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   3858篇
  免费   591篇
  国内免费   423篇
化学   2760篇
晶体学   43篇
力学   183篇
综合类   15篇
数学   430篇
物理学   1441篇
  2024年   3篇
  2023年   74篇
  2022年   128篇
  2021年   155篇
  2020年   156篇
  2019年   143篇
  2018年   116篇
  2017年   115篇
  2016年   172篇
  2015年   179篇
  2014年   202篇
  2013年   296篇
  2012年   375篇
  2011年   366篇
  2010年   219篇
  2009年   271篇
  2008年   223篇
  2007年   228篇
  2006年   220篇
  2005年   155篇
  2004年   145篇
  2003年   111篇
  2002年   89篇
  2001年   59篇
  2000年   68篇
  1999年   92篇
  1998年   66篇
  1997年   59篇
  1996年   77篇
  1995年   36篇
  1994年   40篇
  1993年   40篇
  1992年   33篇
  1991年   25篇
  1990年   24篇
  1989年   22篇
  1988年   14篇
  1987年   21篇
  1986年   9篇
  1985年   8篇
  1984年   14篇
  1983年   6篇
  1982年   6篇
  1981年   2篇
  1977年   1篇
  1976年   1篇
  1975年   1篇
  1974年   1篇
  1973年   1篇
  1957年   2篇
排序方式: 共有4872条查询结果,搜索用时 31 毫秒
101.
8—氮鸟嘌呤的极谱伏安行为   总被引:4,自引:0,他引:4  
张勇 《分析化学》1998,26(6):729-732
用循环伏安法(CV)、电流采样极诸法(SCP,即TAST)、常规脉冲极谱法(NPP)、微分脉冲极谱法(DPP)、线性扫描伏安法(LSV)、Osteryoung方波伏安法(OSWV)和计时库仑法(CC)等电化学技术研究了抗癌药物8-氮鸟嘌呤(8-azaguanine,guanazolo,简称8-AG)的极谱伏安行为.在 0. 1mol/L H2SO4底液中,8-AG有一良好的还原峰,峰电位(Ep)在-0. 95V(vs.Ag/AgCl,下同)附近,8-AG浓度在4×10-6~8×10-4mol/L范围内.峰高与浓度有良好的线性关系,线性相关系数r=0.9999~0.9910,检出限为1× 10-6mol/L.实验证明了该峰具有吸附性.本文提出了电极反应机理,它包括:酸性介质中8-AG的质子化、质子化的8-AG在汞电极上吸附以及完全不可逆的两电子还原过程.同时用量子化学计算方法(全略微分重叠法即CNDO/2)对8-AG和鸟嘌呤的各原子的净电荷以及Wiberg键级进行了计算,从理论上解释了8-AG的电化学还原机理。  相似文献   
102.
A new synthetic approach for the formation of ultrathin polymer films with customizable properties was developed. In this approach, the kinematic nature of proton collisions with simple organic molecules condensed on a substrate is exploited to break C-H bonds preferentially. The subsequent recombination of carbon radicals gives a cross-linked polymer thin film, and the selectivity of C-H cleavage preserves the chemical functionalities of the precursor molecules. The nature and validity of the method are exemplified with theoretical results from ab initio molecular dynamics calculations and experimental evidence from a variety of characterization techniques. Its applicability is demonstrated by the synthesis of ultrathin polymer films with precursor molecules such as dotriacontane, docosanoic acid, poly(acrylic acid) oligomer, and polyisoprene. The approach is fundamentally different from conventional chemical synthesis as it involves an unusual mix of physical and chemical processes including charge exchange, projectile penetration, kinematics, collision-induced dissociation, inelastic energy transfer, chain transfer, and chain cross-linking.  相似文献   
103.
杜卫红  安忠维 《合成化学》1997,5(2):205-208
从环己烯合成了1-酰基-4-氯环己烷,发现在其在AlCl3催化与苯,氯苯,溴苯等优先生成反式1-芳基-4-酰基环己烷,与联苯反应时选择性较差。  相似文献   
104.
