• Journal of Microbiology and Biotechnology
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• v.13 no.2
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• pp.191-195
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• 2003

The in vitro glycosylation of pentapeptide (Arg-Lys-Asp-Val-Tyr; RKDVY) and RNase A was carried out using PNGase F (peptide-N-glycosidase F), and the results were analyzed using MALDI-TOF-MS. Aminated N,N-diretyl chitobiose was used as the sugar in the glycosylation reaction, and the amination yield of N,N'-diacetyl chitobiose was about $60\%$. To reduce the water activity and shift the reaction equilibrium to a reverse reaction, 1,4-dioxane or ethylene glycol was used as the organic solvent in the enzymatic glycosylation. A certain extent of nonenzymatic glycosylaton, known as the Maillard reaction, was also observed, which occurs on an arginine or lysine residue when the length of tie sugar residue is one or two. However, the extent of glycosylation was much higher in the enzymatic reaction, indicating that PNGase F can be effectively used to produce glycopeptides and glycoproteins in vitro.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2377-2381
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• 2007

Solvolyses of 3,4-dimethoxybenzenesulfonyl chloride (DSC) in water, D2O, CH3OD, and in aqueous binary mixtures of acetone, acetonitrile, 1,4-dioxane, ethanol, methanol, and 2,2,2-trifluoroethanol (TFE) have been investigated at 25.0 oC. Kinetic solvent isotope effects (KSIE) in water and in methanol and product selectivities in alcohol-water mixtures are also reported. The Grunwald-Winstein plot of first-order rate constants for the solvolyic reaction of DSC with YCl shows marked dispersions into separated lines for various aqueous mixtures. With use of the extended Grunwald-Winstein equation, the l and m values obtained are 1.12 and 0.58 respectively for the solvolyses of DSC. The relatively large magnitude of l is consistent with substantial nucleophilic solvent assistance. From Grunwald-Winstein plots the rate data are dissected approximately into contributions from two competing reaction channels. This interpretation is supported for alcohol-water mixtures by the trends of product selectivities, which show a maximum for ethanol-water mixtures. From the KSIE of 1.45 in methanol, it is proposed that the reaction channel favored in methanolwater mixtures and in all less polar media is general-base catalysed and/or is possibly (but less likely) an addition-elimination pathway. Also, the KISE value of 1.35 for DSC in water is expected for SN2-SN1 processes, with minimal general base catalysis, and this mechanism is proposed for solvolyses in the most polar media.

• Journal of Photoscience
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• v.11 no.1
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• pp.11-17
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• 2004

Fluorescence quenching of l,4-bis [2-(2-methylphenyl) ethenyl]-benzene (Bis-MSB) by carbon tetrachloride in five different solvents namely hexane, cyclohexane, toluene, benzene and dioxane has been carried out at room temperature with a view to understand the quenching mechanisms. The Stern-Volmer plot has been found to be non-linear with a positive deviation for all the solvents studied. In order to interpret these results we have invoked the Ground state complex and Sphere of action static quenching models. Using these models various rate parameters have been determined. The magnitudes of these parameters imply that sphere of action static quenching model agrees well with the experimental results. Hence the positive deviation in the Stem-Volmer plots is attributed to the static and dynamic quenching. Further, with the use of Finite Sink approximation model, it was possible to check whether these bimolecular reactions as diffusion limited and to estimate independently distance parameter R' and mutual diffusion coefficient D. Finally an effort has been made to correlate the values of R'and D with the values of the encounter distance R and the mutual diffusion coefficient D determined using the Edwardis empirical relation and Stokes-Einstein relation.

• KSBB Journal
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• v.11 no.5
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• pp.511-517
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• 1996

An amphiphilic phase enzyme reaction was used to synthesize alkyl glucosides from glucose and alkyl alcohol with immobilized ${\beta}$-glucosidase using four glycol ether cosolvents(monoglyme, diglyme, 2-methoxyethanol, and 1,4-dioxane). Monoglyme was shown to be the best cosolvent for the amphiphilic phase medium composed of water/cosolvent/alkyl alcohol admixture. To obtain high yield of alkyl glucoside by amphiphilic phase enzyme reaction, hydrophilicity-hydrophobicity of amphiphilic media and enzyme microenvironment was optimized from the viewpoints of substrate solubility, enzyme activity, water activity, and dynamic equilibrium between glucose alcoholysis and glucoside hydrolysis. Under optimum reaction conditions, the highest concentrations of hexyl, octyl, decyl, and dodecyl glucosides were 18.2, 9.68, 7.27, and 6.03g/L, respectively.

