• Title/Summary/Keyword: chiral

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Stereospecific Reaction of S,S-prodien(= 1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triazanonane) (Ⅰ); Synthesis of ${\wedge}-{\alpha}{\beta}$(ffm)-[Co(S,S-prodien)$H_2O$]$ClO_4$ (S,S-prodien(=1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triazanonane)의 입체특이성 반응(I); ${\wedge}-{\alpha}{\beta}$(ffm)-[Co(S,S-prodien)$H_2O$]$ClO_4$의 합성)

  • Lee, Bae Wook;Kim, Jin Woo;Lee, Dong Jin;Kim, Bong Gon;Oh, Chang Eon;Doh, Myung Ki
    • Journal of the Korean Chemical Society
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    • v.41 no.9
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    • pp.465-470
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    • 1997
  • A chiral pentadentate ligand, 1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triaza-nonane, (S,S-prochen) which shows the stereospecific reaction was synthesized from the reaction of S-proline and diethylenetriamine (dien). The red-violet $[Co(SS-prodien)H_2O]ClO_4$ was prepared by the oxidation of the aqueous solution dissolving $CoCl_2{\cdot}6H_2O$ and S,S-prodien. Elemental analysis, electronic absorption spectroscopy, and $^{13}C-NMR$ spectroscopy suggest that the geometrical structure of the Co(III) complex to be an ${\alpha}{\beta}$ (ffm) form, where the dien moiety of the ligand chelates the metal center to comprise a facial isomer, and an aqua ligand coordinates a cis site to the secondary nitrogens of the dien. Based upon the CD spectroscopic analysis, it seems that the absolute configuration of the ${\alpha}{\beta}$(ffm)-$[Co(SS-prodien)H_2O]ClO_4$ has the ${\Lambda}$-form.

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Efficient (3R)-Acetoin Production from meso-2,3-Butanediol Using a New Whole-Cell Biocatalyst with Co-Expression of meso-2,3-Butanediol Dehydrogenase, NADH Oxidase, and Vitreoscilla Hemoglobin

  • Guo, Zewang;Zhao, Xihua;He, Yuanzhi;Yang, Tianxing;Gao, Huifang;Li, Ganxin;Chen, Feixue;Sun, Meijing;Lee, Jung-Kul;Zhang, Liaoyuan
    • Journal of Microbiology and Biotechnology
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    • v.27 no.1
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    • pp.92-100
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    • 2017
  • Acetoin (AC) is a volatile platform compound with various potential industrial applications. AC contains two stereoisomeric forms: (3S)-AC and (3R)-AC. Optically pure AC is an important potential intermediate and widely used as a precursor to synthesize novel optically active materials. In this study, chiral (3R)-AC production from meso-2,3-butanediol (meso-2,3-BD) was obtained using recombinant Escherichia coli cells co-expressing meso-2,3-butanediol dehydrogenase (meso-2,3-BDH), NADH oxidase (NOX), and hemoglobin protein (VHB) from Serratia sp. T241, Lactobacillus brevis, and Vitreoscilla, respectively. The new biocatalyst of E. coli/pET-mbdh-nox-vgb was developed and the bioconversion conditions were optimized. Under the optimal conditions, 86.74 g/l of (3R)-AC with the productivity of 3.61 g/l/h and the stereoisomeric purity of 97.89% was achieved from 93.73 g/l meso-2,3-BD using the whole-cell biocatalyst. The yield and productivity were new records for (3R)-AC production. The results exhibit the industrial potential for (3R)-AC production via whole-cell biocatalysis.

Optimization of the Reaction Conditions for (R)-Phenyl-1,2-ethanediol Preparation by Recombinant Epoxide Hydrolase from Caulobacter crescentus (재조합 Caulobacter crescentus 에폭사이드 가수분해효소를 이용한 광학활성 Diol 제조 조건의 최적화)

  • Lee, Ok-Kyung;Kim, Hee-Sook
    • Microbiology and Biotechnology Letters
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    • v.35 no.4
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    • pp.285-291
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    • 2007
  • Enantioconvergent hydrolysis process for the preparation of chiral diol from racemic epoxides by using the recombinant Caulobacter crescentus epoxide hydrolase (CcEH) in Escherichia coli BL21 (DE3) was optimized. For the optimization, the effects of detergent, temperature and product inhibition on the enantiopurity and the yield of diol were investigated. (R)-phenyl-1,2-ethanediol with 92% enantiomeric excess and 56% yield from 20 mM racemic styrene oxide was obtained by using the recombinant CcEH at the optimal condition of $10^{\circ}C$ and the addition of 2% (w/v) Tween 80. At 50 mM racemic styrene oxide was used as a substrate, (R)-phenyl-1,2-ethanediol was obtained with 87% enantiomeric excess and 77% yield. Racemic phenyl-1,2-ethanediol, (R)-phenyl-1,2-ethanediol and (S)-phenyl-1,2-ethanediol dramatically inhibited the hydrolytic activity of the recombinant CcEH. These results suggested that another EH with the regioselectivity on ${\beta}$-position of (R)-enantiomer and without feedback inhibition by products would be needed as the partner EH of C. crescentus EH.

