• Bulletin of the Korean Chemical Society
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• v.16 no.7
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• pp.657-661
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• 1995

Kinetic studies are carried out on the reaction of S-phenyl dithiobenzoates with benzylamines in acetonitrile at 30.0 ℃. Small magnitude of ρX (βX) as well as ρZ (βZ) obtained suggests rate-limiting nucleophilic attack of the thiocarbonyl carbon. This is supported by the unusually small magnitude of ρXY and ρYZ, albeit their signs do not agree with those expected. Moreover, the inverse secondary kinetic isotope effects (kH/kD<1.0) involving deuterated benzylamine nucleophiles are also in line with the proposed mechanism.

• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.202-205
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• 1987

The reduction of some cyclic conjugated enones with electron-donating substituent on C-3 by sodium borohydride was accelerated on irradiation. The photo-enhanced reduction seems to undergo through zwitterionic species formed from the (n, ${\pi}^{\ast}$) triplet state of conjugated enones, followed by hydride attack to yield unsaturated or saturated alcohols.

• Bulletin of the Korean Chemical Society
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• v.5 no.5
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• pp.207-208
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• 1984

The tris(hydroxymethyl)aminomethane (Tris)-catalyzed hydrolysis of p-nitrotrifluoroacetanilide was kinetically studied. On the contrary to the previously reported results (R. M. Pollack and T. C.Dumsha, J. Am. Chem. Soc., 1973, 95, 4463), the dependence of the rate on [Tris] consists of an initial curve portion and a subsequent linear increase. This indicates that erroneous conclusions were made in the reported work due to the insufficient amount of data. The initial portions of the rate[Tris] profiles are attributed to the catalyzed breakdown of the tetrahedral intermediate, and the linear portions to the general base-catalyzed water attack at the substrate.

• Structural Engineering and Mechanics
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• v.64 no.2
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• pp.243-257
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• 2017

Investigating the properties and durability of high-strength concrete exposed to sulfuric acid attack for the purpose of its application in structures exposed to this acid is of outmost importance. In this research, the resistance and durability of high-strength concrete containing macro-polymeric or steel fibers together with the pozzolans of silica fume or nano-silica against sulfuric acid attack are explored. To accomplish this goal, in total, 108 high-strength concrete specimens were made with 9 different mix designs containing macro-polymeric and steel fibers at the volume fractions of 0.5, 0.75, and 1.0%, as well as the pozzolans of silica fume and nano-silica with the replacement levels of 10 and 2%, respectively. After placing the specimens inside a 5% sulfuric acid solution in the periods of 7, 21, and 63 days of immersion, the effect of adding the fibers and pozzolans on the compressive properties, ultrasonic pulse velocity (UPV), and weight loss of high-strength concrete was investigated and the respective results were compared with those of the reference specimens. The obtained results suggest the dependency of the resistance and durability loss of high-strength concrete against sulfuric acid attack to the properties of fibers as well as their fraction in concrete volume. Moreover, compared with using nano-silica, using silica fume in the fibrous concrete mix leads to more durable specimens against sulfuric acid attack. Finally, an optimum solution for the design parameters where the crushing load of high-strength fibrous concrete is maximized was found using response surface method (RSM).

• Magazine of the Korea Concrete Institute
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• v.18 no.4 s.93
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• pp.49-56
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• 2006

• Bulletin of the Korean Chemical Society
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• v.7 no.1
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• pp.45-50
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• 1986

Separation of optical isomers of some derivatives of amino acids by reversed-phase HPLC has been accomplished by adding a chelate of an optically active amino acid to copper(Ⅱ) to the mobile phase. Cu(Ⅱ) complexes of L-proline and L-hydroxyproline in the mobile phase showed different degrees of separation. Optical isomers of DNS derivatives of amino acids are selectively separated, but those of several other derivatives are not at all. The kinds of buffer agents, the pH, and the concentrations of acetonitrile and the Cu(Ⅱ) ligand all affect the separations. The elution behavior between D and L DNS-amino acids appears to depend on the alkyl side chain of the amino acids. A chromatographic mechanism is proposed that is based on a stereospecificity of the formation of ternary complexes by the D, L-DNS-amino acids and the chiral additive associated with the stationary phase. The steric effects of the ligand exchange reactions are related with the feasibility of cis and/or trans attack of the amino acids to the binary chiral chelate retained on the stationary phase.

