• Advances in materials Research
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• 제2권1호
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• pp.51-64
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• 2013

Enantioselective macromer of trimesic acid was prepared using S(-) menthol with trimesoyl chloride on polyimide (PI) ultrafiltration membrane. The chemical composition of macromer as well as polyimide ultrafiltration membrane was determined by ATR-FTIR Spectroscopy. The optical resolution of chiral alcohols was performed in pressure driven process. The effect of monomer solutions concentration, effect of air-drying time of S(-) menthol solution, effect of reaction time, effect of operating pressure, effect of feed concentration of racemate on the performance of macromer was studied. The synthesised material exhibits separation of chiral alcohols (menthol ~23% and sobrelol ~21%).

• 공업화학
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• 제17권6호
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• pp.565-574
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• 2006

광학순도가 높은 이성체의 응용은 최근 들어 크게 증가되고 있는 추세이다. 여러 가지 방법 중에서도 비대칭 촉매합성반응을 통하여 선택적으로 순수한 광학이성체를 합성하는 것이 가장 매력적인 방법이다. 특히 키랄화합물을 합성하는 비대칭촉매반응에 있어서는 가격이 비싼 촉매를 소량 사용하면서도 활성이나 광학선택성 및 촉매수명을 높이도록 하는 조건이 매우 중요하게 대두된다. 활성이 큰 키랄촉매를 고정화시키면 반응 후에 반응혼합물을 여과법으로 쉽게 제거할 수 있다는 등의 취급상 용이한 점을 제공한다. 키랄촉매반응에서 생성물의 광학선택성을 향상시키고 여러 번 촉매를 재사용할 수 있도록 하려는 다양한 방법이 연구되고 있다. 본 총설에서는 여러 종류의 광학선택적인 불균일촉매에 관한 연구의 현황과 제한점 등을 주로 다루었다.

• Bulletin of the Korean Chemical Society
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• 제27권11호
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• pp.1775-1779
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• 2006

A liquid chromatographic chiral stationary phase (CSP) based on (+)-(18-crown-6)-2,3,11,12-tetracarboxilic acid without extra free aminopropyl groups on silica surface has been demonstrated to be quite effective for the resolution of various $\beta$-amino acids. The retention factors ($k_1$) for the resolution of $\beta$-amino acids on the CSP were quite large and the large retention factors might be quite attractive along with the reasonable separation factors ($\alpha$) for preparative scale enantioselective chromatography. The large retention factors on the CSP were found to be reduced effectively by adding ammonium ion to mobile phase without sacrificing the chiral recognition efficiency of the CSP. Consequently, the CSP is also quite applicable for use in analytical enantioselective chromatography.

• Korean Membrane Journal
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• 제5권1호
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• pp.25-30
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• 2003

Chitosan membranes crosslinked with glutaraldehayde that contained chiral environment were prepared. The chitosan membranes were characterized using FTIR and swelling index measurements. Their swelling index in water ranged from 100 to 70%, depending on the crosslinking time. The separation of D- and L-isomers of tryptophan was achieved through a pressure driven membrane separation process, using the self-supporting crosslinked chitosan membranes. The chiral separation performance of the membranes depended strongly on the swelling index of the membranes and the separation conditions such as concentration of feed solutions and different operating pressures. Especially when a chitosan membrane with a swelling index of 70% was used, almost complete optical resolution of D- and L-tryptophan was obtained ; enantiomeric excess (ee %) of 97.92% and flux of 2.26 g/㎡$.$h.

• Archives of Pharmacal Research
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• 제23권2호
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• pp.178-181
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• 2000

In order to study the simultaneous determination of (+)- and (-)-cetirizine in human urine we have developed a chiral separation method by HPLC. A chiral stationary phase of $\alpha$$_1$-acidglycoprotein, the AGP-CSP was used to separate the enantiomers. The pH of the phosphate buffer, as well as the content of the organic modifier in the mobile phase, markedly affected the chromatographic separation of (+)- and (-)-cetirizine. A mobile phase of 10 m㏖/1 phosphate buffer (pH 7.0)-acetonitrile (95 : 5, v/v) was used for the urine assays. Ultraviolet absorption was monitored at 230nm and roxatidine was employed as the internal standard for quantification. (+)-Cetirizine, (-)-cetirizine and the internal standard were eluted at retention times of 12, 16, and 32 mins, respectively. The detection limit for cetirizine enantiomers was 400 ng/$m\ell$ of urine. A pharmacokinetic study was conducted with the help of 5 healthy female volunteers who were administered with a single oral dose of racemic cetirizine (20 mg). The peak area ratios provided by the cetirizine enantiomers were linear(r>0.997) over a concentration range of 2.5-200 ${\mu}g/ml$. The peak of the excreted cetirizine enantiomers appeared in the urine sample during the period of 1-2 hrs following the administration of the oral dose. The excreted level of (+)-cetirizine was slightly higher than (-)-cetirizine but the difference was not statistically significant. However, this method appears to have applications for enantioselective pharmacokinetic studies of racemic drugs.

