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T. N. Solomoichenko Yu. S. Sadovskii T. M. Prokop’eva E. A. Karpichev I. V. Kapitanov Zh. P. Piskunova V. A. Savelova A. F. Popov 《Theoretical and Experimental Chemistry》2006,42(6):364-370
We have studied the nucleophilicity of the hydroperoxide anion relative to 4-nitrophenyl diethyl phosphonate (NPDEPS) in the
presence of cetyltrimethylammonium bromide (water, 25 °C) while varying the acidity of the medium and the hydroperoxide anion
concentration over a broad range. The increase in the reaction rate when the reaction is transferred to a micellar pseudophase
is as high as ∼10-fold, which is explained by concentration effects. In CTAB micelles, as in water, the hydroperoxide ion
is one of the most effective α-nucleophiles, and the size of the α-effect, characterized by the ratio of the second-order rate constants for reactions of HOO− and OH− anions with NPDEPS, remains practically constant and reaches a value of ∼50-fold.
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Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 357–363, November–December, 2006. 相似文献
24.
MinHAO DaXING QunCHEN JuanWANG 《中国化学快报》2004,15(6):679-682
This paper, for the first time, reports a method that can be used as a highly sensitive probe for singlet oxygen (^1O2) and superoxide anion (O2^-) in vitro or in vivo. FCLA(3,7-dihydro-6-{4-[2-(N‘-(5-fluoresceinyl)thioureido)ethoxy]phenyl}-2-methylimidazo{1,2-a}pyrazin-3-one sodium salt), a chemiluminescence (CL) analysis reagent, has been reported to sensitively react with ^1O2 and O2^- to emit photons with a spectral peak of 525nm. In this work,when human serum albumin (HSA) was added into FCLA solution to enhance the CL intensity,approximately 20 times, compared to that without HSA. The enhanced CL had the same 525 nm spectral peak, identical to that without HSA. By gradually reducing the molecular oxygen content in the solution, we find that the auto-oxidation of oxygen molecules dissolved in the solution plays an important role in the CL process. Based on these experimental evidences, we propose a novel and highly sensitive detection method of ^1O2 and O2^- which may have a great potential in chemical and medical applications. 相似文献
25.
Yu. L. Frolov I. V. Guchik V. A. Shagun A. V. Vashchenko 《Journal of Structural Chemistry》2005,46(6):979-984
Models of alkali metal hydroxide-water-dimethylsulfoxide superbasic media have been constructed using Hartree Fock and DFT (B3LYP) quantum chemical methods; the structure and energies of anion complexes are considered. The hydroxide anion in the models is stabilized as complexes of OH?·H2O and OH?· 2H2O types. 相似文献
26.
The bridged tri-imidazoliums 3.3X^--5.3X^-(X^-=PF6^-,Br^-,I^-)and bis-imidazoliums 6.2PF6^- were synthesized by N-quaternization of imidazole derivative 1 in acetonitrile under reflux.UV spectroscopic titration experiments showed that the halide salts and hexafluorophosphate salts of these imidazoliums exhibited good recognition toward anions in water and in acetonitrile,respectively. 相似文献
27.
Studies of the vibrational spectra of matrix-isolated M+NO
3
–
ion pairs have been extended to glassy aprotic solvents. The deuterated form of the solvents DMSO, THF, and ACN have windows through the 7- nitrate ionv
3(e) mode infrared region, so it was possible to clearly observe the splitting of the degeneracy of this mode,v
3, produced by the contacting, but solvated, alkali metal cation. Primary attention has been directed to the extent to which this splitting is reduced relative to the argon matrix values. This reduction, which reflects electron-density transfer from the solvating molecules to the ion pairs, is comparable to that observed for H2O and NH3 matrices as the splitting is reduced to 20–35% of the argon-matrix values. The extent of reduction ofv
3 for the different solvents has been related to Gutmann's donicity number scale with the correlation holding well for solvent molecules of comparable size, DMSO, THF and DMF, but breaking down for the smaller linear ACN, apparently because of more molecules in the cation solvation sphere. The matrix data have also been used, through comparison with spectra for saturated liquid solutions of Li+NO
3
–
, to show that the contact ion pair is the dominant species in liquid THF and ACN, whereas the ions are largely solvent separated in DMSO. 相似文献
28.
评述了液晶态分子在分析化学中的应用进展,包括其超分子的分子识别作用,液晶在色谱,光谱探针,核磁共振谱等分析化学领域中的应用。 相似文献
29.
《中国化学快报》2020,31(5):1317-1321
Dipyrrolyldiketone difluoroboron complexes (BONEPYs) were synthesized by condensation of the corresponding pyrroles and malonyl chloride followed by treatment with BF3·OEt2. The aryl-substituted pyrrole is introduced to form a cyclic system in order to investigate anion binding studies. In BONEPYs 1–3 the o-H of the aryl group forms hydrogen bonding with F− to give a more table complex. In contrast, the intramolecular hydrogen-bonded BONEPY endo-4 is more stable than its exo isomer. While adding F−, the hydrogen bonds must be broken first to give 4·(3)F−. Owing to the electron-rich group (-OMe), the o-H of the phenyl group can hardly interact with F− via hydrogen bonding to give the less stable complex 4·(5)F−. The energy differences between the different conformations were calculated using DFT methods, which is consistent to the experimental observations. 相似文献
30.
A new series of bisthiosemicarbazone derivative receptors(1,2 and 3)have been synthesized by simple steps ingood yields.Their anion recognition properties were studied by UV-Vis and ~1H NMR spectroscopy.The resultshowed that the receptors 1,2 and 3 all had a better selectivity to F~-,CH_3COO~- and H_2PO_4~-,but no evidentbinding with Cl~-,Br~-,I~-,NO_3~- and HSO_4~-.Upon addition of the three anions to the receptors in DMSO,thesolution acquired a color change from colorless to dark yellow that can be observed by the naked-eyes,thus the re-ceptors can act as fluoride ion sensors even in the presence of other halide ions.The data showed that it was regularthat the three receptors had different binding ability with the three anions.For the same anion,the association con-stants followed the trend:receptor 1>3>2.The UV-Vis data indicates that a 1:1 stoichiometry complex isformed through hydrogen bonding interactions between compound 1,2 or 3 and anions. 相似文献