• 제목/요약/키워드: Isomerization

검색결과 226건 처리시간 0.029초

고려인삼의 화학성분에 관한 고찰 (Recent Studies on the Chemical Constituents of Korean Ginseng (Panax ginseng C. A. Meyer))

  • 박종대
    • Journal of Ginseng Research
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    • 제20권4호
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    • pp.389-415
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    • 1996
  • Panax ginseng C.A. Meyer(Araliaceae) has been traditionally used as an expensive and precious medicine in oriental countries for more than 5, 000 years. Ginseng saponin isolated from the root of Panax ginseng have been regarded as the main effective components responsible for the pharmacological and biological activities. Such as antiaging effects. antidiabetic effects anticancer effects. Protection against physical and chemical stress. Analgesic and antipyretic effects. Effects on the central nervous system, tranquilizing action and others. Thirty kinds of ginsenosides have been so far isolated from ginseng saponin and their chemical structures have been elucidated since 1960's. Among which protopanaxadiol type is 19 kinds. protopanaxatriol type. 10 kinds and oleanane type, one. Since ginsenosides are generally labile under acidic conditions ordinary acid hydrolysis is always accompanied by many side reactions, such as epimerization. hydroxylation and cyclization of side chain of the sapogenins Especially. it is well known that C-20 glycosyl linkage of ginsenoside was hydrolysed on heating with acetic acid to give an equilibrated mixture of 20(S) and 20(R) epimers. And also, the chemical transformations of the secondary metabolites have appeared during the steaming process to prepare red ginseng. Indicating demalonylation of malonyl ginsenosides, elimination of glycosyl residue at C-20 and isomerization of hydroxyl configuration at C-20. But these studies have not provided a comprehensive picture in explaning how these ginsenosides showed val'iotas pharmacological activities of ginseng. Though some of them have been involved in the mechanism of pharmacological actions. Recently, non-saponin components have received a great deal of attention for their antioxidant, anticancer antidiabetic, immunomodulating. anticomplementary activities and so on. To meet the demand for such wide applications, studies on the non-saponin components play an important role in providing a good evidence of pharmacological and biol ogical activities. Among the non-saponin constituents of Korean ginseng, polyacetylenes, phenols. Sesquiterpenes, alkaloids. polysaccharides oligosaccharides, oligopeptides and aminoglycosides together with ginsenosides of terrestrial part are mainly described.

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Infrared Multiphoton Dissociation Spectroscopy of Protonated 1,2-Diaminoethane-water Clusters: Vibrational Assignment via the MP2 Method

  • Boo, Bong Hyun;Kang, Sukmin;Furuya, Ari;Judai, Ken;Nishi, Nobuyuki
    • Bulletin of the Korean Chemical Society
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    • 제34권11호
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    • pp.3327-3334
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    • 2013
  • Infrared multiphoton dissociation (IRMPD) spectra of various protonated 1,2-diaminoethane-water clusters DAE-$H^+-(H_2O)_n$ (n = 1-6) were measured in the wavelength range of 3000-3800 $cm^{-1}$. The IRMPD spectra of the well separated ionic clusters were simulated by the MP2 method employing various basis sets. Comparison of the IRMPD spectra with the theory indicates that each cluster may exist as several low-lying conformers, and the sum spectra of the various conformers reveal almost one to one correspondence between theory and experiment. Free N-H and O-H stretches are observed in the ranges of 3400-3500 and 3600-3800 $cm^{-1}$, respectively. The $O-H{\cdots}N$ and $N-H{\cdots}O$ stretches are, however, observed in the broad region of 3000-3600 $cm^{-1}$. The theoretical calculations on DAE-$H^+-(H_2O)_n$ (n = 1-4) show gradual decrease of the average binding energy between DAE-$H^+$ and $H_2O$ as the cluster size increases, attaining the lowest value of 55 kJ/mol when n = 4. We found a low energy barrier of 21 kJ/mol to the isomerization converting the lowest energy cluster of DAE-$H^+-(H_2O)_n$ to the second lowest one.

변위전류 측정에 의한 수면상 단분자막의 배향변화 관찰 (Investigation of the orientational changes of monolayer on the water surface by measuring the displacement current.)

