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   521篇
  免费   54篇
  国内免费   98篇
化学   367篇
晶体学   13篇
力学   26篇
综合类   5篇
数学   91篇
物理学   171篇
  2024年   1篇
  2023年   9篇
  2022年   21篇
  2021年   20篇
  2020年   20篇
  2019年   34篇
  2018年   19篇
  2017年   23篇
  2016年   28篇
  2015年   36篇
  2014年   50篇
  2013年   38篇
  2012年   44篇
  2011年   65篇
  2010年   29篇
  2009年   34篇
  2008年   34篇
  2007年   33篇
  2006年   19篇
  2005年   18篇
  2004年   21篇
  2003年   6篇
  2002年   7篇
  2001年   7篇
  2000年   6篇
  1999年   9篇
  1998年   5篇
  1997年   5篇
  1996年   3篇
  1995年   6篇
  1994年   2篇
  1993年   2篇
  1992年   9篇
  1991年   3篇
  1990年   1篇
  1989年   1篇
  1986年   1篇
  1984年   1篇
  1983年   2篇
  1982年   1篇
排序方式: 共有673条查询结果,搜索用时 328 毫秒
51.
ABSTRACT

Five multivalent β-D-GalNAc-(1→4)-β-D-Gal oligomers were selected and synthesized as probes for investigating the adhesin-receptor interactions of P. aeruginosa pili with multivalent receptors. They were synthesized by the amide coupling reactions of 8-(N-2-aminoethyl)carboxamidooctyl 4-O-(2-acetamido-2-deoxy-β-D-galactopyranosyl)-β-D-galactopyranoside (7) with EDTA dianhydride, EDTA, Kemp's triacid and adipic acid with EDC, DIC and DCC combined with HOBt as coupling reagents and by the reaction of per-O-acetylated 7 with 1,3,5-benzenetricarbonyl trichloride followed by de-O-acetylation. These resulting multivalent compounds contain flexible C9 spacer arms as linkers attached to either flexible hydrophilic moieties or rigid hydrophobic cores.  相似文献   
52.
Yu  Ningxiang  Peng  Hailong  Xiong  Hua  Wu  Xiaqing  Wang  Xiaoyan  Li  Yanbin  Chen  Lingxin 《Mikrochimica acta》2015,182(13):2139-2146

A fluorescent probe for the sensitive and selective determination of sulfide ions is presented. It is based on the use of graphene quantum dots (GQDs) which emit strong and stable blue fluorescence even at high ionic strength. Copper(II) ions cause aggregation of the GQDs and thereby quench fluorescence. The GQDs-Cu(II) aggregates can be dissociated by adding sulfide ions, and this results in fluorescence turn on. The change of fluorescence intensity is proportional to the concentration of sulfide ions. Under optimal conditions, the increase in fluorescence intensity on addition of sulfide ions is linearly related (r 2 = 0.9943) to the concentration of sulfide ions in the range from 0.20 to 20 μM, and the limit of detection is 0.10 μM (at 3 σ/s). The fluorescent probe is highly selective for sulfide ions over some potentially interfering ions. The method was successfully applied to the determination of sulfide ions in real water samples and gave recoveries between 103.0 and 113.0 %.

Graphene quantum dots (GQDs) emit strong blue fluorescence which, however, is quenched by copper(II) ions due to the formation of GQDs-Cu(II) aggregates. Fluorescence is recovered by sulfide ions due to the dissociation of GQDs-Cu(II) aggregates.

