• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.303-308
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl benzoate (5a), 4-nitrophenyl 4-methoxybenzoate (5b), and 4-nitrophenyl 4-hydroxybenzoate (5c) with alkali metal ethoxides, $EtO^-M^+$ ($M^+=Li^+$, $Na^+$ and $K^+$) in anhydrous ethanol (EtOH) at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [$EtO^-M^+$] exhibit upward curvatures in all cases, indicating that $M^+$ ions catalyze the reactions and ionpaired $EtO^-M^+$ species are more reactive than dissociated $EtO^-$. Second-order rate constants for reactions with dissociated $EtO^-$ and ion-paired $EtO^-M^+$ (i.e., $k_{EtO^-}$ and $k_{EtO^-M^+}$, respectively) have been calculated from ion-pair treatment for the reactions of 5a and 5b. However, such ion-pair treatment has failed to determine $k_{EtO^-}$ and $k_{EtO^-M^+}$ values for the reactions of 5c. It has been concluded that reactions of 5a and 5b are catalyzed by one metal ion, which increases electrophilicity of the reaction center through coordination on the carbonyl oxygen. In contrast, reactions of 5c have been suggested to involve two metal ions, i.e., the one coordinated on the carbonyl oxygen increases the electrophilicity of the reaction center while the other one associated on the phenoxy oxygen decreases the charge repulsion between the anionic reagents (i.e., $EtO^-$ and deprotonated 5c). It has been found that the rate equation derived from the mechanism involving two metal ions fits nicely to the kinetic results obtained for the reactions of 5c.

• YAKHAK HOEJI
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• v.35 no.1
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• pp.15-21
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• 1991

Quaternary amines which are widely used as medicines are nitrogen compounds. Metanil yellow(MY) and benzalkonium chloride(BKC) were mixed and added to 10ml of the buffer solution and then the solution was shaken for 5 minutes. The maximum absorption wavelength of the reaction product was 402 nm. Dichloromethane was the best extracting solvent among the several organic solvents and the most suitable pH range was 2~8. When the BKC-MY calibration curve was made in the best experimental condition, the Lambert-Beer's law was obeyed in the range of BKC concentration of 2$\times$$10^{-6}$~9$\times$$10^{-6}$M by UV spectrophotometer. This method was possible to determine quaternary ammonium salts in the pharmaceutical preparation.

• Bulletin of the Korean Chemical Society
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• v.28 no.2
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• pp.183-187
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• 2007

A simple and sensitive extractive spectrophotometric method has been described for the determination of buprenorphine either in raw material or in pharmaceutical formulations. The developed method is based on the formation of a colored ion-pair complex (1 : 1 drug/dye) of buprenorphine and bromocresol green (BCG) in buffer pH 3 and extracting in chloroform. The extracted complex shows absorbance maxima at 415 nm. Beer's law is obeyed in the concentration range of 1.32-100.81 μ g mL-1. The proposed method has been applied successfully for the determination of drug in commercial sublingual tablets and injectable dosage form. No significant interference was observed from the excipients commonly used as pharmaceutical aids with the assay procedure.

• YAKHAK HOEJI
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• v.18 no.2
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• pp.133-144
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• 1974

The metal indicator, acidic azo dyes NN, EBT and Calcon are utilized to analyse quantitatively chlorpheniramine, tripelenamine and diphenhydramine forming insoluble ion pair in aqueous solution at proper pH values between the acidic azo dyes and the sample molecules, these compexes are extracted by organic polar solvents, and organic layer is determined spectrophotometrically. Generally, the absorption maxima of the complexes are shifted to longer wavelengths compare to the absorption maxima of the dyes themselves. The binding ratio of the ion pair forming complex molecules in chloroform soln, are as follows ; NN-antihistamines (chlorpheniramine, tripelennamine, diphenhydramine) are NN-1 to antihisamine-1, EBT-antihistamines are EBT-2 to antithistamines a and Calcon-antihistamines are Calcon-3 to antithistamines-1. These coomplexes in chloroform soln. are very stable, and show higher absorbance than the other organic polar solvents. The binding state of complexes were presumed intermolecular hydrogen bond by their infrared spectra. In the mixture solution of three samples, the aqueous phase is buffered at pH 1.0, and benzene is used to extract ion pair of diphenhydramine EBT complex selectively. At pH 1.0 of aqueous layer, Calon-diphenhydramine complex is also extracted selectively by benzene. However, in this case very small amount of chlorpheniramine-calcon calcon simultaneously. The binding state of diphenhydramine-EBT and diphenhydramine-calcon in benzene are smae as the complexes in chloroform. But the absorption maxima of the complexes in benzene are shifted to shorter wavelenlgths than the complexes in chloroform.

• KSBB Journal
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• v.25 no.5
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• pp.459-465
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• 2010

A simple and efficient analytical method for the simultaneous determination of seven tar color additives was developed using ion pair high performance liquid chromatography. The conditions for HPLC analysis were as follows: column, ${\mu}$-Bondapak C18 (10 ${\mu}m$, 300 ${\times}$ 3.9 mm i.d.); gradient mobile phase, 0.025 mol/L ammonium acetate (containing 0.01 mol/L tetrabutylammonium bromide)-acetonitrile-methanol (65:25:10) as a mobile for fraction A and 0.025 mol/L ammonium acetate (containing 0.01 mol/L tetrabutylammonium bromide)-acetonitrilemethanol (40:50:10) as a mobile for fraction B; flow rate, 1.0 mL/ min; detection wavelength, 254/520/620 nm. We could attain to the detection limits as 0.01~0.05 ${\mu}$g/mL (254 nm) and 0.005~0.01 ${\mu}$g/mL (520 nm) for six red tar color additives, and 0.05 ${\mu}$g/mL (254 nm) and 0.002 ${\mu}$g/mL (620 nm) for Fast green FCF. This analytical method was applicable to determine the tar color additives contained in several commercial cold syrups.

