• Journal of Chest Surgery
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• v.43 no.4
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• pp.345-355
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• 2010

Background: Extracellular and intracellular pH ($pH_o$ and $pH_i$), which can be changed in various pathological conditions such as hypoxia, affects vascular contractility. To elucidate the mechanism to alter vascular contractility by pH, the effects of pH on reactivity to vasocontracting agents, intracellular $Ca^{2+}$ influx, and $Ca^{2+}$ sensitivity in vascular smooth muscle were examined. Material and Method: Isometric contractions in rat superior mesenteric arteries (SMA) were observed. Intracellular $Ca^{2+}$ concentration ($[Ca^{2+}]_i$) was recorded by microfluorometer using Fura-2/acetoxylmethyl ester in muscle cells. $pH_o$ was increased from 7.4 to 7.8 or decreased to 6.9 or 6.4. $pH_i$ was decreased by applying $NH_4^+$ or propionic acid or modulated by changing $pH_o$ after increasing membrane permeability using $\beta$-escin. Result: Decreases in $pH_o$ from 7.4 to 6.9 or 6.4 shifted concentration-response curve by norepinephrine (NE) or serotonin (SE) to the right and significantly increased half maximal effective concentration (EC50) to NE or SE. Increase in $pH_o$ from 7.4 to 7.8 shifted concentration-response curve by norepinephrine (NE) or serotonin (SE) to the left and significantly reduced EC50 to NE or SE. NE increased $[Ca^{2+}]_i$ in cultured smooth muscle cells from SMA and the increased $[Ca^{2+}]_i$ was reduced by decreases in $pH_o$. NE-induced contraction was inhibited by $NH_4^+$, whereas the resting tension was increased by $NH_4^+$ or propionic acid. When the cell membrane of SMA was permeabilized using ${\beta}$-escin, SMA was contracted by increasing extracellular $Ca^{2+}$ concentration from 0 to $10{\mu}M$ and the magnitude of contraction was decreased by a decrease in $pH_o$ and vice versa. Conclusion: From these results, it can be concluded that a decrease in $pH_o$ might inhibit vascular contraction by reducing the reactivity of vascular smooth muscle to vasoactive agents, $Ca^{2+}$ influx and the sensitivity of vascular smooth muscle to $Ca^{2+}$.

• Bulletin of the Korean Chemical Society
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• v.18 no.8
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• pp.865-868
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• 1997

Second-order rate constants have been measured spectrophotometrically for the reactions of p-nitrophenyl phenylacetate (1) and benzoate (2) with a series of alicyclic amines in H2O containing 20 mole % DMSO at 25.0 ℃. 1 appears to be more reactive than 2 toward all the amines studied, although phenylacetic acid is a weaker acid than benzoic acid. The higher reactivity of 1 can be attributed to resonance and/or steric effect, since the ground state of 2 can be stabilized by resonance and 1 would experience less steric hindrance due to the presence of CH2 group between phenyl and C=O group. The reactivity of the amines increases with increasing their basicity. The Bronsted-type plots for aminolysis of 1 and 2 show good linearity with βnuc values of 0.81 and 0.85, respectively, indicating that the TS structures of the aminolyses of 1 and 2 are similar. Besides, the linear Bronsted plots obtained in the present system clearly suggest that there is no mechanism change for the given series of the amines and the reactions of 1 and 2 proceed in a same mechanism.

• Journal of the Korean Chemical Society
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• v.58 no.3
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• pp.289-296
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• 2014

Electrochemical copolymerization of o-chlorophenol (oCP) with o-hydroxyphenol (oHP) was carried out in aqueous $H_2SO_4$ by using cyclic voltammetry (CV) technique. In addition, CV was used to evaluate the differences in electrochemical characteristics of the copolymer in comparison with the corresponding homopolymers, poly(o-chlorophenol) (PoCP) and poly(o-hydroxyphenol) (PoHP). The variation of peak currents with respect to sweep rates was compared between copolymer and homopolymers, PoCP and PoHP, films. Further support for copolymer characterization was obtained by recording UV-visible, IR spectra and elemental analysis. The mechanism of the electrochemical polymerization has been discussed. The monomer reactivity ratios ($r_1$ and $r_2$) were calculated using Fineman-R$\ddot{o}$ss method and was found to be 0.4 and 1.3 repetitivelly and the copolymer structure is a block structure and more rich in oHP units.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1912-1920
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• 2011

