Macromer Technology

Iwhan Cho 한국고분자학회 1980 폴리머 Vol.4 No.3

Solvolysis of Hydrophobically Hidden p-Nitrophenyl Esters in Mixed Micelles. Dramatic Counterion Effect on the Solvolysis at High pH Values

Iwhan Cho,Gi-Chae Kim 한국고분자학회 1988 한국고분자학회 학술대회 연구논문 초록집 Vol.1988 No.10

Clean 1,5-Ring-Opening Polymerization of 1-(p-Substituted Phenyl)-2-Vinylcyclopropanes by Radical and Ziegler-Natta Catalysts

Iwhan Cho,Soo Suk Song 한국고분자학회 1988 한국고분자학회 학술대회 연구논문 초록집 Vol.1988 No.10

Hydrophobic and Ionic Interactions in the Ester Hydrolysis by Imidazole-Containing Polymers

Cho Iwhan,Shin Jae-Sup Korean Chemical Society 1982 Bulletin of the Korean Chemical Society Vol.3 No.1

N-Methacryloyl-L-histidine and N-methacryloyl-L-histidine methyl ester were synthesized and polymerized to obtain polymeric catalysts with different functions. In the presence of each of these polymers the solvolytic reactions of p-nitrophenyl acetate (PNPA), 3-nitro-4-acetoxybenzoic acid(NABA), 3-acetoxy-N-trimethylanilinium iodide(ANTI) and 3-nitro-4-decanoyloxybenzoic acid(NDBA) were performed in 20% aqueous ethanol. For the purpose of comparison the low molecular weight analogs(LMWA's), L-histidine, L-histidine methyl ester and N-acetyl-L-histidine were also subjected to catalyze the solvolyses of above substrates. In the solvolysis of PNPA the polymeric catalysts exhibited lower activities than the LMWA's. However the ionic substrates, NABA and ANTI were solvolyzed at anomalous rate by polymeric catalyst, indicating that electrostatic effects are operative in the catalysis by polymers. Furthermore in the solvolysis of hydrophobic monomer NDBA, polymeric catalysts exhibited highly enhanced activities compared with the LMWA's implying that hydrophobic interaction can be the most important contribution to the high catalytic activity of imidazole-containing polymers.

Vesicle의 성질에 대한 콜레스테롤의 효과

조의환,문권기,신재섭 한국약제학회 1993 Journal of Pharmaceutical Investigation Vol.23 No.1

Polymerized vesicles were prepared from monomeric cholesterol-containing surfactant. These vesicles were used to extract the free cholesterol. To introduce spacer group into [cholesteryloxycarbonylmethyl] [2-(methacryloyloxy)ethyl]dimethylammonium chloride (CHODAMA), [5-[(cholesteryloxy)carbonyl]pentyl] [2-(methacryloyloxy)ethyl]dimethylammonium bromide (CHODAMA-5) and [10-[(cholesteryloxy)carbonyl]decyl] [2-(methacryloyloxy)ethyl]dimethylammonium bromide (CHODAMA-10) were synthesized. In both case of polymerized vesicle with CHODAMA-5 and CHODAMA-10, the permeability was decreased and the amount of extracted cholesterol was also decreased, compared with the polymerized vesicle of CHODAMA.

Cholesterol기를 갖는 고분자화된 Vesicle들의 투과 특성

조의환,신재섭,배덕환 한국약제학회 1993 Journal of Pharmaceutical Investigation Vol.23 No.2

Polymerized vesicles were prepared from the monomeric cholesterol-containing surfactant. Spacer groups were introduced into [(cholesteryloxy)carbonylmethyl] [2-(methacryloyloxy)ethyl]dimethylammonium chloride (CHODAMA). In case of introducing the spacer groups to the cholesterol moiety, both permeability of vesicles and that of polymerized vesicles were decreased. In case of introducing the spacer groups to monomeric moiety, permeability of vesicles was increased, while that of polymerized vesicles was decreased.