  相似文献   
53.
The activity and selectivity of heterogeneous catalysts can be significantly improved by dispersion of another active component in the metal substrate. The impact of Rh promoter on the formation of dimethyl carbonate (DMC) via oxidative carbonylation of methanol on Cu–Rh/AC (activated carbon) catalyst was investigated by density functional theory calculations. The most stable configurations of reacting species (CO, OH, CH3O, monomethyl carbonate, and DMC) adsorbed on the Cu0(zero‐valent copper)/AC and Cu–Rh/AC surfaces were determined on the basis of the calculated results. The reaction energy and activation energy of the rate‐limiting steps on the Cu–Rh/AC and Cu0/AC surfaces were compared. The activation energies of the rate‐limiting step of CO insertion into dimethoxide are 206.3 and 304.8 kJ mol?1 on the Cu–Rh/AC and Cu0/AC surfaces, respectively. The activation energies of the rate‐limiting step of CO insertion into methoxide are 78.5 and 92.7 kJ/mol on the Cu–Rh/AC and Cu0/AC surfaces, respectively. The calculated results indicate that the addition of Rh atom has a significant effect on decreasing the active energy the main pathway for DMC formation. © 2015 Wiley Periodicals, Inc.  相似文献   
54.
为了研究复合光催化剂在光催化中的制氢效率,采用水热法制备了Mo S2纳米片,然后通过水热法在Mo S2纳米片上负载了TiO_2纳米颗粒,形成了Mo S2/TiO_2异质结复合催化剂。采用冷场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、紫外-可见吸收光谱(UV-Vis)、拉曼光谱(Raman),X射线光电子能谱(XPS)对材料的结构和光学性能表征并进行分析。通过光催化制氢测试对光催化剂进行评价,实验结果表明,在波长为365 nm的紫外光照射下,最高光催化制氢速率为1004μmol·h-1·g-1,对应的催化剂的Mo S2含量为30%,其催化速率远大于单一的Mo S2和TiO_2,表明Mo S2/TiO_2复合催化剂在紫外光照下能显著提高光催化产氢性能。基于Mo S2/TiO_2复合光催化剂优越的光催化产氢性能,本文对复合光催化剂的产氢机理做了研究和分析。  相似文献   
55.
A graph is symmetric if its automorphism group acts transitively on the set of arcs of the graph. In this paper, we classify hexavalent symmetric graphs of order 9p for each prime p.  相似文献   
56.
通过将金属金嵌入到上下两层波导结构中,与ZnO随机粒子相结合,设计出一种新型结构的随机激光器。采用时域有限差分法(FDTD),数值模拟了该随机激光器系统的光场分布和模式频谱图,并针对金粒子和金薄膜两种情况进行对比分析。结果显示,采用金粒子作夹层时,出射激光模式数量减少,单色性较好;采用金薄膜作夹层时,出射激光光强较大。  相似文献   
57.
Tian J  Li H  Lu W  Luo Y  Wang L  Sun X 《The Analyst》2011,136(9):1806-1809
The chemical oxidation polymerization of m-phenylenediamine (MPD) by ammonium persulfate (APS) at room temperature results in the formation of poly(m-phenylenediamine) (PMPD) microparticles. The subsequent treatment of such microparticles with an aqueous AgNO(3) solution produces Ag nanoparticle (AgNP)-decorated PMPD microparticles. It was found that as-formed AgNPs exhibited remarkable catalytic performance toward the reduction of hydrogen peroxide (H(2)O(2)). The enzymeless H(2)O(2) sensor constructed with such composites showed a fast amperometric response time of less than 5 s, and the corresponding linear range and detection limit were estimated to be from 0.1 to 30 mM and 4.7 μM, respectively, at a signal-to-noise ratio of 3.  相似文献   
58.
Morphology control of functional materials is generally performed by controlling the growth rates on selected orientations or faces. Here, we control particle morphology by "crystal templating": by choosing appropriate precursor crystals and reaction conditions, we demonstrate that a material with rhombohedral symmetry-namely the layered, positive electrode material, LiCoO(2)-can grow to form a quadruple-twinned crystal with overall cubic symmetry. The twinned crystals show an unusual, concaved-cuboctahedron morphology, with uniform particle sizes of 0.5-2 μm. On the basis of a range of synthetic and analytical experiments, including solid-state NMR, X-ray powder diffraction analysis and HRTEM, we propose that these twinned crystals form via selective dissolution and an ion-exchange reaction accompanied by oxidation of a parent crystal of CoO, a material with cubic symmetry. This template crystal serves to nucleate the growth of four LiCoO(2) twin crystals and to convert a highly anisotropic, layered material into a pseudo-3-dimensional, isotropic material.  相似文献   
59.
Li H  Zhai J  Sun X 《The Analyst》2011,136(10):2040-2043
In this Communication, we report water-soluble nano-C(60) in the first use as an effective fluorescent sensing platform for the highly sensitive and selective detection of Ag(+). The general concept used in this approach is based on a fluorescently labeled single-stranded DNA (ssDNA) probe that adsorbs on nano-C(60), leading to substantial dye fluorescence quenching; however, in the presence of Ag(+), C-Ag(+)-C coordination induces the probe to fold into a hairpin structure, which does not adsorb on nano-C(60) and thus retains the dye fluorescence. This sensing system exhibits a detection limit as low as 1 nM and has a high selectivity against other metal ions. Finally and most importantly, we demonstrate its performance in real sample analysis.  相似文献   
60.
采用高效液相色谱-串联质谱法(HPLC-MS/MS)建立了食品中非法添加的碱性橙、碱性嫩黄、酸性橙I、酸性橙II和酸性黄36这5种黄色工业染料的定量定性分析方法。使用Agilent ODS C18分离柱(50 mm×2.0 mm, 1.8 μm),以5 mmol/L乙酸铵水溶液(0.1%甲酸)-乙腈(3:2, v/v)为流动相,流速为0.3 mL/min。采用电喷雾离子化源,以多反应监测(MRM)方式分别在正、负离子模式下进行检测。在最佳检测条件下,得到了较宽的线性范围和较低的定量检出限。碱性橙和碱性嫩黄的线性范围均为5.0~80.0 mg/L;酸性橙I、酸性橙II及酸性黄36的线性范围均为10.0~160.0 μg/L。食品中碱性橙、碱性嫩黄、酸性橙I、酸性橙II及酸性黄36的定量限分别为20、20、40、40、40 ng/g。该方法重现性较好,保留时间和峰面积的相对标准偏差分别不大于0.50%和2.14%。本研究还测定了鸡肉、豆制品和黄鱼中添加的5种化工染料,回收率在79.8%~95.2%之间,结果令人满意。  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