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   23769篇
  免费   3940篇
  国内免费   3704篇
化学   17581篇
晶体学   387篇
力学   1486篇
综合类   298篇
数学   2696篇
物理学   8965篇
  2024年   50篇
  2023年   397篇
  2022年   667篇
  2021年   811篇
  2020年   926篇
  2019年   894篇
  2018年   762篇
  2017年   809篇
  2016年   1075篇
  2015年   1073篇
  2014年   1377篇
  2013年   1828篇
  2012年   2031篇
  2011年   2105篇
  2010年   1570篇
  2009年   1598篇
  2008年   1714篇
  2007年   1554篇
  2006年   1459篇
  2005年   1250篇
  2004年   960篇
  2003年   757篇
  2002年   693篇
  2001年   630篇
  2000年   507篇
  1999年   503篇
  1998年   497篇
  1997年   386篇
  1996年   360篇
  1995年   309篇
  1994年   315篇
  1993年   219篇
  1992年   198篇
  1991年   176篇
  1990年   180篇
  1989年   116篇
  1988年   98篇
  1987年   98篇
  1986年   99篇
  1985年   82篇
  1984年   51篇
  1983年   39篇
  1982年   38篇
  1981年   29篇
  1980年   21篇
  1979年   18篇
  1978年   14篇
  1976年   9篇
  1975年   9篇
  1973年   10篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
881.
This paper considers the consensus tacking problem for nonlinear fractional‐order multiagent systems by presenting a PDα‐type iterative learning control update law with initial learning mechanisms. The asymptotical convergence of the proposed distributed learning algorithm is strictly proved by using the properties of fractional calculus. A sufficient condition is derived to guarantee the whole multiagent system achieving an asymptotic output consensus. An illustrative example is given to verify the theoretical results.  相似文献   
882.
Importing intramolecular hydrogen bond in phosphorescent transition metal complexes has been considered one of the excellent approaches to improve the electroluminescence performance of organic light-emitting diodes in real applications. However, the relationships between such H-bond structure and phosphorescent properties have not been theoretically revealed yet. In this study, two types of intramolecular hydrogen bonds are introduced into the two classes of traditional materials, that is, Pt(II) and Ir(III) complexes ( 1a and 2a ) to completely elucidate their influence on the structures and properties by comparing with the original phosphors ( 1b and 2b ) using density functional theory/time-dependent density functional theory for the first time. A comprehensive analysis of the geometric structures, molecular orbitals, and luminescence properties (including phosphorescence emission wavelengths and radiative and nonradiative decay processes) has been carried out. Our theoretical model highlights that complexes 1a and 2a embedded with H-bonds significantly promote the phosphorescence emission band blue-shifted and restrict molecular deformations compared with the corresponding 1b and 2b , which can provide helpful guidance to regulate and design several aspects of highly efficient blue phosphorescent emitters.  相似文献   
883.
荒漠地区由于气候干燥,降水稀少,水分常成为制约植被生长的因素之一,水分胁迫对植物长势和产量的影响比任何其他胁迫都要大。随着高光谱技术的发展,国内外已有众多学者利用高光谱数据研究植被遭受胁迫作用,然而这些研究对象多集中于甜菜、棉花、玉米、水稻等作物,针对干旱区盐生植被遭受胁迫作用的研究较少。梭梭作为荒漠、半荒漠地区的典型盐生植被之一,具有极高的经济和生态效益。选择梭梭作为研究对象,培育一年生梭梭,并设置三个水分梯度,形成受不同水分量胁迫的梭梭。使用原始光谱、红边位置参数,结合植被指数及二维相关光谱研究其叶片光谱特征,为干旱区利用高光谱遥感监测盐生植被提供借鉴。结果表明:(1)分析梭梭叶片反射光谱曲线发现,在可见光至中红外各波段范围内,受不同水分量胁迫作用的梭梭叶片光谱反射率有显著差异。在可见光(350~610 nm)波段,各水分处理的梭梭叶片反射率依次为100 mL>500 mL>200 mL,这是由于100和200 mL水分促进梭梭内部叶绿素合成,使该波段反射率降低,而过多的水分(500 mL)对梭梭内部的叶绿素合成没有更大的促进作用。在红光区(611~738 nm),随着水分量的增多,受不同水分量胁迫的梭梭叶片光谱反射率依次减小。在738~1 181和1 228~1 296 nm波段,受不同水分量胁迫作用的梭梭叶片光谱反射率为:200 mL>100 mL>500 mL;在1 182~1 227 nm波段,受不同水分量胁迫作用的梭梭叶片光谱反射率为:100 mL>200 mL>500 mL。这是由于植被细胞结构对近红外区域的反射率影响较大,因而受不同水分胁迫作用的梭梭叶片光谱反射率有显著差异。在1 300~1 365和1 392~1 800 nm波段,受各水分胁迫作用的梭梭叶片反射率为:100 mL>200 mL>500 mL。这表明在500 mL水分胁迫量范围内,水分越多,叶子的细胞液、细胞膜对水分的吸收能力越强,使得反射率下降。通过对原始光谱求取一阶导数并提取红边位置参数发现,各水分处理下的梭梭叶片一阶微分光谱曲线中红边位置未发生移动。这是由于梭梭在长期的干旱环境影响下,形成了特殊的适应机制,水分对其红边位置影响不敏感。(2)选取若干植被指数分析各水分处理下的梭梭光谱指数变化。当水分胁迫量由100 mL增至200 mL时,WI/NDWI,MSI和NDII指数值变化显著,可用于研究水分胁迫下梭梭的光谱特征。(3)使用二维相关光谱技术分析受各水分胁迫作用的梭梭光谱特征,得出在100 mL水分胁迫下,在536,643,1 219和1 653 nm波段处,吸收峰对水分的微扰敏感;在200 mL水分胁迫下,在846和1 083 nm波段处,吸收峰对水分的微扰敏感;在500 mL水分胁迫下,在835和1 067 nm波段处,吸收峰对水分的微扰敏感。总之,在近红外波段,与100 mL水分量相比,梭梭受200和500 mL水分量胁迫时,吸收峰对水分的微扰敏感度上升。由100 mL水分胁迫下梭梭的二维同步相关谱图可知,1 044和1 665 nm,1 072和903 nm,903和1 264 nm,1 230和1 061 nm波段处形成正交叉峰,表明这些波段处光谱强度随水分的干扰同时变化。  相似文献   
884.
