Won-Moon Choi

Syntheses and biological activities of α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil and its polymers

The new monomer, α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil (MMTFU), was synthesized from 5-fluorouracil (5-FU) and α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl chloride (MMTC). Poly(α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil) [poly(MMTFU)], poly(α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil-co-acrylicco-AA), and poly(α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil-co-vinyl acetate) [poly(MMTFU-co-VAc)] were synthesized by photopolymerizations using 2,2-dimethoxy-2-phenylacetophenone (DMP) as the photoinitiator. The synthesized MMTFU and the polymers were identified by FT-IR, 1H-NMR, and 13C-NMR spectroscopies. The contents of MMTFU in poly(MMTFU-co-AA) and poly(MMTFU-co-VAc) determined by elemental analysis were 63 and 57 mol %, respectively. The number average molecular weights and polydispersity indices of synthesized polymers determined with GPC were in range of 7,700–19,100 and 1.6–2.7. The in vitro cytotoxicities of samples were evaluated with mouse mammary carcinoma (FM3A), mouse leukemia (P388), and human histiocytic lymphoma (U937) as cancer cell lines and mouse liver cells (AC2F) as a normal cell line. The cytotoxicities of 5-FU and synthesized samples against cancer cell lines increased in following orders: 5-FU > MMTFU > poly(MMTFU) > poly(MMTFU-co-AA) > poly(MMTFU-co-VAc). The in vivo antitumor activities of the synthesized samples against mice bearing the sarcoma 180 tumor cell line were evaluated. The in vivo antitumor activities of the polymers were greater than that of 5-FU at a dose of 80 mg/kg.

Syntheses and photobiodegradable properties of graft copolymers of vinyl ketones and starch

Abstract Graft copolymerizations of methyl vinyl ketone (MVK) or phenyl vinyl ketone (PVK) on to starch (S) were carried out with cerie ammonium nitrate (CAN) as initiator. The structures of the synthesized graft copolymers, S-g-poly(MVK) and S-g-poly(PVK), were identified by FT-IR spectroscopy. The thermal stability was also determined by TGA. The photodegradation of the graft copolymers was investigated by Fade-o-Meter and the biodegradation was estimated for the samples incubated with Aspergillus niger . The weight average molecular weights of the grafted side chains isolated from the original graft copolymers after UV irradiation were in the ranges of 3700~6400 compared to those of the same chains with 68 000~168 000 of samples before irradiation. The graft copolymers showed higher photodegradable properties because of the carbonyl-containing polymers in the graft copolymers. In photobiodegradation tests, the graft copolymers exhibited extensive grooves and pits due to photobiodegradable properties of carbonyl and starch moieties.

Syntheses and biological activities of α‐methoxy‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthaloyl‐5‐fluorouracil and its polymers

The new monomer, α-methoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil (METFU), was synthesized by the reaction of 5-fluorouracil (5-FU) and exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (ETA) in order to prepare polymers containing 5-FU moiety. Poly(α-methoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil) [poly(METFU)], poly(α-methoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouraci-co-acrylic acid) [poly(METFU-co-AA)], and poly(α-methoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil-co-vinyl acetate) [poly(METFU-co- VAc)] were synthesized by photopolymerizations using 2,2-dimethoxy-2-phenylacetophenone (DMP) as an initiator. The synthesized METFU and the polymers were identified by FTIR and 1H-NMR spectroscopies. The contents of METFU in poly(METFU-co-AA) and poly(METFU-co-VAc) determined by elemental analysis were 52 and 60 mol %, respectively. The average molecular weights and polydispersity indices determined with GPC were as follows: Mn = 9,400, Mw = 11,400 Mw/Mn = 1.21 for poly(METFU), Mn = 14,400, Mw = 26,800, Mw/Mn = 1.86 for poly(METFU-co-AA), and Mn = 23,100, Mw = 33,000, Mw/Mn = 1.43 for poly(METFU-co-VAc). The in vitro cytotoxicities of samples were evaluated with mouse mammary carcinoma (FM3A), mouse leukemia (P388), and human histiocytic lymphoma (U937) as cancer cell lines, and mouse liver cells (AC2F) as a normal cell line. The in vivo antitumor activities of synthesized polymers against mice bearing the sarcoma 180 tumor cell line were greater than those of 5-FU at concentrations of 0.8 and 80 mg/kg.

