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   8608篇
  免费   1338篇
  国内免费   1339篇
化学   6476篇
晶体学   103篇
力学   673篇
综合类   94篇
数学   1129篇
物理学   2810篇
  2024年   18篇
  2023年   163篇
  2022年   170篇
  2021年   248篇
  2020年   322篇
  2019年   311篇
  2018年   232篇
  2017年   249篇
  2016年   429篇
  2015年   348篇
  2014年   441篇
  2013年   597篇
  2012年   734篇
  2011年   701篇
  2010年   568篇
  2009年   490篇
  2008年   547篇
  2007年   464篇
  2006年   448篇
  2005年   439篇
  2004年   370篇
  2003年   346篇
  2002年   394篇
  2001年   356篇
  2000年   251篇
  1999年   264篇
  1998年   204篇
  1997年   192篇
  1996年   193篇
  1995年   154篇
  1994年   137篇
  1993年   109篇
  1992年   78篇
  1991年   79篇
  1990年   46篇
  1989年   29篇
  1988年   39篇
  1987年   23篇
  1986年   30篇
  1985年   20篇
  1984年   9篇
  1983年   14篇
  1982年   10篇
  1981年   9篇
  1980年   4篇
  1979年   1篇
  1974年   1篇
  1957年   3篇
  1936年   1篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Two patterns of signal amplification lateral flow immunoassay (LFIA), which used anti-mouse secondary antibody-linked gold nanoparticle (AuNP) for dual AuNP-LFIA were developed. Escherichia coli O157:H7 was selected as the model analyte. In the signal amplification direct LFIA method, anti-mouse secondary antibody-linked AuNP (anti-mouse-Ab-AuNP) was mixed with sample solution in an ELISA well, after which it was added to LFIA, which already contained anti-E. coli O157:H7 monoclonal antibody-AuNP (anti-E. coli O157:H7-mAb-AuNP) dispersed in the conjugate pad. Polyclonal antibody was the test line, and anti-mouse secondary antibody was the control line in nitrocellulose (NC) membrane. In the signal amplification indirect LFIA method, anti-mouse-Ab-AuNP was mixed with sample solution and anti-E. coli O157:H7-mAb-AuNP complex in ELISA well, creating a dual AuNP complex. This complex was added to LFIA, which had a polyclonal antibody as the test line and secondary antibody as the control line in NC membrane. The detection sensitivity of both LFIAs improved 100-fold and reached 1.14 × 103 CFU mL−1. The 28 nm and 45 nm AuNPs were demonstrated to be the optimal dual AuNP pairs. Signal amplification LFIA was perfectly applied to the detection of milk samples with E. coli O157:H7 via naked eye observation.  相似文献   
992.
A carboxylated graphene oxide/polyvinyl chloride (CGO/PVC) material was prepared as a sorbent for the selective extraction of sulphonamides from complex sample. After being dispersed in buffer solution, sample was transferred into the prefabricated solid-phase extraction (SPE) column, which integrated extraction and cleanup into one single-step. A multi-response optimization based on the Box-Behnken design was used to optimize factors affecting extraction efficiency. Compared with the commonly commercial sorbents including MCX, WCX and C18, CGO/PVC hybrid material had higher extraction selectivity and capacity to sulphonamides. The limits of detection and quantification for seven target compounds were in the range of 3.4–7.1 μg/L and 11.4–23.7 μg/L, respectively. The self-assembly SPE cartridge was successfully used to enrich seven analytes in anti-acne cosmetics prior to ion chromatography detection with good recoveries of 87.8–102.0% and relative standard deviations of 1.2–6.4%, implying that this method was suitable for routine analysis of cosmetics.  相似文献   
993.
The activity and selectivity of heterogeneous catalysts can be significantly improved by dispersion of another active component in the metal substrate. The impact of Rh promoter on the formation of dimethyl carbonate (DMC) via oxidative carbonylation of methanol on Cu–Rh/AC (activated carbon) catalyst was investigated by density functional theory calculations. The most stable configurations of reacting species (CO, OH, CH3O, monomethyl carbonate, and DMC) adsorbed on the Cu0(zero‐valent copper)/AC and Cu–Rh/AC surfaces were determined on the basis of the calculated results. The reaction energy and activation energy of the rate‐limiting steps on the Cu–Rh/AC and Cu0/AC surfaces were compared. The activation energies of the rate‐limiting step of CO insertion into dimethoxide are 206.3 and 304.8 kJ mol?1 on the Cu–Rh/AC and Cu0/AC surfaces, respectively. The activation energies of the rate‐limiting step of CO insertion into methoxide are 78.5 and 92.7 kJ/mol on the Cu–Rh/AC and Cu0/AC surfaces, respectively. The calculated results indicate that the addition of Rh atom has a significant effect on decreasing the active energy the main pathway for DMC formation. © 2015 Wiley Periodicals, Inc.  相似文献   
994.