Holographic phase gratings in back- and frontlights for LCD's

  • Bastiaansen, C.W.M.;Heesch, C. van;Broer, D.J.
    • 한국정보디스플레이학회:학술대회논문집
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    • 2006.08a
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    • pp.421-421
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    • 2006
  • The light and energy-efficiency of classical liquid crystal displays is notoriously poor due to the use of absorption-based linear polarisers and colour filters. For instance, the light efficiency of PVAL polarisers is typically between 40 and 45 % and the colour filters have a typical efficiency below 35 % which results in a total light and energy-efficiency of the display below 10 %. In the past, a variety of polarizers were developed with an enhanced efficiency in generating linearly polarized light. Typically, these polarizers are based on the polarisationselective reflection, scattering or refraction of light i.e. one polarisation direction of light is directly transmitted to the LCD/viewer and the other polarization direction of light is depolarised and recycled which results in a typical efficiency for generating linearly polarized light of 70-85 %. Also, special colour filters have been proposed based on chiral-nematic reactive mesogens which increase the efficiency of generating colour. Despite the enormous progress in this field, a need persists for improved methods for generating polarized light and colour based on low cost optical components with a high efficiency. Here, the use of holographic phase gratings is reported for the generation of polarized light and colour. The phase grating are recorded in a photopolymer which is coated onto a backor frontlight for LCDs. Typically the recording is performed in the transmisson mode or in the waveguiding mode and slanted phase gratings are generated with their refractive index modulation at an angle between 20o and 45o with the normal of the substrate. It is shown that phase gratings with a high refractive index modulation and a high efficiency can be generated by a proper selection of the photopolymer and illumination conditions. These phase gratings coupleout linearly polarized light with a high contrast (> 100) and the light is directed directly to the LCD/viewer without the need for redirection foils. Dependent on the type of phase grating, the different colours are coupled-out at a slightly different angle which potentially increases the efficiency of classical colour filters. Moreover, the phase gratings are completely transparent in direct view which opens the possibility to use them in frontlights for LCDs. Holographic polarization gratings posses a periodic pattern in the polarization state of light (and not in the intensity of light). A periodic pattern in the polarization direction of linearly polarized light is obtained upon interference of two circularly polarized laser beams. In the second part of the lecture, it is shown that these periodic polarization patterns can be recorded in a linear photo-polymerizable polymer (LPP) and that such an alignment layer induces a period rotation in the director of (reactive and non-reactive) liquid crystals. By a proper design, optical components can be produced with only first order diffraction and with a very high efficiency (>0.98). It is shown that these diffraction gratings are potentially useful in projection displays with a high brightness and energy efficiency

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Effect of Length of Alkyl Group on Thermal-Liquid Crystalline Properties of Cholesteryl 4-n-Alkoxybenzoate (알킬기의 길이가 콜레스테릴 4-n-알콕시벤조에이트의 열적-액정 특성에 미치는 영향)

  • Yoon, Doo-Soo;Bang, Moon-Soo
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.18 no.10
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    • pp.69-74
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    • 2017
  • In this study, cholesteryl 4-n-alkoxybenzoates (Chol-n), with alkyl groups used for controlling the temperature of transition to the liquid crystal phase, were synthesized, and the effects of the length of the alkyl groups on the physical properties of the liquid crystal compounds were investigated. The chemical structures and thermal and liquid crystalline properties of the synthesized compounds were investigated by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy ($^1H$-NMR), differential scanning calorimetry (DSC), and polarizing optical microscopy (POM). The synthesized compounds showed melting transition temperatures ($T_m$) in the range of $103^{\circ}C$ to $143^{\circ}C$ and all of the compounds except Chol-6 exhibited a wide liquid crystal phase temperature range of about $60^{\circ}C$ to $100^{\circ}C$. No correlation between the number of carbon atoms in the molecule and the thermal properties of the compounds was found. All of the synthesized compounds showed an enantiotropic cholesteric phase, which was accompanied by a chiral smectic phase in the compounds Chol-6, Chol-8, Chol-9, and Chol-10. All of the compounds exhibited thermochromism in the liquid crystal state, and their color changed from red to blue as the temperature was increased.

