全文获取类型
收费全文 | 3497篇 |
免费 | 298篇 |
国内免费 | 442篇 |
专业分类
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 |
出版年
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.
72.
73.
74.
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.
P. A. Stuzhin E. A. Pozdysheva O. V. Mal’chugina I. A. Popkova C. Ercolani 《Chemistry of Heterocyclic Compounds》2005,41(2):246-254
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.
Paul W. Chun 《International journal of quantum chemistry》2001,85(6):697-712
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.
Surface modification of soft-glass capillaries for gas chromatography by treatment with water vapour
“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