• Biotechnology and Bioprocess Engineering:BBE
• /
• 제6권5호
• /
• pp.326-331
• /
• 2001

With the aim of developing of pH-sensitive controlled drug release system, a poly(Llysine) (PLL) based cationic semi-interpenetrating polymer network (semi-IPN) has been synthesized. This cationic hydrogel was designed to swell at lower pH and de-swell at higher pH and therefore be applicable for achieving regulated drug release at a specific pH range. In addition to the pH sensitivity, this hydrogel was anticipated to interact with an ionic drug, providing another means to regulate the release rate of ionic drugs. This semi-IPN hydrogel was prepared using a free-radical polymerization method and by crosslinking of the polyethylene glycol (PEG)-methacrylate polymer through the PLL network. The two polymers were penetrated with each other via interpolymer complexation to yield the semi-IPN structures. The PLL hydrogel thus prepared showed dynamic swelling/de-swelling behavior in response to pH change, and such a behavior was influenced by both the concentrations of PLL and PEG-methacrylate. Drug release from this semi-IPN hydrogel was also investigated using a model protein drug, streptokinase. Streptokinase release was found to be dependent on its ionic interaction with the PLL backbones as well as on the swelling of the semi-IPN hydrogel. These results suggest that a PLL semi-IPN hydrogel could potentially be used as a drug delivery platform to modulate drug release by pH-sensitivity and ionic interaction.

• Korea-Australia Rheology Journal
• /
• 제20권3호
• /
• pp.109-116
• /
• 2008

The effect of intermolecular aggregation induced by hydrophobic and electrostatic interactions on shear and elongational flow properties of aqueous acrylic thickener solutions is discussed. Complex shear modulus is determined at frequencies up to $10^4$ rad/s employing oscillatory squeeze flow. Extensional flow behavior is characterized using Capillary Break-up Extensional Rheometry. Aqueous solutions of poly(acrylic acid)(PAA)/poly(vinylpyrrolidone-co-vinylimidazole) (PVP-VI) mixtures exhibit unusual rheological properties described here for the first time. Zero-shear viscosity of the mixtures increases with decreasing pH and can exceed that of the pure polymers in solution by more than two orders of magnitude. This is attributed to the formation of complexes induced by electrostatic interactions in the pH range, where both polymers are oppositely charged. PAA/PVP-VI mixtures are compared to the commercial thickener Sterocoll FD (BASF SE), which is a statistical co-polymer including (meth) acrylic acid and ethylacrylate (EA) forming aggregates in solution due to "sticky" contacts among hydrophobic EA-sequences. PAA/PVP-VI complexes are less compact and more deformable than the hydrophobic Sterocoll FD aggregates. Solutions of PAA/PVP-VI exhibit a higher zero-shear viscosity even at lower molecular weight of the aggregates, but are strongly shear-thinning in contrast to the weakly shear-thinning solutions of Sterocoll FD. The higher ratio of characteristic relaxation times in shear and elongation determined for PAA/PVP-VI compared to Sterocoll FD solutions reflects, that the charge-induced complexes provide a much stronger resistance to extensional flow than the aggregates formed by hydrophobic interactions. This is most likely due to a break-up of the latter in extensional flow, while there is no evidence for a break-up of complexes for PAA/PVP-VI mixtures. These flexible aggregates are more suitable for the stabilization of thin filaments in extensional flows.

• 한국전기전자재료학회:학술대회논문집
• /
• 한국전기전자재료학회 1994년도 추계학술대회 논문집
• /
• pp.198-201
• /
• 1994

Stability improvement of fragile LB films was attempted by polyion complexation of monolayers at the air-water interface and crosslinking of the resulting LB films. The spreading polymers were synthesized by radical copolymerization of monoalkyl itaconate with oligoethyleneglycol methyl vinylether, and poly(allylamine) was employed as the subphase polymer. Formation and characteristic of the monolayers were comfirmed by surface pressure-area($\pi$-A) isotherms. The two different polymers formed polyion-complexed monolayer through the formation of carboxylate/ammonium salt at the air-water interface. Y-type deposition occurred on solid substrates, and the transfer ratio was over 0.7. Pores (diameter, 0.1$\mu\textrm{m}$) of a membrane filter could be covered by polyion-complexed 6 layers. Interactions of the polymers with metal ions were investigated of the air-water interface and in the LB films. The structure change and macroscope morphology of the LB films were confirmed by FT-lR and SEM, respective1y.

