• Progress in Medical Physics
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• v.31 no.4
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• pp.135-144
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• 2020

Purpose: Gafchromic films for proton dosimetry are dependent on linear energy transfers (LETs), resulting in dose underestimation for high LETs. Despite efforts to resolve this problem for single-energy beams, there remains a need to do so for multi-energy beams. Here, a bimolecular reaction model was applied to correct the under-response of spread-out Bragg peaks (SOBPs). Methods: For depth-dose measurements, a Gafchromic EBT3 film was positioned in water perpendicular to the ground. The gantry was rotated at 15° to avoid disturbances in the beam path. A set of films was exposed to a uniformly scanned 112-MeV pristine proton beam with six different dose intensities, ranging from 0.373 to 4.865 Gy, at a 2-cm depth. Another set of films was irradiated with SOBPs with maximum energies of 110, 150, and 190 MeV having modulation widths of 5.39, 4.27, and 5.34 cm, respectively. The correction function was obtained using 150.8-MeV SOBP data. The LET of the SOBP was then analytically calculated. Finally, the model was validated for a uniform cubic dose distribution and compared with multilayered ionization chamber data. Results: The dose error in the plateau region was within 4% when normalized with the maximum dose. The discrepancy of the range was <1 mm for all measured energies. The highest errors occurred at 70 MeV owing to the steep gradient with the narrowest Bragg peak. Conclusions: With bimolecular model-based correction, an EBT3 film can be used to accurately verify the depth dose of scanned proton beams and could potentially be used to evaluate the depth-dose distribution for patient plans.

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.287-292
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• 1992

The rate constants of the nucleophilic addition reaction of amines (piperidine and diethylamine) to phenylvinylketone in various solvents have been determined by UV spectrophotometry at $25^{\circ}C$. On the basis of the high sensitivity of the rate to the polarity of the medium, it may be concluded that the reaction intermediate has zwitterionic character. The effect of the solvents on the rate of the bimolecular nucleophilic addition reaction is described well by the Kirkwood equation: The transition state of the reaction has a cyclic structure formed through an intramolecular hydrogen bond. The addition reaction of primary and secondary amines to phenylvinylketone in all solvents take place considerably faster than that of tertiary amine and this results also can be explained by the intermediate products in the reaction have a cyclic structure formed through an intramolecular hydrogen bond for the primary and secondary amines but not for the tertiary amine.

• YAKHAK HOEJI
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• v.33 no.1
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• pp.64-71
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• 1989

Since time-dependent inactivation of MAO was found to be complete in a few minutes when high concentration ratios of tranylcypromine to MAO were used, a method to obtain kinetic parameters was sought suitable to the conditions in which concentrations of tranylcypromine analogs did not exceed that of MAO. For the purpose, kinetic equations were derived and the method applied to the kinetic studies of tranylcypromine enantiomers. It was found that (E)-(+)-2-phenylcyclopropylamine inhibited MAO by the mechanism following bimolecular reaction scheme with $\tilde{K}_i$ of $2.0\;{\times}\;10^6M^{-1}min^{-1}$. Whereas, MAO-inhibitory pattern of the (-)-enantiomer was to be interpreted by suicide inhibition scheme and measured $k_{in}\;and\;\tilde{K}'$ were $0.457\;min^{-1}\;and\;$5.4{\mu}M$, respectively.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.291-294
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• 2002

The reactions of triplet oxygen atom with halomethanes as a potential fire extinguisher were studied by a discharge flow-chemiluminescence imaging method. The experiments were carried out under second order conditions. The bimolecular atom-molecule reaction rate constants were determined in terms of the initial rate method. The initial concentration of oxygen atom was also determined under second order rate law instead of the pseudo-first order conditions with $[O(^3P)]_0{\ll}[sample]_0$. The second order conditions were more reliable than pseudo-first order conditions for the determinations of rate constants. The rate constants of the reactions $CF_3I\;+\;O(^3P)$, $CH_3PI\;+\'O(^3P)$, and $CHBrCl_2\;+\;O(^3P)$ were determined to be $5.0\;{\times}\;10^{-12}$ , $1.1\;×\;0^{-11}$ , and $1.9\;{\times}\;10^{-14}cm^3molecule^{-1}s^{-1}$, respectively.

• Bulletin of the Korean Chemical Society
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• v.34 no.10
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• pp.2989-2994
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• 2013

The solvolysis rate constants of 3,4- (1) and 3,5-dimethoxybenzoyl (2) chlorides were measured in various pure and binary solvents at $25.0^{\circ}C$, and studied by application of the extended Grunwald-Winstein (G-W) equation, kinetic solvent isotope effect in methanolysis and activation parameters. The solvolysis of 1 was interpreted as the unimolecular pathway due to a predominant resonance effect from para-methoxy substituent like 4-methoxybenzoyl chloride (3), while that of 2 was evaluated as the dual mechanism, with unimolecular or bimolecular reaction pathway according to the character of solvent systems (high electrophilic/nucleophilic) chosen, caused by the inductive effect by two meta-methoxy substituents, no resonance one. In the solvolyses of 1 and 2 with two $-OCH_3$ groups, the resonance effect of para-methoxy substituent is more important to decide the mechanism than the inductive effect with other corresponding evidences.

