• Journal of the Korean Chemical Society
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• v.31 no.5
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• pp.419-424
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• 1987

Kinetic studies on the solvolysis of para-methyl benzyl nitrate and benzyl nitrate were carried out in aqueous methanol, ethanol, acetonitrile, acetone, tetrahydrofuran and dioxane mixtures at 60$^{\circ}$C. The rates were faster in protic solvent mixtures than in aprotic solvent mixtures. This was considered in the light of transition state stabilization by hydrogen bonding solvation of protic solvent mixtures. Grunwald-Winstein equation, extended Grunwald-Winstein equation and correlation between E$_T$(30) and rate constant were applied in order to discuss the transition state variations caused by changing benzyl substituents and solvents. The results showed that strong electrophilic assistance of solvent is operative in the the water-rich solvents.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.123-131
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• 2002

Solvolyses rate constant of 1- and 2- naphthoyl chlorides (1 and 2) are reported for aqueous binary mixtures with methanol, ethanol, fluorinated alcohol, acetonitrile and dioxane. Kinetic solvent isotope effects (KISE) in methanol and product selectivities (S) of 2-naphthoyl chloride (2) in alcohol-water are also reported. Dispersions in Grunwald-Winstein correlations $(r{\leq}0.901)$ are discussed by multiple regression analysis incorporating ionizing power $(Y_{Cl})$ scale and rate-rate profiles. Major causes for these phenomena are investigated as an aromatic ring solvation effects, in conjunction with weakly nucleophilic solvation effects ($S_N2$ character), for solvolyses of 1 and for solvolyses of 2, as dual reaction channels, described as $S_N1$-$S_N2$ and $S_AN$-$S_N2$ processes. Distinct border lines between the two pathways are derived from solvolyses rates of 2 in 18 solvent using the results of $log(k/k_o)=mY_{Cl}+lN_T+hI$ plot with values of 1.13 for m, 0.37 for l and 0.15 for h value in 5 aqueous fluorinated alcohol mixtures. Using rate-product correlation, the validity of a third order model based on a general base catalyzed by solvent and contribution from these rate constants, $k_{aa},\;k_{aw}$ and $k_{aw}$, are investigated for $S_AN$-$S_N2$ solvolyses of 2 favored in more rich alcohol media and gradual addition of water to alcohol solvent shows a great shift away from stoichiometric solvation to predominantly medium effects. Rate-rate correlation between solvolyses of 2 and trimethyl acetylchloride (5) with alkyl group in the 29 aqueous solvent mixtures shows appreciable linearity (slope = 0.84, r = 0.987), caused by the same pathway ($S_N1$-$S_N2$ process), even if this correlation coincides with appreciable dispersion (different solvation effect).

• YAKHAK HOEJI
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• v.32 no.4
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• pp.251-257
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• 1988

A simple and sensitive HPLC method was developed for the simultaneous determination of ten kinds of active ingredients formulated in commercial cough-cold mixtures. A group of Pseudoephedrine HCl, dl-Methylephedrine HCl, Noscapine, Chlorophenylamine maleate, Dextromethorphan HBr and Phenylpropanolamine HCl were determined at 254nm using a Novapak $C_{18}$ column with mobile phase consisting of a mixture of methanol-acetonitrile-1, 4dioxane-tetrahydrofuran-water(12 : 20 : 20 : 5 : 43, pH4.7) containing 0.013M-dioctyl sodium sulfosuccinate. The another group of Acetoaminophen, Caffeine, Guaifenesin and Ethenzamide were also determined at 254nm using a Novapak $C_{18}$ column as the stationary phase, and a mixture of methanol-1% aqueous acetic acid (3 : 7). The results indicate that these methods are accurate and precise with relative standard deviation of not more than 1% (n=5) for the above active ingredients.

• Journal of Pharmaceutical Investigation
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• v.33 no.1
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• pp.7-14
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• 2003