Two new diterpenoids, named paecilomycine A ( 1 ) and paecilomycine B ( 2 ), including a novel skeleton with a five‐membered lactone ring, together with three known labdane diterpenoids, rel‐(1R,3S,4aS,5R,8aS)‐5‐[(3E)‐4‐carboxy‐3‐methylbut‐3‐en‐1‐yl]decahydro‐3‐hydroxy‐1,4a‐dimethyl‐6‐methylidenenaphthalene‐1‐carboxylic acid ( 3 ), botryosphaerin E ( 4 ), and agathic acid ( 5 ), were isolated from solid culture of the insect pathogenic fungi strain Paecilomyces sp. The structures of all compounds were established on the basis of comprehensive spectroscopic studies. The relative configurations of 1 and 2 were determined by single‐crystal X‐ray diffraction analyses.  相似文献   
995.
996.
刘杰  周维友  吴中  孙富安  何明阳  陈群 《应用化学》2015,32(9):1033-1039
采用共沉淀法制备了不同Co2AlMgx(x=0.5、1、1.5和2)原子比的类水滑石,用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)、表面孔吸附(BET)及电感耦合等离子光谱(ICP)等技术手段表征了催化剂的结构、组成和比表面积,并考察了其催化苯甲醇选择氧化制苯甲醛的性能。 结果表明,随着Mg含量的增加,催化剂的碱性增强,苯甲醛的选择性提高。 在优化条件:苯甲醇0.02 mol,催化剂Co2AlMg1类水滑石100 mg,过氧化氢叔丁醇0.04 mol,溶剂乙腈8 mL,反应温度60 ℃,反应时间9 h下,苯甲醇的转化率为39.5%,苯甲醛的选择性达到89.2%。 催化剂重复使用5次后其活性与选择性未见明显降低,表明催化剂具有较好的稳定性。  相似文献   
997.
为了探讨2,3-二氢黄酮类化合物在发光材料方面的应用,首先合成了2,3-二氢黄酮类衍生物[3-(2-萘甲酰基)-2-苯基苯并二氢吡喃-4-酮(L)]配体,然后利用Eu(III)与此配体和水/邻菲罗啉(Phen)反应得到两种新型的红色荧光配合物。运用元素分析、红外光谱与荧光光谱等手段对相关物质进行了系统的表征。表征结果表明:两个新配合物的组成分别为Eu(L)3·2H2O和Eu(L)3·Phen;荧光光谱研究显示,两种配合物的配体能将吸收的能量有效地传递给铕离子,从而使配合物发射出强的铕离子的特征荧光,且两个配合物Eu(L)3·2H2O和Eu(L)3·Phen均以5D0→7F2跃迁的荧光发射最强。得到了两种新的高效的红色荧光材料。  相似文献   
998.
为了防止稀土的低附加值滥用,控制陶瓷色釉料中的稀土含量尤为重要,本方法为制订出入境检验检疫行业标准《陶瓷色釉料中稀土总量的测定电感耦合等离子体原子发射光谱法》提供可靠依据。由于陶瓷色釉料极其稳定的化学性质,因此不能采用传统的消解方法进行样品前处理,本文提出了用改进后的氢氧化钠和过氧化钠体系高温碱熔陶瓷色釉料,再用电感耦合等离子体原子发射光谱仪测定La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y 15种稀土元素总量的方法。在陶瓷色釉料的消解方法、待测元素波长的选择和基体干扰校正方面进行重点研究。选取具有代表性的陶瓷色釉料样品进行回收率、精密度及重现性试验,测得方法的回收率在94.7%~102.7%,精密度小于2.7%,重现性小于4.3%。计算了15种稀土元素的检出限均小于0.51 mg·kg-1。  相似文献   
999.
Based on the generalized gradient approximation (GGA), Perdew-Wang-91 (PW91) combined with a periodic slab model has been applied to study the catalytic activity of chlorine evolution on TinRumO2(1 1 0) surface. Metal oxide model TinRumO2 has been established with pure TiO2 and RuO2 on the basis set of Double Numerical plus polarization (DNP), in which the proportion of n:m was 3:1, 1:1, or 1:3. Analysis on the reaction activity in the electrochemical reaction and the electrochemical desorption reaction was based on Frontiermolecular orbital theory. The results show that the TinRumO2 with a ratio of Ti:Ru at 3:1 is best facilitates the electrochemical reaction and electrochemical desorption reaction to produce M-Clads intermediate and precipitate Cl2. In addition, the adsorption energy of Cl on the surface of Ti3Ru1O2 possesses the minimum value of 2.514 eV, and thus electrochemical desorption reaction could occur most easily.  相似文献   
1000.
A tetra(pyrid-2-yl)-pyrazine-bridged cyclometalated diosmium complex 1(PF6)2with two distal redoxactive organic amine substituents has been synthesized and characterized. This complex displays four consecutive and separated anodic redox waves at +0.24, +0.38, +0.64, and +0.71 V vs. Ag/Ag Cl. Upon stepwise oxidation, four-step absorption spectral changes in the visible to near-infrared region have been observed. The different redox states of 1(12+through 16+) can be distinguished by the significantly different absorption spectra in the visible and near-infrared region. DFT calculations of 13+show that the spin is delocalized on both osmium–amine components.  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