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   608篇
  免费   27篇
  国内免费   9篇
化学   455篇
晶体学   4篇
力学   20篇
数学   61篇
物理学   104篇
  2023年   8篇
  2022年   22篇
  2021年   61篇
  2020年   24篇
  2019年   34篇
  2018年   30篇
  2017年   13篇
  2016年   42篇
  2015年   26篇
  2014年   36篇
  2013年   56篇
  2012年   56篇
  2011年   46篇
  2010年   28篇
  2009年   27篇
  2008年   34篇
  2007年   22篇
  2006年   12篇
  2005年   11篇
  2004年   9篇
  2003年   6篇
  2002年   5篇
  2001年   3篇
  2000年   1篇
  1999年   1篇
  1998年   4篇
  1997年   1篇
  1996年   1篇
  1995年   3篇
  1994年   3篇
  1993年   2篇
  1992年   2篇
  1991年   3篇
  1990年   2篇
  1987年   2篇
  1985年   1篇
  1984年   1篇
  1983年   2篇
  1982年   1篇
  1981年   2篇
  1979年   1篇
排序方式: 共有644条查询结果,搜索用时 15 毫秒
611.
Carbon paste electrodes were modified by nickel phosphate nanoparticles and nickel phosphate Versailles Santa Barbara-5 molecular sieves. Then, transition metal ions of Ni(II) were incorporated to the nickel phosphate by immersion of the modified electrode in a 0.1-M nickel chloride solution. The electrochemical behaviors of the modified electrodes were studied using cyclic voltammetry. These modified electrodes were used as anode for the electrocatalytic oxidation of methanol in alkaline medium. The influence of some parameters such as different molecular sieves, scan rate of potential, and methanol concentration was investigated on the anodic peak height of the methanol oxidation. The best result was obtained by nickel phosphate nanoparticles.  相似文献   
612.
613.
通过离子液体氯化1-苄基-3-甲基咪唑(BenzMeIm-Cl)与PtCl2的反应,合成了配合物(BenzMeIm)2[PtCl4],并用元素分析、红外光谱、紫外-可见光谱、1H NMR、13C NMR和单晶X射线衍射对其进行了表征。单晶X射线分析表明,配合物结构属于P21/c空间群,晶胞参数和结构解析参数为:a=0.981 80(5)nm,b=0.861 47(3)nm,c=0.144 332(7)nm,β=92.480(2)°,V=121.96(1)nm3,R1=0.014 4,wR2=0.038 8。  相似文献   
614.
Syntheses and antimicrobial behavior of the alkyl linked new bispyrazolines 4a , 4b , 4c , 4d , 4e , 4f , 4g have been investigated. These compounds exhibited better antimicrobial activities as compared with their corresponding bischalcones. The structures of the prepared compounds ( 3a , 3b , 3c , 3d , 3e , 3f , 3g and 4a , 4b , 4c , 4d , 4e , 4f , 4g ) were determined from the rigorous analysis of their IR, 1H NMR, 13C NMR, and mass spectral parameters.  相似文献   
615.
合成了Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),Mn(Ⅱ),Zn(Ⅱ)和Cd(Ⅱ)的乙基3-(2-氨硫化亚肼基)-2-(羟胺基)丁烯酸酯配合物(H2L)并用元素分析,DTA热分析,IR,UV-Vis,1H-NMR,质谱,顺磁共振以及磁矩,电导率测量等对合成的配合物进行表征。摩尔电导率测量结果证明合成的配合物为非电解质。光谱数据表明配体分别表现为一元的三齿配体,一元的二齿配体,中性的二齿配体,中性的三齿配体,一元的四齿配体或二元的四齿配体通过席夫碱的氮原子,氨基硫脲中的氮原子,肟中的氮原子和硫酮中的硫原子与金属离子键合生成围绕金属离子的四面体或平面正方形构型。固态Cu(Ⅱ)(2),(3),(4)和(5)的配合物顺磁共振谱表明其为轴向对称,但(10~15)的配合物却为各向异性。配体和配合物(2),(3),(10),(13),(16)和(19)由于它们对乳腺癌(MCF-7细胞系)和肝癌(HePG-2细胞系)的抑制作用而表现出潜在的抗癌活性。  相似文献   
616.