本文研究了二(2,4,4-三甲基戊基)膦酸(Cyanex272)-上胺205-正庚烷乳状液膜分离Sc(Ⅲ)、Fe(Ⅲ)和Lu(Ⅲ)。考察了外相酸度、表面活性剂浓度、流动载体浓度及内相盐酸浓度对Sc(Ⅲ)迁移的影响。并探讨了该液膜体系分离Sc(Ⅲ)、Fe(Ⅲ)和Lu(Ⅲ)的可能性,结果表明,该体系对于稀土矿中Sc(Ⅲ)的分离与分析有良好的应用前景。  相似文献   
105.
The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.  相似文献   
106.
A general method for the synthesis of 2-xylose or glucuronic acid branched (1→3)-linked mannose oligosaccharides has been developed. As a typical example, the synthesis of the methyl glycoside of β-d-GlcpA-(1→2)-α-d-Manp-(1→3)-[β-d-Xylp-(1→2)-]α-d-Manp-(1→3)-[β-d-Xylp-(1→2)-]α-d-Manp, the repeating unit of the exopolysaccharide from Cryptococcus neoformans serovar A, was achieved in a regio- and stereoselective manner.  相似文献   
107.
During the fight against the new coronavirus epidemic, the "Physical Chemistry" team of Beijing Normal University used various network platforms and tools, such as MOOC of China University, Rain Classroom and WeChat Group in the teaching process. The exploration and practice of online learning of "Physical Chemistry" is carried out based on MOOC teaching, with student learning as the center and teacher guidance as the support. Taking the most difficult chapter of "fundamentals for statistical thermodynamic" as an example, we designed a complex teaching program that includes previews, watching MOOC videos in class, real-time online exercises, teachers' answers, and after-class reflection and questioning. The students were encouraged to learn independently through the reserved information, designed activities and assignments. Practice shows that the online course has cultivated the students' self-management ability, trained their critical thinking skills, and achieved good teaching results.  相似文献   
108.
利用X-射线衍射,扫描电镜,拉曼光谱,等离子发射光谱和比表面测定等方法研究了不同状态下失活及新鲜催化剂的结构,杂种类及含量。结果表明,超温使催化剂晶化明显,制备方法对催化剂结构有直接影响,再生使其强度降低,条形催化剂比较容易粉化,无机杂质是次要的失活原因。  相似文献   
109.
A novel hydrogen peroxide biosensor was developed based on the immobilization of horseradish peroxidase (HRP) in a TiO(2) sol-gel matrix on an electropolymerized phenazine methosulfate (PMS) modified electrode surface. Such membranes are of interest due to their high surface area, biological compatibility, and ease of fabrication. HRP entrapped in the TiO(2) matix was stable and retained its activity to a large extent. Cyclic voltammetry and amperometric measurements were employed to demonstrate the feasibility of electron transfer between immobilized HRP and the glassy carbon electrode via electropolymerized PMS. The influence of various experimental parameters such as operating potential, pH, temperature, and stability was investigated for optimum analytical performance. The biosensor provided a wide linear calibration range from 4.0x10(-6) M to 1.0x10(-3) M, with a detection limit of 8.0x10(-7) M at a signal-to-noise ratio of 3. The sensor retained 80% of its original activity after two months of operation.  相似文献   
110.
Silicon nitride powders were synthesized in an atmospheric-pressure convection-stabilized arc using silicon and ammonia as reactants. The morphology and particle size distributions of the silicon nitride particles were characterized by SEM, TEM, and electron diffraction analyses. The silicon nitride particles collected in the plasma reactor were formed by either gas-condensed phase reactions or chemical vapor reactions. The morphologies of the particles formed by gas-condensed phase reactions consisted of -Si3N4 prisms, -Si3N4 matte, -Si3N4 needles, and spaghetti-like whiskers. For the homogeneously nucleated particles, the morphologies included dendrites, needles, platelets, and amorphous particles. Most of the particles formed were aggregates with particle size distributions ranging from 500 to 1500 Å depending on the location of injection of the reactants.  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