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   16448篇
  免费   2498篇
  国内免费   3347篇
化学   12950篇
晶体学   455篇
力学   742篇
综合类   383篇
数学   1929篇
物理学   5834篇
  2024年   49篇
  2023年   210篇
  2022年   559篇
  2021年   578篇
  2020年   583篇
  2019年   608篇
  2018年   484篇
  2017年   593篇
  2016年   684篇
  2015年   825篇
  2014年   1033篇
  2013年   1280篇
  2012年   1434篇
  2011年   1492篇
  2010年   1253篇
  2009年   1229篇
  2008年   1441篇
  2007年   1198篇
  2006年   1152篇
  2005年   1000篇
  2004年   749篇
  2003年   620篇
  2002年   665篇
  2001年   529篇
  2000年   420篇
  1999年   295篇
  1998年   201篇
  1997年   147篇
  1996年   137篇
  1995年   117篇
  1994年   106篇
  1993年   101篇
  1992年   79篇
  1991年   105篇
  1990年   53篇
  1989年   64篇
  1988年   26篇
  1987年   36篇
  1986年   32篇
  1985年   27篇
  1984年   18篇
  1983年   12篇
  1982年   7篇
  1981年   18篇
  1980年   11篇
  1979年   8篇
  1978年   6篇
  1977年   4篇
  1976年   5篇
  1973年   2篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
201.
A highly sensitive and selective glucose biosensor has been developed based on immobilization of glucose oxidase within mesoporous carbon nanotube–titania–Nafion composite film coated on a platinized glassy carbon electrode. Synergistic electrocatalytic activity of carbon nanotubes and electrodeposited platinum nanoparticles on electrode surface resulted in an efficient reduction of hydrogen peroxide, allowing the sensitive and selective quantitation of glucose by the direct reduction of enzymatically‐liberated hydrogen peroxide at ?0.1 V versus Ag/AgCl (3 M NaCl) without a mediator. The present biosensor responded linearly to glucose in the wide concentration range from 5.0×10?5 to 5.0×10?3 M with a good sensitivity of 154 mA M?1cm?2. Due to the mesoporous nature of CNT–titania–Nafion composite film, the present biosensor exhibited very fast response time within 2 s. In addition, the present biosensor did not show any interference from large excess of ascorbic acid and uric acid.  相似文献   
202.
203.
Many cancer treatments including photodynamic therapy (PDT) utilize reactive oxygen species (ROS) to kill tumor cells. However, elevated antioxidant defense systems in cancer cells result in resistance to the therapy involving ROS. Here we describe a highly effective phototherapy through regulation of redox homeostasis with a biocompatible and versatile nanotherapeutic to inhibit tumor growth and metastasis. We systematically explore and exploit methylene blue adsorbed polydopamine nanoparticles as a targeted and precise nanocarrier, oxidative stress amplifier, photodynamic/photothermal agent, and multimodal probe for fluorescence, photothermal and photoacoustic imaging to enhance anti-tumor efficacy. Remarkably, following the glutathione-stimulated photosensitizer release to generate exogenous ROS, polydopamine eliminates the endogenous ROS scavenging system through depleting the primary antioxidant, thus amplifying the phototherapy and effectively suppressing tumor growth in vitro and in vivo. Furthermore, this approach enables a robust inhibition against breast cancer metastasis, as oxidative stress is a vital impediment to distant metastasis in tumor cells. Innovative, safe and effective nanotherapeutics via regulation of redox balance may provide a clinically relevant approach for cancer treatment.

Amplified oxidative stress achieved by modulating redox homeostasis with PDA–MB for highly effective synergistic phototherapy to inhibit primary tumors and metastases.  相似文献   
204.
23-Hydroxybetulinic acid is a newly isolated derivative of betulinic acid. The agent exhibits potential anti-tumor activity and functions in this regard via apoptosis. In support of pharmacokinetic and toxicological evaluations, a new assay based on liquid chromatography/mass spectrometry (LC/MS) was developed for the quantitative analysis of 23-hydroxybetulinic acid. Sample preparation consisted of extraction of the plasma by the addition of methylene chloride followed by centrifugation. Aliquots of the supernatant were analyzed using an isocratic reversed-phase high-performance liquid chromatography (HPLC) system coupled to a negative ion electrospray mass spectrometer. Molecules of 23-hydroxybetulinic acid and the internal standard limonin were detected using selected ion monitoring at m/z 471 and 469, respectively. The limit of detection of 23-hydroxybetulinic acid was 0.05 pg (0.11 fmol) injected on-column (10 pg/mL, 5 microL injection volume), and the limit of quantitation was 10 pg (21.19 fmol, 2 ng/mL, 5 muL injection volume). 23-Hydroxybetulinic acid was stable in plasma samples at -20 degrees C for at least 3 weeks. The intra-day and inter-day coefficients of variation of the assay were 3.0 and 4.8%, respectively. The utility of the assay was demonstrated by measuring 23-hydroxybetulinicacid in mouse plasma following intragastric administration (IG) in vivo. Pharmacokinetic parameters were calculated using the 3P97 pharmacokinetic software package. A two-compartment, first-order model was selected for pharmacokinetic modeling. The result showed that after IG of 200 mg/kg 23-hydroxybetulinic acid, the plasma concentrations reached peaks at 2 h with C(max) of 3.1 microg/mL. The 200 mg/kg 23-hydroxybetulinic acid suspension IG doses were found to have long elimination half-lives of 25.6 h and low bioavailability of 2.3%. No interference was noted due to endogenous substances. These analytical methods should be of value in future studies related to the development and characterization of 23-hydroxybetulinic acid.  相似文献   
205.