Syntheses and biological activities of N-alaninylmaleimide and its polymers

Abstract A new monomer, N-alaninylmaleimide (AMI), was synthesized by the reaction of maleic anhydride and β-alanine. Poly(N-alaninylmaleimide) [poly(AMI)], poly(N-alaninylmaleimide-co-methacrylic acid) [poly-(AMI-co-MA)], and poly(N-alaninylmaleimide-co-vinyl acetate) [poly-(AMI-co-VAc)] were synthesized by photopolymerizations. The synthesized AMI and its polymers were characterized by IR and 1H-NMR spectroscopies, elemental analysis, and gel permeation chromatography (GPC). The average molecular weights as determined by GPC were is follows: M n = 4200, M w = 4300, M w/M n = 1.02 for poly(AMI); M n = 4000, M w = 4100, M w/M n = 1.03 for poly(AMI-co-MA); and M n = 21,500, M w = 23,300, M w/M n = 1.08 for poly(AMI-co-VAc). In-vitro cytotoxicities of polymers against mouse mammary carcinoma (FM-3A/s), mouse leukemia (P-388/s), and human histiocytic lymphoma (U-937/s) cell lines were lower than those of AMI. The in-vivo antitumor activities of polymers against sarcoma 180 cells were greater than those of 5-...

Synthesis and photo- and biodegradabilities of poly[(hydroxybutyrate-co-hydroxyvalerate)- g-phenyl vinyl ketone]

The graft copolymer, poly[(hydroxybutyrate-co-hydroxyvalerate)-g-phenyl vinyl ketone] [P(HBV-g-PVK)], was synthesized by graft polymerization of phenyl vinyl ketone (PVK) onto poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) under nitrogen atmosphere using benzoyl peroxide. The structure of P(HBV-g-PVK) was identified by Fourier transform IR and 1 H-NMR spectra. The effects of weight ratio of PVK to PHBV in feed, initiator concentration, reaction time, and reaction temperature on the grafting ratio and grafting efficiency were investigated. The thermal decomposition temperature of P(HBV-g-PVK) was 272°C. The tensile strengths of P(HBV-g-PVK) after photo- or biodegradation were significantly decreased due to degradation by UV irradiation or Aspergillus niger. The value of color difference (ΔE) of P(HBV-g-PVK) was greater than that of PHBV. The film surfaces of P(HBV-g-PVK) treated with UV irradiation and Aspergillus niger showed many pits as compared with the untreated P(HBV-g-PVK). It has been found that the photo- and biodegradabilities of P(HBV-g-PVK) was excellent.

Syntheses and properties of photodegradable polystyrene‐containing carbonyl group

The copolymerizations of styrene (St) and methyl vinyl ketone (MVK) or phenyl vinyl ketone (PVK) were carried out in benzene by using azobisisobutylonitrile (AIBN). The synthesized copolymers, poly(St-co-MVK) and poly(St-co-PVK), were identified by infrared (IR) spectroscopy. Under the presence of oxygen, the copolymers containing carbonyl group after UV irradiation showed photodegradable properties that caused by Norrish Type II reaction. The new IR characteristic peaks, such as carbonyl and vinyl groups of the photooxidized copolymers, increased by increasing UV irradiation time. In the photodegradation property, the color differences of the synthesized copolymers were higher than those of polystyrene with increasing UV irradiation time, which was caused by the inherent photodegradable property of carbonyl unit in copolymers. The average molecular weights of samples after UV irradiation for 300 h decreased, as compared with polymers before irradiation.

Synthesis and biological activity of medium molecular weight polymers containing 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl‐5‐fluorouracil

A new monomer, 3,6-endo-methylene-1,2,3,6-tetrahydrophthalimidobutanoyl-5-fluorouracil (ETBFU), was synthesized by reaction of 3,6-endo-methylene-1,2,3,6-tetrahydrophthalimidobutanoyl chloride and 5-fluorouracil. The homopolymer of ETBFU and its copolymers with acrylic acid (AA) or vinyl acetate (VAc) were prepared by photopolymerization using 2,2-dimethoxy-2-phenylacetophenone as an initiator at 25 °C. The synthesized ETBFU and its polymers were identified by FTIR, 1H NMR and 13C NMR spectroscopies. The ETBFU content in poly(ETBFU-co-AA) and poly(ETBFU-co-VAc) was 43 and 14 mol%, respectively. The apparent number-average molecular weight (Mn) of the polymers determined by GPC ranged from 8400 to 11 300. The in vitro cytotoxicity of the samples against mouse mammary carcinoma (FM3A), mouse leukaemia (P388), and human histiocytic lymphoma (U937) cancer cell lines decreased in the order 5-FU ≥ ETBFU > poly(ETBFU) > poly(ETBFU-co-AA) > poly(ETBFU-co-VAc). The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5-fluorouracil at all doses tested. © 2000 Society of Chemical Industry