The N-alkylation of the 3,3′-diaminobenzidine with innocent substituents leads to unusual properties. The emission of the benzidine core can be fine-tuned by subtle modifications, and the N-substitution with benzylic groups results in photoinduced exciplexes with distinct and increased emission. This compound constitutes the first example of intramolecular exciplex containing benzidine unit. We also show that these photoinduced processes could be modulated by proton input, and that the diprotonation of the benzidine core disrupted the intramolecular communication in the excited states with a concomitant inhibition of the ligand-centred fluorescence. Furthermore, upon photo-irradiation at 254 nm, semiquinone imine and quinone diimine systems are produced in CH2Cl2 of which the photolysis generates Cl radicals, which rapidly oxidize the tetraamine compounds.  相似文献   
617.
Ionisable amino-lipid is a key component in lipid nanoparticles (LNPs), which plays a crucial role in the encapsulation of RNA molecules, allowing efficient cellular uptake and then releasing RNA from acidic endosomes. Herein, we present direct evidence for the remarkable structural transitions, with decreasing membrane curvature, including from inverse micellar, to inverse hexagonal, to two distinct inverse bicontinuous cubic, and finally to a lamellar phase for the two mainstream COVID-19 vaccine ionisable ALC-0315 and SM-102 lipids, occurring upon gradual acidification as encountered in endosomes. The millisecond kinetic growth of the inverse cubic and hexagonal structures and the evolution of the ordered structural formation upon ionisable lipid-RNA/DNA complexation are quantitatively revealed by in situ synchrotron radiation time-resolved small angle X-ray scattering coupled with rapid flow mixing. We found that the final self-assembled structural identity, and the formation kinetics, were controlled by the ionisable lipid molecular structure, acidic bulk environment, lipid compositions, and nucleic acid molecular structure/size. The implicated link between the inverse membrane curvature of LNP and LNP endosomal escape helps future optimisation of ionisable lipids and LNP engineering for RNA and gene delivery.  相似文献   
618.
619.
This study was aimed at providing the baseline data of terrestrial gamma dose rates and natural radioactivity to assess the corresponding health risk in the ambient environment of the Pahang State. Terrestrial gamma radiation (TGR) from 640 locations was measured with the mean value found to be 176?±?5 nGy h?1. Ninety-eight soil samples were analysed using a high-purity germanium detector (HPGe), and the mean concentrations of the radionuclides 226Ra, 232Th and 40K are 110?±?3, 151?±?5 and 542?±?51 Bq kg?1, respectively.226Ra and 232Th concentrations were found to be three times the world average, while that of 40K is quite higher than the world average value. The acid-intrusive geological formation has the highest mean concentrations for 226Ra (215?±?6 Bq kg?1), 232Th (384?±?12 Bq kg?1) and 40K (1564?±?153 Bq kg?1). The radium equivalent activities (Req) and the external hazard index (Hex) for the various soil types were also calculated. Some of the soil types were found to have values exceeding the internationally recommended levels of 370 Bq kg?1 and the unity value, respectively.  相似文献   
620.
Membranes of chitosan-based proton conductor polymer electrolyte were prepared by dissolving chitosan powder, ammonium nitrate (NH4NO3) salt and ethylene carbonate (EC) plasticizer in acetic acid solution. The temperature dependence of the chitosan-based membrane system was found to obey the Arrhenius relationship. The sample with the highest conductance, 18 wt.% CA + 12 wt.% NH4NO3 + 70 wt.% EC (CA40N70E), also possesses the lowest activation energy. From linear sweep voltammetry (LSV) results, the membrane is electrochemically stable at a potential of 1.6–1.8 V and a temperature of 298–353 K. The cells were fabricated using zinc powder (Zn) + zinc sulfate heptahydrate (ZnSO4·7H2O) + acetylene black (AB) + polytetrafluoroethylene (PTFE)|CA40N70E|manganese (IV) oxide (MnO2) + AB + PTFE. The open circuit voltages of the cells are decreases as temperature increases, the same trend as that obtained by LSV. The cell performance is excellent at 333 K, with discharge capacity of 42.7 mAh, internal resistance of 16.8 Ω, maximum power density of 14.6 mW cm−2 and a short-circuit current density of 31.0 mA cm−2. However, at temperatures above 333 K, decomposition of the membrane degraded the electrochemical properties of the cells.  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