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   3497篇
  免费   298篇
  国内免费   442篇
化学   907篇
晶体学   7篇
力学   128篇
综合类   138篇
数学   2525篇
物理学   532篇
  2024年   5篇
  2023年   19篇
  2022年   55篇
  2021年   89篇
  2020年   91篇
  2019年   91篇
  2018年   83篇
  2017年   95篇
  2016年   111篇
  2015年   78篇
  2014年   162篇
  2013年   289篇
  2012年   154篇
  2011年   203篇
  2010年   180篇
  2009年   230篇
  2008年   232篇
  2007年   247篇
  2006年   196篇
  2005年   191篇
  2004年   186篇
  2003年   193篇
  2002年   177篇
  2001年   123篇
  2000年   98篇
  1999年   119篇
  1998年   104篇
  1997年   94篇
  1996年   58篇
  1995年   54篇
  1994年   44篇
  1993年   26篇
  1992年   24篇
  1991年   16篇
  1990年   20篇
  1989年   17篇
  1988年   12篇
  1987年   9篇
  1986年   9篇
  1985年   8篇
  1984年   10篇
  1983年   5篇
  1982年   3篇
  1981年   8篇
  1980年   5篇
  1979年   3篇
  1977年   3篇
  1974年   2篇
  1959年   1篇
  1936年   2篇
排序方式: 共有4237条查询结果,搜索用时 31 毫秒
71.
刘秀贵 《数学进展》2006,35(6):733-738
本文证明:当p≥7任意奇素数,3≤s相似文献   
72.
73.
74.
吴贝  杨大成  沈怡  邓勇  钟裕国 《有机化学》2007,27(9):1110-1115
根据RGD序列肽的构效关系, 设计并合成了一系列以5-氨基-1,3-二氢-1,3-二氧-异吲哚-2-丙酸为分子骨架的新化合物. 其中间体和目标物的化学结构经1H NMR, MS和元素分析确证. 体外初步生物活性筛选结果表明, 目标物在10-5 mol/L浓度下对bFGF诱导的鸡胚绒毛尿囊膜新生血管生成有显著抑制活性.  相似文献   
75.
The Fermi and Coulomb holes of the 21 S state of the helium isoelectronic sequence are investigated. Several interesting differences between the results obtained and those which might be expected on the basis of the corresponding 23 S state are pointed out and discussed.  相似文献   
76.
77.
Heat divided by ligand concentration vs. heat, similar to the Scatchard plot, was introduced to obtain the equilibrium constant (K) and the enthalpy of binding (DH) using isothermal titration calorimetry data. Values of K and DH obtained by this linear pseudo-Scatchard plot for a system with a set of independent binding sites (such as binding fluoride ions on urease and monosaccharide methyl a-D-mannopyranoside on concavalin A) were remarkably like that obtained from a normal fitting Wiseman method and other our technical methods. On applying this graphical method to study the binding of copper ion on myelin basic protein (MBP), a concave downward curve obtained was consistent with the positive cooperativity in the binding. A graphical fitting by simple method for determination of thermodynamic parameters was also introduced. This method is general, without any assumption and restriction made in previous method. This general method was applied to the product inhibition study of adenosine deaminase. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   
78.
AM1 calculations gave the proton affinities of different types of donor sites in tetrakis-3,4-(1,2,5-thiadiazolo)porphyrazine, H2{[SN2)4PA}, and protonation of the meso-nitrogen atoms was found to be favored. A spectrometric study showed that the basicity of the meso-nitrogen atoms of the porphyrazine macrocycle is strongly diminished and these atoms in CF3CO2H are involved in an incomplete acid-base interaction (ABI) to give acid solvates, while a complete ABI (protonation) is found only in the presence of sulfuric acid. The basicity constants of the meso-nitrogen atoms were determined spectrophotometrically in CF3CO2H-H2SO4. The kinetics of decomposition of the macrocyclic chromophore in concentrated sulfuric acid was studied and a possible mechanism for this process was proposed.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 278–287, February, 2005.  相似文献   
79.
This communication will demonstrate the existence of a thermodynamic molecular switch in the pairwise, sequence‐specific hydrophobic interaction of Ile–Ile, Leu–Ile, Val–Leu, or Ala–Leu over the temperature range of 273–333 K reported by Nemethy and Scheraga in 1962. Based on Chun's development of the Planck–Benzinger methodology, the change in inherent chemical bond energy at 0 K, ΔH°(T0), is 3.0 kcal mol?1 for Ile–Ile, 2.4 for Leu–Ile, 1.8 for Val–Leu, and 1.2 kcal mol?1 for Ala–Leu. The value of ΔH°(T0) decreases as the length of the hydrophobic side chain decreases. It is clear that the strength and stability of the hydrophobic interaction is determined by the packing density of the side chains, with Ala–Leu being the most stable. At 〈Tm〉, the thermal agitation energy, $\int^{T}_{0}\Delta Cp^{\circ}(T)\,dT$, is about five times greater than ΔH°(T0) in each case. Additionally, the thermal agitation energy for the same series, evaluated at 〈Tm〉, decreases in the same order, that is, as the length of the side chain decreases. This pairwise, sequence‐specific hydrophobic interaction is highly similar in its thermodynamic behavior to that of other biological systems, except that the negative Gibbs free energy change minimum at 〈Ts〉 occurs at a considerably higher temperature, 355 K compared to about 300 K. The melting temperature, 〈Tm〉, is also high, 470 K compared to 343 K in a biological system. The implication is that the negative Gibbs free energy minimum at a well‐defined 〈Ts〉 has it origin in the hydrophobic interactions, which are highly dependent on details of molecular structure. In addition to the four specific dipeptide interactions described, we have shown in our unpublished work the existence of a thermodynamic molecular switch in the interactions of 32 dipeptides wherein a change of sign in ΔCp°(T)reaction leads to a true negative minimum in the Gibbs free energy of reaction, and hence, a maximum in the related Keq. Indeed, all interacting biological systems that we have thus far examined using the Planck–Benzinger approach point to the universality of thermodynamic molecular switches. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001  相似文献   
80.
“Leaching” or “etching” by strong mineral acids seems to be a necessary pretreatment step for the most commonly used deactivation procedures of glass capillaries by reaction with either polyethylene glycol or silylation reagents. The acidic sites which are formed on the surface during this acid treatment cannot be completely removed by the subsequent deactivation process. This drawback can be overcome by performing the leaching with water vapour, resulting in an accumulation of cations at the surface and a decrease in the number of silanol groups. Capillaries of this type show excellent properties for the chromatography of strongly basic compounds. After the wash-out of the alkaline surface layer, the acidity of the support is suited for the chromatography of strongly basic as well as strongly acidic compounds. Due to a lack of reactive acidic sites, special deactivation procedures have to be applied to capillaries produced in this way.  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