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   5415篇
  免费   295篇
  国内免费   489篇
化学   4861篇
晶体学   91篇
力学   25篇
综合类   4篇
数学   8篇
物理学   1210篇
  2024年   2篇
  2023年   125篇
  2022年   69篇
  2021年   72篇
  2020年   114篇
  2019年   101篇
  2018年   151篇
  2017年   166篇
  2016年   131篇
  2015年   128篇
  2014年   248篇
  2013年   225篇
  2012年   724篇
  2011年   361篇
  2010年   299篇
  2009年   300篇
  2008年   327篇
  2007年   404篇
  2006年   305篇
  2005年   278篇
  2004年   250篇
  2003年   194篇
  2002年   146篇
  2001年   135篇
  2000年   119篇
  1999年   126篇
  1998年   121篇
  1997年   85篇
  1996年   95篇
  1995年   78篇
  1994年   58篇
  1993年   51篇
  1992年   60篇
  1991年   51篇
  1990年   38篇
  1989年   21篇
  1988年   7篇
  1987年   4篇
  1986年   7篇
  1985年   6篇
  1984年   5篇
  1983年   2篇
  1981年   1篇
  1980年   3篇
  1979年   2篇
  1975年   1篇
  1974年   1篇
  1969年   1篇
  1966年   1篇
排序方式: 共有6199条查询结果,搜索用时 218 毫秒
1.
低维硅锗材料是制备纳米电子器件的重要候选材料,是研发高效率、低能耗和超高速新一代纳米电子器件的基础材料之一,有着潜在的应用价值。采用密度泛函紧束缚方法分别对厚度相同、宽度在0.272 nm~0.554 nm之间的硅纳米线和宽度在0.283 nm~0.567 nm之间的锗纳米线的原子排布和电荷分布进行了计算研究。硅、锗纳米线宽度的改变使原子排布,纳米线的原子间键长和键角发生明显改变。纳米线表层结构的改变对各层内的电荷分布产生重要影响。纳米线中各原子的电荷转移量与该原子在表层内的位置相关。纳米线的尺寸和表层内原子排列结构对体系的稳定性产生重要影响。  相似文献   
2.
A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.  相似文献   
3.
New tetradentatebis-benzimidazole ligands have been synthesized and utilized to prepare copper (II) complexes. Some of these copper (II) complexes have been characterized structurally. The copper (II) in these complexes is found to possess varying geometries. A distorted octahedral geometry is found with a highly unsymmetrical bidentate nitrate group. An unusual polymeric one-dimensional structure is observed where copper (II) is in a distorted square pyramidal geometry with a monodentate nitrate ion, having long Cu-O bond, while a distorted triagonal bipyramidal geometry is found with two carbonyl O atoms and a Cl atom in the equatorial plane, and two benzimidazole imine N atoms occupy the axial position. These compounds are found to activate the cumylperoxyl group, and this has been utilized in the facile oxidation of aromatic alcohols to aldehydes, where they act as catalysts with large turnovers. The yields of the respective products vary from 32 to 65%. The role of molecular oxygen has been studied and an attempt has been made to identify the “active copper species”. Activation of molecular oxygen has also been observed and has been used for oxidative dealkylation of a hindered phenol, producing di-butyl quinones with yields of 20–25% and 10–12 fold catalytic turnover. Dihydroxybenzenes and substituted catechols are also readily oxidized to the corresponding quinones, in oxygen-saturated solvents. Yields of 84% have been observed with 34-fold catalyst turnover, with di-t-butylcatechol. The activity of these copper (II) —bis-benzmidazolediamide compounds is reminiscent of the functioning of copper centres in galactose oxidase, tyrosinase and catechol oxidase.  相似文献   
4.
本文研究了胆绿素的表面增强拉曼光谱。结果表明,在溶液酸度不同时,拉曼光谱特征频率的变化表现出胆绿素的质子化。铜离子与胆绿素的相互作用实验结果说明金属铜离子可与胆绿素生成金属配合物。  相似文献   
5.