Wedge-shaped molecules, such as dendrons, are among the most important building blocks for directed supramolecular self-assembly. Here we present a new approach aimed at widening the range and complexity of potential mesophases by introducing double-tapered mesogens. Two series of compounds are presented, both alkali metal salts (Li, Na, Cs) of 3,4,5-tris-alkoxybenzoic acid with a second tapered tris-alkoxyaryl group attached at the end of an alkoxy chain. The double-tapered compounds all display an unusual hexagonal columnar phase consisting of one ionic and three non-ionic columns per unit cell. The cation size has an unexpectedly drastic effect on unit cell size. Unlike most columnar phases, the current phases show unusually high dimensional stability on heating, and high stiffness in spite of being 80–85 % aliphatic, attributed to their molecular topology. The described approach may lead to co-assemblies of multifunctional materials, for example, parallel p- and n-semiconducting nanowires or parallel ionic and electronic conductors.  相似文献   
885.
Cyanide is extremely hazardous to living organisms and the environment. Owing to its wide range of applications and high toxicity, the development of functional materials for cyanide detection and sensing is highly desirable. Host–guest complexation between bis(p-phenylene)-34-crown-10 H and N-methylacridinium salt G remarkably decreases the detection limit for cyanide anions compared with that of the guest itself. The [2]pseudorotaxane selectively recognizes the cyanide anion with high optical sensitivity as a result of the nucleophilic addition of the cyanide anion at the 9-position of G . The host–guest complexation is further incorporated into supramolecular materials for the visual detection of cyanide anions, especially the detection of cellular cyanide excretion with a detection limit of 0.6 μm . This supramolecular method provides an extremely distinct strategy for the visual detection of cyanide anions.  相似文献   
886.
From Abies nukiangensis, two novel 13,14-seco-abietane diterpenes, nukiangendines A (1) and B (2) were isolated. Their relative structures were determined by extensive NMR and HRMS spectroscopic analysis. The absolute configuration of 1 was established by ECD calculations. Compound 1 showed significant anti-hepatitis C virus (HCV) effects.  相似文献   
887.
Cerebrovascular diseases (CVDs) are among the most serious diseases with high mortality and disability rates. The prevalent diagnosis and treatment methods of CVDs include imaging and interventional therapy. With the development of nanotechnology, large numbers of nanomaterials have been applied to the diagnosis and treatment of CVDs, mainly including carbon nanotubes, quantum dots, fullerenes, and dendrimers. In this review, the applications of nanomaterials in the field of diagnosis and treatment of CVDs, mainly including drug target delivery, imaging, therapy, endovascular treatment, and angiogenesis, are summarized. The applications of nanomaterials in the field of CVD are almost in the laboratory, and more effort is needed for clinical translation. The aim of this review is to provide useful information for future research and equipment development.  相似文献   
888.
Development of effective organocatalysts for the living ring‐opening polymerization (ROP) of lactones is highly desired for the preparation of biocompatible and biodegradable polyesters with controlled microstructures and physical properties. Herein, a new class of hydrogen‐bond donating bisurea catalysts is reported for the ROP of lactones under solvent‐free conditions. ROP of lactones mediated by the bisurea/7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD) catalyst exhibits a living/controlled manner, affording the polymers and copolymers with the well‐defined structure, predictable molecular weight, narrow molecular weight distribution, and high selectivity for monomer at low catalyst loadings at ambient temperature. The possible mechanism of bisurea/MTBD‐catalyzed ROP of lactones is proposed, in which the bisurea activates the carbonyl group of lactones while MTBD facilitates the nucleophilic attack of the initiating/propagating alcohol by hydrogen bonding. Moreover, the poly(ε‐caprolactone‐co‐δ‐valerolactone) [P(CL‐co‐VL)] random copolymers with various compositions were synthesized using the bisurea/MTBD catalyst. The measurements of thermal properties and crystalline structure demonstrate that the CL and VL units are cocrystallized in the crystalline phase of P(CL‐co‐VL) copolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 90–100  相似文献   
889.
Octahedral iridium(III) complexes containing two bidentate cyclometalating 5‐tert‐butyl‐2‐phenylbenzoxazole ( IrO ) or 5‐tert‐butyl‐2‐phenylbenzothiazole ( IrS ) ligands in addition to two labile acetonitrile ligands are demonstrated to constitute a highly versatile class of asymmetric Lewis acid catalysts. These complexes feature the metal center as the exclusive source of chirality and serve as effective asymmetric catalysts (0.5–5.0 mol % catalyst loading) for a variety of reactions with α,β‐unsaturated carbonyl compounds, namely Friedel–Crafts alkylations (94–99 % ee), Michael additions with CH‐acidic compounds (81–97 % ee), and a variety of cycloadditions (92–99 % ee with high d.r.). Mechanistic investigations and crystal structures of an iridium‐coordinated substrates and iridium‐coordinated products are consistent with a mechanistic picture in which the α,β‐unsaturated carbonyl compounds are activated by two‐point binding (bidentate coordination) to the chiral Lewis acid.  相似文献   
890.
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