The $SnO_2$ with a particle size of about 300 nm instead of Ni is used in this study to overcome rapid catalytic deactivation by the formation of a $NiAl_2O_4$ spinal structure on the conventional Ni/${\gamma}$-$Al_2O_3$ catalyst and simultaneously impregnated the catalyst with potassium (K). The $SnO_2-K_2O$ impregnated Zeolite Y catalyst ($SnO_2-K_2O$/ZY) exhibited significantly higher ethanol reforming reactivity that that achieved with $SnO_2$ 100 and $SnO_2$ 30 wt %/ZY catalysts. The main products from ethanol steam reforming (ESR) over the $SnO_2$-$K_2O$/ZY catalyst were $H_2$, $CO_2$, and $CH_4$, with no evidence of any CO molecule formation. The $H_2$ production and ethanol conversion were maximized at 89% and 100%, respectively, over $SnO_2$ 30 wt %-$K_2O$ 3.0 wt %/ZY at 600 $^{\circ}C$ for 1 h at a $CH_3CH_2OH:H_2O$ ratio of 1:1 and a gas hourly space velocity (GHSV) of 12,700 $h^{-1}$. No catalytic deactivation occurred for up to 73 h. This result is attributable to the easier and weaker of reduction of Sn components and acidities over $SnO_2-K_2O$/ZY catalyst, respectively, than those of Ni/${\gamma}$-$Al_2O_3$ catalysts.

• Proceedings of the Korean Nuclear Society Conference
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• 1995.10a
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• pp.35-40
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• 1995

Considering the higher discharge burnup, lower channel refuelling rate, lower linear element rating(LER), lower coolant void reactivity and axial power shape, CANFLEX-RU fuel bundle is optimized for CANDU-6 by grading the fissile composition in the ring-wise of the bundle and by applying fuel management scheme appropriately. The fissile composition of the fuel bundle is graded as the recovered uranium (0.9 w/o U-235) in the outer and intermediate elements, depleted Uranium (0.2 w/o U-235) in the center element, natural uranium (0.71 w/o U-235) in the inner elements. Enrichment is not required for these fuel. The fissile composition is optimized by lattice calculation and by time-averaged reactor simulation. CANFLEX-RU optimized for CANDU-6 resulted to be the 15% lower channel refuelling rate, acceptable axial power profile and power envelope, 70% higher discharge burnup, 15% lower LER and not increase coolant void reactivity compared with the 37-element natural uranium bundle for CANDU-6.

• Bulletin of the Korean Chemical Society
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• v.2 no.4
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• pp.132-138
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• 1981

Ab initio molecular orbital calculations have been performed in an effort to determine which types of chemical interactions play essential roles for the system, , $H_2O+CH_2SH^+$, and $H_2O+ CH_2S$. The most important contribution to the interaction energy in controlling reaction path is the exchange repulsion energy, EX, which is largely responsible for the shape of the total interaction energy curve. In the ion-molecule reaction, prior protonation of thioformaldehyde or prior deprotonation of water leads to formation of the corresponding ionic adducts ($H_2O+CH_2SH$ and $HOCH_2S^-$), with no barrier to reaction, simulating specific acid and base catalysis, respectively, as in the case of formaldehyde. Otherwise, approach of water to thioformaldehyde gives rise to a completely repulsive interaction.

• Journal of the Korean Chemical Society
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• v.30 no.6
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• pp.516-520
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• 1986

This study is related to reactivity of dioxygen bridged palladium complexes having ${\pi}$-allyl ligands. In this case, new dioxygen bridged palladium complexes were prepared using superoxide ion$(O_2^-)$ as an oxygen source. Reactions of the dioxygen palladium complexes prepared in the study were examined in order to clarify the nature of the coordinated dioxygen. Treatments of a solution of the dioxygen bridged palladium complexes in benzene by water, methanol and acetic acid gave hydrogen peroxide $(H_2O_2)$ as hydroxy-, methoxy-, and acetoxybridged palladium complexes, respectively. The dioxygen bridged palladium complexes reacted also with substitution phenols of salicylaldehyde, 8-hydroxyquinoline and active methylenes of acetylacetone, dimethyl malonate to afford mononuclear complexes of palladium and hydrogen peroxide. The results suggest that dioxygen is coordinated as peroxo $(O_2^{2-})$ in the complexes and behaves as a strong base.

