• Korean Journal of Materials Research
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• v.12 no.11
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• pp.889-893
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• 2002

The reactions of $Cu/Ti/SiO_2$ structures at temperatures ranging from 200 to $700^{\circ}C$ have been studied for various Ti thicknesses. The reaction products initially formed, at around $300^{\circ}C$, were a series of Cu-Ti intermetallics ($Cu_3$Ti/CuTi) with the oxygen dissolved in the Ti moving from the compounds into the remaining unreacted Ti. At $500^{\circ}C$, the $Cu_3$Ti was converted into Cu-rich intermetallics, $Cu_4$Ti, which grew at the expense of the CuTi due to the increased oxygen content in the Ti. In addition, the outdiffusion of Ti, to the Cu surface, and the $Ti-SiO_2$ reactions, caused an abrupt increase in the oxygen content in the Ti layer, which placed thermodynamic restraints on further Ti reactions. Furthermore, thinner Ti layers showed a higher increasing rate of oxygen accumulation for the same consumption of Ti, which led to significantly reduced Ti consumption. The $SiO_2$ film under the Ti diffusion barrier was more easily destroyed with increasing Ti thickness.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.941-952
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• 2012

In the present contribution the Encounter Theory (ET) (the prototype of the classical Collision Theory in rarefied gases) concepts for widely occurring diffusion assisted irreversible bulk reactions A + A ${\rightarrow}$ C and A + B ${\rightarrow}$ C in liquid solutions examined by the authors in the literature are analyzed and compared with each other for these different types of reactions. It is shown that for a particular case of equal initial concentrations $[A]_0=[B]_0$ in the reaction A + B ${\rightarrow}$ C, when the kinetics of both reactions A + A ${\rightarrow}$ C and A + B ${\rightarrow}$ C in the framework of formal chemical kinetics and ET are the same, the accumulation of macroscopic correlations breaking the concepts of independent encounters and leading to the Generalized Encounter Theory (GET) are drastically different. The influence of the force interaction and the decay of nonstable reactants on the time behavior the macroscopic correlations is also briefly discussed.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1009-1014
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• 2012

The influence of magnetic fields on chemical processes has long been the subject of interest to researchers. For this time numerous investigations show that commonly the effect of a magnetic field on chemical reactions is insignificant with impact less than 10 percent. However, there are some papers that point to the observation of external magnetic field effect on chemical and biochemical systems actually having a significant impact on the reactions. Thus, of great interest is an active search for rather simple but realistic models, that are based on physically explicit assumptions and able to account for a strong effect of low magnetic fields. The present work theoretically deals with two models explaining how an applied weak magnetic field might influence the steady state of a non-equilibrium chemical system. It is assumed that external magnetic field can have effect on the rates of radical reactions occurring in a system. This, in turn, leads to bifurcation of the nonequilibrium stationary state and, thus, to a drastic change in the properties of chemical systems (temperature and reagent concentration).

• Bulletin of the Korean Chemical Society
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• v.29 no.8
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• pp.1459-1463
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• 2008

Second-order rate constants (kN) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl 2-thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide at 25.0 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature for the aminolysis of 2. The curved Brønsted-type plot is similar to that reported for the corresponding reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (1). The reactions of 1 and 2 have been suggested to proceed through the same mechanism, i.e., through a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step. Substrate 2 is less reactive than 1 toward weakly basic amines (e.g., $pK_a$ < 10.4) but becomes more reactive as the basicity of amines increases further. Dissection of kN into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but larger $k_1$ than the corresponding reaction of 1. Steric hindrance exerted by the ortho-nitro group has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2099-2104
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• 2013

We present here an efficient and simple method for preparation of highly active Pd heterogeneous catalyst (CNT-Pd), specifically by reaction of dichlorobis(triphenylphosphine)palladium ($Pd(PPh_3)_2Cl_2$) with thiolated carbon nanotubes (CNTs). The as-prepared CNT-Pd catalysts demonstrated an excellent catalytic activity for the carbon-carbon (C-C) cross-coupling reactions (i.e. Suzuki, Stille, and decarboxylative coupling reactions) under mild conditions. The CNT-Pd catalyst could easily be removed from the reaction mixture; additionally, in the decarboxylative coupling of iodobenzene and phenylpropiolic acid, it showed a six-times recyclability, with no loss of activity. Moreover, once its activity had decreased by repeated recycling, it could easily be reactivated by the addition of phosphine ligands. The remarkable recyclability of the decarboxylative coupling reaction is attributable to the high degree of dispersion of Pd catalysts in CNTs. Aggregation of the Pd catalysts is inhibited by their strong adhesion to the thiolated CNTs during the chemical reactions, thereby permitting their recycling.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1722-1726
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• 2013

A kinetic study on nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5j) with ethylamine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ is reported. The plots of $k_{obsd}$ vs. [amine] are linear for the reactions of substrates possessing a strong electron-withdrawing group (EWG) but curve upward for those of substrates bearing a weak EWG, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. The reactions have been concluded to proceed through a stepwise mechanism with one or two intermediates (a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$) depending on the nature of the substituent Y. Analysis of Bronsted-type plots and dissection of $k_{obsd}$ into microscopic rate constants have revealed that the reactions of substrates possessing a strong EWG (e.g., 5a-5f) proceed through $T^{\pm}$ with its formation being the rate-determining step, while those of substrates bearing a weak EWG (e.g., 5g-5j) proceed through $T^{\pm}$ and $T^-$.

