• Bulletin of the Korean Chemical Society
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• 제11권2호
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• pp.99-105
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• 1990

The Gutmann acceptor number(AN), solvatochromic parameters $({\alpha},{\beta}\;and\;{\pi}^{\ast})$ and hydrogen bonding equilibrium constants (KHB) were determined for three binary systems of methanol with 1,2-dimethoxyethane(DME), 1,2-dichloroethane(DCE) and pyridine (PYD). The solvolysis rate constants of t-butyl chloride, bromide and iodide were also determined in the three binary systems. Solvent properties and solvolysis rates have been discussed in the light of various solvent parameters. Solvolysis of t-butyl halides are most conveniently explained by the two-stage mechanism involving ion-pair intermediate with the ion-pair formation for chloride and ion pair dissociation for iodide as rate limiting.

• Bulletin of the Korean Chemical Society
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• 제22권8호
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• pp.821-826
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• 2001

Solvent sublation has been studied for the separation and determination of trace Zn(Ⅱ) and Pb(Ⅱ) in water samples. A synergy producing method was utilized to improve the efficiency of extraction in the sublation using an ion-pair of metal-naphth oate {M-(Nph)3- } complexes and tetra-n-butylammonium (TBA+ ) ion. After the M-(Nph)3- complexes were formed by adding 1-naphthoic acid to the sample solution, tetra-n-butylammonium bromide was added in the solution to form the ion-pair. And sodium lauryl sulfate (SLS) was added to make the ion-pair hydrophobic. The ion-pairs of the metal complexes were floated and extracted into methylisobutyl ketone (MIBK) from the aqueous solution by bubbling with nitrogen gas in a flotation cell. Metal ions in MIBK solution were measured by graphite furnace-AAS. Experimental conditions were optimized as follow so. After the pH of a 1.0 L water sample was adjusted to 5.0, 6.0 mL of 0.1 M 1-HNph and 10 mL of 0.03 M TBA-bromide were added to the sample to form ion-pairs, and 2.0 mL of 0.2%(w/v) SLS was added to make the ion-pairs hydrophobic. The solution was bubbled with 30 mL/min N2 gas for 5 minutes in a flotation cell. Linear calibration curves were obtained for the determination of Zn(Ⅱ) and Pb(Ⅱ) in several water samples. Reproducible results of showing a relative standard deviation of < 10% and recoveries of 80-100% could be obtained.

• 공업화학
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• 제3권1호
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• pp.100-110
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• 1992

수용액에서 amlne류와 arylsulfonyl carbamate류를 반응시켜 다음과 같은 arylsulfonyl urea유도체들을 좋은 수율로 쉽게 합성할 수 있다 : 1) N-Arylsulfonyl-N'-arylurea 유도체, 2) N-Arylsulfonyl-N'-alkyl urea 유도체, 3) N-Arylsulfonyl-N'-heterocyclic urea 유도체. Arylsulfonyl urea의 합성에 관한 반응메카니즘은, 먼저 산-염기 반응에 의해 ion-pair형태가 만들어지고, 그 다음 사면체형 중간체를 형성하는 친핵성첨가반응, 그리고 산촉매에 의한 alkoxide ion과 양성자의 제거반응에 따라 일어난다.

• 대한화학회지
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• 제42권4호
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• pp.416-421
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• 1998

귀금속-티아크라운에테르 착물들의 역상 이온쌍 고성능 액체크로마토그래피(RPIP-HPLC)용리 거동에서 이온쌍 시약의 농도와 리간드 종류 효과를 연구하였다. 귀금속 이온 분석의 선택성은 사용한 티아크라운에테르의 고리를 구성하는 원자들의 수가 작을수록 좋았고, 귀금속-티아크라운에테르 착물의 용리 메카니즘은 이동상 중 이온쌍 시약인 도데실술폰산나트륨염(SDS)의 농도가 10 mM 이하일 경우 이온쌍 형성 메카니즘으로, 10 mM 이상일 경우 미쎌 형성 메카니즘으로 설명되었다. 결론적으로 몇 가지 귀금속-티아크라운에테르 착물들을 최적 조건에서 성공적으로 분리하였고, 흑백사진 정착액 중 Ag(Ⅰ) 이온 분리와 정량에 유용함을 증명하였다.

