• Bulletin of the Korean Chemical Society
• /
• v.19 no.3
• /
• pp.328-332
• /
• 1998

Anionic ring-opening polymerization of 3,4-[(dimethylsilyl)isopropyl]benzo-1,1-dimethyl-1-silacyclopentene in the presence of n-butyllithium and HMPA in THF at - 78 ℃ afforded poly[3,4-(dimethylsilylisopropyl)benzo-1,1-dimethyl-1-silapentene]. The characteristic Si-H stretching frequency in the IR is observed at 2100 cm-1. The polycarbosilane has been modified by chloroplatinic acid catalyzed addition of styrene to the polycarbosilane SiH units. Molecular weights and thermal properties of the polymers were compared. The sol-gel polymerization of 3,4-[(dimethoxysilyl)isopropyl]benzo-1,1-dimethoxy-1-silacyclopentene in the presence of aqueous HCl or NaOH in THF resulted in a cross-linked polysiloxane. The xerogel has a low surface area of 13-14 m2/g and is stable up to about 400 ℃ with only 5% weight loss under a nitrogen atmosphere.

• Journal of Applied Biological Chemistry
• /
• v.54 no.1
• /
• pp.1-6
• /
• 2011

${\gamma}$-PGA(poly-${\gamma}$-glutamic acid) is an unusual anionic polypeptide that is made of D- and L-glutamic acid units connected by amide linkages between ${\alpha}$-amino and ${\gamma}$-carboxylic acid groups. ${\gamma}$-PGA has been isolated from many kinds of organisms. Many Bacillus strains produce ${\gamma}$-PGA as a capsular material of an extracellular viscous material. It is safe for eating as a viscosity element of fermented soybean products such as Chungkookjang and Natto. It is biodegradable, edible and nontoxic toward humans and the environment and its molecular weight varies from ten thousand to several hundred thousand depending on the kinds of strains used. Therefore, potential applications of ${\gamma}$-PGA and its derivatives have been of interest in the past few years in a broad range of industrial fields such as food, cosmetics, medicine, water-treatment, etc. In this study, a bacterium, Bacillus subtilis GS-2 isolated from the Korean traditional seasoning food, Chungkookjang could produce a large amount of ${\gamma}$-PGA with high productivity and had a simple nutrient requirement. Based on carbon utilization pattern and partial 16S rRNA sequence analysis, the GS-2 strain was identified as B. subtilis. The determination of purified ${\gamma}$-PGA was confirmed with thin layer chromatography (TLC), high performance liquid chromatography (HPLC), fourier transform infrared (FT-IR) spectra, and $^1H$-nuclear magnetic resonance ($^1H$-NMR) spectroscopy.

• Macromolecular Research
• /
• v.9 no.2
• /
• pp.107-115
• /
• 2001

Poly(L-lactide-co-glycolide)(PLGA) was blended with poly[$\omega$-methacryloyloxyethyl phospho-rylcholine-co-ethylhexylmethacrylate (PMEH)] (PLGA/PMEH) to endow with new functionality i.e., to improve the cell-, tissue- and blood-compatibility. The characteristics of surface properties were investigated by measurement of contact angle goniometer, Fourier-transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR) and electron spectroscopy for chemical analysis (ESCA). NIH/3T3 fibroblast and bovine aortic endothelial cell were cultured on control and PLGA/PMEH surfaces for the evaluation of ceil attachment and proliferation in terms of surface functionality such as the concentration of phosphoryl-choline. Also, the behavior of platelet adhesion on PLGA/PMEH was observed in terms of the surface functionality. The contact angles on control and PLGA/PMEH surfaces decreased with increasing PMEH content from 75$^{\circ}$ to about 43$^{\circ}$. It was observed from the FTIR-ATR spectra that phosphorylcholine groups are gradually increased with increasing blended amount of MPC. The experimental P percent values from ESCA analysis were more 3.28∼7.4 times than that of the theoretical P percent for each blend films. These results clearly indicated that the MPC units were concentrated on the surface of PLGA/PMEH blend. The control and PLGA/PMEH films with 0.5 to 10.0 wt% concentration of PMEH were used to evaluate cell adhesion and growth in terms of phosphorylcholine functionality and wettability. Cell adhesion and growth on PLGA/PMEH surfaces were less active than those of control and both cell number decreased with increasing PMEH contents without the effect of surface wettability. It can be explained that the fibronectin adsorption decreased with an increase in the surface density of phosphorylcholine functional group. One can conclude the amount of the protein adsorption and the adhesion number of cells can be controlled and nonspecifically reduced by the introduction with phosphorylcholine group. Morphology of the adhered platelets on the PLGA/PMEH surface showed lower activating than control and the number of adhered platelets on the PLGA/PMEH sample decreased with increasing the phosphorylcholine contents. The amount of fibrinogen adsorbed on the PLGA/PMEH surface demonstrated that the phospholipid polar group played an important role in reducing protein adsorption on the surface. In conclusion, this surface modification technique might be effectively used PLGA film and scaffolds for controlling the adhesion and growth of cell and tissue, furthermore, blood compatibility of the PLGA was improved by blending of the MPC polymer for the application of tissue engineering fields.

