• Journal of the Korean Chemical Society
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• v.27 no.6
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• pp.399-404
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• 1983

Raman spectra for the carbonyl stretching mode of the amides, and amide-solvent systems have been recorded to investigate the effect of alkyl substitutions at the carbonyl carbon and at the nitrogen on the amide hydrogen-bonding. The data have shown that the interaction affinities are in the order of amide-amide > amide-water > amide-alcohol in formamide system, and amide-water > amide-amide > amide-alcohol in acetamide and propionamide systems. The strength of the proton acceptor of the carbonyl oxygen is increased by the presence of alkyl group to the carbonyl carbon and the proton donorcity of the amide is decreased by the alkyl substitution at the nitrogen. The above results are in good agreement with the ab initio SCF MO calculation.

• Bulletin of the Korean Chemical Society
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• v.35 no.10
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• pp.3111-3114
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• 2014

• Bulletin of the Korean Chemical Society
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• v.20 no.9
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• pp.1017-1020
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• 1999

The aminolysis reactions of thiophenyl phenylacetates with benzylamines are investigated in acetonitrile at 55.0℃. Relatively large selectivity parameters, βx≒ 1.5, βz = -1.5~-1.8 and βxz = 0.92 together with the valid reactivity-selectivity principle are consistent with stepwise acyl transfer mechanism with rate limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T ± . The first order kinetics with respect to the benzylamine concentration and the realtively large secondary kinetic isotope effect (kH / kD = 1.2-1.7) involving deuterated benzylamine nucleophiles suggest a four center type transition state in which concurrent leaving group departure and proton transfer are involved.

• Journal of the Korean Electrochemical Society
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• v.18 no.2
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• pp.75-80
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• 2015

Multi-block sulfonated poly(arylene ether sulfone) (SPAES) copolymer was synthesized via nucleophilic aromatic substitution reaction for proton exchange membrane fuel cell application. After synthesizing the hydrophilic and hydrophobic precursor oligomers having different end-groups (F-terminated or OH-terminated), the effect of end group on the molecular weight was investigated. Hydrophilic oligomers with hydroquinone showed better performance as fuel cell membranes. SPAES membranes showed comparable proton conductivity to that of Nafion at $80^{\circ}C$ and above 70% RH. In particular, SPAES 9 with hydroquinone showed higher proton conductivity than SPAES 10 in the whole RH range studied. Increased local concentration of sulfonic acids within hydrophilic block might develop the hydrophilic-hydrophobic phase separation in the block copolymers.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.262-266
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• 2002

Computations are presented for the ortho- and para-substituted benzyl alcohol-$H_2O$ clusters. A variety of conformers are predicted, and their relative energies are compared. Binding energies of the clusters are computed, and detailed analysis is presented on the effects of substitution on the strength of the hydrogen bond in the clusters. F- and $NH_2-$ substituted clusters are studied to analyze the effects of electron-withdrawing and electron-pushing groups. In para-substituted clusters, the inductive effects are dominant, affecting the binding energies in opposite way depending on whether the hydroxyl group is proton-donating or -accepting. For ortho-substituted clusters, more direct involvement of the substituting group and the resulting geometry change of the hydrogen bond should be invoked to elucidate complicated pattern of the binding energy of the clusters.

• Membrane Journal
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• v.18 no.4
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• pp.282-293
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• 2008

Partially sulfonated poly(aryl ether sulfone) membranes were prepared from the sulfonated sulfone monomer, which was synthesized by a nucleophilic substitution, non-sulfonated monomers and potassium carbonate by a direct polymerization method and a subsequent solution casting technique with mixed solvents of N-methyl-2-pyrrolidone (NMP) and dimethylacetamide (DMAc). To investigate the effect of mixed solvent, the volume ratios of NMP and DMAc were varied in the range of $0{\sim}100%$ and the degrees of sulfonation of the copolymers were fixed as 50%. The surface properties of the resulting membranes were examined by scanning electron microscope (SEM) and atomic force microscope (AFM), and a comparative study of the morphology changes and the physicochemical properties such as proton conductivity and methanol permeability was achieved. It was found that proton conductivities depend on the volume ratio of NMP-DMAc mixed solvents, and the proton conductivity determined at the condition of $25^{\circ}C$ and 100% relative humidity was $1.38{\times}10^{-1}\;S/cm$ for the membrane prepared in the 50:50 v/v-% of NMP : DMAc mixed solvent.