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   8394篇
  免费   851篇
  国内免费   723篇
化学   3327篇
晶体学   94篇
力学   1287篇
综合类   120篇
数学   1391篇
物理学   3749篇
  2023年   82篇
  2022年   147篇
  2021年   264篇
  2020年   253篇
  2019年   193篇
  2018年   200篇
  2017年   246篇
  2016年   230篇
  2015年   243篇
  2014年   299篇
  2013年   680篇
  2012年   414篇
  2011年   559篇
  2010年   399篇
  2009年   471篇
  2008年   458篇
  2007年   492篇
  2006年   493篇
  2005年   423篇
  2004年   417篇
  2003年   398篇
  2002年   344篇
  2001年   262篇
  2000年   250篇
  1999年   188篇
  1998年   234篇
  1997年   189篇
  1996年   146篇
  1995年   127篇
  1994年   116篇
  1993年   106篇
  1992年   96篇
  1991年   60篇
  1990年   68篇
  1989年   52篇
  1988年   57篇
  1987年   34篇
  1986年   42篇
  1985年   50篇
  1984年   37篇
  1983年   14篇
  1982年   33篇
  1981年   14篇
  1980年   16篇
  1979年   20篇
  1978年   13篇
  1977年   6篇
  1976年   10篇
  1973年   7篇
  1957年   4篇
排序方式: 共有9968条查询结果,搜索用时 468 毫秒
61.
《中国化学》2017,35(10):1575-1585
Binder‐free, nano‐sized needlelike MnO2 ‐submillimeter‐sized reduced graphene oxide (nMnO2‐srGO ) hybrid films with abundant porous structures were fabricated through electrophoretic deposition and subsequent thermal annealing at 500 °C for 2 h. The as‐prepared hybrid films exhibit a unique hierarchical morphology, in which nMnO2 with a diameter of 20—50 nm and a length of 300—500 nm is randomly anchored on both sides of srGO . When evaluated as binder‐free anodes for lithium‐ion half‐cell, the nMnO2‐srGO composites with a content of 76.9 wt% MnO2 deliver a high capacity of approximately 1652.2 mA •h•g−1 at a current density of 0.1 A•g−1 after 200 cycles. The high capacity remains at 616.8 mA •h•g−1 (ca. 65.1% capacity retention) at a current density as high as 4 A•g−1. The excellent electrochemical performance indicates that the nMnO2‐srGO hybrid films could be a promising anode material for lithium ion batteries (LIBs ).  相似文献   
62.
《Electroanalysis》2017,29(5):1316-1323
Total antioxidant capacity is an important parameter for the evaluation of the oxidative status in different kinds of biological samples such as plant extracts, or in food industry. We report a fast, easy, portable, cost‐effective electroanalytical method to measure total antioxidant capacity, based on the reaction of natural antioxidants with electrogenerated iodine using disposable platinum screen‐printed electrodes. This reaction can be measured by the increment of the electrochemical current signal of iodide oxidation to iodine during a voltammetric cycle. Iodine reacts with reducing compounds such as glutathione, ascorbate, gallic acid and NADH without interference of the corresponding oxidized counter‐parts. The addition of ascorbate oxidase also allows the concentration of ascorbate to be determined. The method was tested with real samples of plant extracts and the results correlated well with those obtained with a standard spectrophotometric method.  相似文献   
63.
《Electroanalysis》2017,29(12):2818-2831
Immobilization of biomolecules with a proper orientation is considered as a basis for diverse biotechnological applications. Herein, we report a host‐guest inclusion complexation between β‐cyclodextrin (β‐CD) and biotin as a versatile approach for the immobilization of biomolecules. As a practical application, a sandwich‐type electrochemical immunosensor was designed for the determination of prostate specific antigen (PSA). The immunosensor was fabricated by in situ electropolymerization of poly(N‐acetylaniline) onto a rGO‐modified Pt electrode. Then, β‐CD was covalently grafted onto the over‐oxidized polymer backbone. For improving the efficiency of the assay, AuNPs were casted on the polymeric film, on the surface of which thionine (TH) as an electron mediator was covalently immobilized. Using a host‐guest inclusion complexation between β‐CD and biotin, a β‐CD/biotin‐Ab1/PSA/Ab2‐horseradish peroxidase (HRP) sandwich was formed on the electrode surface. The analytical signal was produced via electrochemical reduction of THox, generated by biocatalytic oxidation of the THred in the presence of HRP/H2O2. Under optimal conditions, the proposed sensor responded linearly to PSA in the range from 10.0 pg mL−1 to 25.0 ng mL−1, with a low detection limit of 6.7 pg mL−1 (S/N=3). Kinetic parameters of the interaction of β‐CD with Ab1 were also investigated. Finally, the applicability of the immunosensor was successfully investigated for the detection of PSA in human serum samples.  相似文献   
64.