Characterization of Nitrile-hydrolyzing Enzymes Produced from Rhodococcus erythropolis (니트릴 분해효소 생산균인 Rhodococcus erythropolis의 발굴 및 효소 특성 연구)

  • Park Hyo-Jung;Park Ha-Joo;Uhm Ki-Nam;Kim Hyung-Kwoun
    • Microbiology and Biotechnology Letters
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    • v.34 no.3
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    • pp.204-210
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    • 2006
  • Ethyl (S)-4-chloro-3-hydroxybutyrate is a useful intermediate for the synthesis of Atorvastatin, a chiral drug to hypercholesterolemia. In this research, two 4-chloro-3-hydroxybutyro-nitrile-degrading strains were isolated from soil sample. They were identified as Rhodococcus erythropolis strains by 16S rRNA analysis. The nitrile-degrading enzyme(s) were suggested to be nitrile hydratase and amidase rather than nitrilase from the result of thin layer chromatography analysis. The corresponding genes were obtained by PCR cloning method. The predicted protein sequences had identities more than 96% with nitrile hydratase ${\alpha}-subunit$, nitrile hydratase ${\beta}-subunit$, and amidase of R. erythropolis. The 4-chloro-3-hydroxybutyronitrile-hydrolyzing activities in both strains were increased dramatically by ${\varepsilon}-caprolactam$ which was known as good inducer for nitrile hydratase. Both intact cells and cell-free extract could hydrolyze the nitrile compound. So, the intact cell and the enzymes could be used as potential biocatalyst for the production of 4-chloro-3-hydroxybutyric acid.

The Search of Pig Pheromonal Odorants for Biostimulation Control System Technologies: III. Comparative Molecular Field Analysis (CoMFA) on Binding Affinities between Ligands of 2-(Cyclohexyloxy) Tetrahydrofurane Derivatives and Porcine Odorant Binding Protein (생물학적 자극 통제 수단으로 활용하기 위한 돼지 페로몬성 냄새 물질의 탐색: III. 2-(Cyclohexyloxy) Tetrahydrofurane 유도체와 Porcine Odorant Binding Protein 사이의 결합 친화력에 관한 비교 분자장 분석)

  • Sung Nack-Do;Park Chang-Sik;Jung Hoon-Sung;Seong Min-Kyu
    • Reproductive and Developmental Biology
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    • v.30 no.1
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    • pp.13-19
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    • 2006
  • To search of new porcine pheromonal odorants for biostimulation control system technologies to improve reproductive efficiency in livestock species, the comparative molecular field analysis (CoMFA) for binding affinity constant $(p(Od)_{50})$ between porcine odorant binding protein (pOBP) and ligands of odorant 2-(cyclohexyloxy) tetrahydrofurane derivatives as substrate molecule was conducted and discussed. In the optimized CoMFA model AIV with chirality $(C_1'(R),\;C_2(S))$ in substrate molecule and atom based fit alignment (A) of odorants, the statistical results showed the best predictability of the binding affinities $(p(Od)_{50})$ based on the LOO cross-validated value $r^2_{cv}.\;(q^2=0.886)$ and non-cross-validated conventional coefficient $(r^2_{ncv}.=0.984)$. the binding affinity constants exhibited a good correlation with steric (40.8%), electrostatic (14.6%) and hydrophobic (44.6%) factors of the substrate molecules. from the analytical results of the contour maps, which may give us some valuable informations to the modification of odorants for effective binding affinity.

Efficient Stereoselective Synthesis of (2S,3S,4S)-3,4-Dihydroxyglutamic Acid ((2S,3S,4S)-3,4-다이하이드록시글루타믹산의 효율적인 입체선택적 합성)

  • Jeon, Jongho;Shin, Nara;Lee, Jong Hyup;Kim, Young Gyu
    • Applied Chemistry for Engineering
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    • v.25 no.4
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    • pp.392-395
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    • 2014
  • (2S,3S,4S)-3,4-Dihydroxyglutamic acid (DHGA), a biologically active ${\alpha},{\beta}$-dihydroxy-${\gamma}$-amino acid, was efficiently synthesized from a readily available D-serine derivative in 30% overall yield over 11 steps. The key stereoselective $OsO_4$-catalyzed dihydroxylation reaction controlled by an N-diphenylmethylene group on the amino group of ${\gamma}$-amino-${\alpha},{\beta}$-unsaturated (Z)-ester successfully introduced the diol moiety of the intermediate 5a in 86% with more than 10 : 1 diastereomeric ration. Then it was in turn successfully converted to the desired target compound, (2S,3S,4S)-3,4-DHGA, via simple oxidation and hydrolysis in a highly stereoselective manner and a higher yield than the previous syntheses. This result strongly supports that our synthetic methodology of stereoselective $OsO_4$-catalyzed dihydroxylation should be useful in stereoselctive synthesis of various bioactive compounds with an amino diol moiety.

