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   972篇
  免费   89篇
  国内免费   297篇
化学   752篇
晶体学   6篇
力学   54篇
综合类   3篇
数学   279篇
物理学   264篇
  2024年   6篇
  2023年   29篇
  2022年   50篇
  2021年   41篇
  2020年   66篇
  2019年   39篇
  2018年   42篇
  2017年   27篇
  2016年   27篇
  2015年   41篇
  2014年   77篇
  2013年   149篇
  2012年   139篇
  2011年   116篇
  2010年   77篇
  2009年   76篇
  2008年   63篇
  2007年   67篇
  2006年   50篇
  2005年   33篇
  2004年   14篇
  2003年   12篇
  2002年   7篇
  2001年   16篇
  2000年   8篇
  1999年   13篇
  1998年   6篇
  1997年   5篇
  1996年   3篇
  1993年   2篇
  1992年   1篇
  1989年   3篇
  1988年   8篇
  1987年   20篇
  1986年   14篇
  1985年   3篇
  1984年   1篇
  1983年   1篇
  1982年   1篇
  1978年   3篇
  1977年   1篇
  1957年   1篇
排序方式: 共有1358条查询结果,搜索用时 15 毫秒
121.
A novel cedar-like Au nanoparticles (AuNPs) coating was fabricated on an etched stainless steel (SS) wire by direct chemical deposition and used as an efficient and unbreakable solid phase microextraction (SPME) fiber. The etched SS wire offers a rough surface structure for subsequent growth of AuNPs in chloroauric acid solution. As a result, the uniform cedar-like AuNPs coating with larger surface area was tightly attached to the etched SS wire substrate. The AuNPs coated etched SS fiber (AuNPs/SS) was examined for SPME of ultraviolet (UV) filters, phthalate esters and aromatic hydrocarbons coupled to high-performance liquid chromatography with UV detection. The fabricated fiber exclusively exhibited excellent extraction efficiency and selectivity for some aromatic hydrocarbons. Influential parameters of extraction and desorption time, temperature, stirring rate and ionic strength were investigated and optimized. The limits of detection ranged from 0.008 μg L−1 to 0.037 μg L−1. The single fiber repeatability varied from 3.90% to 4.50% and the fiber-to-fiber reproducibility ranged from 5.15% to 6.87%. The recovery of aromatic hydrocarbons in real water samples spiked at 2.0 μg L−1 and 20 μg L−1 ranged from 94.38% to 106.2% with the relative standard deviations below 6.44%. Furthermore the growth of the cedar-like AuNPs coating can be performed in a highly reproducible manner. This fabricated fiber exhibits good stability and withstands at least 200 extraction and desorption replicates.  相似文献   
122.
The reduced graphene oxide (RGO)/bisphenol A (BPA) composites were prepared by an adsorption‐reduction method. The composites are characterized by X‐ray diffraction (XRD), UV‐vis, thermogravimetric (TG) analysis, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM). The results confirm that BPA is adsorbed on the basal plane of RGO by π‐π stacking interaction. Furthermore, the electrochemical behaviors were evaluated by cyclic voltammetry, galvanostatic charge/discharge techniques and electrochemical impedance spectroscopy (EIS). The results show that the RGO/BPA nanocomposites exhibit ultrahigh specific capacitance of 466 F·g?1 at a current density of 1 A·g?1, excellent rate capability (more than 81% retention at 10 A·g?1 relative to 1 A·g?1) and superior cycling stability (90% capacitance decay after 4000 cycles). Consequently, the RGO/BPA nanocomposites can be regarded as promising electrode materials for supercapacitor applications.  相似文献   
123.
A novel and general carbon-nitrogen and carbon-carbon cross-coupling reaction between 3,4-dihydropyrimidine-2-thiones and copper(I) carboxylates were performed in the presence of palladium acetate. The copper(I) carboxylates act not only as desulfurative reagents but also as sources of carbon nucleophiles. A wide array of highly substituted and functionalized pyrimidines scaffolds were synthesized in good yields.  相似文献   
124.
Ma  Guofu  Li  Jindan  Sun  Kanjun  Peng  Hui  Feng  Enke  Lei  Ziqiang 《Journal of Solid State Electrochemistry》2017,21(2):525-535
Journal of Solid State Electrochemistry - Nitrogen-doped porous activated carbons have been fabricated through a simple and efficient carbonization method at 700 °C with the waste...  相似文献   
125.