  • 박태곤;송경호;박근호;권영수;강도열
    • 대한전기학회:학술대회논문집
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    • 대한전기학회 1994년도 하계학술대회 논문집 C
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    • pp.1320-1322
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    • 1994
  • Photoisomerization characteristics of 4-octyl-4'-(5-carboxy-pentamethyleneoxy) azobenzene molecules (8A5H) were attained by measurement of absorbtion spectra. 8A5H in chroloform($6.0{\times}10^{-5}[M/l]$) shows trans to cis and cis to trans isomerization by irradiation of lights of 360[nm] and 450[nm] wavelength. From LB monolayer films of 8A5H, also the cis/trans photoisomerization was obtained and it has reversibility and memory characteristics. We are now trying to detect these properties of 8A5H electrically. On this paper, we investigated the structural changes of monolayer on the water surface by measuring the displacement current as a preliminary experiment. The measuring system was constructed at home-made Kuhn type LB(Langmuir-Blodgett) deposition apparatus. 8A5H solution was spreaded at the air-water interface and the currents induced by the dynamic behavior of molecules were measured when the molecules were pressed by barrier. The reversibility of displacement currents by compression and expansion was obtained from 8A5H molecules, which shows the compressed molecules have a tendency to disperse after the compression. From this experiment, we conclude that the behavior of molecules on water surface can be monitored electrically by using this current measuring method, and this method can also be applied to detect the photoisomerization of monolayers on water surface.

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Exploration of Essential Structure of Malloapelta B for the Inhibitory Activity Against TNF Induced $NF-{\kappa}B$ Activation

  • Luu, Chinh Van;Chau, Minh Van;Lee, Jung-Joon;Jung, Sang-Hun
    • Archives of Pharmacal Research
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    • 제29권10호
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    • pp.840-844
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    • 2006
  • For the exploration of pharmacophoric moiety of malloapelta B (1) possessing the inhibitory activity of $NF-{\kappa}B$ activation, structural variation of ${\alpha},{\beta}-unsaturated$ carbonyl motif was attempted. 1 was reduced by catalytic hydrogenation, sodium borohydride, and lithium aluminumhydride. Catalytic hydrogenation with 30 psi or 15 psi of $H_2$ gas of 1 generated 8-butyl-5,7-dimethoxy-2,2-dimethylchroman (2) and 1-(5,7-dimethoxy-2,2-dimethylchroman-8-yl)butan-1-one (3), respectively. Reduction with sodium borohydride occurred at the double bond of ${\alpha},{\beta}-unsaturated$ ketone of 1 to give 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)butan-1-one (4). Reduction of 1 with lithium aluminumhydride and then quenched with methanol and water produced unexpected products, 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)-3-methoxy-1-butene (5) and 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)-3-hydroxy-1-butene (6). These are formed from the isomerization of initial product 9 through the continuous conjugate carbocation intermediate 11. Addition of ethylmagnesium bromide and dimethyl malonate anion to 1 gave the conjugate adducts 7 and 8. Ethylmagesium bromide and sodium borohydride reduction unusually gave the conjugate addition due to steric congestion around carbonyl group of 1. Compound 2 exhibits the reduced inhibitory activity against $NF-{\kappa}B$ activation and the others do not show the activity. Therefore ${\alpha},{\beta}-unsaturated$ carbonyl group of 1 should be important for its inhibitory activity.

Kinetic Studies of Peptidylprolyl cis-trans Isomerase from Porcine Spleen

  • Kim, Soo-Ja;Lee, Chan
    • BMB Reports
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    • 제29권6호
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    • pp.519-524
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    • 1996
  • Peptidylprolyl cis-trans isomerase (PPlase) catalyzes the cis-trans isomerization of prolyl peptide and facilitates the folding of cellular proteins and peptides. PPlase consists of two distinct immunophilins, each specifically binding to the immunosupressive drug cyclosporin A (CsA) or FK506, respectively. A PPlase was isolated and partially purified from porcine spleen. The molecular weight of porcine spleen PPlase was determined to be ~14,000 on the basis of SDS-PAGE. The purified enzyme was strongly inhibited by FK506, but not by CsA. The inhibition constant and the true concentration of enzyme preparations were determined by active site titration using the tight binding inhibitor FK506: $K_{i}=18.7$ nM and $E_{t}=172$ nM. The equilibrium ratio of conformer. [cis]/[trans], of prolyl peptide substrates (N-Suc-Ala-Xaa-Pro-Phe-p-NA) in anhydrous trifluoroethanol/LiCl solvent system varied from 0.24 to 0.85 depending on the nature of Xaa. Overall. in this solvent-salt system, the populations of the cis conformer of substrates in equilibrium are higher than in an aqueous solution so that the substantial error caused by high background absorption can be reduced. The reactivities of porcine spleen PPlase are shown to be highly sensitive to changes in the structure of substrates. Thus, $k_{cat}/K_m$ value for the most reactive substrate (Xaa Leu) is $4.007+10^{6}M^{1}s^{1}$ and, is 2,636 fold higher than that for the least reactive peptide substrate tested, Xaa=Glu.

