• Bulletin of the Korean Chemical Society
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• v.13 no.3
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• pp.274-279
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• 1992

Immobilization method of lariat azacrown ethers, containing hydroxyl group in the side arm of crown ring, on the polymer matrix and the phase-transfer catalytic activity of thus obtained immobilized lariat azacrown ethers were studied. Polystyrene resins with crown ether structures and hydroxyl groups adjacent to the macrorings were prepared by the reaction of crosslinked polystyrene resins containing epoxy groups with monoaza-15-crown-5 or monoaza-18-crown-6. Microporous crosslinked polystyrene resins containing epoxy group for the syntheses of these immobilized lariat crown catalysts were prepared by suspension polymerization of styrene, divinylbenzene (DVB 2%) and vinylbenzylglycidyl ether. The immobilized lariat catalysts with 10-20% ring substitution exhibited maximal activity for the halogen exchange reactions of 1-bromooctane with aqueous KI or NaI under triphase heterogeneous conditions. Immobilized catalyst exhibited higher activity than corresponding catalyst without the hydroxyl group and this result was suggested that the active site have a structure in which the $K^+$ ion was bound by the cooperative coordination of the crown ring donors and the hydroxyl group in the side arm.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.301-301
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• 2006

The physical properties of well-defined star-shape polystyrenes with high number of arms (6 to 57 arms) in good and theta solvents were studied using synchrotron X-ray scattering. The scattering profiles for multi-armed polystyrenes shown the molecular shape is changed according to increasing of number of arm. From various parameters which were obtained from scattering profiles, the molecular shape was determined more detail. As results, the molecular shape was changed from a fuzzy-ellipsoid for 6-armed PS to a fuzzy-sphere sphere for 57-armed PS according to increasing of number of arm.

• Polymer(Korea)
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• v.30 no.2
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• pp.146-151
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• 2006

Linear and branched copolymers consisting of poly(ethylene glycol) (PEG) and $Poly({\varepsilon}-caprolactone)$ (PCL) were prepared to compare the characterization of star-shaped copolymers with various molecular architecture. Linear and branched PEG-PCL (1-arm, 2-arm, 4-arm, and 8-arm) copolymers were synthesized by the ring-opening polymerization of ${\varepsilon}-caprolactone$ in the presence of HCl $Et_2O$ as a monomer activator at room temperature. The synthesized copolymers were characterized with $^1H-NMR$, GPC, DSC, and XRD. As a result of the DSC and XRD, each copolymers showed different thermal properties and crystallinity according to the number of ms. The micellar characterization of linear and branched copolymers in an aqueous phase was carried out by using NMR, dynamic light scattering, AM, and fluorescence techniques. The critical micelle concentration (CMC) and diameters of micelles depended on the number of arms. Most micelles exhibited a spherical shape in AFM. In this study, we characterized star-shaped PEG-PCL copolymers and investigated their molecular architecture effect on the various properties. Furthermore, we confirmed that the micelles termed with linear and branched PEG-PCL copolymers have possibility as a potential hydrophobic drug delivery vehicle.

• Journal of the Korean Applied Science and Technology
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• v.26 no.3
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• pp.306-316
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• 2009

In this study, block copolymer of polystyrene and polyethylene glycol methyl ether methacrylate(PEGMA) by ATRP(atom transfer radical polymerization) method was synthesized. 4 arm-molecule which contained halogen atom was synthesized for an initiator. With 4 arm-molecule monodispered polystyrene were synthesized by ATRP method. The molecular change of synthesized monodispersed polystyrene with respect to time was investigated and living polymer characteristic was confirmed. Block copolymer of polystyrene and polyethylene glycol methyl ether methacrylate(PEGMA) was synthesized by ATRP with macroinitiator which was synthesized from the monodispersed polystyrene(Mn=12000). The molecular weight of obtained PS-b-PEGMA was 22,000.

• Macromolecular Research
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• v.16 no.1
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• pp.66-69
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• 2008

• Macromolecular Research
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• v.9 no.3
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• pp.164-170
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• 2001

Recently in order to describe the complex rheological behavior of polymer melts with long side branches like low density polyethylene, new constitutive equations called the pom-pom equations have been derived by McLeish and Larson on the basis of the reptation dynamics with simplified branch structure taken into account. In this study mathematical stability analysis under short and high frequency wave disturbances has been performed for the simplified differential version of these constitutive equations. It is proved that they are globally Hadamard stable except for the case of maximum constant backbone stretch (λ = q) with arm withdrawal s$\_$c/ neglected, as long as the orientation tensor remains positive definite or the smooth strain history in the now is previously given. However this model is dissipative unstable, since the steady shear How curves exhibit non-monotonic dependence on shear rate. This type of instability corresponds to the nonlinear instability in simple shear flow under finite amplitude disturbances. Additionally in the flow regime of creep shear flow where the applied constant shear stress exceeds the maximum achievable value in the steady now curves, the constitutive equations will possibly violate the positive definiteness of the orientation tensor and thus become Hadamard unstable.

