• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3657-3664
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• 2012

Reactions of 1-adamantylmethyl chloroformate ($1-AdCH_2OCOCl$, 1) and 1-adamantylmethyl fluoroformate ($1-AdCH_2OCOF$, 2) in hydroxylic solvents have been studied. Application of the extended Grunwald-Winstein (G-W) equation to solvolyses of 1 in a variety of pure and binary solvents indicates an addition-elimination pathway in the majority of the solvents except an ionization pathway in the solvents of relatively low nucleophilcity and high ionizing power. The solvolyses of 2 show an addition-elimination pathway in all of the mixed solvents. The leaving group effects ($k_F/k_{Cl}$), the kinetic solvent isotope effects (KSIEs, $k_{MeOH}/k_{MeOD}$), and the enthalpy and entropy of activation for the solvolyses of 1 and 2 were also calculated. The selectivity values (S) for each solvent composition are reported and discussed. These observations are compared with those previously reported for other alkyl haloformate esters.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.383-388
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• 2009

Rates of solvolyses of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone and 2,2,2-trifluoroethanol (TFE) are reported. For four representative solvents, studies were made at several temperatures and activation parameters were determined. The 30 solvents gave a reasonably precise extended Grunwald-Winstein plot, correlation coefficient (R) of 0.989. The sensitivity values (l = 1.29 and m = 0.64) of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) were similar to those obtained for diphenyl phosphorochloridate ($(PhO)_2$POCl, 2), diphenylphosphinyl chloride ($Ph_2$POCl, 3) and diphenylthiophosphinyl chloride ($Ph_2$PSCl, 4). As with the previously studied of 3~4 solvolyses, an $S_N$ pathway is proposed for the solvolyses of diphenyl thiophosphorochloridate (1). The activation parameters, ${\Delta}H^{\neq}\;(=11.6{\sim}13.9\;kcal{\cdot}mol^{-1})\;and\;{\Delta}S^{\neq}\; (=\;-32.1\;{\sim}\;-42.7\;cal{\cdot}mol^{-1}{\cdot}K^{-1})$, were determined, and they were in line with values expected for an $S_N$2 reaction. The large kinetic solvent isotope effects (KSIE, 2.44 in MeOH/MeOD and 3.46 in $H_2O/D_2$O) are also well explained by the proposed $S_N$2 mechanism.

• KSBB Journal
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• v.28 no.2
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• pp.92-98
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• 2013

This research was to investigate physicochemical properties and antioxidative activities of rapeseed meal for the development of functional cosmetic material. Seventeen kinds of amino acid at rapeseed meal were found and glutamic acid concentration was significantly the highest (28.4 mg/g), followed by glycine, proline, arginine, isoleucine, and aspartic acid. Among various vitamins, cloline content was the highest (459.1 mg/kg), followed by niacin, tocopherol, and pantothenic acid. Among various fatty acids of rapeseed meal, oleic acid was the highest (36.7%), followed by linoleic acid and linolenic acid. DPPH radical scavenging activities of methanol and acetone extract of rapeseed meal at 2.0 mg/mL were 80.4 and 78.9%, respectively. The methanol and acetone extracts of rapeseed meal were a stable at the range of pH 3-9 on DPPH radical scavenging activity. The maximum reducing powers of methanol and acetone extract of rapeseed meal at 4.0 mg/mL were 0.7 and 0.68 OD 700 nm, respectively. The maximum superoxide inhibition activities of hot water, acetone, and methanol extract of rapeseed meal were 70.2, 75.2, and 81.4%, respectively. These results showed that the methanol and acetone extract of rapeseed meal can be used as a new source of functional cosmetic material.

• Bulletin of the Korean Chemical Society
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• v.31 no.4
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• pp.835-839
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• 2010

The rate constants of solvolyses of 2,2,2-trichloro-1,1-dimethylethyl chloroformate ($\underline{I}$) in 33 solvents can be well correlated using the extended Grunwald-Winstein equation, with incorporation of the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivities towards changes in the scale having values of $1.42\;{\pm}\;0.09$ for l and $0.39\;{\pm}\;0.05$ for m, respectively. The activation enthalpies are ${\Delta}H^{\neq}\;=\;12.3$ to $14.5\;kcal{\cdot}mol^{-1}$ and the activation entropies are -28.2 to $-35.5\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$, consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.14 in MeOH/MeOD is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• BMB Reports
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• v.38 no.3
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• pp.294-299
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• 2005