Both proteinogenic and non proteinogenic α-amino acids are of particular interest as constituents of peptide factors, peptidomimetics and antibiotics for the construction of modern selective drugs. [1] Furthemore, α-amino acid derivatives are interesting building units for chiral-pool syntheses of enantiomerically pure natural products. [2] Numerous efforts in modern organic synthesis are centered on the synthesis of enantiomerically pure α-amino acids. [3] During the past three decades efficient methods of asymmetric synthesis of α-amino acids have been developed; most of them are based on electrophilic transformations of organometallic intermediates. [4] Using the concept that the chirality of the carbohydrates can be exploited for diastereoselective reactions, Kunz and his cooperator had developed a Strecker synthesis with glycosyl amines as chiral auxiliaries. [5]  相似文献   
206.
戴志晖  方敏 《分析测试学报》2006,25(Z1):199-200
β-烟酰胺腺嘌呤二核苷酸(NADH),俗称还原型辅酶, 是参与酶催化反应中的一种重要的辅酶, 大约有几百种脱氢酶催化底物反应后能引起NADH含量的变化,因此,电化学检测NADH是传感器研究中1个重要的课题.由于在电极上的氧化有较大的过电位并且不可逆[1],如果在高电位下检测 NADH,试样中其他的电活性物质就会干扰测定,并且NADH在高电位氧化过程中会发生副反应而污染电极,使测定重复性变差[2].人们正努力寻找能够降低NADH氧化过电位的新的材料.近来,介孔分子筛子以其独特的结构和催化作用能够为电子传递提供环境以及可以抵抗生物降解而受到关注[3].介孔分子筛具有大的比表面, 高机械、热、化学稳定性, 好的吸附和渗透性,有着适度的维度能够作为一种通用的纳米反应器.这里采用Ti-MCM-41修饰GCE来降低NADH的过电位.实验表明该修饰电极对NADH的催化电流很大,稳定性好,响应速度快,实现了对NADH的低电位检测.  相似文献   
207.
惠国华  吴莉莉  潘敏  陈裕泉  李婷  张孝彬 《分析化学》2006,34(12):1813-1816
介绍了一种基于定向纳米碳管的气敏传感器,以生长定向纳米碳管的氧化铝模板作为阳极,铝板作为阴极,利用纳米碳管的尖端发射效应,在较低的电压下使气体产生放电现象。通过对纳米碳管在气体中击穿电压和放电电流的测量,实现对气体的定性定量检测。同时纳米碳管气敏传感器还具有体积小、灵敏度高、稳定性好、响应速度快、在常温常压下即可进行检测等优点,具有较好的应用前景。  相似文献   
208.
芳基-芳基偶联反应的研究进展   总被引:4,自引:0,他引:4  
肖玉梅  傅滨  覃兆海 《有机化学》2005,25(7):751-762
综述了近年来芳基-芳基偶联反应的研究进展, 包括不同类型芳基-芳基偶联反应的特点、机理和应用, 尤其是对立体选择性和区域选择性的偶联方法进行了重点介绍.  相似文献   
209.
草莓型SiO2/PMMA纳米复合微球的制备   总被引:5,自引:0,他引:5  
在纳米二氧化硅水分散体系中,借助于碱性辅助单体1-乙烯基咪唑(1-VID)与未改性纳米二氧化硅表面羟基之间的酸-碱作用,通过1-VID与甲基丙烯酸甲酯(MMA)的自由基共聚合,制备了草莓型的SiO2/PMMA复合微球.整个反应过程中,纳米二氧化硅无需表面处理,体系中无需另外加入乳化剂或助乳化剂,微球表面吸附的纳米二氧化硅对颗粒起稳定作用.用动态光散射粒度分布仪测得复合微球粒径在120-330nm之间,热重分析结果表明,复合微球中二氧化硅含量介于15%-20%之间.透射电镜和扫描电镜显示所得复合微球具有草莓型结构,二氧化硅富集在表面.  相似文献   
210.
1 INTRODUCTION The chemistry of copper compounds has been extensively investigated and the relationship be- tween structure and reactivity, ranging from indus- trial catalysis to biochemistry activity, is of major importance. For binuclear copper(II) complexes equa- torially bridged by pair of hydroxide[1] or alkoxide[2, 3] groups, satisfactory linear correlation is found be- tween the Cu–O–Cu bridging angle and spin coupling between the metal centers. However, for binuclear copper(I…  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