• Applied Chemistry for Engineering
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• v.3 no.3
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• pp.471-481
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• 1992

This study is related to the reactivity of dioxygen bridged palladium complexes having amine ligands. New dloxygen bridged palladium complexes were prepared using superoxide ion(${O_2}^-$) as an oxygen source. The reactions of dioxygen palladium complexes prepared in the study were examined in order to clarify the nature of the coordinated dioxygen. Treatments of a solution of the dioxygen bridged palladium complexes in benzene by water, methanol, acetic acid gave hydrogen peroxide($H_2O_2$) and hydroxy, methoxy, acetoxy-bridged palladium complexes, respectively. The dioxygen bridged palladium complexes reacted with substitution phenols of salicylaldehyde, 8-hydroxyquinoline and active mothylenes of acetylacetone, dimethyl malonate to afford mononuclear complexes of palladium and hydrogen peroxide. Furthermore, she dioxygen bridged palladium complexes changed to acetonyl bridged palladium complex and hydrogen peroxide reacting with acetone. The results suggest that dioxygen is coordinated as peroxo (${O_2}^{2-}$) in the complexes and behaves as a strong base.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1551-1555
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• 2012

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of benzyl 2-pyridyl carbonate $\mathbf{7}$ and $t$-butyl 2-pyridyl carbonate $\mathbf{8}$ with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. Substrate $\mathbf{8}$ is less reactive than $\mathbf{7}$. Steric hindrance exerted by the bulky $t$-Bu group of $\mathbf{8}$ has been suggested to be responsible for the decreased reactivity. The Br${\o}$nsted-type plots for the reactions of $\mathbf{7}$ and $\mathbf{8}$ are linear with ${\beta}_{nuc}=0.49$ and 0.44, respectively, which is typical for reactions reported previously to proceed through a concerted mechanism. Aminolyses of $\mathbf{7}$ and $\mathbf{8}$ were expected to proceed through a zwitterionic tetrahedral intermediate $T^{\pm}$, which would be stabilized through an intramolecular H-bonding interaction. However, the kinetic results suggest that the reactions proceed through a concerted mechanism. The H-bonding interaction in $T^{\pm}$ has been suggested to accelerate the rate of leaving-group expulsion from $T^{\pm}$. Another factor that might accelerate expulsion of the leaving group is the "push" provided by the RO group in $T^{\pm}$ through resonance interactions. Thus, it has been concluded that the enhanced nucleofugality through the H-bonding interaction and the "push" provided by the RO group forces the reactions to proceed through a concerted mechanism.

• Applied Biological Chemistry
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• v.37 no.2
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• pp.124-129
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• 1994

The rate of hydrolysis of insecticidal $O,O-diethyl-{\alpha}-cyanobenzylideneamino-oxyphosphorothioate\;(Volaton^{\circledR})$ has been studied in 25% (v/v) aqueous dioxane. On the basis of solvent effect (pH 6.0; m=0.21, n=1.55, pH 12.0; m=0.42, n=3.14 & $|m|{\ll}|l|$), general base catalysis, hydrolysis product analysis, calculation of molecular orbital (MO) and rate equation, it may be concluded that the hydrolysis of Volaton proceeds through the $A_{AC}2$ mechanism via trigonal bipyramidal $(sp^3d^2)$ intermediate below pH 7.0, while above pH 9.0 the hydrolysis proceeds through the $B_{AC}2$ mechanism. Hydrolysis reactivity of Volaton depends on positive charge strength $(p{\gg}{\alpha}C_2)$ rather than steric hindrance. In the range between pH 7.0 and pH 9.0, these two reactions occur competitively.