• Polymer(Korea)
• /
• v.33 no.4
• /
• pp.297-306
• /
• 2009

A homologous series of side chain liquid crystalline polymers, poly [1-{4-(4'-cyanophenylazo)phenoxyalkyloxy}ethylene]s(CAPETn, where n, the number of methylene units in the spacer, is $2{\sim}10$) were synthesized from poly(vinyl alcohol) and 1-{4-(4'-cyanophenylazo)phenoxy}alkylbromides(CAPBn, n=$2{\sim}10$), and their thermotropic liquid crystalline phase behaviors were investigated. The CAPBn with n of $2{\sim}5$ did not show any liquid crystalline behavior, while those with n of 6 and $7{\sim}10$ showed enantiotropic and monotropic nematic phases, respectively. In contrast, among the CAPETn polymers, only CAPET5 exhibited an enantiotropic nematic phase, while other polymers showed monotropic nematic phases. The isotropic-nematic transition temperatures of CAPETns and their entropy variation at the phase transition that were higher values than those of CAPBns, demonstrated a typical odd-even effect as a function of n. These phase transition behaviors were disscussed in terms of the 'virtual trimer model' by Imrie. The mesophase properties of CAPETns were largely different from those reported for the polymers in which the (cyanophenylazo) phenoxy groups are attached to polyacrylate, polymethacrylate, and polystyrene backbones through polymethylene spacers. The results indicate that the mode of chemical linkage of the side group with the main chain plays an important role in the formation, stabilization, and type of mesophase.

• 한국신재생에너지학회:학술대회논문집
• /
• 2009.06a
• /
• pp.24-27
• /
• 2009

Solid-state dye-sensitized solar cells (DSSCs) have been constructed employing supramolecular electrolytes with multiple hydrogen bonding. A supramolecule was facilely synthesized by one-pot reaction between the amines of methyl isocytosine (MIC) and the epoxy groups of poly(ethylene glycol diglycidyl ether) (PEGDGE) to produce quadruple hydrogen bonding units. Hydrogen bonding interactions and dissolution behavior of salt in supramolecular electrolytes are investigated. The ionic conductivity of the supramolecular electrolytes with ionic liquid, i.e. 1-methyl-3-propylimidazolium iodide (MPII) reaches $8.5{\times}10^{-5}$ S/cm at room temperature, which is higher than that with metal salt (KI). A worm-like morphology is observed in the FE-SEM micrographs of $TiO_2$ nanoporous layer, due to the connection of $TiO_2$ nanoparticles resulting from adequate coating by electrolytes. DSSCs employing the supramolecular electrolytes with MPII and KI exhibit an energy conversion efficiency of 2.5 % and 0.5 %, respectively, at 100 $mW/cm^2$, indicating the importance of the cation of salt. Solar cell performances were further improved up to 3.7 % upon introduction of poly(ethylene glycol dimethyl ether) (PEGDME) with 500 g/mol.

• Polymer(Korea)
• /
• v.36 no.3
• /
• pp.309-314
• /
• 2012

To control degradation rate of biodegradable poly(lactide)s (PLA), the stereochemical PLAs with different ratios of $d$-lactide and $l$-lactide units were synthesized by the ring open polymerization and a degradation behavior was measured by a Langmuir film balance. Degradation rates of mixture monolayers on alkaline subphase were investigated as a function of optical purity of mixture component, 100, 99, 97 and 95%. As increasing their optical purity, melting temperatures of mixtures from stereocomplexation increased. The degradation rate of mixture monolayer with 100% optical purity was much slower than that of each homopolymer one and the others showed 2 step degradation behaviors. In the first step, the degradation which is faster than that of each homopolymer occurs in the uncomplexed region, and secondly, the degradation occurred in the complexed region which showed similar degradation rate to that of 100% optical purity. These results indicate that the alkaline degradation of stereochemical PLAs could be controlled by stereochemistry and stereocomplexation between enantiomer PLAs.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.2
• /
• pp.651-655
• /
• 2011

We synthesized a novel cationic dendrimer consisting of a poly(amidoamine) dendrimer (PAMAM, generation 4) backbone with both L-arginine (Arg) at the termini and 6-aminohexanoic acid (Ahx) between the original core polymer and the peripheral Arg units. The sequential chemical modification of PAMAM G4 with Ahx and Arg resulted in higher transfection efficiency with much less cytotoxicity. PAMAM G4-Ahx-Arg formed stable polyplexes at weight ratios of 8:1 or higher (polymer: plasmid DNA), and the mean polyplex diameter was $180{\pm}20nm$. PAMAM G4-Ahx-Arg showed much higher transfection ability than PAMAM G4 or PAMAM G4-Ahx. Furthermore, PAMAM G4-Ahx-Arg was much less cytotoxic than PEI25KD and PAMAM G4-Arg. In addition to Arg grafting of the PAMAM dendrimer, which endows a higher transfection capability, the addition of Ahx spacer increased dendrimer hydrophobicity, introduced flexibility into the conjugated amino acids, and reduced cytotoxicity. Overall, it appears that the concomitant modification of PAMAM with Ahx and Arg could lead to new PAMAM conjugates with better performances.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.8
• /
• pp.2245-2250
• /
• 2014