• The Korean Journal of Pesticide Science
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• v.2 no.1
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• pp.46-52
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• 1998

The hydrolysis rate of insecticidal buprofezin(IUPAC : tert-butylimino-3-isopropyl-5-phenylperhydro-1,3,5-thiadiazin-4-one) in the range of pH 2.0 and 12.0 have been examined in 15%(v/v) aqueous dioxane at $45^{\circ}C$. The hydrolysis mechanism of buprofezin is proposed from the pH-effect, solvent effect(${\ell}{\gg}m$), thermodynamic parameter(${\Delta}H^{\neq}$=11.12 $Kcal{\cdot}mol^{-1}$ &, ${\Delta}S^{\neq}=5.0e.u.$), rate equation and hydrolysis product, l-isopropyl-3-phenyl urea. General acid catalyzed hydrolysis and specific acid catalyzed($k_{H3O+}$) hydrolysis through $A-S_{E}2$ and A-2(or $A_{AC}2$) reaction mechanism with orbital-control reaction proceed below pH 8.0 and above pH 9.0, the nucleophilic addition-elimination, $Ad_{N}-E$ mechanism via tetrahedral($sp^{3}$) intermediate is initiation by general base catalyzed($k_{H2O}$) reaction. Buprofezin was more stable in alkaline ($k=10^{-8}sec.^{-1}$) than acid solutions from the sigmoid pH-rate profile. And the half-life($t=\frac{1}{2}$) of hydrolysis reaction in neutral aqueous solution(pH 7.0) at $45^{\circ}C$ was about 3 months.

• Korean Chemical Engineering Research
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• v.55 no.2
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• pp.214-219
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• 2017

In this work, we fabricated PS-b-P4VP block copolymer membranes from self-assembly and non-solvent induced phase separation (SNIPS), which combines the block copolymer self-assembly and conventional NIPS process. While previous studies mostly focused on the fabrication of well-defined structures, we systematically examined various processing parameters such as polymer concentration, solvent evaporation duration, solvent composition, and humidity, to optimized the membrane structures. As a result, the morphology of PS-b-P4VP membranes was optimized at a certain polymer concentration in solution and composition of volatile solvent at low humidity conditions, resulting in SNIPS separation membranes with well-defined nanopores on the surface, 75% of membrane porosity, and 18% of surface porosity.

• Journal of the Korean Chemical Society
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• v.54 no.1
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• pp.13-22
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• 2010

The photophysical properties of 7-diethylaminocoumarin (DEAC) laser dye have been measured in different solvents. The emission spectrum of DEAC has also been measured in cationic (CTAC) and anionic (SDS) micelles. The laser parameters have been calculated in different solvents namely acetone, dioxane, ethanol and dimethylforamide(DMF). The photoreactivity of DEAC has been studied in $CCl_4$ solvent using 366 nm light. The values of photochemical yield (${\Phi}_c$) and rate constant (k) are determined. The interaction of organic acceptors such as picric acid (PA), tetracyanoethylene (TCNE) and 7,7,8,8-tetracynoquinonedimethane (TCNQ) with DEAC are also studied using fluorescence measurements in acetonitrile ($CH_3CN$). The electrochemical investigation of (DEAC) has been carried out using cyclic voltammetry and convolutive voltammetry combined with digital simulation technique at a platinum electrode in 0.1 mol $L^{-1}$ tetrabutyl ammonium perchlorate (TBAP) in $CH_3CN$ solvent. The electrochemical parameters of the investigated compound were determined using cyclic and convolutive voltammetry. The extracted electrochemical parameters were verified and confirmed via digital simulation method.