In this report, we describe the high-yield secretory expression of the recombinant human anti-HBsAg Fab fragment from Pichia pastoris that was achieved by co-integration of the genes encoding the heavy and light chains (both under the control of alcohol oxidase promoter) into the genome of the yeast cells. The fed-batch fermentations were carried out in a 5 L scale. Both chains of the Fab were successfully expressed upon methanol induction. The absorbance ($OD_{600}$) of the broth can reach 350~500 at the end of fed-batch phase. After the induction, the expression level of the recombinant Fab (soluble) reached 420~458 mg/L. The recombinant Fab fragment was purified from the crude culture supernatant by ion exchange chromatography and the purity of the recombinant Fab fragment was over 95%. The affinity activities of the crude fermentation supernatant and the purified Fab were analyzed by indirect ELISA, which showed that the purified recombinant Fab fragment had high affinity activity with hepatitis B surface antigen.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4117-4121
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• 2012

The solvolysis rate constants of allyl chloroformate ($CH_2=CHCH_2OCOCl$, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with the sensitivity values of $0.93{\pm}0.05$ and $0.41{\pm}0.02$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.5 to 13.4 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -34.4 to -37.3 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.16 was also in accord with the $S_N2$ mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.

• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.615-621
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• 2013

Solvolyses of isobutyl chloroformate (4) in 43 binary solvent mixtures including highly aqueous media, water, $D_2O$, $CH_3OD$, 2,2,2-trifluoroethanol (TFE) as well as aqueous 1,1,1,3,3,3-hexafluoro-isopropanol (HFIP) solvents were performed at $45^{\circ}C$, in order to further investigate the recent results of D'Souza, M. $J^1$. et al.; solvolyses of 4 are found to be consistent with the proposed mechanism ($Ad_E$). The variety of solvent systems was extended to comprise highly ionizing power solvent media ($Y_{Cl}$ > 2.7 excepted for aqueous fluorinated solvents and pure TFE solvent) to investigate whether a mechanistic change occurs as solvent compositions are varied. However, in case of 18-solvent ranges having aqueous fluorinated solvent systems (TFE-$H_2O$ and HFIP-$H_2O$) and/or having $Y_{Cl}$ > 2.7 solvent systems, the solvent effect on reactivity for those of 4 are evaluated by the multiple regression analysis as competition with $S_N2$ - type mechanism. And in pure TFE and 97 w/w % HFIP solvents with high $Y_{Cl}$ and weak $N_T$, these solvolyses are understood as reactions which proceed through an ionization ($S_N1$) pathway.

• Journal of Korean society of Dental Hygiene
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• v.13 no.5
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• pp.787-795
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• 2013

Objectives : The aim of the study is to investigate the possible influences of health behaviors and oral symptoms on subjective oral health status and to provide basic data for the development of oral health education programs. Methods : Subjects were 274 nursing home workers in Jeollabukdo, Korea. A self- reported survey was carried out. Results : Eighty four persons (30.7%) subjectively perceived their subjective oral health was good in the meanwhile forty nine persons (17.9%) reported poor oral health status. Health behaviors had much influence on their subjective oral health status. Good subjective oral health status coincided with quitting od smoking and drinking alcohol. Periodontal diseases and dental caries, and tooache had bad influences on subjective oral health status. Conclusions : Quitting program for smoking and drinking alcohol will make the nursing home workers in good healthy oral health status.

• 한국정보통신설비학회:학술대회논문집
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• 2008.08a
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• pp.414-417
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• 2008

This paper presents the design and analysis of 2.45GHz Low-IF Mixer using CMOS 0.18um. The Mixer is implemented by using the Gilbert-type configuration, current bleeding technique, and the resonating technique for the tail capacitance. And the design of this Double Balance Mixer is based on its lineaity since it is important in the interference cancellation system. The low flicker noise mixer is implemented by incorporating a double balanced Gilber-type configuration, the RF leakage-less current bleeding technique, and Cp resonating technique. The proposed mixer has a simulated conversion gain of 16dB a simulated IIP3 of -3.3dBm and P1dB is -19dBm. A simulated noise figure of 6.9dB at l0MHz and a flicker corner frequency of 510kHz while consuming only 10.65mW od DC power. The layout of Mixer for one-chip design in a 0.18-um TSMC process has 0.474mm$\times$0.39 mm size.

• Bulletin of the Korean Chemical Society
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• v.13 no.2
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• pp.140-145
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• 1992

The excited state intramolecular proton transfer and physical properties of 7-hydroxyquinoline are studied in various solutions and heterogeneous systems by measuring steady state and time-resolved fluorescence, reflection and NMR spectra. Proton transfer is observed only in protic solvents owing to its requirement of hydrogen-bonded solvent bridge for proton relay transfer. The activation energies of the proton transfer are 2.3 and 5.4 kJ/mol in $CH_3OH$ and in $CH_3OD$, respectively. Dimers of normal molecules are stable in microcrystalline powder form and undergo an extremely fast concerted double proton transfer upon absorption of a photon, consequently forming dimers of tautomer molecules. In the supercage of zeolite NaY, its tautomeric form is stable in the ground state and does not show any proton transfer.