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To investigate the molecular interaction study between secondary amine with aryl and alkyl ether, we report densities, speeds of sound, viscosities and refractive indices of N-ethylaniline (NEA) with aryl (anisole, phenetole) and alkyl (tert-butyl methyl ether) ether over the entire composition regime and in the temperature range of 293.15–323.15 K at 5 K intervals. Various excess and transport properties were derived from the experimental data and the excess parameters were fitted to the Redlich–Kister polynomial equation using multiparametric non-linear regression analysis to derive the binary coefficients and to estimate the standard deviation. Molecular interactions between the unlike molecules were analysed through dipole–dipole interactions, cross-association between the components of the mixtures and H-bond formation. Viscosity and refractive index of the mixtures were predicted through several empirical equations and compared with the experimental results. Prigogine–Flory–Patterson statistical theory was used to predict the excess molar volume results. 相似文献
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The contrasting photophysical properties of two silicon (IV) tetraphenylporphyrins, Si(TPP)(py)2 and Si(TPP)Cl2, have been investigated using static absorption and fluorescence spectroscopy and ultrafast transient absorption measurements. The parent Si(TPP)Cl2, in which the porphyrin macrocycle has its normal 2- oxidation state, has a fluorescence yield of 0.027, and a lifetime of 1.8 ns for the lowest excited singlet state. In marked contrast, the reduced, anti-aromatic complex Si(TPP)(py)2, with the macrocycle in the 4- oxidation state, has an extremely low fluorescence yield (< or =0.0004) and a 750-fold shorter excited-state lifetime (2.4 ps) in the same solvent (pyridine). The rapid deactivation of photoexcited Si(TPP)(py)2 to the ground state is likely associated with its ruffled structure and the presence of low-energy excited states in its electronic manifold. 相似文献
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Ahmad I Fasihullah Q Vaid FH 《Journal of photochemistry and photobiology. B, Biology》2005,78(3):229-234
The effect of phosphate buffer on aerobic photodegradation reactions of riboflavin (RF) at pH 7.0 has been studied. The photoproducts of the two major reactions, viz., intramolecular photoreduction and intramolecular photoaddition, have been determined by a specific multicomponent spectrophotometric method. The overall photodegradation of riboflavin in the presence of phosphate buffer involves the participation of both H2PO4-and HPO4(2-) species. The second-order rate constants for the H2PO4(-)-catalysed photodegradation of riboflavin (normal photolysis) to lumichrome (LC) and HPO4(2-)-catalysed photodegradation of riboflavin (photoaddition) to cyclodehydroriboflavin (CDRF) are 0.93 x 10(-4) and 4.0 x 10(-4) M(-1) s(-1), respectively. The addition of 0.25-2.00 M phosphate to RF solutions at pH 7.0 gives rise to RF-HPO4(2-) complex and hence the quenching of 4-36% fluorescence, respectively. This results in the suppression of normal photolysis leading to the formation of LC in favour of photoaddition to yield CDRF. The present study shows the involvement of H2PO4- anions in the base-catalysed degradation of riboflavin by normal photolysis vis-a-vis the involvement of HPO42- anions in photoaddition reactions of riboflavin suggested earlier [M. Schuman Jorns, G. Schollnhammer, P. Hemmerich, Intramolecular addition of the riboflavin side chain. Anion-catalysed neutral photochemistry, Eur. J. Biochem. 57 (1975) 35-48]. 相似文献
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The molecule 4,4'-di-n-octyl-p-quaterphenyl was synthesized in one step by a nickel-catalyzed cross-coupling reaction. Powder X-ray diffraction shows that it crystallizes in a layered structure with the long axis of the molecule nearly perpendicular to the layer plane. Differential scanning calorimetry indicates a transition to a liquid-crystalline phase at 81 degrees C. Reaction of 4,4'-bis(4-pyridyl)biphenyl with 1-bromooctane yields the dication 2(2+) 2Br-, an "extended viologen" isostructural with 4,4'-di-n-octyl-p-quaterphenyl. Reduction of 2(2+) 2Br- with sodium amalgam in DMF yields 2, the first neutral extended viologen to be isolated. The molecule 2 is, to the best of our knowledge, the most reducing neutral organic molecule that has been synthesized. Single-crystal X-ray diffraction shows that a diradical form, either singlet or triplet, makes an important contribution to the electronic structure of 2. The broadened 1H NMR spectrum of 2 indicates the presence of a triplet, but it has not been possible to observe the triplet by ESR spectroscopy. The electronic structure of 2 appears to be closely related to that of a classic molecule, Chichibabin's hydrocarbon. 相似文献
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Dukhan Kim Prof. Melanie S. Sanford Dr. Thomas P. Vaid Prof. Anne J. McNeil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(25):e202200149
We describe the nonaqueous redox-matched flow battery (RMFB), where charge is stored on redox-active moieties covalently tethered to non-circulating, insoluble polymer beads and charge is transferred between the electrodes and the beads via soluble mediators with redox potentials matched to the active moieties on the beads. The RMFB reported herein uses ferrocene and viologen derivatives bound to crosslinked polystyrene beads. Charge storage in the beads leads to a high (approximately 1.0–1.7 M) effective concentration of active material in the reservoirs while preventing crossover of that material. The relatively low concentration of soluble mediators (15 mM) eliminates the need for high-solubility molecules to create high energy density batteries. Nernstian redox exchange between the beads and redox-matched mediators was fast relative to the cycle time of the RMFB. This approach is generalizable to many different redox-active moieties via attachment to the versatile Merrifield resin. 相似文献
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The fragmentation of the title compounds on electron impact has been studied and the major processes interpreted. The base peak invariably appears at [M ? 43]+ whose origin from the butyl chain has been traced with the help of metastable ion studies and accurate mass measurements. Loss of methyl cyanide, involving the decomposition of the pyrazole moiety, is observed only from the fragment ions. 相似文献
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Various amines and amino derivatives such as (tert-butylamine, 4-amino-1,2,4-triazole-p-toluenesulfonamide), and cyanamide, when treated with |(diacetoxy)iodo|benzene in the presence of nitroso compounds (2) yield unsymmetrically substituted azoxy compounds (3). 相似文献