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RISS 인기검색어
- 검색키워드
- 저자 : 한만정(Man Jung Han) (검색결과 12 건)
- 무료
- 기관 내 무료
- 유료
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The Kinetic Study of Propylene Sulfide Polymerization Initiated by o-Sulfobenzoic Anhydride
한만정,Man Jung Han Korean Chemical Society 1978 대한화학회지 Vol.22 No.4
Propylene sulfide를 o-sulfobenzoic anhydride로 중합시키면 양성이온 메카니즘에 의하여 중합이 진행되며, 이 반응의 속도를 연구하였다. 반응계중의 단위체와 개시제의 농도는 IR과 NMR를 이용하여 측정하였다. 성장반응속도가 개시반응속도보다 $10^3$정도 빠르며 이러한 결과는 양성이온 메카니즘에 의하여 생긴것으로 사료된다. The kinetics of the bulk polymerization of propylene sulfide initiated by o-sulfobenzoic anhydride were investigated, which proceeded by a zwitterionic mechanism.The instantaneous concentrations of monomer and initiator were determined by means of ir-and nmr-spectroscopy. The rate constant of propagation was found to be about three order of magnitude higher than that of initiation and this should be caused by a zwitterion mechanism.
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Changes in Solution Properties of Poly(trans-5-methylproline) During Mutarotation
한만정,Han Man Jung Korean Chemical Society 1979 대한화학회지 Vol.23 No.1
Poly(trans-5-methylproline) (PTMP)의 변광회전에 따른 CD, ORD 및 uv 스펙트럼의 변화를 관찰하였다. PTMP의 정방향 변광회전은 유기강산이나 trifluoroethanol (TFE) 속에서 일어나며 역방향 변광회전은 TFE용액을 과량의 지방족 알코올로서 회전시킬때 일어났다. 정방향과 역방향 변광회전시의 CD, ORD, 및 uv 스펙트럼의 변화는 polyproline 변광회전시의 변화와 평형하게 일어났다. PTMP의 정방향 변광회전시 ${\alpha}CH-$양성자의 화학적이동은 0.3 ppm downfield로 이동하였고 환원 점도는 0.15에서 0.26(dl/g)로 증가하였다 적당한 용매의 혼합물에서는 형태 I 과 II는 평형을 이루었다. 이러한 모든 용액성질의 변화는 polyproline의 변화와 유사하기 때문에 I, II의 두 형태는 polyproline 형태 I, II와 같을 것이며 형태 I은 모두 시스아미드 결합을 가진 helix이고, 형태 II는 모두 트란스 아미드 결합을 가진 helix일 것이다. Changes in CD, ORD and uv-spectra during the mutarotation of poly(trans-5-methyl-L-proline) (PTMP) were studied. The forward mutarotion of PTMP occurred in strong organic acids and trifluoroethanol, while the reverse mutarotation was observed by dilution of the trifluoroethanol solution with excess aliphatic alcohols. The changes in CD, ORD and uv-spectra during the forward and reverse mutarotation proceeded paralell to those found for the mutarotation of polyproline. The chemical shift of the ${\alpha}CH-$proton was shifted downfield about 0.3 ppm during the forward mutarotation. The reduced viscosity for the forward mutarotation increased from 0.15 to 0.26 (dl/g) during 5 days. The equilibrium between form I and form II was estabilished in an appropriate solvent mixture. All changes in solution properties mentioned above are similar to those found for polypoline. These results support that the two forms of PTMP are the same conformations as polyproline form I and form II, i. e., a right-handed helix with all cis amide bonds and a lefthanded helix with all trans amide bonds.
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The Initiation Mechanism in the Polymerization of Trioxane with Titanium Tetrachloride
한만정,Han Man Jung Korean Chemical Society 1978 대한화학회지 Vol.22 No.6
트리옥산을 니트로벤젠 용매중에서 Ti$Cl_4$로서 중합시킬때 개시 반응기구를 연구하였다. 중합반응속도를 측정한결과 미량의 물이나 메탄올을 첨가하면 반응속도가 급격히 감소하였으며 중합을 개시하는 데는 조촉매로서 다른 물질이 필요 없음이 알려졌다. 유전상수 측정결과에 의하면 중합과정중 양성이온이 생기지 않으며 중합제나 개시제 용액의 전기전도도를 측정한 결과 개시 반응은 니트로벤젠 용매중에서 개시제가 동종간 주고 받기반응에 의하여 생긴 Ti$Cl_3^+$ 양이온에 의하여 일어난다는 것이 판명되었다. The initiation mechanism of trioxane polymerization catalyzed by Ti$Cl_4$ in nitrobenzene was investigated. The kinetic studies revealed that the rate of polymerization was drastically decreased by the addition of a minute amount of water or methanol. A third substance as cocatalyst was not required for the polymerization. Measurements of dielectric constants gave no evidence for the zwitterionic mechanism of the polymerization. The electric conductivity measurements of polymerization system and the initiator solution showed that the initiation was started by Ti$Cl_3^+$ cation, formed by a disproportionation of the initiator in nitrobenzene.
