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801.
Guangyong Xie Changtao Qian 《Journal of polymer science. Part A, Polymer chemistry》2008,46(1):211-217
A series of new mono β‐diiminato titanium complexes [(N(Ar)C(CH3))2 CH]TiCl3 ( 3a : Ar = 2.6‐F2C6H3; 3b : Ar = C6F5; 3c : Ar = 2.6‐Me2C6H3) have been synthesized and characterized. The crystal structure of 3a revealed that the β‐diiminato ligand in our complex is more close to the η2‐coordination mode with little delocalization of the double bonds, which is different from the strong delocalization in the ligands of η5‐coordinated (Tolnacnac)TiCl3 and η2‐coordinated (Dipnacnac)ZrCl3. The significant electronic effects of fluoro‐substituents on the olefin polymerization activity of mono β‐diiminato titanium complexes were found. Titanium complexes with fluorine‐containing β‐diiminato ligands, on activation with MMAO, are extremely active catalysts for polymerization of ethylene. The activity of copolymerization of ethylene and 1‐hexene is higher than homopolymerization of ethylene and increases with the increase of 1‐hexene concentrations, which show the positive “comonomer effect.” The molar percentage of 1‐hexene incorporation and polymer microstructures can also be modulated by the initial comonomer concentrations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 211–217, 2008 相似文献
802.
Tonggang Jiu Yuliang Li Huibiao Liu Xiaofeng Liu Li Jiang Junbo Li Cuihong Li Shu Wang 《Tetrahedron》2007,63(15):3168-3172
A simple and effective strategy for synthesis of bis-dipolar trimeric OPVs (a-g) with same push-pull electron groups at the two ends is presented. Their photophysical and electrochemical properties were investigated by UV-vis, fluorescence spectroscopies, and voltammetry techniques. A successful tuning in the emission color was achieved and the LUMO energy level was found to correlate with the Hammett constant of the respective substituents, providing a powerful strategy for prediction of the photoelectrical properties of the new chromophores. 相似文献
803.
In this study we present ab initio Hartree Fock molecular orbital calculations with complete geometry optimizations on some phenylalkylamines (PAAs) that are
clinically used as antiarrhythmic drugs. Pharmacophoric features of PAAs have been derived. An explanation of potency regulation
in PAAs has been suggested based on ion capturing vs. ion holding by the drug. Ion capturing by the drug is always electrostatically
highly favourable but has to be analysed in terms of conformational changes required and physiological accessibility of the
situation. Our results also seem to offer an explanation for inhibitory effect of Ca2+ ion concentration on binding affinity of PAAs. 相似文献
804.
Raj K. Bansal Neelima Gupta Govind Dixit Surendra K. Kumawat 《Journal of Physical Organic Chemistry》2009,22(2):125-129
Effect of the number and positions of the methoxycarbonyl substituents in 2‐phosphaindolizine on the feasibility of its Diels–Alder (DA) reaction with 1,3‐butadiene has been investigated theoretically at the density functional theory (DFT) level. Among the series of four differently substituted 2‐phosphaindolizines, 3‐methoxycarbonyl‐2‐phosphaindolizine does not undergo the DA reaction due to the highest activation barrier (29.49 kcal mol?1) and endothermicity, whereas the activation barrier of the corresponding reaction of 1,3‐bis(methoxycarbonyl)‐2‐phosphaindolizine is lowest (22.43 kcal mol?1) with exothermicity making it possible to occur. This reactivity trend is corroborated by FMO energy gaps as well as by global electrophilicity powers of the reactants. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
805.