A new accepter unit, 6,7-difluoro-2,3-dihexylquinoxaline, was prepared and utilized for the synthesis of the conjugated polymers containing electron donor-acceptor pair for OPVs. New series of copolymers with dioctyloxybenzodithiophene as the electron rich unit and 6,7-difluoro-2,3-dihexylquinoxaline as the electron deficient unit are synthesized. The solid films of poly[2,6-(4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene)-alt-5,8-(6,7-difluoro-2,3-dihexylquinoxaline)] (PBQxF) and poly[2,6-(4,8-bis(2-ethylhexyloxy) benzo[1,2-b:4,5-b']dithiophene)-alt-5,8-(6,7-difluoro-2,3-dihexyl-5,8-di(thiophen-2-yl) quinoxaline)] (PBDTQxF) show absorption bands with maximum peaks at about 599 and 551 nm and the absorption onsets at 692 and 713 nm, corresponding to band gaps of 1.79 and 1.74 eV, respectively. The devices comprising PBQxF with $PC_{71}BM$ (1:2) showed open-circuit voltage ($V_{OC}$) of 0.64 V, short-circuit current density ($J_{SC}$) of $1.58mA/cm^2$, and fill factor (FF) of 0.39, giving power conversion efficiency (PCE) of 0.39%. To obtain absorption in the longer wavelength region, thiophene units without any alkyl group are incorporated as one of the monomers in PBDTQxF, which may result in low solubility of the polymers to lead lower efficiency.

• Korean Chemical Engineering Research
• /
• v.49 no.1
• /
• pp.95-100
• /
• 2011

During the development of low band-gap organic materials(p-type semiconducting organic compounds) for organic solar cells, an oligomer consisting of 2,5-dioctyloxyphenylene(OP), 3-hexylthiophene(HT), and 2,3-dimethylthieno[ 3,4-b]pyrazine(TP) as repeat units, oligo(OP-HT-TP), was synthesized. The oligomer was amorphous in nature in the temperature range studied, and well soluble in common organic solvents such as chloroform. The maximum absorption wavelength was 716 nm in solid state. The band-gap and HOMO/LUMO energy levels of oligo(OP-HT-TP) were measured to be 1.20 eV and -5.27/4.04 eV, respectively. However, the absorbance of the oligomer at maximum absorption wavelength was less than one fifth of that of poly(3-hexylthiophene) which has been most frequently used in fabrication of organic solar cells.

• Bulletin of the Korean Chemical Society
• /
• v.2 no.4
• /
• pp.142-147
• /
• 1981

A blend polymeric system composed of poly(methyl methacrylate) (PMMA or PM) and polystyrene (PS) dissolved in chloroform was rheologically studied. The viscosities ${\eta}_{bl}$ of the blend system with various blending ratios ${\chi}$ changing from zero (pure PS solution) to unity (pure PMMA solution) were measured at $25{\circ}C$ as a function of shear rates ${\dot{s}}$ by using a Couette type viscometer. ${\eta}_{bl}$ at a given ${\dot{s}}$ decreased exponentially with ${\chi}$ reaching asymptotic constant value of ${\eta}_{bl}$ ; ${\eta}_{bl}$ at a given ${\chi}$ is greater at a smaller ${\dot{s}}$. These results are explained by using Ree-Erying's theory of viscosity, ${\eta}_{bl}=(x_1{\beta}_1/{\alpha}_1)_{b}_1＋ (x_2{\beta}_2/{\alpha}_2)_{bl}[sinh^{-1}{\beta}_2(bl) {\dot{s}}]/{\beta}_2(bl){\dot{s}}$. The Gibbs activation energy ${\Delta}G_i^\neq$(i = 2 for non-Newtonian units) entering into the intrinsic relaxation time ${\beta}$ is represented by a linear combination ${\Delta}G_i^\neq(bl) ={\chi}{\Delta}G_i^{\neq}_{iPM}+(1-{\chi}){\Delta}G_i^{\neq}_{iPS}$;the intrinsic shear modulus$[[\alpha}_i]^{-1}$ is also represented by $[{\alpha}_i(bl)]^{-1}={\chi}[{\alpha}_{iPM}]^{-1}+(1-{\chi})[{\alpha}_{iPS}]^{-1}$ and the fraction of area on a shear surface occupied by the ith flow units $x_i(bl)$ is similarly represented, i.e., $x_i(bl) = {\chi}x_{iPM}+(1-{\chi})x_{iPS}$. By using these ideas the Ree-Eyring equation was rewritten which explained the experimental results satisfactorily.