• Analytical Science and Technology
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• v.30 no.3
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• pp.138-145
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• 2017

Microwave-assisted organic synthesis has gained a remarkable interest over the past years because of its advantages - (i) rapid energy transfer and superheating, (ii) higher yield and rapid reaction, (iii) cleaner reactions. Ionic liquids are well known for their unique properties such as negligible vapor pressure and high thermal stability. With these properties, ionic liquids have gained increasing attention as green, multi-use reaction media. Recently, ionic liquids have been applied as reaction media for biocatalysis. Lipase-catalyzed reactions in ionic liquids provide high activity and yield compared to conventional organic solvents or solvent free system. Since polar molecules are generally good absorbent to microwave radiation, ionic liquids were investigated as reaction media to improve activity and productivity. In this study, therefore, the effect of microwave irradiation in ionic liquids was investigated on lipase catalyzed reactions such as benzyl acetate synthesis and caffeic acid phenethyl ester synthesis. Comparing to conventional heating, microwave heating showed almost the same final conversion but increased initial reaction rate (3.03 mM/min) compared to 2.11 mM/min in conventional heating at $50^{\circ}C$.

• Preventive Nutrition and Food Science
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• v.22 no.3
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• pp.211-215
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• 2017

The individual Maillard reactions of glucose, glucosamine, cyclohexylamine, and benzylamine were studied at a fixed temperature of $120^{\circ}C$ under different durations by monitoring the absorbance of the final products at 425 nm. Glucosamine was the most individually reactive compound, whereas the reactions of glucose, cyclohexylamine, and benzylamine were not significantly different from each other. Maillard reactions of reaction mixtures consisting of glucosaminecyclohexylamine, glucosamine-benzylamine, glucose-cyclohexylamine, and glucose-benzylamine were also studied using different concentration ratios under different durations at a fixed temperature of $120^{\circ}C$ and pH 9. Maillard reactions in the pairs involving glucosamine were observed to be more intense than those of the pairs involving glucose. Finally, with respect to the concentration ratios, it was observed that in most instances, optimal activity was realized, when the reaction mixtures were in the ratio of 1:1.

• Toxicological Research
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• v.11 no.1
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• pp.23-29
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• 1995

Microsomes from human liver sample HL 110 oxidized aflatoxin $B_1$ $(AFB_1)$ to $AFB_1$ exo-8, 9-epoxide which was detected as a glutathione (GSH) conjugate with excess GSH S-transferase and to aflatoxin $Q_1$ ($AFB_1$; 3$\alpha$-hydroxyafiatoxin $B_1$), and testosterone to 6$\beta$-hydroxytestosterone. Anti-P450 3A4 nearly completely inhibited all of the reactions. Some fiavonoids inhibited all of the reactions. While other fiayonolds stimulated 8, 9-epoxidation and inhibited 3$\alpha$-hydroxylation. Gestodene inhibited all of the reactions when gestodene was metabolized by human liver microsomal P450 3A4 prior to adding substrate. But, ges-todene was added in the enzyme mixtures in the presence of $AFB_1$, it could not inhibit 8, 9-epoxidation of $AFB_1$. Nifedipine and troleandomycin inhibited both of the reactions of $AFB_1$ but only 3$\alpha$-hydroxylation was inhibited by the oxidation product of nifedipine. Although, troleandomycin was known as a mechanism-based inhibitor, the chemical did not show any detectable inhibitory effect on 6$\beta$-hydroxylation of testosterone. The results suggest that there are several different substrate-binding sites on P450 3A4.

• Korean Journal of Air-Conditioning and Refrigeration Engineering
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• v.23 no.6
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• pp.383-391
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• 2011

Numerical simulations have been conducted for the cylindrical steam reformer having various boundary temperature distributions. $CH_4$, $H_2O$, CO, $H_2$ and $CO_2$ are often generated or destroyed by the reactions, namely the Steam Reofrming(SR) reaction, the Water-Gas Shift (WGS) reaction and the Direct Steam Reforming(DSR) reaction. The SR and the DSR reactions are endothermic reactions, and the WGS reaction is an exothermic reaction. The rate of reactions can be slightly controlled by artificially given boundary temperature distributions. Therefore, the component ratio of the gases at the outlet are different for various boundary temperature distributions, namely the constant, cubic and linear distributions. Among these distributions, the linear temperature distribution is outstanding for efficient hydrogen production of the steam reformer.