ion via the interruption of photoinduced electron transfer (PET) process, which has been utilized as the basis of the fabrication of the Cd(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Cd(II)-sensitive chemosensor were investigated. It shows a linear response toward Cd(II) in the concentration range of 3.2 × 10−6 to 3.2 × 10−4 M with a limit of detection of 1.2 × 10−6 M. The chemosensor shows good selectivity for Cd(II) over a large number of cations, such as alkali, alkali earth and transitional metal ions except Cu(II) and Zn(II). The sensor has been used for determination of Cd(II) in water samples with satisfactory recoveries.  相似文献   
5.
Four chiral polymers P-1, P-2, P-3 and P-4 were synthesized by the polymerization of (S)-2,2'-dioctoxy-1,1'- binaphthyl-6,6'-boronic acid (S-M-3) with (S)-6,6'-dibromo-1,1'-binaphthol (S-M-1), (R)-6,6'-dibromo-1,1'- binaphthol (R-M-1), (S)-3,3'-diiodo-1,1'-binaphthol (S-M-2) and (R)-3,3'-diiodo-1,1'-binaphthol (R-M-2) under Pd-catalyzed Suzuki reaction, respectively. All four polymers can show good solubility in some common solvents due to the nonplanarity of the polymers in the main chain backbone and flexible alkyl groups in the side chain. The analysis results indicate that specific rotation and circular dichroism (CD) spectral signals of the alternative S-S chiral polymers P-1 and P-3 are larger than those of S-R chiral polymers P-2 and P-4, but their UV-Vis and fluorescence spectra are almost similar. The results of asymmetric enantioselectivity of four polymers for diethylzinc addition to benzaldehyde indicate that catalytically active center is (R) or (S)-1, 1'-binaphthol moieties.  相似文献   
6.
掺硼多晶金刚石膜的电化学性能研究   总被引:1,自引:0,他引:1  
采用EACVD(Electron Assisted Chemical Vapor Deposition)方法制备了掺硼金刚石膜, 并用扫描电镜、拉曼光谱及霍尔效应等测试方法对其表面形貌、生长特性、载流子浓度以及导电性能进行了分析. 测试结果表明, 掺硼金刚石膜是由微米级晶粒组成的多晶膜, 其载流子浓度为4.88×1020 cm-3, 电阻率为0.03 Ω·cm, 是高品质金刚石膜. 用该金刚石膜制作电化学电极, 利用循环伏安法分别测量了金刚石膜电极在氯化钾空白底液、亚铁氰化钾溶液和左旋半胱氨酸溶液中的循环伏安曲线, 发现该金刚石膜电极在水溶液中具有宽的电化学窗口(约为3.7 V)和接近零的背景电流, 在生物制剂的检测中具有很高的灵敏度和良好的稳定性, 是一种理想的电化学电极材料.  相似文献   
7.
A new CoW11Mn/PANI/TiO2 ternary composite was synthesized with K8[Co(H2O)MnW11O39] (CoW11Mn) and PANI/TiO2 by electrostatic self-assembly. These catalysts were characterized using infrared (IR) spectroscopy, X-ray diffraction, scanning electron microscopy, ultraviolet–visible spectroscopy, and N2 adsorption–desorption. CoW11Mn/PANI/TiO2 was used to photodegradate the example contaminant, gentian violet (GV). Under the optimum photodegradation conditions, 92.63% degradation was achieved, indicating that the introduction of polyoxometalate and polyaniline greatly enhanced the photocatalytic performance of the catalyst. Moreover, CoW11Mn/PANI/TiO2 exhibits stable performance with little loss in activity after three successive runs. Thus, CoW11Mn/PANI/TiO2 ternary composite could be a promising photocatalyst in photodegradation of organic pollutants.  相似文献   
8.
以3-硝基邻苯二甲酸和咪唑及2,2’-联吡啶为配体构筑了2种配合物[Zn2(npa)2(Im)4](1)和[Cd2(npa)2(2,2’-bipy)2(H2O)2]·2H2O(2)(npa2-=3-硝基邻苯二甲酸根,Im=咪唑,2,2’-bipy=2,2’-联吡啶)。用元素分析、红外光谱对其进行了表征,并用单晶X-射线衍射测定了配合物的晶体结构;测定了配合物12的热稳定性。2个配合物均为双核分子,具有M2C8O4十四元大环结构。配合物1的双核单元通过分子间氢键形成3D网络结构,配合物2的双核单元通过分子间氢键和π-π堆积形成2D层状结构。  相似文献   
9.
A rhodamine spirolactam derivative (1) was developed as a colormetric and fluorescent chemosensor for adenosine-5′-triphosphate (ATP) via hydrogen bonds interaction. As far as we know, this is the first case to explore ATP-induced ring-opening of spirolactam in rhodamine derivatives. It exhibited a highly sensitive “turn-on” fluorescent response toward ATP with a 47-fold fluorescence intensity enhancement under 20 equiv. of ATP added. The chemosensor can be applied to the quantification of ATP with a linear range covering from 1.0 × 10−7 to 2.0 × 10−4 M and a detection limit of 2.5 × 10−8 M. The experiment results show that the response behavior of 1 toward ATP is pH independent in medium condition (pH 6.0–8.0). Most importantly, the novel chemosensor has well solved the problem of serious interferences from other nucleoside polyphosphates such as ADP and AMP generally met by previously reported typical fluorescent chemosensors for ATP. Moreover, the response of the chemosensor toward ATP is fast (response time less than 3 min). In addition, the chemosensor can be used for the fluorescence assay for protein kinase activity with satisfactory results. The chemosensor for ATP based on hydrogen bonds interaction provided a novel strategy for the design of colormetric and ratiometric fluorescent probes for other target anions with high sensitivity and selectivity.  相似文献   
10.
以dpa衍生配体合成2个单核铜配合物[CuL(NO32](1)和[CuL(OAc)(H2O)]ClO42),并对其进行了表征。单晶结构显示,配合物1中的Cu中心可以描述为畸变的五角双锥构型,而2的Cu中心为畸变的八面体构型。运用电子吸收和发射光谱法研究了配合物与CT-DNA的键合作用,结果表明2个配合物与DNA的相互作用均为部分插入模式。通过改变浓度、时间进一步检测配合物切割DNA的能力,以及验证其切割机理,结果表明在外界诱导剂存在下,2个配合物均表现出强的切割DNA的能力,其作用机理为氧化切割机理,其中活性氧可能为·OH和1O2。利用MTT法测定了配合物对体外HeLa、HepG-2和SGC-7901肿瘤细胞增殖的抑制能力。  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