• 제목/요약/키워드: Asymmetric reactions

검색결과 62건 처리시간 0.024초

A New Strategy to Improve the Efficiency and Sustainability of Candida parapsilosis Catalyzing Deracemization of (R,S)-1-Phenyl-1,2-Ethanediol Under Non-Growing Conditions: Increase of NADPH Availability

  • Nie, Yao;Xu, Yan;Hu, Qing Sen;Xiao, Rong
    • Journal of Microbiology and Biotechnology
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    • 제19권1호
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    • pp.65-71
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    • 2009
  • Microbial oxidoreductive systems have been widely used in asymmetric syntheses of optically active alcohols. However, when reused in multi-batch reaction, the catalytic efficiency and sustainability of non-growing cells usually decreased because of continuous consumption of required cofactors during the reaction process. A novel method for NADPH regeneration in cells was proposed by using pentose metabolism in microorganisms. Addition of D-xylose, L-arabinose, or D-ribose to the reaction significantly improved the conversion efficiency of deracemization of racemic 1-phenyl-1,2-ethanediol to (S)-isomer by Candida parapsilosis cells already used once, which afforded the product with high optical purity over 97%e.e. in high yield over 85% under an increased substrate concentration of 15 g/l. Compared with reactions without xylose, xylose added to multi-batch reactions had no influence on the activity of the enzyme catalyzing the key step in deracemization, but performed a promoting effect on the recovery of the metabolic activity of the non-growing cells with its consumption in each batch. The detection of activities of xylose reductase and xylitol dehydrogenase from cell-free extract of C. parapsilosis made xylose metabolism feasible in cells, and the depression of the pentose phosphate pathway inhibitor to this reaction further indicated that xylose facilitated the NADPH-required deracemization through the pentose phosphate pathway in C. parapsilosis. moreover, by investigating the cofactor pool, the xylose addition in reaction batches giving more NADPH, compared with those without xylose, suggested that the higher catalytic efficiency and sustainability of C. parapsilosis non-growing cells had resulted from xylose metabolism recycling NADPH for the deracemization.

Surface Modification of Silica Spheres for Copper Removal

  • Kim, Byoung-Ju;Park, Eun-Hye;Kang, Kwang-Sun
    • 대한화학회지
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    • 제60권5호
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    • pp.317-320
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    • 2016
  • Efficient copper removal from water was achieved by using surface modified silica spheres with 3-mercaptopropyltrimethoxysilane (MPTMS) using base catalyst. The surface modification of silica spheres was performed by hydrolysis and condensation reactions of the MPTMS. The characteristic infrared absorption peaks at 2929, 1454, and 1343 cm−1 represent the −CH2 stretching vibration, asymmetric deformation, and deformation, respectively. The absorption peaks at 2580 and 693 cm−1 corresponding the −SH stretching vibration and the C-S stretching vibration indicate the incorporation of MPTMS to the surface of silica spheres. Field emission scanning electron microscope (FESEM) image of the surface modified silica sphere (SMSS) shows nano-particles of MPTMS on the surface of silica spheres. High concentration of copper solution (1000 ppm) was used to test the copper removal efficiency and uptake capacity. The FESEM image of SMSS treated with the copper solution shows large number of copper lumps on the surface of SMSS. The copper concentration drastically decreased with increasing the amount of SMSS. The residual copper concentrations were analyzed using inductively coupled plasma mass spectrometer. The copper removal efficiency and uptake capacity with 1000 ppm of copper solution were 99.99 % and 125 mg/g, respectively.

새로운 구조의 키랄 살렌 촉매상에서 페놀유도체에 의한 에폭사이드의 광학선택적 개환반응 (Enantioselective Phenolic Kinetic Resolution of Epoxides Catalyzed by New Chiral Salen Complexes)

  • 카테카라울;이광연;김건중
    • 공업화학
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    • 제18권6호
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    • pp.630-635
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    • 2007
  • 구조중에 1개의 tert-부틸기를 가진 새로운 형태의 키랄살렌 착체를 합성하여 비대칭반응 촉매로서 활용하였다. 알루미늄족의 금속염을 소유한 이량체형의 키랄 살렌 촉매는 에폭사이드의 산소고리를 페놀류로 여는 비대칭반응에서 매우 높은 활성과 선택성을 나타내었다. 또한 무기담체에 고정화된 살렌 착체도 이 반응에 대하여 효과적인 촉매로 사용할 수 있었다. 새로운 키랄 살렌촉매 중에 존재하는 금속염의 종류는 광학선택적 반응에서 중요한 영향을 나타내었다.