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포도당 이성화 효소의 세포 고정화에 관한 연구 - 제 2 보 : 회분식 및 연속 반응조를 사용한 포도당의 이성화 - (Studies on Whole Cell Immobilized Glucose Isomerase - II. Operational Studies on the Batchwise and Continuous Isomerization of D-Glucose -)

  • 안병윤;변시명
    • 한국식품과학회지
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    • 제11권4호
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    • pp.249-257
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    • 1979
  • 전보에서 저자들을 물리적 견고성이 우수한 포도당 이성화 효소를 세포 고정화 시킨 제품을 얻었다.(한국 식품 과학 회지, 11(No. 3), 192(1979). 이 효소 제품을 사용하여 실험실 조건에서 회분식 반응조와 충진식 반응조를 운영하여 효소의 반응 특성과 생산성, 활성 감소 현상을 비교 하였다. 본 고정화 효소의 비활성 역가는 회분식 반응조와 충진식 반응조에서 1 g당 각각 48 및 114 units였으며 연속적인 공정에서 더 높은 생산성과 이성화율을 보였다. 효소의 생산성은 체장 시간, 기질의 농도, 효소 부하율(附荷率) 및 반응조의 외형에 영향을 받았으며 충진 밀도가 450 g/l일 때 실제 공간율은 0.36이었으며 비교적 좋은 충진 현상을 보였다. 연속 공정중 효소의 활성 감퇴 현상을 고찰하기 위하여 2.5 M 포도당 용액을 체장 시간이 5.3시간이 되도록 약 220시간 동안 반응시켜 본 결과, 효소 활성 감퇴 곡선은 일차 반응을 따르며 활성 반감기는 115일로 연속 공정에 이용 가능함을 알았다. 이 고정화 효소 제품은 물리적 안정성이 높은 반면 물질 전달 계수가 반응 속도에 큰 영향을 미치는 것으로 나타났다.

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기능성 덴드리머 박막의 광학적 거동 및 전기적 특성 (Optical Behavior and Electrical Properties of Functional Dendrimer Thin Films)

  • 박재철;정상범;권영수
    • 대한전기학회논문지:전기물성ㆍ응용부문C
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    • 제52권5호
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    • pp.201-205
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    • 2003
  • We synthesized dendrimers containing light switchable units, azobenzene group. And the dendrimer containing 48 pyridinepropanol functional end group, which could form a complex structure with metal ions was synthesized. To apply to the molecular level devices or data storage system using Langmuir-Blodgett(LB) film, we firstly investigated the monolayer behavior using the surface pressure-area($\pi$-A) isotherms at air-water interface. And then the surface pressure shift of monolayer by light irradiation was also measured to the dendrimer with azobezene group. As a result, the monolayer of dendrimer with azobenzene group showed the reversible photo-switching behavior by the isomerization of azobenzene group in their periphery. The samples for electrical measurement were fabricated to two types which were pure dendrimer with pyridinepropanol group and its complexes with $Pt^4+$ ions by LB method. We have studied the electrical properties of the ultra thin dendrimer LB films investigated by the current-voltage(I-V) characteristics of Metal/Dendrimer LB films/Metal(MIM) structure. And we have investigated different results in the surface activity at the air-water interface as well as the electrical properties for the monolayers of pure dendrimer with pyridinevopanol group and its complex with $Pt^4+$ ions. In conclusion, it is demonstrated that the metal ion around dendrimer with pyri야nepropanol group can contribute to make formation of network structure among dendrimers and it result from the change of electrical properties. This results suggest that the dendrimers with azobenzene group and pvridinedropanol group can be applied to high efficient nano-device of molecular level.