2-(2-喹啉偶氮)-5-二甲氨基苯胺光度法测定铜   总被引:1,自引:0,他引:1  
在pH=4.0的磷酸盐缓冲介质中,CTMAB存在下,2-(2-喹啉偶氮)-5-二甲氨基苯胺(QADMAA)与铜反应生成2:1稳定络合物,络合物λmax=580nm,ε=1.14×105L·mol-1·cm-1.铜含量在0.01-0.6μg/mL内符合比耳定律,方法用于环境样品中铜的测定,结果令人满意.  相似文献   
6.
Two methods for multi-element preconcentration from copper by reductive matrix precipitation are presented. In systematic investigations on the coprecipitation behaviour of Ag, Al, Au, Bi, Cd, Co, Cr, Fe, Ga, In, Mn, Mo, NJ, Pb, Sb, Se, Sn, Te and Zn during precipitation of the copper matrix as Cu2O or CuSCN, the separation parameters were optimized. By combination with a hexamethyleneammonium hexamethylenedithiocarbamate collector precipitation, a concentration of 8 elements (Cu2O precipitation) or 13 elements (CuSCN precipitation) in a small volume was achieved. The limits of detection of the procedures are, depending on the element, 0.1–5 μg g?1 for flame atomic absorption spectrometry (AAS) and 0.01–0.1 μg g?1 for graphite furnace AAS. The relative standard deviations are about 3%. The analytical performance of the procedures is compared with that of an electrolytic copper separation.  相似文献   
7.
The results of laser induced deposition of copper on polyimide substrate from copper electrolyte solution are reported. Unlike most work reported in the literatures where CW Ar+ lasers were used, a second harmonic (532 nm wavelength) Q-switch Nd:YAG laser was used for our experiments. The deposition process was conducted by laser-catalyzing of the polyimide surface and subsequent photothermal-accelerated reduction of copper-complex ions in an alkaline reducing environment. The characteristics of the deposited copper line were investigated in terms of laser beam scanning speed, and the number of scans. The surface morphology and chemical composition of the deposited copper were analyzed using field emission scanning electron microscope (FESEM) and energy dispersive spectrometer (EDX). The optimum processing conditions have been identified. The copper deposit was found to adhere well to the substrate.  相似文献   
8.
Copper bromide was used as a catalyst for the addition of pyrroles to enones. When both the reactants were used in equimolar amounts, mono and dialkylated products were obtained. However, the use of excess enone furnished only dialkylated products. Thus, copper bromide was shown to be an efficient catalyst for the dialkylation of pyrroles.  相似文献   
9.
离子交换富集-导数火焰原子吸收法测定自来水中Cu,Fe和Zn   总被引:7,自引:0,他引:7  
本文研究了用 2 0 1× 7阳离子交换树脂对自来水中的微量元素进行交换富集 ,采用微量脉冲进样 导数火焰原子吸收法测定富集后溶液中的Cu ,Fe和Zn ,该方法灵敏度分别为 0 2 9,0 5 9和 0 0 6 μg·L- 1 ,精密度分别为 4 2 8% ,1 95 %和 2 2 8% ,检测限分别为 1 2 8,5 85和 0 6 8μg·L- 1 ,回收率分别为 91 13% ,10 1 34%和99 84 % ,本方法大大减少了需样量 ,简便快速 ,灵敏度高。  相似文献   
10.
室温下,通过双核配合物[Cu(dppm)(NO3)]2(dppm=双二苯基膦甲烷)与四苯基硼钠在甲醇和二氯甲烷混合溶剂中反应制备了三核铜(I)配合物[Cu3(dppm)3(NO3)(OH)](NO3),经过红外光谱、热重分析、核磁和ES-MS等现代分析手段表征了配合物的物理化学性质,并进一步研究了配合物在室温下的荧光光谱特征。  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