Influense of the high-voltage conductivity on peculiarity of polarization ferroelectric polymer on based vinylidenefluoride

  • Kochervinskii, V.V.;Chubunova, E.V.;Lebedinskii, Y.Y.;Pavlov, A.S.;Pakuro, N.I.
    • Advances in materials Research
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    • 제4권2호
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    • pp.113-132
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    • 2015
  • The phenomena of high-voltage polarization and conductivity in oriented vinylidenefluoride and tetrafluoroethylene copolymer films have been investigated. It was shown that under certain electric fields, injection of carriers from the material of electrodes appears The barrier for holes injection in the copolymer was found to be lower than that for electrons. It results in more effective screening of the external field near the anode than near cathode. Electrones, ejected from cathode, creating negative charge by trapping on the surface. It is shown that the electrons injected from cathodes create a negative homocharge on the copolymer surface and then become captured on the surface shallow traps. Their nature has been studied by the x-ray photoelectron spectroscopy. It was shown that these traps may consist of chemical defects in the form of new functional groups formed by reactions of surface macromolecules with sputtered atoms of aluminum. The asymmetric shape of hysteresis curves was explained by the difference in mobility of injected holes and electrons. These factors caused appearance of "non-closed" hysteresis curves for fluorine-containing polymer ferroelectrics. Hysteresis phenomena observed at low electric fields (below coercive ones) are to associate with the behavior of the domains localized in the ordered regions formed during secondary crystallization of copolymers.

글로벌 금융위기하에서 주식시장 변동성의 연관성에 대한 연구 (A study on the Linkage of Volatility in Stock Markets under Global Financial Crisis)

  • 이경희;김경수
    • 경영과정보연구
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    • 제33권1호
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    • pp.139-155
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    • 2014
  • 본 연구는 글로벌 경제통합화를 통한 인도의 주식시장과 다른 주식시장의 변동성간에 연관성을 파악하고자 하였다. 본 연구의 결과, 첫째, 분산비검정에서 모든 기간의 주식시장은 자기상관이 존재하지 않았고 또한 고전적 RS모형에서 모든 기간이 자기상관이 존재하지 않았으나, 수정된 RS모형에서도 거의 모든 기간에서 장기기억이 존재하였다. 둘째, 단위근검정에서 모든 기간이 단위근이 존재하지 않아 시계열이 안정적이고, 모든 수정$R^2$는 높은 설명력을 나타냈다. 또한 ARFIMA모형에서 모두 정상적 조건을 만족하고 모든 시계열이 장기기억을 나타내었다. 셋째, VAR과 다변량 비대칭 BEKK모형에서 글로벌 금융위기전의 경우, 조건부 평균식에서 영국과 대만의 자국시장이 강하고, 일방향으로 일본에서 인도로, 대만에서 중국(한국, 미국)으로, 미국(일본)에서 영국으로 강한 조건부 평균전이효과가 존재하였다. 조건부 분산식에서 GARCH는 시장자체의 ARCH계수의 결과와 동일한 방향의 강한 조건부 변동성전이효과를 보여주었다. 세 자국시장에서 비대칭효과가 존재하며, 시장간 일방향의 비대칭효과가 존재하였다. 넷째, 글로벌 금융위기후의 경우, 조건부 평균식에서 대만의 자국시장만이 강하게 영향을 나타내고, 일방향으로 인도에서 미국으로, 대만에서 일본으로, 한국에서 독일로 강한 조건부 평균전이효과가 존재하였다. 조건부 분산식에서는 위기전의 결과와 동일한 강한 조건부 변동성전이효과가 존재하였고 영국의 자국시장에서 비대칭효과가 존재하며, 대만에서 독일로 일방향의 비대칭효과가 존재하였다. 다섯째, 우도비검정에서는 다른 검정결과와는 다르게 모든 기간에서 인도는 타국의 주식시장에 영향을 미치지 않고 동시에 타국의 주식시장에 의해 영향을 받지 않았다. 따라서 본 연구는 글로벌 경제통합화를 통한 인도와 다른 주식시장의 변동성간에 연관성을 파악함으로써 타국의 주식시장에서 인도로의 수익률(변동성)전이효과와 타국의 주식시장간 일(양)방향의 비대칭적 반응을 관찰함으로써 타국의 주식시장간의 여러 인과관계를 확인하였다.