• Bulletin of the Korean Chemical Society
• /
• 제16권12호
• /
• pp.1167-1172
• /
• 1995

A coverage of about 1 μm-sized pores of a membrane filter by four monolayers of maleic acids copolymers and poly(allylamine) (PAA) was attained by Langmuir-Blodgett (LB) technique through a covalent cross-linking followed a polyion complexation at the air-water interface. The copolymers were prepared to have side chains of hydrocarbon tail, carboxyl, and/or oligoether in the repeat unit. The surface pressure-area isotherms showed that the monolayers on an aqueous PAA have more expanded area than on pure water. The monolayers were transferable on a calcium fluoride substrate and a fluorocarbon membrane filter as Y deposition type, and the resulting LB films were characterized by FT-IR spectroscopy and scanning electron microscopy. A polymer network produced through interchain amide formation was confirmed in as-deposited films. The films were heat-treated in order to complete the cross-linking. SEM observation of the heat-treated film on a porous membrane filter showed that the four layer film was sufficiently stable to cover the filter pore of about 1 μm. Immersion of the film in water or in chloroform did not cause any change in its appearance on SEM and in FT-IR spectra.

• Bulletin of the Korean Chemical Society
• /
• 제32권9호
• /
• pp.3295-3305
• /
• 2011

Thermal behavior of poly (methyl methacrylate) was analyzed in the presence of tin (IV) chloride. Five different proportions - polymer to additive - were selected for casting films from common solvent. TG, DTG and DTA were employed to monitor thermal degradation of the systems. IR and py-GC-MS helped identify the decomposition products. The blends start degrading at a temperature lower than that of the neat polymer and higher than that of the pure additive. Complex formation between tin of additive and carbonyl oxygen (pendent groups of MMA units) was noticed in the films soon after the mixing of the components in the blends. The samples were also heated at three different temperatures to determine the composition of residues left after the expulsion of volatiles. The polymer, blends and additive exhibited a one step, two-step and three-step degradation, respectively. $T_0$ is highest for the polymer, lowest for the additive and is either $60^{\circ}C$ or $70^{\circ}C$ for the blends. The amount of residue increases down the series [moving from blend-1 (minimum additive concentration) to blend-5 (maximum additive concentration)]. For blend-1, it is 7% of the original mass whereas it is 16% for blend-5. $T_{max}$ also goes up as the concentration of additive in the blends is elevated. The complexation appears to be the cause of observed stabilization. Some new products of degradation were noted apart from those reported earlier. These included methanol, isobutyric acid, acid chloride, etc. Molecular-level mixing of the constituents and "positioning effect" of the additive may have brought about the formation of new compounds. Routes are proposed for the appearance of these substances. Horizontal burning tests were also conducted on polymer and blends and the results are discussed. Activation energies and reaction orders were calculated. Activation energy is highest for the polymer, i.e., 138.9 Kcal/mol while the range for blends is from 51 to 39 Kcal/mol. Stability zones are highlighted for the blends. The interaction between the blended parts seems to be chemical in nature.

• 폴리머
• /
• 제25권5호
• /
• pp.642-648
• /
• 2001

암모니아 흡착제를 제조하기 위하여 먼저 광(자외선)조사법으로 스티렌을 폴리프로필렌 부직포에 그라프트 중합시키고, 이를 술폰화한 다음에 금속이온과 반응시켜 금속 착체를 제조하였다. 스티렌 농도가 증가할수록 그라프트율은 증가하였으며, 반응시간이 길어질수록 그라프크율은 증가하였다. 한편 제조된 각종 시료의 암모니아 흡착 능력은 치환된 술폰산기의 함량, 흡착시판 및 암모니아 기체 압력이 증가할수록 증가하였으며, 술폰산기의 함량이 4.25 mmol $H^+$/g인 시료의 경우에 6.51 mmol/g의 흡착량을 나타내었다. 금속이온을 착물로 한 시료는 착물화 전의 시료에 비해 흡착능이 우수하였으며, $cO^{+2}$를 착물로 한 경우에 9.90mmo1/g의 암모니아 흡착능을 나타내어, 기존의 활성탄이나 실리카겔보다 효과가 우수하였다.

