全文获取类型
收费全文 | 724篇 |
免费 | 41篇 |
国内免费 | 4篇 |
专业分类
化学 | 615篇 |
晶体学 | 4篇 |
力学 | 6篇 |
数学 | 39篇 |
物理学 | 105篇 |
出版年
2024年 | 1篇 |
2023年 | 10篇 |
2022年 | 20篇 |
2021年 | 36篇 |
2020年 | 26篇 |
2019年 | 25篇 |
2018年 | 34篇 |
2017年 | 21篇 |
2016年 | 42篇 |
2015年 | 27篇 |
2014年 | 29篇 |
2013年 | 55篇 |
2012年 | 47篇 |
2011年 | 74篇 |
2010年 | 22篇 |
2009年 | 29篇 |
2008年 | 37篇 |
2007年 | 34篇 |
2006年 | 41篇 |
2005年 | 35篇 |
2004年 | 28篇 |
2003年 | 27篇 |
2002年 | 22篇 |
2001年 | 3篇 |
2000年 | 13篇 |
1999年 | 3篇 |
1998年 | 5篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1994年 | 6篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1985年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1975年 | 2篇 |
1969年 | 1篇 |
排序方式: 共有769条查询结果,搜索用时 718 毫秒
101.
Synthesis,Characterization, and Catalytic Activity of New Cu(II) Complexes of Schiff Base: Effective Catalysts for Decolorization of Acid Red 37 Dye Solution
下载免费PDF全文
![点击此处可从《国际化学动力学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
In this paper, three new Cu(II) Schiff base complexes with three different anions (acetate, chloride, and nitrate) were successfully synthesized and characterized by elemental analysis, mass spectra, molar conductance, FT‐IR, NMR,UV–vis spectroscopy, magnetic moment, ESR, and thermal analysis. The catalytic performances of these complexes in decolorization of azo dye, Acid Red 37, were evaluated. Copper(II) complexes were found to be an efficient catalyst for decolorization of Acid Red 37 in the presence of hydrogen peroxide. The catalytic investigation revealed that the Cu(II) complex with acetate anion (complex 1 ) performed the highest catalytic activity. The kinetics of the decolorization of AR37 with this catalyst was studied, and the observed rate constant was determined. The effects of different reaction parameters such as catalyst dosage, solution pH, initial concentration of H2O2, dye solution, and reaction temperature on the reaction rate constant were studied. The best reacting conditions should be catalyst dosage = 0.004 g, initial pH 4.0, [H2O2]0 = 0.8 M, and [AR37]0 = 1.16 M at temperature 25°C. Under these conditions, about 99% of AR37 was decolorized within 60 min. The results indicated that the Cu(II) complex with the acetate anion is a promising catalyst for wastewater treatment. 相似文献
102.
Twist bend nematic (NTB)-forming 9OCCHP5 and 11OCCHP5 dimers were synthesised by one-step condensation of 4-(4-pentylcyclohexyl) benzoic acid and alkyl diol with yields as high as 80%. Although each dimer formed the NTB phase only during the cooling process in a narrow temperature width as large as 4°C, their equiweight mixture formed an NTB phase during both the heating and cooling processes, displaying elliptical polygonal domains and rope-like optical texture. The NTB temperature range became wider by 29–38°C and reduced the orientational order parameter significantly from 0.39 to 0.29 with decreasing temperature. 相似文献
103.
M. S. A. Abdel-Mottaleb E. Hamed M. Saif Hoda S. Hafez 《Journal of inclusion phenomena and macrocyclic chemistry》2018,92(3-4):319-327
This paper addresses modelling the nature of interactions between β-CD and some coumarins including recently reported novel sulphur analogues to form inclusion complexes of appealing medicinal, photochemical and photophysical properties. The binding energy and the total stabilization energy (EONIOM) are used to confirm the most favorable inclusion complex structure. Thermodynamic parameters reveal exothermic inclusion reaction in gas phase. Thermal stability of fluorescent enzyme substrate of coumarin nucleus increases in the order: gas?<?cyclohexane?<?water, indicating better stability in water. Furthermore, molecular characteristics such as optimized geometries, MO’s and electrostatic potential energy map surfaces and energies are reported and correlated with some reactivity indices. Our results validated the experimentally available data reported in the literature. Inclusion complexes of β-CD with coumarins should result in improving its laser efficiency in environmentally benign aqueous medium. 相似文献
104.
Ahmed M. M. Gabr Hoda B. Mabrok Emam A. Abdel-Rahim Mohamed K. El-Bahr Iryna Smetanska 《Natural product research》2018,32(15):1867-1871
Hairy root culture is a promising alternative method for the production of secondary metabolites. In this study, transformed root of Linum usitatissimum was established using Agrobacterium rhizogenes A4 strain from root cultures for lignans, phenolic acids and antioxidant capacity determination. Total lignin content (secoisolariciresinol diglucoside, secoisolariciresinol and matairesinol) was 55.5% higher in transformed root cultures than in the non-transformed root culture. Secoisolariciresinol was detected in higher concentration (2.107 μmol/g DM) in the transformed root culture than non-transformed culture (1.099 μmol/g DM). Secoisolariciresinol diglucoside and matairesinol were exclusively detected in the transformed root culture, but were not found in the non-transformed root culture. The overall production of phenolic acids in transformed roots was approximately 3.5 times higher than that of the corresponding non-transformed culture. Free radical scavenging DPPH˙ and ABTS˙+ assays showed 2.9-fold and 1.76-fold higher anti-oxidant activity in transformed root culture as compared to non-transformed. 相似文献
105.