Recent studies demonstrate that resource competition is an essential component of T-cell proliferation in HIV progression, which can contribute instructively to the disease development. In this paper, we formulate an age-structured within-host HIV model, in the form of a hyperbolic partial differential equation (PDE) for infected target cells coupled with two ordinary differential equations for uninfected T-cells and the virions, to explore the effects of both the T-cell competition and viral shedding variations on the viral dynamics. The basic reproduction number is derived for a general viral production rate which determines the local stability of the infection-free equilibrium. Two special forms of viral production rates, which are extensively investigated in previous literature, the delayed exponential distribution and a step function rate, are further investigated, where the original system can be reduced into systems of delay differential equations. It is confirmed that there exists a unique positive equilibrium for two special viral production rates when the basic reproduction number is greater than one. However, the model exhibits the phenomenon of backward bifurcation, where two positive steady states coexist with the infection-free equilibrium when the basic reproduction number is less than one.  相似文献   
126.
梁腾  马堃  陈曦  颉录有  董晨钟  邵曹杰  于得洋  蔡晓红 《物理学报》2015,64(15):153401-153401
基于多组态Dirac-Fock理论方法和冲量近似, 对Xe54+与Xe在197 MeV/u碰撞能量下, 炮弹离子的俘获及退激发过程进行了理论研究. 计算了炮弹离子从中性靶原子俘获一个电子到nl (n=1, 2, 3, 4, 5; l=s, p, d) 轨道上的辐射电子俘获截面和相应的辐射光子能量, 以及俘获末态退激发辐射跃迁的能量和概率. 结合这些计算结果, 进一步模拟了碰撞产生的炮弹离子的退激发X射线谱的结构, 并与兰州重离子加速器装置上的最新实验观测结果进行了比较, 符合得很好.  相似文献   
127.
A new type of tryptophan-functionalized graphene nanocomposite (Trp-GR) was synthesized by utilizing a facile ultrasonic method via ππ conjugate action between graphene (GR) and tryptophan (Trp) molecule. The material as prepared had well dispersivity in water and better conductivity than pure GR. The surface morphology of Trp-GR was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The electrochemical behaviors of ascorbic acid (AA), dopamine (DA), and uric acid (UA) were investigated by cyclic voltammetry (CV) on the surface of Trp-GR. The separation of the oxidation peak potentials for AA–DA, DA–UA and UA–AA was about 182 mV, 125 mV and 307 mV, which allowed simultaneously determining AA, DA, and UA. Differential pulse voltammetery (DPV) was used for the determination of AA, DA, and UA in their mixture. Under optimum conditions, the linear response ranges for the determination of AA, DA, and UA were 0.2–12.9 mM, 0.5–110 μM, and 10–1000 μM, with the detection limits (S/N = 3) of 10.09 μM, 0.29 μM and 1.24 μM, respectively. Furthermore, the modified electrode was investigated for real sample analysis.  相似文献   
128.
N-Alkoxymethylation of heterocyclic compounds with diethyl phosphite via cleavage of P-O bond was investigated and a series of N3-ethoxymethylated heterocyclic compounds were synthesized. A mechanism in which diethyl phosphite acts as an efficient surrogate of ethanol was proposed and supported by several evidences.  相似文献   
129.
The Biginelli 3,4-dihydropyrimidin-2(1H)-one was converted to various C2-multifunctionalized pyrimidines via the dehydrogenation and Mitsunobu reaction using amines, alcohols, phenols and carboxylic acids as nucleophiles. A possible mechanism was also proposed to rationalize the formation of products.  相似文献   
130.
设计并合成了4个对称联苯双酯类液晶化合物,化合物结构通过红外和核磁表征,它们的介晶性通过差示扫描量热仪(DSC),X射线衍射仪(XRD)和热台偏光显微镜(POM)进行了研究.并测定了4,4'-3,3',5,5'-四甲基联苯-二(4-甲基苯甲酸酯)(Ⅲa)的单晶结构,结果显示:晶体属于单斜晶系,P21/c空间群,晶胞参数为a=18.525(3)(A),b=12.196(2)(A),c=12.195(2)(A),β=97.142(2)°,V=2733.7(9)(A)3,Z=4,Dc=1.163 Mg/m3,R=0.0521,Rw=0.1161.化合物均为热致型互变液晶,并讨论了氧原子、不饱和端基和端基链长对介晶性的影响.  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