Thermal Rearrangement of 1,1-Disubstituted 2-Vinylcyclopropanes to 4,4-Disubstituted Cyclopentenes

안광덕,Cho, Iwhan,Ahn, Kwang-Duk 대한화학회 1978 대한화학회지 Vol.22 No.3

The four 1,1-disubstituted 2-vinylcyclopropanes, 1,1-diphenyl-2-vinylcyclopropane (1a), 1,1-dicyano-2-vinylcyclopropane(1b), ethyl 1-cyano-2-vinylcyclopropanecarboxylate(1c), and diethyl 2-vinylcyclopropane-1,1-dicarboxylate(1d) rearranged below $300{\circ}C$ to the corresponding 4,4-disubstituted cyclopentenes, 4,4-diphenylcyclopentene(2a), 3-cyclopentene-1,1-dicarboxylate(2d). Diphenpyl derivative 1a rearranged almost quantitatively to 4,4-diphenylcyclopentene(2a) at the temperature of $250{\circ}C$. Although dicyano derivative 1b in solution underwent the thermal rearrangement at rather low temperature of $170{\circ}C$, the other vinylcyclopropanes, 1c and 1d, in solution rearranged thermally above $220{\circ}C$. In the thermal reaction of 1b, 1c, and 1d considerable amounts of polymers 3 were also produced. Also detected product was the ring-opened diene, ethyl 2-cyano-2,4-hexadienoate(4), in case of the pyrolysis of 1c. The observed facile rearrangement of disubstituted vinylcyclopropanes was explained by the radical stabilization effect of substituents on the diradical intermediates 5. 1-위치에 두개의 극성치환체를 가진 2-비닐시클로프로판 1a, 1b, 1c, 1d를 300$^{\circ}C$ 이하로 가열한 결과 4,4-위치에 치환된 대응하는 시클로펜텐 2a, 2b, 2c, 2d로의 자리 옮김반응이 용이하게 일어났다. 시아노기가 치환된 1b는 용매로 희석시켜서 170${\circ}C$로 반응시켰을 때 2b로의 자리옮김이 관찰되었지만, 1c와 1d는 $200^{\circ}C$ 이상의 온도에서 반응이 일어났고, 페닐기가 치환된 1a는 $250{\circ}C$ 이상의 온도에서 반응이 일어났고, 페닐기가 치환된 1a는 250$^{\circ}C$ 에서 용매 사용없이 열반응으로 2a가 생성되었다. 1a의 시클로펜텐으로의 열적 자리옮김반응은 거의 정량적이었지만 1b, 1c, 1d의 경우에는 시클로펜텐외에 상당량의 고분자물질 3이 생성되었다. 1c의 경우에는 시클로펜텐외에 시클로프로판 고리가 열린 디엔 4가 관찰되었다. 두 기가 치환된 시클로프로판 1이 용이하게 시클로펜텐 2로 열적 자리옮김 반응을 하는 이유는 두 극성기가 반응 중간물질인 디라디칼 5를 안정화 시키는 효과로서 설명하였다.

단백질에 대한 그라프트 공중합 (제1보). Cerium (IV) 이온에 의한 비닐 단위체의 견섬유에 대한 그라프트 공중합

조의환,안광덕,Iwhan Cho,Kwang-Duk Ahn 대한화학회 1976 대한화학회지 Vol.20 No.4

단백질 섬유인 견섬유에 ceric ammonium nitrate를 촉매로 사용하여 acrylamide 또는 acrylonitrile을 그라프트공중합 하였다. 공중합의 표준반응조건은 세륨염 0.025 M, acryamide 0.5 M, 초산 25%, 온도 30$^{\circ}C$, 반응시간 3시간으로 하였으며 견섬유의 욕비(bath ratio)는 1:200으로 하였다. 이상의 반응조건에서 세륨염의 농도가 0.01 M 일 때와 7% 초산수용액일 때에 그라프트율이 최대로 되었다. Acrylonitrile을 단위체로 사용하면 질산용액에서의 그라프트율이 초산수용액에서 보다 높았지만, acrylamide 사용시와는 달리 그라프트율은 현저히 낮았다. 이밖에 그라프트된 견섬유의 Lowe시약(동-글리세린 수용액)에 대한 용해도, 적외선 분석 및 분자량을 조사하고 호모 중합체의 생성에 대하여 검토 하였다. Cerium (Ⅳ) ion-initiated graft copolymerizations of acrylamide and of acrylonitirile to silk fibroins were investigated. When acrylamide was used, the change in ceric ammonium nitrate concentration exhibited a maximum in degree of grafting at 0.01 M. Also observed was that the change in acetic acid content in reaction media gave a maximum in degree of grafting at 7% acetic acid in water. Degree of grafting was increased generally with increase in acrylamide concentration reaction time and reaction temperature. When acrylonitrile monomer was used for grafting,different results were obtained. Addition of nitric acid was more effective in enhancing the degree of grafting than the addition of acetic acid.Generally the grafting of acrylonitrile to silk fibroins was less efficient than the grafting of acrylamide. The portion of grafted silk fibroins insoluble in Lowe's reagent exhibited the IR absorption bands characteristics to both vinyl polymers and silk fibroins, indicating the grafting of vinyl monomers to silk fibroins. To examine the molecular weight of graft vinyl polymer, a sample of grafted silk was hydrolyzed by 10% sodium hydroxide. Viscosity measurements indicated that the molecular weight of the graft polymer was in the range of 105.