기능성 덴드리머 박막의 광학적 거동 및 전기적 특성 (Optical Behavior and Electrical Properties of Functional Dendrimer Thin Films)

  • 박재철;정상범;권영수
    • 대한전기학회논문지:시스템및제어부문D
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    • 제52권5호
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    • pp.201-201
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    • 2003
  • We synthesized dendrimers containing light switchable units, azobenzene group. And the dendrimer containing 48 pyridinepropanol functional end group, which could form a complex structure with metal ions was synthesized. To apply to the molecular level devices or data storage system using Langmuir-Blodgett(LB) film, we firstly investigated the monolayer behavior using the surface pressure-area($\pi$-A) isotherms at air-water interface. And then the surface pressure shift of monolayer by light irradiation was also measured to the dendrimer with azobezene group. As a result, the monolayer of dendrimer with azobenzene group showed the reversible photo-switching behavior by the isomerization of azobenzene group in their periphery. The samples for electrical measurement were fabricated to two types which were pure dendrimer with pyridinepropanol group and its complexes with $Pt^4+$ ions by LB method. We have studied the electrical properties of the ultra thin dendrimer LB films investigated by the current-voltage(I-V) characteristics of Metal/Dendrimer LB films/Metal(MIM) structure. And we have investigated different results in the surface activity at the air-water interface as well as the electrical properties for the monolayers of pure dendrimer with pyridinevopanol group and its complex with $Pt^4+$ ions. In conclusion, it is demonstrated that the metal ion around dendrimer with pyri야nepropanol group can contribute to make formation of network structure among dendrimers and it result from the change of electrical properties. This results suggest that the dendrimers with azobenzene group and pvridinedropanol group can be applied to high efficient nano-device of molecular level.

Preparation of a Large Quantity of CIS-9, trans-11 and trans-10, cis-12 Conjugated Linoleic Acid(CLA) Isomers from SYnthetic CLA

  • Kim, Seck-Jong;Park, Kyung-Ah;Park, Jung-H.Y.;Kim, Jeong-Ok;Ha, Yeong-Lae
    • Preventive Nutrition and Food Science
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    • 제5권2호
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    • pp.86-92
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    • 2000
  • Conjugated linoleic acid(CLA) refers to a collective term of positional and geometric isomers of linoleic acid, which are different in their biological activities. The predominant isomer of CLA in animal tissues is cis-9, trans-11; smaller amounts of trans-10, cis-12 CLA isomers, CLA methyl ester (CLA-ME) was chemically syn-thesized from linoleic acid by the alkaline isomerization method. The synthetic CLA-ME, mainly composed of cis-9, trans-11 CLA and trans-10, cis-12 CLA, was dissolved in acetone, stored at 68$^{\circ}C$ for 1 day, and the supernatant(cis-9, trans-11 CLA-Me) was separated from the precipitate (trans-10, cis-12 CLA-Me). After the processes were repeated three times at -68$^{\circ}C$, the whole processes were repeated three times at -71$^{\circ}C$ in order to increase the purity of these two isomers. The cis-9, trans-11 CLA-Me and trans-10, cis-12 CLA isomers were further purified by the urea adduct. Purities of the cis-9, trans-11 CLA-Me and trans-10, cis-12 CLA-Me were 90.3 and 99.9%, respec-tively. This method could be employed for the preparation of a large quantity of highly purified cis-9, trans-11 CLA-Me or trans-10, cis-12 CLA-Me from synthetic CLA-Me.

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유량 변화에 따른 exo-tetrahydrodicyclopentadiene의 열분해특성에 관한 연구 (A Study on Thermal Decomposition Characteristics of exo-tetrahydrodicyclopentadiene with Variation of Flow Rate)

  • 강샛별
    • Korean Chemical Engineering Research
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    • 제57권6호
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    • pp.763-767
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    • 2019
  • 본 연구에서는 흐름형 반응기를 활용하여 단일 화합물로 구성된 연료인 exo-tetrahydrodicyclopentadiene (exo-THDCP)의 유량을 변화시킴에 따라 나타나는 열분해 특성에 대해 분석하였다. 실험은 $500^{\circ}C$, 50 bar의 온도와 압력 조건에서 수행하였으며, 각 유량 조건에서 반응을 통해 생성된 물질은 GC/MS를 사용하여 분석하였다. 그 결과, exo-THDCP는 열에 의해 주로 고리형 화합물로 분해됨과 동시에 일부는 이성질화 되는 것을 확인하였다. 또한, 유량이 증가할수록 분해 및 이성질화 반응을 통해 생성되는 화합물의 종류와 비율이 감소하였으며, 이에 따라 연료의 전환율과 분해 반응 시에 발생하는 흡열량도 함께 감소하였다. 열분해 반응 시에 비교적 빠르게 생성되는 화합물은 주로 1-cyclopentylcyclopentene (1-CPCP)의 radical 형태를 중간체로 하여 형성되는 것으로 분석되었는데, 이는 exo-THDCP로부터 생성될 수 있는 중간체 중에서도 특히 1-CPCP가 생성되는 데에 필요한 활성화 에너지가 약 42 kcal/mol로 가장 낮기 때문인 것으로 해석된다.