• Journal of the Korean Chemical Society
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• v.42 no.4
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• pp.416-421
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• 1998

In the reversed-phase ion-pair high performance liquid chromatographic (RPIP-HPLC) elution behavior of noble metal-thiacrown ether complexes, the effects of the concentration of ion-pairing reagent and kind of ligands were studied. It was found that the less the number of atoms in the ring of the thiacrown ether molecule was, the larger the selectivity was, and the elution mechanism of the complexes was explained due to the formation of ion-pair when the concentration of sodium dodecyl sulfate (SDS) in mobile phase was lower than 10 mM and due to the formation of micelle when the SDS concentration was higher than 10 mM. As a conclusion, separations of the noble metal-thiacrown ether complexes in an optimum separation condition were accomplished successfully and the method was proved to be an useful one for the separation and determination of Ag (Ⅰ) ion in a black-white photographic fixing solution.

• Journal of applied mathematics & informatics
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• v.19 no.1_2
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• pp.1-17
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• 2005

In this paper we present a pair of operators (t-norm, t-conorm) dual with a strong negation with n-threshold $a_1,\;{\ldots}, a_n\;{\in}(0,1),\;a_1\;<\;a_2\;<\;{\ldots}\;<\;a_n$. In this way we obtain an extension of operators with threshold, that are obtained for n = 1. The new pair is obtained from given one.

• Journal of the Korean Chemical Society
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• v.29 no.4
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• pp.365-371
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• 1985

A cationic dye, methylene blue $(MTB^+)$ was examined as a counter ion in the separation of organic and inorganic anions by ion-pair chromatography. Nonabsorbing anions could be indirectly detected by photometric detector with the assistance of MTB^+ in visible range (665nm). A mixture of anions was able to be separated with good base line resolution and high sensitivity. The capacity factors were also determined in various experimental conditions to study retention mechanism. The retention followed the ion-interaction model where the $MTB^+$ occupies a primary layer at the stationary phase while the analyte anion and other anions in the system compete for forming the secondary layer.

• Proceeding of EDISON Challenge
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• 2014.03a
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• pp.347-358
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• 2014

본 논문에서는 양자 역학적 분자 동역학(Quantum Mechanical/Molecular Mechanical-Molecular Dynamics, QM/MM-MD)을 통해 수용액에 녹아 있는 Potassium Thiocyanate의 dynamics를 연구했다. Umbrella sampling technique을 활용하여 association/dissociation에 해당하는 Free energy surface를 구했다. 두 개의 Free energy minimum이 녹아 있는 두 이온의 center of mass 사이의 거리가 $4{\AA}$일 때와 $5{\sim}6{\AA}$ 부근일 때 나타났으며 $4{\AA}$일 때 더 안정 했다. 본 논문에서는 $4{\AA}$일 때를 Contact Ion Pair(CIP) $6{\AA}$일 때를 Dissociation Ion Pair(DlP)라고 칭했다. 이 minimum들이 무엇인 지를 밝혀 내기 위해 추가 연구를 수행하였다. Free energy 상에서 가장 안정 할 때(CIP) solute인 Potassium thiocyanate의 구조를 살펴 봤더니 Potassium ion은 Thiocyanate ion의 Sulfur보다 Nitrogen side를 선호하였다. 그 원인을 알아보기 위해 salvation shell의 구조를 Radial distribution function을 통해 살펴 봤더니 물 분자가 Nitrogen보다 Sulfur와 더 강한 상호작용을 하고 있었다. 그로 인해 Potassium ion이 Nitrogen을 선호한단 결과가 나온 것이다. 한편, 두 번째 minimum은 물 분자가 Potassium 이온과 Thiocyanate 이온 사이에 flexible하게 bridging을 하는 구조였다. 또한 단순 양자 계산을 통해서도 비슷한 구조를 얻을 수 있었다. 그러나 QM 계산은 0K에서 수행하는 것이기 때문에 엔트로피 효과가 없는 계산이지만 본 연구는 온도 300K로 실제 용매와 가깝게 수행함으로써 고정되어 있는 구조가 아니라 엔트로피와 엔탈피가 균형적으로 존재하는 실제 용액 속에서의 구조를 처음으로 보여주는 것이다.

• Proceedings of the Korean Society of Precision Engineering Conference
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• 1995.10a
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• pp.1093-1097
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• 1995

A micro ion drag pump with planar electrodes on a glass substrate is fabricated and tested. the pump consisted of a 2- dimensional electrode pair array is driven by DC voltage using unipolar conduction. Ethy alcohol is pumped in both directions, and the flow rate and the pressure are measured, in channels of depth 100 .mu m or 200 .mu. m and width fixed at 3mm. It is found that the pump could be fabricated easily and at lower cost than the micro ion drag pumps previously investigated.