• 한국응용과학기술학회지
• /
• 제35권4호
• /
• pp.1031-1037
• /
• 2018

수용성 비이온고분자인 Polyvinylalcohol (PVA), Polyvinylpyrrolidone (PVP), Hydroxypropyl cellusoe (HPC)와 iodine과의 착물 형성에 대한 계면활성제의 영향을 알아보기 위해 Sodiumdodecylsulfate을 포함하는 수용액에서 이들 사이의 반응을 수행하였다. PVP와 HPC에서 tri-iodide band의 적색 이동에 의하여 착물이 만들어졌다는 것을 알게되었고, PVA-iodine 착물에서는 500 nm 부근에서 고유의 특색있는 띠를 나타내었다. SDS 계면활성제의 존재는 PVA-iodine 착물의 파괴를 가져왔고, 고유의 푸른색도 사라지게 만들었다. 그러나 SDS 단량체는 PVP, HPC와 iodine의 착물 형성을 도와주는 경향을 나타내었다. 고분자 용액에서 겔이 만들어지는 것을 방해하는 n-propanol은 고분자-iodine 착물이 형성되는 것을 도와주었다. SDS가 있을 때와 없을 경우의 영향을 알아보기 위해 순수한 HPC와 HPC-iodine 착물을 만들고 이들의 성질을 조사하였다.

• Journal of Pharmaceutical Investigation
• /
• 제20권1호
• /
• pp.13-18
• /
• 1990

Hydrocortisone (HC) sustained-release suppositories were prepared by using a solid matrix of methacrylic acid-methacrylic acid methyl ester copolymer $(Eudragit\;L_{100}^{R}:\;EL)$ as a poorly water soluble carrier and polyethylene glycole 1540 (PEG) as an water soluble carrier. HC release rate was controlled by complexation with ${\beta}-cyclodextrin$ $({\beta}-CyD)$ which was confirmed by X-ray diffractometry, IR-spectroscopy and differential scanning calorimetry. Release rate of HC from the EL-PEG matrix suppositories decreased with increase of EL contents. The release rale from $HC-{\beta}-CyD$ complex decreased in the following order: $HC-{\beta}-CyD/PEG$ > HC/PEG > $HC-{\beta}-CyD/EL_{10%}-PEG$ > $HC/EL_{10%}-PEG$ > $HC-{\beta}-CyD/EL_{15%}-PEG$ > $HC/EL_{15%}-PEG$ > $HC-{\beta}-CyD/EL_{20%}-PEG$ > $HC/EL_{20%}-PEG$. The crystallinity of HC in polymer matrix was identified using X-ray diffractometer and the surface of matrix suppositories after release test was examined by scanning electron microscopy. The sustained release of HC from these matrix suppositories was attributed to the network structure of EL.

• 대한전기학회논문지:전기물성ㆍ응용부문C
• /
• 제51권7호
• /
• pp.287-291
• /
• 2002

We fabricated the crosslinked films using p-hexadecoxyphenol (p-HP), which is amphiphilic and can form polyion complexes with formaldehyde at the air-water interface. The behavior of polyion complexation at the air-water interface and the surface structure of LB films was investigated by Brewster angle microscope(BAM) and scanning Maxwell-stress microscope (SMM), respectively. Also, the electrical properties for crosslinking in phenol-formaldehyde LB films were investigated by measuring conductivity and dielectric constant. The conductivities of p-HP LB films are as follows: heat-treatment of 1% formaldehyde subphase(3.76$\times$10$^{-15}$ ~4.76$\times$10$^{-1}$5[S/cm])$\times$10$^{-14}$ ~1.74$\times$10$^{-14}$ [S/cm]). Also, relative dielectric constants of p-HP LB films were reduced from 6.76~7.84 (pure water) to 2.97~3.25 (heat-treatment of 1% formaldehyde subphase))

• Macromolecular Research
• /
• 제17권2호
• /
• pp.104-109
• /
• 2009

Solid-state facilitated, olefin transport membranes were prepared by complexation of poly(styrene-b-iso-prene-b-styrene) (SIS) block copolymer and silver salt. Facilitated olefin transport was not observed up to a silver mole fraction of 0.14, representing a threshold concentration, above which transport increased almost linearly with increasing silver salt concentration. This was because firstly the silver ions were selectively coordinated with the C=C bonds of PI blocks up to a silver mole fraction of 0.20, and secondly the coordinative interaction of the silver ions with the aliphatic C=C bond was stronger than that with the aromatic C=C bond, as confirmed by FT-Raman spectroscopy. Small angle X-ray scattering (SAXS) analysis showed that the cylindrical morphology of the neat SIS block copolymer was changed to a disordered structure at low silver concentrations ($0.01{\sim}0.02$). However, at intermediate silver concentrations ($0.15{\sim}0.20$), disordered-ordered structural changes occurred and finally returned to a disordered structure again at higher silver concentrations (>0.33). These results demonstrated that the facilitated olefin transport of SIS/silver salt complex membrancs was significantly affected by their coordinative interactions and nano-structural morphology.