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   1209篇
  免费   34篇
  国内免费   179篇
化学   1355篇
晶体学   2篇
力学   1篇
综合类   16篇
数学   1篇
物理学   47篇
  2024年   3篇
  2023年   10篇
  2022年   19篇
  2021年   21篇
  2020年   34篇
  2019年   16篇
  2018年   21篇
  2017年   31篇
  2016年   28篇
  2015年   32篇
  2014年   28篇
  2013年   60篇
  2012年   88篇
  2011年   47篇
  2010年   31篇
  2009年   55篇
  2008年   38篇
  2007年   88篇
  2006年   74篇
  2005年   61篇
  2004年   64篇
  2003年   57篇
  2002年   38篇
  2001年   29篇
  2000年   43篇
  1999年   45篇
  1998年   49篇
  1997年   27篇
  1996年   40篇
  1995年   37篇
  1994年   37篇
  1993年   40篇
  1992年   36篇
  1991年   28篇
  1990年   24篇
  1989年   14篇
  1988年   10篇
  1987年   2篇
  1986年   11篇
  1984年   3篇
  1982年   2篇
  1979年   1篇
排序方式: 共有1422条查询结果,搜索用时 15 毫秒
991.
Binding properties and structural changes of human growth hormone (hGH) due to the interaction by cobalt ion (Co2+) were done at 27°C in NaCl solution, 50 mM, using different techniques of UV-Vis spectroscopy, circular dichroism (CD), isothermal titration calorimetry (ITC) and differential scanning calorimetry (DSC) techniques. There is a set of three identical and non-interacting binding sites for cobalt ions. The intrinsic association equilibrium constant and the molar enthalpy of binding obtained by ITC are 0.80 mM−1 and −16.70 kJ mol−1, respectively. The intrinsic association equilibrium constant obtained by a standard isothermal titration UV-Vis spectrophotometry method is also 0.79 mM−1, which is in good agreement with the value obtained from ITC. The Gibbs free energy and entropy changes due to the binding of cobalt ion on hGH are −16.67 kJ mol−1 and −0.1 J K−1 mol−1, respectively. Energetic domains analysis by DSC shows that phase transition of hGH in the presence of cobalt occurs at one main transition. Deconvolution of the main transition provides two sub-transitions with different values of the melting point and enthalpy of unfolding (33°C and 164 kJ mol−1 for the first and 49°C and 177 kJ mol−1 for the second, respectively). Interaction of cobalt ions with hGH prevents aggregation by an affect on the hydrophobicity of the protein macromolecule and provide useful information about its structure due to becoming reversible of protein thermal denaturation.  相似文献   
992.
Thermodynamics of the formation of molecular complexes of synthetic and natural zinc(ii) porphyrins with n-propylamine and glycine methyl ester in benzene was investigated. Study of the — complexes of zinc(ii) porphyrins with benzene demonstrated that thermodynamic stability of the axial complexes depends on both the structure of the porphyrin macrocycle and the ability of the corresponding metalloporphyrins to form energetically stable — complexes with aromatic molecules.  相似文献   
993.
Meloun M  Syrový T  Vrána A 《Talanta》2004,62(3):511-522
The mixed dissociation constants of five drug acids—ambroxol, antazoline, naphazoline, oxymetazoline and ranitidine—at various ionic strengths I of range 0.01 and 1.0 and at temperatures of 25 and 37 °C were determined using SQUAD(84) regression analysis of the pH-spectrophotometric titration data. A proposed strategy of efficient experimentation in a protonation constants determination, followed by a computational strategy for the chemical model with a protonation constants determination, is presented on the protonation equilibria of ambroxol. The thermodynamic dissociation constant pKaT was estimated by non-linear regression of {pKa, I} data at 25 and 37 °C: for ambroxol and 8.25 (4), log  and 11.83 (8), for antazoline and 7.83 (6), and 9.55 (2), for naphazoline and 10.63 (1), for oxymethazoline and 10.77 (7), pKa,2T=12.03(3) and 11.82 (4) and for ranitidine and 1.77 (1). Goodness-of-fit tests for various regression diagnostics enabled the reliability of the parameter estimates to be found.  相似文献   
994.