Density functional theory study of substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of m‐G‐C6H4OFe(CO)2(η5‐C5H5) and m‐G‐C6H4SFe(CO)2(η5‐C5H5) 下载免费PDF全文
Qing Zeng Zucheng Li Yi‐Bo Wang Huaqiang Zhai Bin Liu Ou Tao Ling Dong Jun Guan Yujie Zhang 《Journal of Physical Organic Chemistry》2017,30(1)
The knowledge of accurate bond strengths is a fundamental basis for a proper analysis of chemical reaction mechanisms. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–O and Fe–S bond energies of (meta‐substituted phenoxy)dicarbonyl(η5‐cyclopentadienyl) iron [m‐G‐C6H4OFp ( 1 )] and (meta‐substituted benzenethiolato)dicarbonyl(η5‐cyclopentadienyl) iron [m‐G‐C6H4SFp ( 2 )] complexes. In this study, Fp is (η5‐C5H5)Fe(CO)2, and G is NO2, CN, COMe, CO2Me, CF3, Br, Cl, F, H, Me, MeO, and NMe2. The results show that Tao–Perdew–Staroverov–Scuseria and Becke's power‐series ansatz from 1997 with dispersion corrections functionals can provide the best price/performance ratio and accurate predictions of ΔHhet(Fe–O)'s and ΔHhet(Fe–S)'s. The excellent linear free energy relations [r = 1.00 (g, 1e), 1.00 (g, 2b)] among the ΔΔHhet (Fe–O)'s and δΔG0 of O?H bonds of m‐G‐C6H4OH or ΔΔHhet(Fe–S)'s and ΔpKa's of S?H bonds of m‐G‐C6H4SH imply that the governing structural factors for these bond scissions are similar. And, the linear correlations [r = ?0.97 (g, 1 g), ?0.97 (g, 2 h)] among the ΔΔHhet (Fe–O)'s or ΔΔHhet(Fe–S)'s and the substituent σm constants show that these correlations are in accordance with Hammett linear free energy relationships. The inductive effects of these substituents and the basis set effects influence the accuracy of ΔHhet(Fe–O)'s or ΔHhet(Fe–S)'s. The ΔΔHhet(Fe–O)'s(g) (1) and ΔΔHhet(Fe–S)'s(g)(2) follow the capto‐dative Principle. The substituent effects on the Fe–O bonds are much stronger than those on the less polar Fe–S bonds. Insight from this work may help the design of more effective catalytic processes. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
806.
807.
Simple method for determining of the isokinetic temperature value for the SNAr reactions in solution 下载免费PDF全文
The changes of the free energy of activation δ?G≠exp and the activation entropy δ?S≠ in the framework of the isokinetic relationship δ?G≠exp versus (Tiso ? Texp) δ?S≠ were explored quantitatively to predict the isokinetic temperature Tiso for the aromatic nucleophilic substitution reactions in solution. 相似文献
808.
为了探究褐煤热解过程中氧桥键C-O均裂这一重要反应, 选取α-O-4和β-O-4类结构单元作为褐煤模型化合物, 运用不同密度泛函计算了部分模型化合物中C-O的离解焓, 并以CBS-QB3作为理论基准值进行比较, 最后选取M05-2X进行离解焓计算. 结果显示, 对于选定的α-O-4和β-O-4类模型化合物, 其平均离解焓分别为51.0 kcal/mol和66.1 kcal/mol. 周围取代环境能显著影响C-O离解焓, 芳环上存在给电子基团(OH, OCH3和CH3)能降低C-O离解焓, 而吸电子基团COOH则能增加其离解焓. 然后深层次分析了取代基效应对C-O离解焓的影响. 此外, 分子内氢键的形成对离解焓也有很大的影响. C-O的离解焓与其键长没有特定的相关性, 不能简单的通过C-O键长来预测其离解焓. 相似文献
809.
提出了计算苯甲醛亚胺、N-苯基亚胺、N-甲基亚胺、N-异丙基亚胺中亚胺基氮原子15N NMR化学位移的经验公式:δcal=δ0n+Δα+Δβ+Δγ+c. 按亚胺基氮原子和碳原子上两类取代基的不同分别结合最小二乘法通过线性回归各得到5种取代基参数,计算结果分别以其化学位移数据为样本点作回归检验,置信度为99.5%,最大误差Δδ≤3.1,大约有95%的15N NMR化学位移计算值的计算误差小于3.0(相对误差小于0.3%). 初步分析了芳香族亚胺苯环上对位取代基对亚胺基氮原子化学位移的影响. 相似文献
810.