• Journal of Pharmaceutical Investigation
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• 제23권3호spc1호
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• pp.41-50
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• 1993

The iontophoretic delivery across rat skin of quaternary ammonium salts (isopropamide: ISP, pyridostigmine: PS), which are positively charged over a wide pH range, was measured ill vitro. The study showed that: (a) iontophoresis significantly enhanced delivery of ISP and PS compared to respective passive transport; (b) delivery of ISP and PS was directly proportional to the applied continuous direct current density over the range of $0-0.69\;mA/cm^2;$ (c) delivery of ISP and PS was also proportional to the drug concentration in the donor compartment over the range of $0-2{\time}l0^{-2}M:$ (d) sodium ion in the donor compartment inhibited the drug transport possibly due to decreasing the electric transference number of the drug; (e) delivery of ISP and PS increased as the pH of the donor solution increased over the pH range 2-7 suggesting permselective nature of the epidermis, and inhibition of the transference number of the drugs by hydronium ion; (f) some organic anions such as taurodeoxycholate, salicylate and benzoate which form lipophilic ion-pair complexes with ISP inhibited the delivery of ISP. The degree of inhibition by the organic anions was linearly proportional to the extraction coefficient $(K_e)$ of ISP from the partition system with each counteranion between phosphate buffer (pH 7.4) and n-octanol. For PS, however, taurodeoxycholate, but not salicylate and benzoate inhibited the iontophoretic delivery. It suggests that not only sodium ion and hydronium ion but also the counteranions which form lipophilic ion-pairs with quaternary ammonium drugs are not favorable components in formulating the donor solution of the drugs to achieve an effective iontophoretic delivery.

• Archives of Pharmacal Research
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• 제19권6호
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• pp.435-440
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• 1996

The effect of benzalkonium chloride on skin permeability of partially modified antisense phosphorothioate oligonucleotides (PS-ODN), which are designed as scar formation inhibitor, was investigated using Franz Diffusion Cell. When the concentration ratio of PS-ODN-quarternary ammonium salt complex is more than 1:100, the apparent partition coefficient (APC) of each complex was increased in the following order; tetraphenyl phosphonium chloride (TPP) < cetyltrimethyl ammonium bromide(CTAB) < benzalkonium chloride (BZ). The permeability of PS-ODN through the rat skin increased in the presence of BZ. The fluxs of PS-ODN with BZ were increased by addition of Pluronic F 68 or Triton X-100 to phosphate buffered saline (PBS), respectively. When the mole ratio of PS-ODN to BZ is 1:10, the fluxs penetrated of PS-ODN with BZ was greatest. The increase of the permeability in the presence of BZ might be due to the formation of lipophilic ion-pair complex between PS-ODN and BZ. By regulation of mole ratio of PS-ODN to BZ, the development of topical dosage forms using PS-ODN as scar formation inhibitor will be possible with minimal systemic exposure.

• 분석과학
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• 제6권3호
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• pp.289-296
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• 1993

자연수 중 극미량 몰리브덴[Mo(VI)]을 분리 정량하기 위하여 Mo(VI)의 킬레이트이온을 이온쌍으로 만들어 유기용매로 상승 용매추출시키는 방법에 대해 검토하였다. 자연수 시료 100mL를 분별 깔때기에 취하였다. pH 4.0인 시료에 0.01M alizarin red S 용액 0.5mL를 가하여 Mo(VI)-ARS의 킬레이트이온을 형성시킨 다음, aliquat-336을 0.2% 되게 녹인 chloroform 10mL를 가해 30초 정도 격렬하게 흔들어 모든 킬레이트이온이 이온쌍을 형성하여 용매층으로 분배되도록 하였다. 90분간 방치하여 두 쌍이 완전히 분리되면 chloroform층을 받아서 520nm에서 흡광도를 측정하여 검정곡선법으로 Mo(VI)을 정량하였다. 이상의 과정에서 용액의 pH, alizarin red S와 aliquat-336의 가해 주는 양, 흔들어 주고 방치하는 시간 등과 같은 추출조건에 대해서 검토하였다. 실제 시료인 강물과 수돗물의 분석에 응용하였다. 이들 시료에 Mo(VI)을 일정량 가하여 분석한 회수율은 모두 99% 이상으로 본 방법이 정량적임을 확인하였다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제40회 동계학술대회 초록집
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• pp.333-333
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• 2011