Optical Resolution of Free Amino Acids with Addition of Copper(II) Chelates in a Reversed-Phase Liquid Chromatography (구리(II) 킬레이트의 첨가에 의한 자유아미노산 광학이성질체의 역상 액체크로마토그래피적 분리)

  • Sun Haing Lee;Tae Sub Oh;Hong Yeup An;Kyung Sug Park;Sang Oh OH
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.879-888
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    • 1992
  • Separation of the optical isomers of free amino acids by a reversed phase high performance liquid chromatography has been studied by adding a copper(II) complex of L-proline or L-proline derivatives (hydroxy-L-proline, N-benzyl-L-proline, p-xylenyl-L-proline, p-xylenyl-hydroxy-L-proline) in the mobile phase. An OPA postcolumn detection system was used for the detection of amino acids. The chromatographic properties for the free amino acids were discussed in terms of the pH, the kinds and concentration of chelate or organic modifier. The retention behaviors of the free amino acids were considerably different from, those of DNS-amino acids or DABS-amino acids. The enantioselectivity of the free amino acids was better than that of derivatized amino acids. The enantioselectivity between the optical isomers observed by use of the Cu(II)-p-xylenyl-L-proline chiral cheleate was the best among the several copper(II) chelate. A separation mechanism could be illustrated not only by the hydrophobic interaction of the diastereomer with stationary phase but also by the steric effect of the ligand exchange reaction between the free-amino acids and copper chelate.

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D-$\Pi$-A designed dye chromophores and nanoparticles: optical properties, chemosensor effects and PE/Aramid fiber colorations

  • Son, Young-A;Kim, Su-Ho;Kim, Young-Sung
    • Proceedings of the Korean Society of Dyers and Finishers Conference
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    • 2010.03a
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    • pp.40-40
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    • 2010
  • Studies on attractive color changing property of dye chromophore and fluorophore have been greatly enjoyed in the related industrial and research fields such as optoelectronics, chemosensor, biosensor and so on. The optical property based on D-$\Pi$-A intramolecular charge transfer (ICT) system of chromophore molecules can be utilized as suitable sensing probes for checking media polarity and determining colorimetric chemosensing effect, especially heavy metal detection. These finding are obtained by absorption and emission properties. In this work, donor-acceptor D-$\Pi$-A type fluorescent dyes were designed and synthesized with the corresponding donor and acceptor groups. The selected donor moieties might be provided prominent amorphous properties which are very useful in designing and synthesizing functional polymers and in fabricating devices. Another reasons to choose are commercial availabilities in high purity and low price. Donor-bridge-acceptor (D-A) type dyes can produce impressive optical-physical properties, yielding them potentially suitable for applications in the synthesis of small functional organic molecules. Small organic functional molecules have unique advantages, such as better solubility, amorphous character, and represent an area of research which needs to be explored and developed. Currently, their applications in metalorganic compounds is rapidly expanding and becoming widespread in self-assembly processes, photoluminescence applications, chiral organocatalysts, and ingrafts with nanomaterials. Colloidal nanoparticles have received great attentions in recent years. The photophysical properties of nanoparticles, particularly in terms of brightness, photostability, emission color purity and broad adsorption range, are very attractive functions in many applications. To our knowledge background, colloidal nanoparticles have been enjoyed their applications in bio-probe research fields. This research interest can be raised by the advantages of the materials such as high photoluminescence quantum yields, sharp emission band, long-term photostability and broad excitation spectra. In recent, the uses of nanoparticles being embedded in a polymer matrix and binded on polymer surface have been explored and their properties such as photo-activation and strong photoluminescence have been proposed. The prepared chromophores and nanoparticles were investigated with absorption and emission properties, solvatochromic behaviors, pH induced color switching effects, chemosensing effects and HOMO/LUMO energy potentials with computer simulation. In addition, synthesized fluorophore dyes and particles were applied onto PE/Aramid fiber fluorescing colorations. And the related details were then discussed.

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