단백질에 대한 그라프트 공중합 (제3보). Cerium (IV) 이온에 의한 비닐 단위체의 그라프트 공중합에 대한 메카니즘

조의환,안광덕,Iwhan Cho,Kwang-Duk Ahn 대한화학회 1976 대한화학회지 Vol.20 No.4

Based on the results of graft copolymerization to proteins, an attempt is made to derive the rate equations to explain the mechanism of Ce(IV) ion-initiated graft copolymerizations. In this system the oxidative termination by Ce(IV) $[R{\cdot}+ Ce(IV) ${\rightarrow}$ R(inert) + Ce(III) + H^+]$ is considered characteristic particularly in higher concentration of Ce(IV) ion. The change in the mode of termination reactions with change in Ce(IV) ion concentration makes possible the presence of an optimum Ce(IV) ion concentration for maximum graft copolymerization yield. This effect is reflected in presently derived equations. 단백질에 대한 비닐 단위체의 그라프트 공중합 실험결과를 기초로하여 유기물과 Ce(IV)이온의 산화환원계에 의하여 개시되는 중합반응에 대하여 중합반응 메카니즘을 추구하였다. Ce(IV) 이온에 의한 산화성 종결반응을 고려하여 반응속도식을 유도 하였으며 Ce(IV) 이온 농도가 클때와 작을 때를 별개로 취급하여 Ce(IV) 이온 농도의 변화에 따라 그라프트 수득률의 최대점이 나타나는 현상을 설명하였다.

단백질에 대한 그라프트 공중합 (제2보). 세리신의 분리, 정제 및 아크릴로니트릴의 그라프트 공중합

조의환,김광건,Iwhan Cho,Kwang-Kun Kim 대한화학회 1976 대한화학회지 Vol.20 No.4

누에고치로 부터 온수로 추출된 세리신을 Sephadex G-75와 G-150을 사용하여 $25^{\circ}C$와 $70^{\circ}C$의 두 온도에서 겔 여과함으로써 분자량 분포를 조사한 결과, 온수추출 세리신의 분자크기에 따른 분포는 가열시 가수분해를 고려한다면 한가지 프렉숀임이 밝혀졌다. 수용성 단백질인 세리신과 아크릴로니트릴의 공중합반응에서 세리신/아크릴로니트릴/물-계는 균일계를 이루며 개시제로서는 단백질에 대하여 효과적이라고 알려진 ceric ammonium nitrate를 사용하였다. 개시제 농도가 증가함에 따라 공중합체의 수득량도 증가하나 어느 특정농도 (0.03 M 세륨염)에서 최대 수득량을 주고 그 이상의 농도에서는 오히려 감소하였다. 세리신 농도의 증가, 아크릴로니트릴 단위체 농도의 증가에 따라서는 일반적으로 공중합체의 수득량도 증가하였다. 그라프트 공중합체의 확인과 조성은 주로 IR 스펙트럼에 의하였고 그라프트율은 200% 내지 1,900%의 넓은 분포를 보였다. 공중합체의 세리신 부분을 가수분해한 후 그라프트된 아크릴로니트릴 중합체의 분자량을 측정한 결과 약 7,000 정도였다. An efficient separation method and the utilization of sericin are searched. Sericin was extracted with hot water from cocoons under atmospheric pressure. The separated sericin was gel-filtrated with Sephadex G-75 and G-150 at room temperature and at $70^{\circ}C$. The results indicated that sericin is consisted of only one fraction in elution diagram. In the graft copolymerization of acrylonitrile to sericin ceric ammonium nitrate was chosen as an initiatior. A maximum yield was obtained at certain concentration of the initiator confirming our previous experiments. Viscosity measurement of alkali-hydrolyzed graft copolymers indicated that the polyacrylonitrile graft had the molecular weight in the range of 7,000.