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   3446篇
  免费   93篇
  国内免费   398篇
化学   3081篇
晶体学   27篇
力学   51篇
数学   9篇
物理学   769篇
  2024年   26篇
  2023年   298篇
  2022年   81篇
  2021年   87篇
  2020年   109篇
  2019年   109篇
  2018年   83篇
  2017年   93篇
  2016年   104篇
  2015年   85篇
  2014年   110篇
  2013年   183篇
  2012年   304篇
  2011年   203篇
  2010年   168篇
  2009年   224篇
  2008年   199篇
  2007年   220篇
  2006年   180篇
  2005年   141篇
  2004年   147篇
  2003年   89篇
  2002年   62篇
  2001年   72篇
  2000年   57篇
  1999年   62篇
  1998年   68篇
  1997年   60篇
  1996年   49篇
  1995年   39篇
  1994年   30篇
  1993年   35篇
  1992年   24篇
  1991年   27篇
  1990年   17篇
  1989年   11篇
  1988年   9篇
  1987年   7篇
  1986年   7篇
  1985年   7篇
  1984年   8篇
  1983年   5篇
  1982年   4篇
  1981年   4篇
  1980年   7篇
  1979年   7篇
  1975年   15篇
  1968年   1篇
排序方式: 共有3937条查询结果,搜索用时 14 毫秒
121.
Atomic resolution images of layered transition metal-dichalcogenide ReS2 single-crystals (n-type semiconductor) were obtained using a scanning tunneling microscope with a positive tip. In most cases only unresolved clusters of four rhenium atoms could be seen. Occasional images with higher resolution showed that these bright structures consist of four separated atoms. The symmetry of the imaged atoms is identical to that of the rhenium sublattice but not to that of the sulfur atoms. We conclude therefore that the main contribution to the tunneling current is due to the rhenium atoms, although the sulfur atoms are placed by about 0.15 nm closer to the tip. Thus for our positive bias of the tip the tunneling electrons originate from occupied rhenium states in the valence band of the semiconductor.  相似文献   
122.
This paper presents size exclusion chromatography data with on-line coupling to UV and inductively coupled plasma mass spectrometry (ICP-MS) of water soluble metal-binding compounds present in zinc, copper, chromium and iodine enriched yeast nutritional supplements. Molecular weight estimates of the extracted metal-containing compounds are given and are shown to vary substantially from 1.2 kDa to larger than 668 kDa. Seven proteins suspected of containing chromium were identified from one of the chromium-containing fractions. Four of these identified proteins are known to form complexes with other metal ions. The metal chromatographic profiles of zinc, copper and chromium-enriched yeasts were compared to their respective native metal profiles in non-enriched yeast samples. The chromium profiles are shown to be markedly different while those of zinc and copper are qualitatively similar. Only iodide ions or weakly bound, non-aromatic, low molecular weight ( 1.2 kDa) iodine species were observed in the iodine-enriched yeast samples.  相似文献   
123.
采用两种密度泛函方法对中性单核Ru(CO)n(n=5,4,3)和双核Ru2(CO)n(n=9,8)化合物进行理论计算,优化出16个稳定异构体.研究发现,和Os(CO)5类似,Ru(CO)5存在两个能量接近的最低异构体.Ru(CO)4的能量最低异构体为C2v对称性的单态构型.Ru(CO)3能量最低异构体为G对称性的单态构型.Ru2(c0)。的两个能量接近的最低异构体分别含有单个桥羰基和3个桥羰基.双核不饱和Ru2(CO)8的能量最低异构体为含有两个桥羰基的单态Q构型.通过比较M2(CO)n(M=Fe,Ru,Os;n=9,8)的能量最低构型,发现Fe和Ru倾向于形成含有多个桥配位羰基的构型,而Os则更倾向于形成不含桥配位羰基的构型.对离解能的研究表明,和失去一个羰基生成Ru2(CO)8相比,Ru2(CO)9更容易离解为Ru(CO)5和Ru(CO)4.  相似文献   
124.
比较与研究金属离子与三种蛋白的配位机理   总被引:6,自引:0,他引:6  
本文通过测定牛血红蛋白、人血清蛋白、伴刀豆球蛋白A与过渡态金属离子Cr(Ⅲ)、Fe(Ⅲ)在不同条件下的荧光强度变化来揭示蛋白质与金属离子形成络合物的配位点,从而确定所形成配合物的结构,并讨论了溶液PH值对蛋白质荧光强度的影响。另外,对金属离子与蛋白质体系进行了荧光偏振的研究。  相似文献   
125.
本文提出了阿莫西林[(2S,5R,6R)-3,3-二甲基-6-[(R)-(-)-2-氨基-2-(4-羟基苯基)乙酰氨基]-7-氧化-4-硫杂-1-氮杂双环[3,2,0]庚烷-2-甲酸三水化合物]荧光分析的方法。并对影响阿莫西林荧光性质(光谱和光谱强度)的各种因素,包括pH值、表面活性剂的增效作用、无机离子的配合作用以及其他介质条件等进行了较为详细的研究。实验结果表明,阿莫西林具有良好的荧光性质,在微碱性条件下荧光发射最强,CTAB对其有增效作用,与无机离子(Mg  相似文献   
126.