Syntheses and antitumor activities of medium molecular weight polymers containing ?-ethoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil

The new monomer, α-ethoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil (EETFU), was synthesized from 5-fluorouracil (5-FU) and α-ethoxy-exo-3,6-epoxy-1,2,3,6-tetrahydrophthaloyl chloride. Its homopolymer and copolymers with acrylic acid (AA) and vinyl acetate (VAc) were synthesized by photopolymerizations using 2,2-dimethoxy-2-phenylaceto-phenone. The synthesized samples were characterized by FT-IR, 1 H-NMR and 13 C-NMR spectroscopes, elemental analysis, and gel permeation chromatography. The EETFU contents in poly(EETFU-co-AA) and poly-(EETFU-co-VAc) were 40 and 37 mol %, respectively. The number average molecular weights were in range from 8,400 to 10,300. The in vitro cytotoxicities of synthesized samples were evaluated against mouse mammary carcinoma (FM3A), mouse leukemia (P388), and human histiocytic lymphoma (U937) as cancer cell lines and mouse liver cells (AC2F) as a normal cell line. The range of IC 50 values obtained from the in vitro test for synthesized samples were 0.03-0.16 μg/mL against cancer cell lines. The in vitro cytotoxicities of polymers were beter than 5-FU. The in vivo antitumor activities of synthesized monomer and polymers were also investigated by mice bearing the sarcoma 180 tumor cells. The in vivo antitumor activities of the synthesized monomer and polymers were greater than those of 5-FU at corresponding dosage concentrations.

Synthesis of copolymers from 3,5‐dioxo‐4,10‐dioxatricyclo‐[5.2.02,6]dec‐8‐ene and vinyl monomers by photopolymerization and their biological activities

Photocopolymerizations of 3,5-dioxo-4,10-dioxatricyclo[5.2.0 2,6 ]dec-8-ene (DDTD) with methacrylic acid (MA) acrylamide (AAm) and vinyl pyrrolidone (VP) were carried out in 2-butanone using dimethoxy benzoin (DMB) as an initiator at 25°C. The structures of the polymers obtained from photopolymerizations of corresponding monomer pairs were confirmed to be poly(DDTD-co-MA), poly(DDTD-co-AAm) and poly(DDTD-co-VP) by 1 H NMR and 13 C NMR spectroscopies, and the average molecular weights were determined by gel permeation chromatography (GPC). The weight average molecular weights (M w ) of the polymers were in the range 9500-17 300. The polymers were soluble in water, dimethyl sulphoxide (DMSO) and dimethyl formamide (DMF). The contents of DDTD units in the copolymers were 19, 37 and 45%. The in vitro cytotoxicities of the polymers were evaluated using mouse mammary carcinoma (FM-3A), mouse leukaemia (P-388) and human histiocytic lymphoma (U-937) cell lines. The in vivo antitumour activities of the polymers were estimated by the survival time of sarcoma 180 tumour-bearing mice. The in vivo antitumour activities of the polymers were greater than those of 5-fluorouracil (5-FU) and monomeric DDTD at a dose of 0.8 mg kg -1 . Poly(DDTD-co-AAm) and poly(DDTD-co-VP) showed higher antitumour activity than 5-FU and monomeric DDTD at all doses tested.

Synthesis and photodegradable properties of methyl vinyl ketone–EPDM–styrene graft terpolymer

The graft terpolymerization of methyl vinyl ketone (MVK) and styrene (St) onto ethylene–propylene–diene terpolymer (EPDM) was carried out under various polymerization conditions. The synthesized graft terpolymer, MVK–EPDM–St (MVES), was identified by infrared (IR) spectroscopy. The effects of monomer concentration, mole ratio of MVK to St, reaction time, reaction temperature, and initiator concentration on the graft terpolymerization were examined. Upon UV irradiation in the presence of oxygen, the MVES-containing carbonyl group showed photodegradable properties caused by Norrish type II reaction. The new IR characteristic peaks, such as carbonyl, vinyl, and hydroxy groups of the photodegraded MVES, increased with increasing UV irradiation time. The tensile strength and elongation at break of MVES after UV irradiation were lower than those of before UV irradiation. The color difference of the irradiated MVES was higher than that of EPDM.