• Applied Chemistry for Engineering
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• 제20권3호
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• pp.258-265
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• 2009

An anionic polyurethane dispersions (PUDs) were synthesized from the poly (tetramethylene glycol) (PTMG, Mw = 2000 g/mol), mixed isocyanate of dicyclohexylmethane-4,4'-diisocyanate $(H_{12}-MDI)$ and 4,4'-diphenylmethane diisocyanate (MDI), and dimethylol propionic acid (DMPA) as anionic site, following a prepolymer mixing process. Triethylamine (TEA) was used as a neutralization agent and the ethylenediamine (EDA) as the chain extender of the prepolymer. The effects of the DMPA molar ratio and aromatic diisocyanate content in the mixed isocyanate on the particle size and viscosity of PUD were studied. Also, the mechanical and thermal properties of the PUD cast films were discussed according to the molar ratio of DMPA and aromatic isocyanate content. It was found that the particle size and the viscosity of an anionic PUD decreased with increasing DMPA molar ratio but increased with increasing aromatic isocyanate (MDI) content in the mixed isocyanate at the constant DMPA content. Tensile strength of the PUD cast films increased and elongation at break decreased with increasing DMPA content at the constant mixed isocyanate molar ratios. In thermal degradation temperature of PUD cast films, the effect of DMPA contents was great but the effect of aromatic isocyanate contents at the low DMPA content was very slight respectively.

• Proceedings of the Korean Society for Applied Microbiology Conference
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• 한국미생물생명공학회 2002년도 학술발표대회
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• pp.18-25
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• 2002

The pikromycin biosynthetic system in Streptomyces venezuleae is unique for its ability to produce two groups of antibiotics that include the 12-membered ring macrolides methymycin and neomethymycin, and the 14-membered ring macrolides narbomycin and pikromycin. The metabolic pathway also contains two post polyketide-modification enzymes, a glycosyltransferase and P450 hydroxylase that have unusually broad substrate specificities. In order to explore further the substrate flexibility of these enzymes a series of hybrid polyketide synthases were constructed and their metabolic products characterized. The plasmid-based replacement of the multifunctional protein subunits of the pikromycin PKS in S. venezuelae by the corresponding subunits from heterologous modular PKSs resulted in recombinant strains that produce both 12- and 14-membered ring macrolactones with predicted structural alterations. In all cases, novel macrolactones were produced and further modified by the DesVII glycosyltransferase and PikC hydroxylase leading to biologically active macrolide structures. These results demonstrate that hybrid PKSs in S. venezuelae can produce a multiplicity of new macrolactones that are modified further by the highly flexible DesVII glycosyltransferase and PikC hydroxylase tailoring enzymes. This work demonstrates the unique capacity of the S. venezuelae pikromycin pathway to expand the toolbox of combinatorial biosynthesis and to accelerate the creation of novel biologically active natural products. The polyketide backbone of rifamycin B is assembled through successive condensation and ${\beta}$-carbonyl processing of the extender units by the modular rifamycin PKS. The eighth module, in the RifD protein, contains nonfunctional DH domain and functional KR domain, which specify the reduction of the ${\beta}$-carbonyl group resulting in the C-21 bydroxyl of rifamycin B. A four amino acid substitution and one amino acid deletion were introduced in the putative NADPH binding motif in the proposed KR domain encoded by rifD. This strategy of mutation was based on the amino acid sequences of the corresponding motif of the KR domain of module 3 in the RifA protein, which is believed dysfunctional, so as to introduce a minimum alteration and retain the reading frame intact, yet ensure loss of function. The resulting strain produces linear polyketides, from tetraketide to octaketide, which are also produced by a rifD disrupted mutant as a consequence of premature termination of polyketide assembly. Much of the structural diversity within the polyketide superfamily of natural products is due to the ability of PKSs to vary the reduction level of every other alternate carbon atom in the backbone. Thus, the ability to introduce heterologous reductive segments such as ketoreductase (KR), dehydratase (DH), and enoylreductase (ER) into modules that naturally lack these activities would increase the power of the combinatorial biosynthetic toolbox. The dehydratase domain of module 7 of the rifamycin PKS, which is predicted to be nonfunctional in view of the sequence of the apparent active site, was replaced with its functional homolog from module 7 of rapamycin-producing polyketide synthase. The resulting mutant strain behaved like a rifC disrupted mutant, i.e., it accumulated the heptaketide intermediate and its precursors. This result points out a major difficulty we have encountered with all the Amycolatopsis mediterranei strain containing hybrid polyketide synthases: all the engineered strains prepared so far accumulate a plethora of products derived from the polyketide chain assembly intermediates as major products instead of just analogs of rifamycin B or its ansamycin precursors.

• Applied Chemistry for Engineering
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• 제8권4호
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• pp.575-581
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• 1997

UDs were synthesized from two different polyols(PTMG, PBEAG), ionic chain extender(DMPA), EDA with $H_{12}-MDI$. PU/PMMA hybrids were prepared with free radical polymerization of MMA monomer in MMA-swelled PUD. PUD particle size and film properties were investigated ionic content and polyol type. Mechanical and thermal properties of PU/PMMA hybrid film were studied in terms of PU's ionic content and the venation of PU/PMMA compositions. As DMPA content increased from 2wt% to 10wt% in PUD, particle size of PUD decreased. PUD's particle size with ester type polyol was found to be smaller then ether type polyol used. Phase separation between hard segment(HS) and soft segment(SS) with ionic contents in PU was shown by the thermal, mechanical property measurement. Although the composition of MMA was changed from 0 to 40 wt% in PU/PMMA hybrid, the particle size of the hybrid did not increase. Using the ester type polyol, tensile strength of hybrid was found to increase by 2wt% - 6wt% DPMA content, but as higher content the strength of hybrid decreased. Moreover with the ether type polyol, tensile strength of hybrid was observed to increase by 2wt% - 4wt% DMPA content, while decreasing at higher content. PU and PMMA polymer molecule being mixed in molecular level was confirmed from the pattern of $T_g$ in DSC thermogram.

• Applied Chemistry for Engineering
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• 제3권4호
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• pp.605-613
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• 1992

NCO-terminated prepolymers were synthesized by reacting carbonate-type polyol(PTMCG)($M_w=1,000$ and 2,000) with MDI and N-methyldiethanolamine, as a chain extender. Carbonate-type polyurethane containg zwitterionic group was prepared by reacting the prepolymer with 1,3-propane sultone. From the IR and NMR spectra of model reactions, it was known that the ionization occurred under the same condition. The structure of zwitterionic carbonate-type polyurethane(ZPU) therefore could be confirmed from the model reactions. Glass transition temperature(Tg) ranged between $-15{\sim}-30^{\circ}C$ from the thermal data. Tg was between $-15{\sim}-18^{\circ}C$ for a series of ZPU10 samples and between $-25{\sim}-26^{\circ}C$ for a series of ZPU20 polymers. Tensile strength increased with mole ratio of ionic content. On the contrary, elongation was rather dropped with mole ratio of ionic content. ZPU10-30 having better tensile strength and less elongation was selected as a membrane for the concentration of ethanol aqueous solution through pervaporation. To obtain the better selectivity, it was crosslinked with HMDI. In the swelling test, it showed the higher swelling degree at around 50wt% ethanol concentration due to the plastization effect of ethanol. To optimize the separation capacity, two operating factors-feed concentration and temperature-were considered. The overall separation capacity was as follows : separation factor, 2~83.2 ; the flux, $25.4{\sim}58.8g/m^2hr$.