Herein, we report the synthesis and adsorption property of a novel chelating fiber containing azido group. Firstly, the brominated fiber (PP‐St‐DVB‐Br) was obtained via the reaction of polypropylene‐(g)‐styrene‐divinylbenzene fiber (PP‐St‐DVB) with bromine in CH2Cl2 solution. Then, azido chelating fiber (PP‐St‐DVB‐N3) was prepared by azidation of PP‐St‐DVB‐Br fiber. Its structure and properties were characterized by Fourier transform infrared, elemental analysis, thermogravimetric analysis, and chemical titration, respectively. The micromophology and functional group distribution in fibrous matrix were investigated by scanning electron microscopy‐energy dispersive spectroscopy. The results show that the chelating fiber has high functional group contents (2.11 mmol/g for PP‐St‐DVB‐N3) and uniform distribution. Different from granulate chelating resin, the novel fibrous adsorbent possesses excellent adsorption ability for Hg(II) and Pb(II) ions (408.9 mg/g for Hg2+ and 334.4 mg/g for Pb2+), and the adsorption capacity of the fiber has no loss until five cycles. The novel absorbent material shows the potential application prospect in the treatment of heavy metal wastewater. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   
65.
林松竹  崔巍  贾若琨  刘畅 《应用化学》2017,34(6):631-635
酚醛树脂(PF)因其具有良好的耐热性能和机械性能而被广泛应用。但其耐热性能已经满足不了现代航空航天技术的需求,研究发现,采用硼酸对酚醛树脂进行改性,可以制得具有优良耐高温性能的硼酚醛树脂(BPF)。采用硼酸酯法合成硼酚醛树脂,n(苯酚)∶n(甲醛)=1∶1.5时耐热性最佳。热分析结果表明,合成的BPF在1000℃条件下的残炭率为78%,其耐热性能明显优于传统的酚醛树脂。同时讨论了不同硼酸含量对BPF耐热性能的影响,当n(硼酸)∶n(苯酚)0.33∶1时,残炭率趋于稳定。此外,利用差示扫描量热仪(DSC)方法确定BPF预固化温度为160℃,后固化温度为220℃。  相似文献   
66.
氧化石墨(GO)结构层上的碳羟基(―C―OH)和边缘羧基(―COOH)在水介质中发生质子化反应解离出的H+具有阳离子可交换性。实验采用甲醛缩合法测量了GO的阳离子交换容量(CEC),用X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱和X射线光电子能谱(XPS)分析测试手段对GO阳离子交换过程中间产物的结构变化进行了分析。结果表明,GO的CEC高达541.48 mmol/100 g。NH_4~+和Ca~(2+)交换后的GO,保持稳定的层状结构,c轴方向层间距分别增大了0.1499和0.2905 nm。NH_4+和Ca~(2+)主要以层间可交换阳离子形式存在于层间域中,并与水分子形成可交换水化阳离子层,部分以[NH_4(H_2O)_6]+和[Ca(H_2O)_6]_2+的形式存在于结构层的边缘附近,共同平衡结构层水解产生的负电荷。  相似文献   
67.
介绍一种利用二乙基二硫代氨基甲酸钠分离后以EDTA滴定测定矿石中铝的新方法。锰矿样品用Na OH,Na_3PO_4和Na_2O_2混合熔剂熔融,消除Ca,Mg,Ti的干扰,用含无水乙醇的热水浸取,其中的Mn变为Mn O2沉淀析出,干过滤,定容。将滤液中和至弱酸性,加入二乙基二硫代氨基甲酸钠,一些金属阳离子形成难溶水的络合物而分离,再次过滤,一定量的滤液与过量的EDTA标准溶液反应,用锌标准溶液滴定剩余的EDTA,即得氧化铝的含量。该法采用二甲酚橙为指示剂,同时加入少量氯化十六烷基吡啶,滴定终点颜色突变明显,改善了测量精密度,操作易于掌握。样品测定结果的相对标准偏差为0.42%~1.08%(n=5),加标回收率为97.39%~99.94%。分析过程只需滴定一次,且不使用含铅、铜、氟溶液,方法便捷环保。  相似文献   
68.
主要以经典的算子半群理论为依据,研究了一类具有非线性热效应的耦合杆系统的长时间行为.首先在齐次边界条件和初始条件下,证明了系统解的存在唯一性;其次通过渐近先验估计,证明了系统有界吸收集的存在性;最后利用算子半群的分解技巧,得到了系统全局吸引子的存在性.  相似文献   
69.
研究了一类小容量污染环境中脉冲输入毒素对具有阶段结构的单种群生存问题,分别找到了种群生存与灭绝的阈值,利用不等式放缩技巧,得到了种群灭绝和持久生存的充分条件.利用MATLAB数值仿真,验证了理论结果的正确性,分析了毒素输入量,毒素输入周期及种群成长时间对种群生存的影响.  相似文献   
70.
ABSTRACT

A widely used method for obtaining silver nanoparticles uses plant extracts for reduction because of the presence of phytochemicals such as terpenoids, tannins, and flavonoids. Extracts of Flores sambuci, Hypericum perforatum, Lavandula angustifolia, Origanum vulgare, Rosmarinus officinalis, and Salvia officinalis were used for generating silver nanoparticles. The ultraviolet–visible spectra of silver nanoparticle solutions were correlated with variations of phytochemical characteristics to evaluate the plant extracts. These parameters were the antioxidant activity, total flavonoids, total tannins, total terpenoids, and total phenolics. Correlations between measurements of extracts’ phytoreductive characteristics were explained using Pearson coefficients. The results showed medium linear positive correlations for total tannins with the spectra of silver nanoparticle solutions. The antioxidant activity and total terpenoids presented medium linear negative correlations. Pearson coefficients between total phenolics and relative areas from ultraviolet–visible spectra from 350 to 600?nm were close to zero indicating no linear correlation.  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