• Journal of the Korean Chemical Society
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• v.43 no.1
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• pp.85-91
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• 1999

The second order rate constants for the hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates (2,4-$(NO_2)_2$, 4-$NO_2$, 4-CN, 4-Cl, 4-H)in 20% dioxane-water (v/v) have been determined by UV/Vis spectrophotometric method at various temperatures. The activation parameters (Ea, ${\Delta}H^{\neq}$,${\Delta}S^{\neq}$) were calculated from the rate constants and the reaction constant ($\rho$) was also estimated by Hammett equation. The activation entropies of the title reactions show considerably negative values, this result is not consistent with a dissociative mechanism (EA) in which a positive or a slightly negative value of the entropy of activation should be expected. Further, kinetic evidence for an associative mechanism (AE) was obtained from the linear free energy relationship. By the results of kinetic study for the alkaline hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates, it may be concluded that these reactions proceed through an associative mechanism.

• Archives of Pharmacal Research
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• v.26 no.12
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• pp.1002-1008
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• 2003

Ferulic acid (3-methoxy, 4-hydroxy cinnamic acid) is a flavoid component possessing antioxidant property. The compound is currently under development as a new drug candidate for the treatment of the dementia. The objective of this preformulation study was to determine the physicochemical properties of ferulic acid. The n-octanol to water partition coefficients of ferulic acid were 0.375 and 0.489 at the pHs of 3 and 10, respectively. Accelerated stability study for ferulic acid indicated that the t 90 value for the drug was estimated to be 459 days at $25^{\circ}C$. Ferulic acid was also found to be unstable under the relative humidity of more than 76%, probably because of the hygroscopic nature of the drug. In order to study compatibility of ferulic acid with typical excipients, potential change in differential scanning calorimetry spectrum was studied in 1: 1 binary mixtures of ferulic acid and typical pharmaceutical excipients (e.g., Aerosil, Avicel, CMC, Eudragit, lactose, PEG, PVP, starch and talc). Avicel, CMC, PVP and starch were found to be incompatible with ferulic acid, indicating the addition of these excipients may complicate the manufacturing of the formulation for the drug. Particle size distribution of ferulic acid powder was in the size range of 10-190 $\mu$m with the mean particle size of 61 $\mu$m. The flowability of ferulic acid was apparently inadequate, indicating the granulation may be necessary for the processing of the drug to solid dosage forms. Two polymorphic forms were obtained by recrystallization from various solvents used in formulation. New polymorphic form of ferulic acid, Form II, was obtained by recrystallization from 1,4-dioxane. The equilibrium solubility for Form I was approximately twice of that for Form II. The dissolution rate of Form II was higher than that of Form I in the early phase (<6 min). Therefore, these physicochemical information has to be taken in the consideration for the formulation of ferulic acid.

• Journal of the Korean Chemical Society
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• v.17 no.2
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• pp.85-94
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• 1973

The stability constants of the charge-transfer complexes formed between three derivatives of nitrobenzene, i.e., 1,3,5-trinitrobenzene, m-dinitrobenzene, nitrobenzene and eleven organic molecules such as $\alpha-picoline$, pyridine, dimethylsulfoxide, N, N'-dimethylacetamide, tetrahydrofurane, 1, 4-dioxane, diethyl ether, acetonitrile, propylene oxide, epichlorohydrine, and methyl acetate, have been determined by ultraviolet absorption spectroscopy in carbon tetrachloride solution at 25.0$^{\circ}C$. The parameters of the electrostatic effect ($E_D$) and covalent effect ($C_D$) for the eleven organic compounds have been calculated from the modified equation of the double-scale enthalpy,$logK = E_AC_A+E_DC_D$ and also the shift of C=O vibrational frequency in infrared spectra for N,N'-dimethylacetamide have been measured from the solutions of above organic compounds. The empirical equation, ${\Delta}{\nu}_{C=O} = 37.4-5.47E_D+12.1C_D$, related to the parameters and the frequency shift has been derived. It seems that the stabilities of the complexes principally depend on the covalent effect. Especially it is found that $\pi$ orbitals in molecules, in addition to the parameters, play the important role in forming the charge-transfer complexes.