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한만정,Han Man Jung Korean Chemical Society 1978 대한화학회지 Vol.22 No.6
The rates of the forward mutarotation of poly(trans-5-methyl-L-proline) in trifluoro-ethanol and of the reverse mutarotation in trifluoroethanol-n-butanol (1:4 v/v) have been measured at a number of temperatures and polymer concentrations. It was found that both mutarotations are of first-order with respect to the polymer concentration. A modified Arrhenius equation to evalute the activation energy was derived for the reaction kinetics, in which the relation between the measured physical properties and concentration, and the order of tle reaction are uncertain. The activation energies for the forward and reverse mutarotation were found to be 32.5 and 33.5 kcal per residue mole, respectively, which are about 10 kcal per residue mole higher than the $E_a$ for the mutarotation of polyproline (the resonance energy of amide bonds). The excessive quantity of the activation energy was attributed to the steric barrier between carbonyl and methyl groups during the cis-trans isomerization of amide bonds in the polymer. 여러 농도와 온도에서 Poly(trans-5-methyl-L-proline)을 trifluoroethanol 용매에서 정방향 변광회전, trifluoroethanol-n-butanol (1 : 4) 용매에서 역방향 변광회전을 시키면서 변광회전속도를 측정하였다. 이 두 방향의 변광회전 현상은 폴리머농도에 대하여 1차 반응이었다. 활성화에너지를 측정하기 위하여 변형된 Arrhenius식을 유도하였는데 이식은 물리적 성질과 농도와의 관계나 반응차수가 불확실한 반응에 이용할 수 있다. 정방향과 역방향 변광회전의 활성화에너지는 잔기몰당 각기 32.5와 33.5kcal이었고 이값은 polyproline 변광회전의 활성화에너지 (아미드결합의 공명에너지)보다 잔기몰당 10kcal가 높다. 이 과량의 활성화에너지는 폴리머아미드 결합이 시스-트란스 이성질화현상이 일어날 때 카르보닐기와 메틸기 사이에 생기는 입체장애에 의한 것이다.
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한만정,Man Jung Han Korean Chemical Society 1978 대한화학회지 Vol.22 No.3
o-술포벤조산 무수물을 개시제로 사용하여 프로필렌술피드를 괴상 중합시킨 결과 양성이온 메카니즘에 의하여 중합한다는 것이 판명되었다. 생성된 폴리머를 분석한 결과 이 폴리머는 술포늄양이온과 술폰산음이온을 폴리머 사슬에 가지고 있다는 것이 판명되었다. 음이온과 양이온의 농도가 거의 같으며 이것은 고분자양성이온임을 나타낸다. 중합계중에 존재하는 수분이 조촉매로 이용되었을 가능성은 없으며 말단기 분석을 이용하여 중합메카니즘을 규명하였다. Bulk polymerization of propylene sulfide with o-sulfobenzoic anhydride as initiator was carried out and the polymerization proceeded by a zwitterionic mechanism. Chemical and spectroscopic investigation of the purified polymer revealed that the polymer contained two end groups-thiolester of benzoic acid o-sulfonate anions and acyclic tert-sulfonium ions which were formed by termination of episulfonium ions with sulfide groups in the polymer chains. The concentration of sulfonate anions was nearly the same as the concentration of acyclic tert-sulfonium ions, as expected for macrozwitterions. The cocatalysis mechanism by a trace of water was excluded and the other possible mechanisms were discussed on the basis of end group analysis.
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고분자 중합체 심근 스템트를 이용한 기계적 경심근 혈류재건술의 혈관생성 반응
최호,이철주,문광덕,김영진,강준규,홍준화,지경수,한만정,조상호,Choi, Ho,Lee, Cheol-Joo,Moon, Kwang-Deok,Kim, Young-Jin,Kang, Joon-Kyu,Hong, Jun-Wha,Jee, Kyung-Soo,Han, Man-Jung,Cho, Sang-Ho 대한흉부심장혈관외과학회 2000 Journal of Chest Surgery (J Chest Surg) Vol.33 No.6
Background: Transmyocardial laser revascularization(TMLR) for revascularizing ischemic myocardium in patients was originally based on the assumption that laser channels remain their patency much longer. But recent studies show that laser channels did not remain open and that TMLR could achieve treatment benefits without long-term channel patency. The angiongencesis is currently thought to be induced by non-specific inflammatory response to mechanical tissue injury. This study is to evaluate hypothesis that various transmyocaridal mechanical revascularization(TMMR) may induce the angiogenic responses similar to that seen with TMLR, and transmyocaridal polymer stent revascularization(TMSR), the polymer stent in the myocardial tissue is hydrolyzed in 2 weeks, may enhance the non-specific inflammatory reaction resulting angiogenesis. Furthermore, polymer myocaridal stent channels remain long-term patency. Material and Method: Eight domestic pigs underwent ligation of the proximal circumflex artery, and 2 weeks later they were randomized to undergo transmycardial acupunctural revascularization (TMPR, Group I) of the left lateral wall with 18-G needle(n=2), to undergo transmyocardial (TMDR, Group II) with industrial 2mm steel drill(n=2), to undergo transmyocardial polymer stent revascularization (TMSR, Group III) after drilling the infarcted myocardium(n=2), the stent is poly(lactic acid-co-glycolic acid), which is self-degradated in the myocardium, and to a control group the ischemic zone was unterated(n=2). All the pigs were sacrificed after 4 weeks TMMR. Sections from the ischemic zone were submitted for vascular endothelial growth factor (VEGF) ELISA and histology. Result: There were makedly increase in the VEGF immunoassay in the ischemic zone of the TMMR group compared to the ischemic zone of the control group(control: each 30.85 and 43.15pg/mg protein, TMPR: each 44.14 and 68.61 pg/mg protein, TMDR: each 65.92 and 78.65 pg/mg protein, TMSR: each 177.39 and 168.87 pg/mg protein). TMSR channels caused greatest VEGF expression than channels made by other group and the polymer stent channels remained vacuole after 4 weeks. Conclusion: Transmyocardial polymer stent revascularization promoted the most angiogenci response by the VEGF immunoassay, although our study did not show the statistical significancy. The channels remained but the flow patency was not verified. Transmyocardial polymer stent revascularization (TMSR) is desirable in future experimental trials and in view of the significant cost implications comparable to that of laser.
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