• Bulletin of the Korean Chemical Society
• /
• 제13권3호
• /
• pp.274-279
• /
• 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.

• 한국고분자학회:학술대회논문집
• /
• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
• /
• pp.301-301
• /
• 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.

• 폴리머
• /
• 제30권2호
• /
• pp.146-151
• /
• 2006

폴리(에틸렌 글리콜)(PEG)과 생분해성 폴리에스터 그룹의 폴리카프로락톤(PCL)으로 이루어진 선형 및 분지 구조의 공중합체를 합성하고 분자 구조에 따른 다양한 특성을 비교하였다. 선형 및 분지 구조의 1-arm-PEG-PCL, 2-arm-PEG-PCL, 4-arm-PEG-PCL 및 8-arm-PEG-PCL 공중합체는 단량체 활성화제로서 Hcl $Et_2O$의 존재 하에 상온에서 카프로락톤$({\varepsilon}-CL)$의 개환중합에 의해 합성하였다. 합성된 선형 및 분지 구조의 공중합체는 $^{1}H-NMR$, GPC, DSC 및 XRD의 측정을 통해 특성을 분석하였다. 그 결과 공중합체의 가지 수에 따라 열적 특성 및 결정성이 다르게 나타나는 것을 확인하였다. 그리고 각 공중합체의 수용액상에서의 미셀 특성은 $^{1}H-NMR$, 광산란기, 원자 현미경 및 형광 측정기를 이용하여 확인하였다. 공중합체의 가지 수가 증가할수록 임계 미셀 농도 값과 미셀의 직경이 증가하는 것을 알 수 있었다. 또한 원자 현미경을 통해 관찰된 미셀의 형태는 선형 및 분지 구조의 공중합체 모두 구형으로 존재함을 확인할 수 있었다. 따라서 본 연구에서는 분자 설계를 통해 선형 및 분지 구조의 공중합체를 합성하여 각 공중합체의 분자 구조에 따른 다양한 특성을 비교하였으며 수용액상에서 형성된 미셀의 거동을 검토하여 소수성 약물 전달체로서의 가능성을 확인하였다.

• 한국응용과학기술학회지
• /
• 제26권3호
• /
• pp.306-316
• /
• 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
• /
• 제16권1호
• /
• pp.66-69
• /
• 2008

• Macromolecular Research
• /
• 제9권3호
• /
• pp.164-170
• /
• 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
• /
• 제44권2호
• /
• pp.87-95
• /
• 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
• /
• 제33권8호
• /
• pp.2517-2522
• /
• 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.

• 공업화학
• /
• 제4권1호
• /
• pp.132-143
• /
• 1993

Aminomethyl레진을 chloromethyl레진(Merrifield레진)으로부터 또는 polystyrene레진을 직접 amidoalkylation하여 각각 합성하였다. 두 종류의 aminomethyl레진을 이용하여 5개의 ${\varepsilon}$-aminocaproic acid(ACA)가 차례로 커플링 된 spacer arm을 가진 레진들을 각각 합성하였다. Chloromethyl레진으로부터 합성된 aminomethyl레진의 경우 ACA를 매번 커플링 할 때마다 25~30%의 유리 아미노기의 양이 감소하였으며, 직접 amidoalkylation에 의해 합성한 amlnomethyl 레진의 경우 매 커플링 단계 마다 3~5%의 유리 아미노기의 양이 감소하였다. 4-Nitroso-5-aminopyrazole 기능기를 가진 레진은 직접 amidoalkylation하여 얻은 레진에 ACA를 spacer arm으로 커플링시켜 얻은 레진과 5-phenyl-7-methylpyrazole[4,3-c][1,2,4]oxadiazin-3-one을 반응시켜 얻었다. 4-Nitroso-5-aminopyrazole 기능기를 가진 레진을 이용하여 ${\alpha}$-아미노기가 보호된 여러 가지 아미노산의 활성에스테르 레진들을 합성하였다. 4-Nitroso-5-aminopyrazole 기능기를 가진 활성 에스테르 레진은 N-acylation 반응에 매우 뛰어난 반응성을 나타내었다. 또한 입체장애 효과 없이 아미노산 유도체의 종류에 거의 무관하게 아실화 반응이 일어났으며 90~96%의 수율로 펩티드들을 합성할 수 있었다. 얻어진 펩티드들은 NMR을 비롯한 여러 가지 물리적 방법으로 그 순도를 확인하였다.

• Korea-Australia Rheology Journal
• /
• 제14권1호
• /
• pp.33-45
• /
• 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.