Takashi Mino Kohei Watanabe Takumu Akiyama Yuki Mizutani Kazuki Miura Masatoshi Hashimoto Yasushi Yoshida Masami Sakamoto 《Tetrahedron》2018,74(28):3871-3878
We previously reported the synthesis of BICMAP (1a) via 6-diphenylphosphino-2,3-dihydrobenzofuran as a key intermediate. However, we did not successfully synthesize BICMAP analogues via a similar synthetic route. Herein we report the second-generation synthesis of BICMAP and its derivatives via diethylphosphonate as a key intermediate. 相似文献
106.
Hoda Yahyavi Majid M. Heravi Mohammad Mahdavi Alireza Foroumadi 《Tetrahedron letters》2018,59(2):94-98
The simple and facile strategy for the synthesis of 2,3-disubstituted-chromeno[4,3-b]pyrrole-4(1H)-ones has been established. This method describes the Kornblum oxidation reaction of acetophenones, followed by the Knoevenagle treatment of the resulted (het)arylglyoxals with active methylene compounds and consequently iodine-activated Michael type reaction with 4-amino coumarin in a one-pot manner to afford disubstituted chromeno[4,3-b]pyrrole-4(1H)-one derivatives. 相似文献
107.
Kitani S Sugawara K Tsutsumi K Morimoto T Kakiuchi K 《Chemical communications (Cambridge, England)》2008,(18):2103-2105
3-Arylthiochromone derivatives were synthesized as new photolabile protecting groups, in which the photoreactivity was switchable based on oxidation of the sulfur atom (sulfide and sulfone); the protected substrates , released the corresponding alcohols, amines or carbonxylic acids almost quantitatively under UV-light in neutral condition and the photoproduct showed high fluorescence intensity. 相似文献
108.
Masato Tominaga Kazuki Soejima Isao Taniguchi 《Journal of Electroanalytical Chemistry》2008,617(1):78-84
Ferritin-immobilized poly(l-lysine)-modified electrodes showed well-defined redox waves representing ferritin. Cathodic and anodic peak currents obtained from cyclic voltammograms were proportional to potential sweep rates. From charge flow values during oxidation or reduction reactions calculated by peak areas in cyclic voltammograms, and the surface coverage of ferritin, reacted iron atoms per ferritin molecule were calculated. Obtained numbers of reacted iron atoms were significantly smaller than expected values from iron atoms at ferrihydrite core surfaces of ferritin, which would be caused by the rate-determining ion flow through ion channels of ferritin to compensate for charges in the ferritin cavity. Anodic and cathodic peak potentials in cyclic voltammograms were significantly dependent on cationic species in the solution, though voltammetric shapes and peak currents were independent of cations. From the obtained results that structural changes in ferritin were not detected by fluorescent spectra, it is thought that the cationic dependence on ferritin redox peak potentials is caused by ferritin cores. 相似文献
109.
The size and shape of the chiral cavity of a macrocyclic receptor were tuned by the alteration of the binaphthyl moiety to improve the chiral recognition/discrimination ability. For example, host 3 with the 3,5-bis(trifluoromethyl)phenyl group at the 3,3'-positions showed improved enantioselectivity for small molecules such as 2-chloropropionic acid and methyl lactate as evaluated by the binding constants. This host 3 also had an excellent ability as an NMR chiral solvating agent. 相似文献
110.
Naota T Tannna A Kamuro S Hieda M Ogata K Murahashi S Takaya H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(8):2482-2498
The synthesis, structure, and dynamic behavior of bistable C- and N-bound isomers of transition-metal cyanocarbanions are described. A series of C-bound cyclopentadienyl (Cp) ruthenium phosphane complexes, [Ru{CH(CN)SO2Ph}(Cp)L1L2] (3), and their N-bound isomers, [Ru+(Cp)(NCCH(-)SO2Ph)L1L2] (4), were prepared by treating [RuCl(Cp)(PR3)2] with the sodium salt of phenylsulfonylacetonitrile and performing ligand-exchange reactions with the resulting compounds. Structural characterization by X-ray diffraction indicates that the cyanocarbanion moiety of 3 has an alpha-metalated structure, whereas that of 4 has a zwitterionic, end-on structure. Heating these complexes in aprotic solvents gives rise to irreversible linkage isomerization between C- and N-bound isomers, in which the relative thermal stabilities vary greatly depending on the steric and electronic nature of the ligands. Mechanistic studies of N-to-C isomerization revealed that the reaction proceeds irreversibly in a unimolecular manner without the formation of coordinatively unsaturated species. A metal-sliding process, which occurs over the -C-C triple chemical bond N pi-conjugated surface of the cyanocarbanion moiety, was suggested by results from kinetic studies and density functional theory (DFT) calculations. C-to-N isomerizations proceed by the above-mentioned intramolecular process, with a temperature-dependent contribution from the formation and cleavage of mu2-C,N coordination dimers [{Ru{CH(CN)SO2Ph}(Cp)(PPh3)}2] (15 and 16). 相似文献