We studied the H/D exchange kinetics of pure and acid dopped water-ice film by using the techniques of reactive ions scattering (RIS) and low energy sputtering (LES) with low kinetic energy cesium ion beam (<35 eV). From RIS, neutral water isotopomers were detected in the form of cesium-molecule ion clusters, $CsX^+$ (X= $H_2O$, HDO, $D_2O$). Ionic species, like $H_3O^+$, $DH_2O^+$, $D_2HO^+$, $D_3O^+$, adsorbed on the surface were ejected via LES process. Those techniques allowed us to trace the isotopomeric populations of water-ice film. To show the catalytic effect of excess proton in the H/D exchange reaction, our study was conducted with two types of water-ice films. In film 1, about 0.5 BL of $H_2O$ was adsorbed on HCl (0.1 ML) dopped $D_2O$ (8 BL) film. In film 2, similar amount of $H_2O$ used in film 1 was adsorbed on pure $D_2O$ film. Kinetic data were obtained from each film type for 90-110 K (film 1) and 110-130 K (film 2) and fitted with numerically integrated lines. Through the Arrhenius plot of kinetic coefficient deduced from fitting of the H/D exchange reaction, the activation energy of film 1 and 2 were estimated to be $10{\pm}3kJmol^{-1}$ and $17{\pm}4kJmol^{-1}$. This activation barrier difference could be understood from detailed pictures of H/D exchange. In film 2, both the formation of ion pair, $H_3O^+$ and OH. and proton transfer were needed for the H/D exchange. However, in film 1, only proton transfer was necessary but ion pair formation was not, so this might reduce the activation energy.

• Archives of Pharmacal Research
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• 제9권2호
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• pp.111-114
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• 1986

Bretylium tosylate is a quaternary ammonium compound used for the treatment of ventricular fibrilation in humans. It is advantageous to other cationic compound in the study of biliary excretion in that negligible amount is bound to plasma protein and metabolite is not likely is to be formed. Some researchers reported that the formation of ion-pair complex caused to increase the lipothilicity of cationic compound. The partition of bretylium between water and organic phase was increased with the addition of sodium taurodeoxycholate. Also sensitive gas chromatographical assay procedure using flame ionization detector was studied. This procedure can detect as low as 0.1 mg/ml using 0.1 ml biological sample, but contamination by previous injection is the major problem of this method.

• 분석과학
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• 제6권3호
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• pp.329-334
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• 1993

형성시킨 Mo(VI)의 킬레이드이온과 이온쌍을 만들어 유기용매에로 상승추출시켜 자연수 중 극미량의 몰리브덴[Mo(VI)]을 분리 정량하는 방법을 해수에 응용하였다. pH 2.0과 4.0에서 anthranilic acid를 가해 Cu(II)와 Fe(III), Zn(II)을 침전시켜 그들의 방해를 제거한 해수시료 100mL를 분액 깔때기에 취하였다. pH를 4.6으로 조절한 시료에 0.01M alizarin red S 1.0mL를 가하여 Mo(VI)-ARS의 킬레이트이온을 형성시킨 다음 aliquat-336을 0.6% 되게 녹인 chloroform 10mL를 가해 30초 정도 격렬하게 흔들어 모든 킬레이트이온이 이온쌍을 형성하도록 하였다. 30분간 방치하여 두 상이 완전히 분리되면 chloroform층을 받아서 520nm에서 흡광도를 측정하여 검정곡선법으로 Mo(VI)을 정량하였다. 이상의 과정에서 추출조건인 용액의 pH, alizarin red S와 aliquat-336의 가해 주는 양, 흔들어 주고 방치하는 시간 등과 공존 이온들의 방해와 제거방안에 대해서 검토하였다. 실제 시료인 동해와 황해 해수의 분석에 응용하였으며, 이들 시료에 Mo(VI)을 일정량 가하여 분석한 회수율은 모두 85% 이상으로 본 방법을 해수 중 Mo(VI)의 분석에서도 정량적임을 확인하였다.