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생체분자 퍼셉트론의 신뢰성 향상을 위한 열역학 기반 가중치 코딩 방법 (Thermodynamics-Based Weight Encoding Methods for Improving Reliability of Biomolecular Perceptrons)

  • 임희웅;유석인;장병탁
    • 한국정보과학회논문지:소프트웨어및응용
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    • 제34권12호
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    • pp.1056-1064
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    • 2007
  • 생체분자 컴퓨팅은 DNA와 같은 생체 분자를 이용하여 정보를 표현하고 처리하는 새로운 컴퓨팅 패러다임이다. 작은 부피에 존재하는 무수히 많은 분자와 화학 반응에 내재된 대규모 병렬성은 새로운 개념의 고성능 계산 기법에 영감을 주었고 이를 바탕으로 다양한 계산 모델 및 문제 해결을 위한 분자알고리즘이 개발되었다. 한편 생체 분자를 이용한 정보처리라는 특징은 생물학 문제에 적용될 수 있는 가능성을 시사한다. 유전자 발현 패턴과 같은 생화학적 분자 정보의 분석을 위한 도구로서의 가능성을 가지고 있는 것이다. 이러한 맥락에서 DNA 컴퓨팅 기반의 생체분자 퍼셉트론 모델이 제안되었고 그 실험적 구현 결과가 제시된 바 있다. 생체분자 퍼셉트론의 핵심인 가중치 표현 및 가중치-합 연산은 입력 분자와 가중치를 표현하는 프로브 분자간의 경쟁적 혼성화 반응에 기반하고 있다. 그러나 그 혼성화 반응에서 열역학적 대칭성을 가정하고 있기 때문에 사용하는 프로브에 따라 가중치 표현의 오차가 있을 수 있다. 본 논문에서는 비대칭적인 열역학적 특성을 고려하여 일반화된 혼성화 반응 모델을 제시하고, 이를 바탕으로 신뢰성 있는 생체 분자 퍼셉트론의 구현을 위한 가중치 코딩 방법을 제안한다. 그리고 본 논문에서 제시한 가중치 표현 방법의 정확성을 이전 모델과 컴퓨터 시뮬레이션을 통해 비교하고 한계 오차를 만족하기 위한 조건을 제시한다.

하이브리드 슈퍼커패시터의 음극 및 양극 설계에 따른 전기화학적 거동 (Electrochemical Behavior Depending on Designed-Anode and Cathodes of Hybrid Supercapacitors)

  • 신승일;이병관;하민우;안건형
    • 한국재료학회지
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    • 제29권12호
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    • pp.774-780
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    • 2019
  • The performance of Li-ion hybrid supercapacitors (asymmetric-type) depends on many factors such as the capacity ratio, material properties, cell designs and operating conditions. Among these, in consideration of balanced electrochemical reactions, the capacity ratio of the negative (anode) to positive (cathode) electrode is one of the most important factors to design the Li-ion hybrid supercapacitors for high energy storing performance. We assemble Li-ion hybrid supercapacitors using activated carbon (AC) as anode material, lithium manganese oxide as cathode material, and organic electrolyte (1 mol L-1 LiPF6 in acetonitrile). At this point, the thickness of the anode electrode is controlled at 160, 200, and 240 ㎛. Also, thickness of cathode electrode is fixed at 60 ㎛. Then, the effect of negative and positive electrode ratio on the electrochemical performance of AC/LiMn2O4 Li-ion hybrid supercapacitors is investigated, especially in the terms of capacity and cyclability at high current density. In this study, we demonstrate the relationship of capacity ratio between anode and cathode electrode, and the excellent electrochemical performance of AC/LiMn2O4 Li-ion hybrid supercapacitors. The remarkable capability of these materials proves that manipulation of the capacity ratio is a promising technology for high-performance Li-ion hybrid supercapacitors.