• 한국막학회:학술대회논문집
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• 한국막학회 2003년도 The 4th Korea-Italy Workshop
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• pp.61-64
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• 2003

Optical resolution of a-amino acid (tryptophan and tyrosine) optical isomers was achieved by a pressure driven membrane separation process, using self-supporting crosslinked membranes base on polysaccharide with different swelling indices that ranged from 100 to 70%. The membranes prepared by casting and drying the polymer solution containing 5wt% acetic acid on an acryl plate followed by crosslinking with glutaraldehyde were characterized using such analytical methods as FTIR and swelling index measurements. On the way of separating the optical isomers, several experimental factors such as the concentration of the feed solutions, operating pressure and temperature, and degree of crosslinking of the membranes have been studied. When the chitosan membranes with 70% of swelling index were used , almost complete optical resolution was obtained; 97.92% of enantiomeric excess (ee %) and 2.26 g/$m^2$ㆍh of flux. The operating pressure and the concentration of feed solutions were respectively 1.0 kgf/$\textrm{cm}^2$ and 0.49 mmol/L.

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2934-2938
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• 2010

Some open tubular (OT) molecule imprinted polymer (MIP) silica capillary columns with templates of camphor derivatives such as 10-camphorsulfonic acid (10-CSA), 10-camphorsulfonamide (10-CS) and camphor-p-tosyl hydrazone (CTH) have been successfully prepared by the prior generalized preparation protocol. The three MIP thin layers of different templates showed quite different morphologies. The chiral selectivity of each MIP column for the template enantiomers was optimized by changing eluent composition and pH. The optimization conditions were found to be different for the three MIPs. This work suggests prospective successful extension of the generalized preparation protocol for OT-MIP silica capillary columns toward templates of a variety of chemical groups.

• 한국막학회:학술대회논문집
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• 한국막학회 1998년도 추계 총회 및 학술발표회
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• pp.15-18
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• 1998

Membrane reactors are systems which combine a chemical reactor with a membrane separation process allowing to carry out simultaneously conversion and product separation. The catalyst can be immobilized on the membrane or simply compartmentalized in a reaction space by the membrane. Membrane reactors are today investigated to produce optically pure isomers and/or resolve racemic mixture of enantiomers. The interest towards these systems is due to the increasing demand of enantiomerically pure compounds to be used in the pharmaceutical, food, and agrochemical industries. In fact, enantiomers can have different biological activities, which often influence the efficacy or toxicity of the compound. On the basis of current literature there are basically two schemes on the use of membrane technology to produce enantiomers. In one case, the membrane itseft is intrinsically enantioselective: the membrane is the chiral system which selectively separates the wanted isomer on the basis of its conformation. In the other, a kinetic resolution using an enantiospecific biocatalyst is combined with a membrane separation process; the membrane separates the product from the substrate on the basis of their relative chemical properties (i.e. solubility). This kind of configuration is widely used to carry out kinetic resolutions of low water soluble substrams in biphasic membrane reactors [Giomo, 1995, 1997; Lopez, 1997]. These are systems where enzyme-loaded membranes promote reactions between two separate phases thanks to the properties of enzymes, such as lipases, to catalyse reactions at the org ic/aqueous interface; the two phases are maintained in contact and separated at the membrane level by operating at appropriate transmembrane pressure. A schematic representation of biphasic membrane reactor is shown in figure 1, while an example of enantiospecific reaction and product separation carried out with these systems is reported in figure 2.

• Archives of Pharmacal Research
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• 제27권9호
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• pp.973-977
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• 2004

Carvedilol is administered as a racemic mixture of the R(＋)- and S(-)-enantiomers, although they exhibit different pharmacological effects. To investigate the stereoselective pharmacoki-netics, the enantiomeric separation of carvedilol in human plasma was undertaken using capil-lary electrophoresis (CE). Resolution of the enantiomers was achieved using 2-hydoxypropyl-$\beta$-cyclodextrin as the chiral selector. Phosphate buffer (50 mM, pH 4.0) containing 10 mM of 2-hydoxypropropyl-$\beta$-cyclodextrin was used as electrolytic buffer. Achiral separation was carried out with the same electrolytic buffer without chiral selector. Following a single oral administra-tion of 25-mg carvedilol to 11 healthy, male volunteers, stereoselective pharmacokinetic analy-sis was undertaken. The maximum plasma concentrations ( $C_{max}$) were 48.9 and 21.6 ng/mL for (R)-carvedilol and (S)-carvedilol, respectively, determined by the chiral method. The profiles of the plasma concentration of (RS)-carvedilol showed $C_{max}$ of 71.5, 72.2, and 73.5 ng/mL, as determined by the CE, HPLC/FD methods and calculations from the data of the chiral method, respectively.y.y.

• Bulletin of the Korean Chemical Society
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• 제34권10호
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• pp.2978-2982
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• 2013

A doubly tethered $N-CH_3$ amide chiral stationary phase (CSP 4) based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid was applied to the resolution of an antiarrythmic agent, tocainide, and its analogues and the chromatographic resolution results were compared with those on a singly tethered N-H amide CSP (CSP 1), a singly tethered $N-CH_3$ amide CSP (CSP 2) and a doubly tethered N-H amide CSP (CSP 3) under an identical aqueous mobile phase condition. CSP 4 was found to be generally better than other CSPs in terms of the separation factors (${\alpha}$) and resolutions (RS). The retention times of analytes denoted by the retention factors ($k_1$) on CSP 4 were quite long compared to those on other CSPs because of the improved lipophilicity of CSP 4. The long retention times of analytes on CSP 4 were successfully controlled by the addition of a small amount of ammonium acetate to aqueous mobile phase without hurting the chiral recognition efficiency. The variation of the content and type of organic and acidic modifier in aqueous mobile phase was found not to change the chiral recognition efficiency significantly.