• BMB Reports
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• v.44 no.2
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• pp.87-95
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• 2011

Enzymatic catalysis has been pursued extensively in a wide range of important chemical processes for their unparalleled selectivity and mild reaction conditions. However, enzymes are usually costly and easy to inactivate in their free forms. Immobilization is the key to optimizing the in-service performance of an enzyme in industrial processes, particularly in the field of non-aqueous phase catalysis. Since the immobilization process for enzymes will inevitably result in some loss of activity, improving the activity retention of the immobilized enzyme is critical. To some extent, the performance of an immobilized enzyme is mainly governed by the supports used for immobilization, thus it is important to fully understand the properties of supporting materials and immobilization processes. In recent years, there has been growing concern in using polymeric materials as supports for their good mechanical and easily adjustable properties. Furthermore, a great many work has been done in order to improve the activity retention and stabilities of immobilized enzymes. Some introduce a spacer arm onto the support surface to improve the enzyme mobility. The support surface is also modified towards biocompatibility to reduce non-biospecific interactions between the enzyme and support. Besides, natural materials can be used directly as supporting materials owning to their inert and biocompatible properties. This review is focused on recent advances in using polymeric materials as hosts for lipase immobilization by two different methods, surface attachment and encapsulation. Polymeric materials of different forms, such as particles, membranes and nanofibers, are discussed in detail. The prospective applications of immobilized enzymes, especially the enzyme-immobilized membrane bioreactors (EMBR) are also discussed.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2517-2522
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• 2012

New polynuclear poly(hexaaza macrocyclic) copper(II) complexes $[1](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, $[2](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, and $[3](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$ have been prepared by the one-pot reaction of formaldehyde with ethylenediamine and 1,2-bis(2-aminoethoxy)ethane, 1,3-diaminopropane, or 1,6-diaminohexane in the presence of the metal ion. The polymer complexes contain fully saturated 14-membered hexaaza macrocyclic units (1,3,6,8,10,13-hexaazacyclotetradecane) that are linked by $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-N$, $N-(CH_2)_3-N$, or $N-(CH_2)_6-N$ chains. The mononuclear complex $[Cu(H_2L^5)](ClO_4)_4$ ($H_2L^5$ = a protonated form of $L^5$) bearing two $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-NH_2$ pendant arms has also been prepared by the metal-directed reaction of ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, and formaldehyde. The polymer complexes were characterized employing elemental analyses, FT-IR and electronic absorption spectra, molar conductance, X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron micrograph (SEM). Electronic absorption spectra of the complexes show that each macrocyclic unit of them has square-planar coordination geometry with a 5-6-5-6 chelate ring sequence. The polymer complexes as well as $[Cu(H_2L^5)]^{4+}$ are quite stable even in concentrated $HClO_4$ solutions. Synthesis and characterization of the polynuclear and mononuclear copper(II) complexes are reported.

• Applied Chemistry for Engineering
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• v.4 no.1
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• pp.132-143
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• 1993

Aminomethyl polystyrene resins were prepared either from chloromethyl-resin(Merrifield resin) or from direct amidoalkylation of polystyrene resin. Two kinds of aminomethlyl resin were lengthened with spacer arms via sequential coupling of five ${\varepsilon}$-aminocaproic acids(ACA) respectively. In case of the resin prepared from the Merrifield resin, the amounts of free amino group of the resin were reduced by 25~30% after each coupling of ACA. But the one from direct amidoalkylation showed 3~5% loss after each coupling of ACA. 4-Nitroso-5-aminopyrazole resin was made by reacting ACA spacer arm resin, which was made from direct amidoalkylated resin, with 5-phenyl-7-methylpyrazole [4,3-c][1,2,4]oxadiazin-3-one. Several polymeric active esters of N-blocked amino acids were prepared from the 4-nitroso-5-aminopyrazole bound resins. In anchoring step of the amino acid derivatives on the resin, no substantial effect of bulkiness was found. 4-Nitroso-5-aminopyrazole bound active ester resins were found to be very reactive in N-acylation, The resulting peptides were obtained with 90~95% yield and characterized by NMR and other physical methods.

• Korea-Australia Rheology Journal
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• v.14 no.1
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• pp.33-45
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• 2002

Recent results obtained for the port-pom model and the constitutive equations with time-strain separability are examined. The time-strain separability in viscoelastic systems Is not a rule derived from fundamental principles but merely a hypothesis based on experimental phenomena, stress relaxation at long times. The violation of separability in the short-time response just after a step strain is also well understood (Archer, 1999). In constitutive modeling, time-strain separability has been extensively employed because of its theoretical simplicity and practical convenience. Here we present a simple analysis that verifies this hypothesis inevitably incurs mathematical inconsistency in the viewpoint of stability. Employing an asymptotic analysis, we show that both differential and integral constitutive equations based on time-strain separability are either Hadamard-type unstable or dissipative unstable. The conclusion drawn in this study is shown to be applicable to the Doi-Edwards model (with independent alignment approximation). Hence, the Hadamardtype instability of the Doi-Edwards model results from the time-strain separability in its formulation, and its remedy may lie in the transition mechanism from Rouse to reptational relaxation supposed by Doi and Edwards. Recently in order to describe the complex rheological behavior of polymer melts with long side branches like low density polyethylene, new constitutive equations called the port-pom equations have been derived in the integral/differential form and also in the simplifled differential type by McLeish and carson on the basis of the reptation dynamics with simplifled branch structure taken into account. In this study mathematical stability analysis under short and high frequency wave disturbances has been performed for these constitutive equations. It is proved that the differential model is globally Hadamard stable, and the integral model seems stable, as long as the orientation tensor remains positive definite or the smooth strain history in the flow is previously given. However cautious attention has to be paid when one employs the simplified version of the constitutive equations without arm withdrawal, since neglecting the arm withdrawal immediately yields Hadamard instability. In the flow regime of creep shear flow where the applied constant shear stress exceeds the maximum achievable value in the steady flow curves, the constitutive equations exhibit severe instability that the solution possesses strong discontinuity at the moment of change of chain dynamics mechanisms.