Zeolitic imidazolate frameworks (ZIFs), in particular ZIF-8 (made of Zn2+ and 2-methyilimidazolate) and cobalt-doped-ZIF-8, are found important for many energy and environmental applications. It was reported that ZIFs show excellent structural stability in water and thus ideal for aqueous applications. However, recent studies also found some evidence that ZIF-8 undergoes hydrolysis in water. Despite the importance of ZIF's stability in many aqueous applications, the extent of ZIFs' degradation in water is still not yet fully understood. In this study, we report a quantitative study of the water stability of 0–100 at% cobalt-doped ZIF-8, using a new combination of analytical tools. The study demonstrated the importance of analyzing both filtered powders and the filtrate liquid systematically, in particular by using UV–Vis spectroscopy and thermogravimetric analysis. The combination of analytical tools allowed the study on the effects of ZIF concentrations in water, cobalt doping levels, and amounts of ligands in water on the water stability of ZIF samples. The effect of cobalt-doping was investigated by using ZIF particles with identical sizes (200–400 nm), in order to eliminate the effects of particle size on hydrolysis. Unlike other synthesis methods, a mechanochemical ball milling method allowed the production of nano-scale ZIF-8 particles with similar sizes, independent of cobalt-doping levels. The proposed combination of analytical tools including UV–Vis spectroscopy can be applied to the study of the water stability of other MOF materials.  相似文献   
127.
In this paper, we present a generic mode theory for the three-layer cylindrical waveguides consisting of three arbitrary material mediums. Based on derived eigenvalue equations of the TE, TM, and hybrid modes, the mode conditions of metal/dielectric-coated terahertz hollow waveguides are extracted. In addition, we quantitatively describe both the effective refractive indexes and the loss characteristics of the aurum/polystyrene-coated terahertz hollow waveguides operating at the TE01, TM01, and HE11 modes. It is indicated that the loss coefficient of the TE01 mode can be much lower than that of the TM01, and HE11 modes, and, especially, can tend to that of the terahertz wave in air. So the TE01 mode is very significant for the hollow waveguides in term of low loss propagating of the terahertz wave. We expect these results to enable a variety of new long-distance THz applications in sensing, detecting and communicating.  相似文献   
128.
《Tetrahedron letters》2019,60(34):150932
The visible light mediated oxidation of 1,3,5-trisubstituted pyrazolines under metal-free conditions was developed. Various substituted pyrazolines were oxidized to pyrazoles by irradiation with visible light/sunlight. A plausible mechanism was proposed for the light mediated oxidation proceeding via formation of intermediates with electron rich C-3 positions and electron deficient C-5 positions. Correlation between the electronic effect induced by the aryl substituents and the rate of oxidation was studied by UV–vis spectroscopy. This correlation study supported the proposed mechanism. Electron withdrawing substituents at the 3-phenyl group and electron releasing substituents at the 5-phenyl group enhanced the rate of oxidation; whereas, electron donating substituents at the 3-phenyl group and electron withdrawing substituents at the 5-phenyl group reduced the rate.  相似文献   
129.
We have produced nanophase metal clusters, (Fe)n, (Cr)n, (Mo)n and (W)n, by multiphoton decomposition of the corresponding metal carbonyls with a 10.6 μm CO2 laser in the presence of Ar and SF6. The size distribution was narrow and the average diameter was 6, 3.5, 2 and 1 nm for Fe, Cr, Mo and W clusters, respectively. The structure was found to be bcc for both Fe and Cr clusters, fcc for Mo clusters, and amorphous for W clusters (note that all the bulk metals have bcc structure). Considering the cluster sizes (9630, 1870, 230 and 30 for Fe, Cr, Mo and W clusters, respectively) estimated from their average diameters, it is likely that there exists a structural transition from fcc to bulk bcc with increasing cluster size in these metal clusters.  相似文献   
130.
1-Ethoxycarbonyl-3-ferrocenyl-propane-1,3-dion and Ferrocene-1,1′bis(2,4-dioxobutanoic acid ethylester) as Ligands for Transition Metal Ions. Crystal Structure of Bis(1-ethoxycarbonyl-3-ferrocenyl-propane-1,3dionato)copper(II) The ligands 1-ethoxycarbonyl-3-ferrocenyl-propane-1,3-dion and ferrocene-1,1′-bis(2,4-dioxo-butanoic acid ethylester) have been prepared by reaction of acetylferrocene or 1,1′-diacetylferrocene and diethyl oxalate. They yield neutral chelates with CuII, NiII, ZnII, CoII, and MnII. The acid dissociation constants of the ligands and the stability constants of their metal complexes including FeII complexes are reported. The structure of bis(1-ethoxycarbonyl-3-ferrocenyl-propane-1,3-dionato)copper(II) was determined by X-ray structure analysis. A cis arrangement with a nearly square planar coordination sphere at the Cu atom is found.  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