The PVP-based solid dispersion systems (SDs) containing lovastatin (LOS) and solubilizers (sodium lauryl sulfate, tween 80 and oleic acid) were prepared to enhance dissolution rate of practically water insoluble LOS using solvent evaporation method. Two different organic cosolvents either acetone/ethanol or acetonitrile/ethanol were used for the preparation of SDs. The LOS contents were highly decreased when acetone/ethanol cosolvents were used. The decrease of LOS contents was not caused by acetonitrile or acetone, based on HPLC data. The surface morphology as investigated by scanning electron microscope (SEM) and angle of repose as an index of flowability of SDs were highly dependent on the type and amount of solubilizers used. Based on differential scanning calorimetry (DSC) and X-ray powder diffraction data, the SDs made crystalline LOS into amorphous structure or partially eutectic mixtures. The simultaneous use of the solubilizers in SDs was also useful to increase dissolution rate of LOS in gastric or intestinal fluid. The SDs containing solubilizers reached 76% and 60% in gastric and intestinal fluid, respectively but the commercial tablet gave only less than 4%. These solubilizers in SDs could be also applicable for enhancing dissolution and bioavailability of poorly water-soluble drugs.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.8-14
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• 1980

Solvolysis rate constants for methylchloroformate, $CH_3O$(CO)Cl, methylthiono-chloroformate, $CH_3O$(CS)Cl, and methylthiolchloroformate, $CH_3S$(CO)Cl, have been determined conductometrically in acetone-water and acetonitrile-water mixtures, and activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, have been derived. Results show that in water-rich regions the order of rate increases as $$CH_3O(CO)Cl while in dipolar aprotic solvent-rich region this order reverses. The plots of log k vs. solvent parameters, Y, $\frac{D-1}{2D+1}$ and log($H_2$) show that the order of rate increase in water-rich region is the results of increase in $S_N1$ character. It is concluded that $CH_3S$(CO)Cl solvolyzes via $S_N1$ mechanism whereas $CH_3O$(CO)Cl reacts via $S_N2$ and $CH_3O$(CS)Cl via intermediate mechanism in water-rich region.

• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2229-2237
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• 2012

The two chelates based on calix[4]arene and thiacalix[4]arene have been synthesized and used as neutral ionophores for preparing PVC based membrane sensor selective to $Ho^{3+}$ ion. The addition of potassium tetrakis(4-chlorophenyl)borate (KTpClPB) and various plasticizers, viz., NDPE, o-NPOE, DOP, TEP and DOS have been found to improve significantly the performance of the sensors. The best performance was obtained with the sensor no. 6 having membrane of $L_2$ with composition (w/w) ionophore (2%): KTpClPB (4%): PVC (37%): NDPE (57%). This sensor exhibits Nernatian response with slope $21.10{\pm}0.3mV/decade$ of activity in the concentration range $3.0{\times}10^{-8}-1.0{\times}10^{-2}M\;Ho^{3+}\;ion$, with a detection limit of $1.0{\times}10^{-8}M$. The proposed sensor performs satisfactorily over a wide pH range of 2.8-10, with a fast response time (5 s). The sensor was also found to work successfully in partially non-aqueous media up to 25% (v/v) content of methanol, ethanol and acetonitrile, and can be used for a period of 4 months without any significant drift in potential. The electrode was also used for the determination of $Ho^{3+}$ ions in synthetic mixtures of different ions and the determination of the arsenate ion in different water samples.

• Analytical Science and Technology
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• v.36 no.6
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• pp.281-290
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• 2023

Zidovudine is an antiretroviral agent prescribed for the prevention and treatment of human immunodeficiency virus/acquired immune deficiency syndrome (HIV/AIDS). It is typically recommended to be used in combination with other antiretroviral drugs. Zidovudine has the potential to generate N-nitrosodimethylamine (NDMA) in the presence of dimethylamine and nitrite salt under acidic reaction conditions during the drug manufacturing process. NDMA is a potent human carcinogen that may be detected in drug substances or drug products. An analytical method was developed to determine NDMA in pharmaceuticals including zidovudine using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The analysis involved reversed-phase chromatography on a Kinetex F5 column with a mobile phase comprising water-acetonitrile mixtures. The detection of positively charged ions was conducted using atmospheric pressure chemical ionization (APCI). The calibration curve demonstrated excellent linearity (r = 0.9997) across the range of 1-50 ng/mL with a highly sensitive limit of detection (LOD) at 0.3 ng/mL. The developed method underwent thorough validation for specificity, linearity, accuracy, precision, robustness, and system suitability. This sensitive and specific analytical method was applied for detecting NDMA in zidovudine drug substance and its formulation currently available in the market, indicating its suitability for drug quality management purposes.