• Bulletin of the Korean Chemical Society
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• v.16 no.10
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• pp.938-945
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• 1995

Hydrolysis of p-nitrophenyl acetate (PNPA) and p-nitrophenyldiphenyl phosphate (PNPDPP) by N-chloro compounds in micellar solution were studied. N,N'-dichloroisocyanuric acid sodium salt (DCI) in cetyltrimethylammonium chloride (CTACl) micellar solution gave pseudo first-order kinetics. But, DCI in cetyltrimethylammonium bromide (CTABr) micellar solution showed typical series first-order kinetics - fast hydrolysis of the esters and concomitant slow decay of the hydrolyzed product, p-nitrophenolate. The hydrolysis rate was decreased as the hydrophobicity of N-chloro compounds was increased, which is the opposite trend to the usual bimolecular micellar reaction. This curious behavior of the N-chloro compounds in the catalytic hydrolysis of PNPA and PNPDPP in a cationic micellar system can be best explained by participation of counter ions of the surfactants during hydrolysis.

• Bulletin of the Korean Chemical Society
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• v.28 no.7
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• pp.1135-1140
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• 2007

Pseudo-first-order rate constants (kobs) for the reaction of N-benzylphthalimide (NBPT) with HO- have been determined at 2.0 × 10?4 M NBPT, 1.0 × 10?3 and 2.0 × 10?3 M NaOH as well as varying concentrations of cetyltrimethylammonium bromide ([CTABr]T = 0.0-1.7 × 10?1 M). The effects of [CTABr]T ? CMC (with CMC representing the critical micelle concentration of CTABr) on kobs have been analyzed in terms of Berezin's pseudophase (BPP) model and pseudophase ion-exchange (PIE) model. Although both models give the best observed data fit with least-squares values not significantly different from each other, the calculated values of KS from BPP model appear to be more reliable compared to those from PIE model because the values of KS from BPP model are similar to the corresponding KS values determined spectrophotometrically.

• Journal of Microbiology and Biotechnology
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• v.17 no.4
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• pp.685-690
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• 2007

The deoxysugar biosynthetic gene cluster of Sch 47554/Sch 47555 was cloned from Streptomyces sp. SCC-2136. One of the ORFs, schS6, appeared to encode glucose-1-phosphate thymidylyltransferase, which converts dTTP and glucose-1-phosphate to TDP-D-glucose and pyrophosphate. The dTDP-D-glucose is a key metabolite in prokaryotics as a precursor for a large number of modified deoxysugars, and these deoxysugars are a maj or part of various antibiotics, ranging from glycosides to macrolides. SchS6 was expressed in E. coli vector pSCHS6 and the expressed protein was purified to apparent homogeneity by ammonium sulfate precipitation and Ni-NTA affinity column chromatography. The specific activity of the purified enzyme increased 4.7-fold with 17.5% recovery. It migrated as a single band on SDS-PAGE with an apparent molecular mass of 56kDa. The purified protein showed glucose-1-phosphate thymidylyltransferase activity, catalyzing a reversible bimolecular group transfer reaction. In the forward reaction, the highest activity was obtained with combination of dTTP and ${\alpha}-D-glucose-1-phosphate$, and only 12% of that activity was obtained with the substrates $UTP/{\alpha}-D-glucose-1-phosphate$. In the opposite direction, the purified protein was highly specific for dTDP-D-glucose and pyrophosphate.

• Bulletin of the Korean Chemical Society
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• v.6 no.4
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• pp.196-202
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• 1985

A Very Low Pressure Reactor (VLPR) is constructed for the kinetic study of atom-molecule bimolecular elementary reactions. The basic principles and the versatility of the method are described. By using the VLPR technique the forward (k1) and the reverse (k-1) rate constants for Br atom reaction with trimethylsilane are studied; Br + $(CH_3)_3$SiH k1 ${\leftrightarrow}$ k-1 HBr + $(CH_3)_3$Si. From the kinetic data and the entropy estimation the bond dissociation energy for Si-H bond in trimethylsilane is calculated to be 90.1 kcal/mole $({\pm}1.1$ kcal/mole). The Arrhenius parameters for k1 are found to be log A = 10.6 l/mole·sec, $E_a$ = 4.4 kcal/mole respectively. For the comparison purpose analogous reaction for carbon compound ; Br + $(CH_3)_3$CH ${\rightarrow}$ HBr + $(CH_3)_3$C was also studied. The corresponding rate constant and equilibrium constant at $25^{\circ}C$ are found to be 2.67 ${\times}$ $10^6l$/mole${\cdot}$sec and 160 respectively.

• The Journal of the Korea institute of electronic communication sciences
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• v.13 no.3
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• pp.579-586
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• 2018

With the beginning of the new era of bigdata, information extraction or prediction are an important research area. Here, we present the acquisition of semi-automatically curated large-scale biological database and the prediction of enzyme reaction annotation for analyzing the pharmacological activities of drugs. Because the xenobiotic metabolism of pharmaceutical drugs by cellular enzymes is an important aspect of pharmacology and medicine. In this study, we apply and analyze similarity models to predict bimolecular reactions between human enzymes and their corresponding substrates. Thirteen models select to reflect the characteristics of each cluster in the similarity model. These models compare based on sensitivity and AUC. Among the evaluation models, the Simpson coefficient model showed the best performance in predicting the reactivity between the enzymes. The whole similarity model implement as a web service. The proposed model can respond dynamically to the addition of reaction information, which will contribute to the shortening of new drug development time and cost reduction.