Ab Initio Study of Mechanism of Forming Spiro-Ge-Heterocyclic Ring Compound From C2Ge=Ge: and Formaldehyde

  • Lu, Xiuhui;Li, Yongqing;Ming, Jingjing
    • Bulletin of the Korean Chemical Society
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    • 제34권12호
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    • pp.3690-3694
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    • 2013
  • The $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) is a new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of the cycloaddition reaction between singlet state Cl2Ge=Ge: and formaldehyde has been investigated with CCSD(T)//MP2/$6-31G^*$ method. From the potential energy profile, it could be predicted that the reaction has only one dominant reaction pathway. The reaction rule presented is that the two reactants first form a fourmembered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the ${\pi}$ orbital of formaldehyde forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge: atom in intermediate hybridizes to an $sp^3$ hybrid orbital after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between $H_2Ge=Ge:$ and formaldehyde, and laid the theory foundation of the cycloaddition reaction between $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) and asymmetric ${\pi}$-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds. The study extends research area and enriches the research content of germylene chemistry.

한반도 남부지역에서 산출되는 카올린광물의 고온영역에서의 광물학적 특성 연구 (Mineralogical Characterization and Thermal Behaviours of Kaolins from the Southern Parts of Korea)

  • 이수정;문희수
    • 자원환경지질
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    • 제29권3호
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    • pp.269-279
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    • 1996
  • Dehydroxylation and mullitization of primary and secondary kaolins were investigated in order to compare and understand the differences in thermal behaviours by DTA and TG up to $1,100^{\circ}C$. Chemical analyses and EPMA of the samples revealed nearly ideal unit-cell formulae of kaolins. The weight losses of dickite and halloysite are 14% and 12.5% on the average, respectively. The activation energies of dehydroxylation of kaolin minerals were calculated according to Kissinger's approach which uses various heating rates in DTA to estimate the activation energy of thermal reactions. The activation energies of dehydroxylation of halloysites from Daemoung and Buksam mines are about $163kJmor^{-1}$ (white), $168kJmor^{-1}$ (pink), and $176kJmor^{-1}$ respectively. The activation energies of dickites collected from Sungsan and Ogmae mines are about $166kJmor^{-1}$ and $387kJmor^{-1}$. The asymmetric shape of endothermic peak in DTA, the relative intensities of OH-stretching bands in FTIR spectroscopy and the existence of residual XRD peaks of the samples which were heated at $550^{\circ}C$ for 2 hours indicate that Sungsan dickite may be more disordered than Ogmae dickite. The new phase formed in thermally treated samples in the range of $900^{\circ}C$ to $1,100^{\circ}C$ was identified as mullite by XRD on the basis of disappearing of the characteristic peaks of kaolins and increasing of amorphous background upon heat treatment. On further heating, loss of more water from dehydroxylate resulted in the formation of mullite and the characteristic X-ray diffraction patterns of mullite began to appear at about $900{\sim}1,000^{\circ}C$ in kaolins.

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Successive Synthesis of Well-Defined Star-Branched Polymers by an Iterative Approach Based on Living Anionic Polymerization

  • Higashihara Tomoya;Inoue Kyoichi;Nagura Masato;Hirao Akira
    • Macromolecular Research
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    • 제14권3호
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    • pp.287-299
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    • 2006
  • To successively synthesize star-branched polymers, we developed a new iterative methodology which involves only two sets of the reactions in each iterative process: (a) an addition reaction of DPE or DPE-functionalized polymer to a living anionic polymer, and (b) an in-situ reaction of 1-(4-(4-bromobutyl)phenyl)-1-phenylethylene with the generated 1,1-diphenylalkyl anion to introduce one DPE functionality. With this methodology, 3-, 4-, and 5-arm, regular star-branched polystyrenes, as well as 3-arm ABC, 4-arm ABCD, and a new 5-arm ABCDE, asymmetric star-branched polymers, were successively synthesized. The A, B, C, D, and E arm segments were poly(4-trimethylsilylstyrene), poly(4-methoxystyrene), poly(4-methylstyrene), polystyrene, and poly(4-tert-butyldimethylsilyloxystyrene), respectively. All of the resulting star-branched polymers were well-defined in architecture and precisely controlled in chain length, as confirmed by SEC, $^1H$ NMR, VPO, and SLS analyses. Furthermore, we extended the iterative methodology by the use of a new functionalized DPE derivative, 1-(3-chloromethylphenyl)-1-((3-(1-phonyletheny1)phenyl) ethylene, capable of introducing two DPE functionalities via one DPE anion reaction site in the reaction (b). The number of arm segments of the star-branched polymer synthesized by the methodology could be dramatically increased to 2, 6, and up to 14 by repeating the iterative process.