Conditions are established for quantitative electrochemical generation of cobalt (III) at a glassy carbon working electrode in anhydrous acetic acid in the presence of potassium acetate, sodium acetate or sodium perchlorate. In anhydrous alkali-metal acetate solutions cobalt (III) is as stable as in the presence of acetic anhydride. The concentration of cobalt(III) in the solution is considerably decreased in the presence of small amounts of water. This phenomenon is much more pronounced in sodium perchlorate supporting electrolyte. Coulometric titration methods for the determination of hydroquinone, 2-methylhydroquinone and ascorbic acid with the generated oxidant have been developed. The errors of the determinations are less than ±2%.  相似文献   
995.
陆为林 《分析化学》1995,23(8):937-940
本文报道了铜合金中铜的示波滴定方法。样品酸溶后,用抗坏血酸还的Cu^2+为Cu^+,加入过量的四苯硼钠,在PH5-6的HAc-NaAc缓冲溶液中,定量形成Cu-TPB沉淀,过量的TPB^-,以Tl^+标准溶液进行示波滴定,铜合金中共存元素不干扰测定。铜的测定回收率99.8%-100.1%。进行了多种铜合金中铜含量的测定,结果令人满意。  相似文献   
996.
Iron(II) in acetic acid medium and the presence of pyrophosphate is used as a new reductimetric reagent and utilised for the spectrophotometric titration of microgram quantities of six oxazine dyes. All these dyes are rapidly and quantitatively reduced to their colourless leuco-bases in a 2-electron reduction with iron(II), provided the medium contains 1 or 3M acetic acid (depending on the dye) and at least 0.1M pyrophosphate. The redox potentials of the iron(III)/iron(II) couple at different pyrophosphate and acetic acid concentrations have been measured and a method for purification of some of the commercially impure oxazine dyes is suggested.  相似文献   
997.
将固定pH滴定法结合求解一元线性回归方程组应用于极弱酸(碱)混合体系中各组分含量的同时测定。测定了六次甲基四胺-硫酸钠和六次甲基四胺-乙酸钠混合体系中各组分的含量,回收率为96.7%~103.2%。  相似文献   
998.
本文首次报道了八对磺酸钠八羟基羰基甲氧基杯[8]芳烃酸离解常数的测定结果,还以pH滴定法对该试剂与过渡元素的各种配合物进行系统研究,发现此配体能形成MHnL(n=1-7)型配合物。  相似文献   
999.
电容滴定法测定自组装膜表面酸度   总被引:1,自引:0,他引:1  
聂蓓  杨秀荣 《分析化学》2002,30(5):627-631
利用本实验室自制的电容法时测量装置对巯基丙酸自组装膜的表面酸度进行电容滴定研究,相对于先前的测量和滴定技术。本方法可同时对界面电容值和溶液的PH值进行实时测定。同时对影响电容测定和自组装膜表面pKa值的各种因素进行了详细的讨论。 滴定结果和文献报道相近,证明了测定方法和仪器的可靠性实用性。  相似文献   
1000.
Isothermal titration calorimetry (ITC) and potentiometric titration were used to study the protonation properties of the 4-vinylpyridine (4-VP) moiety in cationic poly(N-isopropylacrylamide-co-4-vinylpyridine) colloidal microgels [poly(NIPAM-co-4-VP)]. Calorimetric pH titrations were performed using microgels of different 4-VP content and the influence of ionic strength and counter ions have been examined. The calorimetric titration output consists of several thermal contributions reflecting the complex nature of the interactions in the aqueous microgel dispersions. In contrast to the potentiometric results, the calorimetric titration data could not be completely described by a theoretical model solely taking into account protonation equilibria. Deviations from the proposed model correlate with swelling or shrinking of the gel particles. The calorimetric results also reveal a pronounced counter-ion effect of perchlorate compared to chloride ions. In the presence of perchlorate ions, small secondary thermal effects accompany protonation of the 4-VP moiety due, in part, to kinetically limited conformational changes in the co-polymer microgel.  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