• Journal of the Korea institute for structural maintenance and inspection
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• v.12 no.5
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• pp.55-64
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• 2008

Shotcrete have become a deterioration which was exposed to harmful environments. In this study, in order to evaluate the deterioration properties of shotcrete, visual examination, compressive strength, adhesive strength, microstructural analysis were investigated up to the 60th weeks of exposure. The attack solutions for test are sodium sulfate and hydrochloric acid solution with different concentrations, respectively. From the results, although the compressive strength of shotcrete specimens and the adhesive strength between specimens and rocks were high at the early immersion age, they rapidly dropped in the subsequent phases, especially in 5% sodium sulfate and pH1 hydrochloric acid solution. With continued exposure, various harmful ions penetrated into the shotcrete specimen, reacted with the cement hydrate, and generated expansion substances. It was verified that the shotcrete specimens suffered a serious deterioration by chemical attack.

• Journal of the Korean Chemical Society
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• v.38 no.12
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• pp.885-890
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• 1994

Kinetics of electrochemical polymerization of aniline on a tungsten electrode in acidic aqueous solution was studied by means of cyclic voltammetry and kinetic measurements of anodic oxidation. Aniline molecule appeared to be intially oxidized via two-electron transfer to produce oxidized deprotonated aniline ion, which subsequently undergoes nucleophilic attack to the parent aniline and results in head to tail coupling to yield a dimerized species. But, being contrary to the case of Pt electrode, the propagation of polymerization occured through attack of the monomer by the oxidized aniline monomer to polymer. The growth rate of polyaniline was slow in comparison with the growth on Pt electrode. The degradation products were confirmed to be not p-benzoquinone(BQ) but p-phenylenediamine(p-PDA) by spectrophotometry, which agrees with the fact that oxidation of p-PDA was not observed below 1.0 V.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.663-669
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• 2012

The nucleophilic substitution reactions of dibutyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse ($k_H/k_D$ = 0.86-0.97) with the strongly basic anilines while primary normal ($k_H/k_D$ = 1.04-1.10) with the weakly basic anilines. The DKIEs, steric effects of the two ligands, activation parameters, cross-interaction constants, variation trends of the kH/kD values with X, and mechanism are discussed for the anilinolyses of the nine ($R_1O$)($R_2O$)P(=O)Cl-type chlorophosphates. A concerted mechanism is proposed with a backside nucleophilic attack transition state for the strongly basic anilines and with a frontside attack involving a hydrogen-bonded four-center-type transition state for the weakly basic anilines on the basis of the magnitudes, secondary inverse and primary normal, and variation trends of the $k_H/k_D$ values with X.

• Bulletin of the Korean Chemical Society
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• v.25 no.4
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• pp.557-559
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• 2004

The aminolyses of anilinothioethers $(C_6H_5N(CH_3)CH_2SC_6H_4Z)$ in acetonitrile with benzylamines $(XC_6H_4CH_2NH_2)$ have been investigated. The rates are much lower in acetonitrile than in methanol (with aniline). The Bronsted ${\beta}_X$ values are similar but ${\beta}_Z$ values are smaller compared to those for the reactions in MeOH with anilines. The large negative ${\rho}_{XZ}({\cong}-0.8$, after correction for fall-off) value is interpreted to indicate a frontside attack $S_N2$ mechanism, in which the two oppositely changed reaction centers in the TS, $-N^{{\delta}+}{\cdots}S^{{\delta}-}-$, are in close vicinity increasing the interaction between nucleophile and leaving group. The inverse secondary kinetic isotope effects ($k_H/k_D$ < 1.0) are observed with deuterated benzylamines $(XC_6H_4CH_2ND_2)$.