• Journal of the Korean Chemical Society
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• v.31 no.1
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• pp.55-63
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• 1987

The systematic investigation of the retention behaviors of 18 monosubstituted benzenes in reversed-phase liquid chromatography(RPLC) was studied in order to predict the separation possibility of their mixtures and study the contribution of substituent group to the retentions of solutes. The columns and mobile phases employed in this study were $\mu$ -Bondapak $C_{18}$, $\mu$-Bondapak phenyl columns and methanol/water, acetonitrile/water, and THF/water, respectively. The polar substituents such as phenol, aniline, acetophenone and benzonitrile have smaller capacity factor(k') values than benzene, while nonpolar ones such as alkylbenzenes and halobenzenes show larger k' value. The capacity factors of all solutes increased on both C18 bonded and phenyl bonded phases as the organic solvent content of three organic solvent-water mixtures decreased. The absolute differences in capacity factor(${\Delta}k$') between substituent and benzene were graphically shown for the prediction of the separation of the mixture and interpretation of the elution behavior of substituent. In addition, the selectivity of solvent system for the separation of the mixture was investigated in both two columns and three mobile phases.

• Korean Journal of Oriental Medicine
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• v.15 no.1
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• pp.85-89
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• 2009

The aim of this study was to study the quantitative analysis of glycyrrhizic acid in Glycyrrhizae Radix extract fermented with Paecilomyces japonica, Ganoderma lucidum, honey or Nuruk. The amounts of dry on loss were measured and the quantitative analysis of glycyrrhizic acid was performed by high performance liquid chromatographic (HPLC). HPLC method was performed on C18 column ($250\;mm\;{\times}\;4.6\;mm$, $5\;{\mu}m$, RS tech) using gradient solvent mixtures of water-acetonitrile with photodiode array detector (254 nm). The flow rate was $1.0\;m{\ell}/min$. Retention time of glycyrrhizic acid was about 23.96 min and linearity of calibration was $R^2$=0.9998. Contents of glycyrrhizic acid in Glycyrrhizae Radix extract (control) was $5.048\;{\pm}\;0.14$; Contents of glycyrrhizic acid in Glycyrrhizae Radix extract fermented with Paecilomyces japonica (SDT) was $1.975\;{\pm}\;0.07$; Contents of glycyrrhizic acid in Glycyrrhizae Radix extract fermented with Ganoderma lucidum (SYT) was $2.676 \;{\pm}\;0.07$; Contents of glycyrrhizic acid in Glycyrrhizae Radix extract fermented with honey (SST) was $5.191\;{\pm}\;0.06$; Contents of glycyrrhizic acid in Glycyrrhizae Radix extract fermented with Nuruk (SNT) was $5.305\;{\pm}\;0.34$, respectively. Contents of glycyrrhizic acid in SDT and SYT were decreased but that in SST and SNT was increased when compared to control.

• Korean Journal of Oriental Medicine
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• v.15 no.2
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• pp.119-124
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• 2009

The purpose of this study was investigation of quantitative analysis of marker substances in Paeonia lactiflora extracts by solid fermentation. High performance liquid chromatography (HPLC) for the determination of albiflorin and paeoniflorin in P. lactiflora extracts by solid fermentation, the separation method was performed on C18 column ($250\;mm\;{\times}\;4.6\;mm$, $5\;{\mu}m$, RS tech) using gradient solvent mixtures of water-acetonitrile with photodiode array detector (230nm). The flow rate was 1.0 ml/min. Retention time of albiflorin and paeoniflorin was about 28.88, 31.92 min and linearity of calibration was showed good result(r2 = 0.9998, 0.9996), respectively. Content of albiflorin was $0.090\;{\pm}\;0.03%$ in P. lactiflora extract(control), $0.102\;{\pm}\;0.00%$ in P. lactiflora extract fermented with Paecilomyces japonica, $0.056\;{\pm}\;0.01%$ in P. lactiflora extract fermented with Ganoderma lucidum, $0.093\;{\pm}\;0.00%$ in P. lactiflora extract fermented with honey and $0.046\;{\pm}\;0.00%$ in P. lactiflora extract fermented with Nuruk. Content of paeoniflorin was $4.506\;{\pm}\;0.13%$ in control, $2.599\;{\pm}\;0.04%$ in P. lactiflora extract fermented with Paecilomyces japonica, $1.222\;{\pm}\;0.03%$ in P. lactiflora extract fermented with Ganoderma lucidum, $2.750\;{\pm}\;0.05%$ in P. lactiflora extract fermented with honey and $0.847\;{\pm}\;0.00%$ in P. lactiflora extract fermented with Nuruk, respectively. Content of the marker substances did not increase in all fermentation experiment group.