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Polymer Matrials Lab.

Polymer Matrials Lab. 고분자신합성법. Hyperbranched polymer Lipid and Protein. 공업화학과 / 고분자재료연구실 / 석사 2 기 윤 경 준. Contents. Hyperbranched polymer Introducton definiton of terms dendrimer 와 hyperbranched polymer 의 비교 history and advantage General polymerization with ABx monomer

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Polymer Matrials Lab.

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  1. Polymer Matrials Lab. 고분자신합성법 Hyperbranched polymer Lipid and Protein 공업화학과/고분자재료연구실/석사2기 윤 경 준 Contents Hyperbranched polymer Introducton definiton of terms dendrimer와 hyperbranched polymer의 비교 history and advantage General polymerization with ABx monomer New approach with A2 and B3 monomer Lipid Introduction Cross-linking polymerization Polymerized liposome Protein Nylon Surface modification with protein 1999. 12. 9

  2. Polymer Matrials Lab. Hyperbranched Polymer • Definition of terms • Dendritic polymer, cascade polymer, starburst polymer, arborol • A highly branched polymer of precisely controlled branching structure produced by a sequence of step-growth polymerization reaction steps. – reference : Polymer Science Dictionary, Synthesis of polymer Dendrimer 와 Hyperbranched Polymer의 비교 Dendrimer : 분자량 분포가 monodisperse하고 구형에 가까우며 최외각에 많은 작용기를 갖 는다. 합성에는 연속적인 반응과 정제과정이 수반되는 어려움이 있다. Hyperbranched Polymer : 분자량 분포가 monodisperse하지는 않지만 globular 구조를 가지 며 외각에 많은 작용기들이 존재한다. ABx 형태의 단량체를 간편하게 “one-pot”중합 하여 제조 가능하다. Linear polymers Log[] Hyperbranched polymers dendrimers Log M The intrinsic viscosity [] of polymers related to their molecular weight.

  3. Polymer Matrials Lab. History 1952년 Flory의 예측 ABx형 단량체 중합 –작용기 A : 1개, 작용기 B : n(x-1)+1개 (n=중합도) 낮은 물성으로 인하여 주목 받지 못함. Advantage Hyperbranched polymers might be a good alternative to dendrimers, as they can be produced on a large scale at a reasonable cost. Hyperbranched Aliphatic Polyesters A. Hult, Macromolecules 1995, 28, 1698-1703 Objects New hyperbranched polymer Large scale production Reaction scheme

  4. Degree of Branching –13C NMR dendritic units + terminal units DB = dendritic units + terminal units + linear units For ideal dendritic substance, DB = 1 Possible repeating units in the hyperbranched polyesters Polymer Matrials Lab. Chemical shift for model compounds in acetone-d6 For theoritical generation 7 DB = 83%

  5. Polymer Matrials Lab. Synthesis of Hyperbranched Aromatic polyamid from Aromatic Diamines and Trimesic Acid – New approach Macromolecules 1999, 32, 2061-2064 General method ABx monomer : not commercially available monomer 합성에 장시간 소요 New method A2 : commercially available for linear + condensation polymer B3 :available as branching or cross linking agent Polymerization A2 and B3in most case Branching, cross-linking, cyclization (insoluble in any organic solvents) Consideration of reaction condition  Hyperbranched polymer from A2 and B3 2 : 3 = feed ratio Reaction condition : polymerzation at 80C for 3 h with the total monomer concentration of 0.21mol/L(3.3 wt%) in 80ml solvent (NMP) no gelation, soluble in organic solvent in 50ml solvent  gelation, insoluble in organic solvent

  6. Polymer Matrials Lab. Introduction • Self-assembly : A process in which a Complex hierarchical structure is established without external intervention. Lipid : 비극성 유기용매의 추출에 의해 세포나 조직으로부터 분리되는 자연계에 존재하는 유기분자 종류: 지방, 왁스 콜레스테롤, 스테로이드 Self assembling lipid soap : 긴사슬 지방산의 sodium 혹은 potassium염의 혼합물 phospholipid : phophoglyceride, sphingolipid

  7. Polymer Matrials Lab. Cross-Linking Polymerization in Two-Dimensional Assemblies Macromolecules 1999, 32, 5519-5524 Macromolecues 1996, 29, 8321-8329 Redox polymerizaton with K2S2O8 and NaHSO3 Diret photoirradiation Introduction monomeric amphiphilic lipid ------- polymerization ---- linear polymer or corss-linked polymer Depending on the number and location of polymerizable groups per monomer Liposome화 Result Various monomeric amphiphilic lipid Stability of polymeric lipids Cross-linked lipid more stable with surfactant polymerization Thermal AIBN polymerization

  8. Polymer Matrials Lab. Emulsion–액체 중에 그 액체와 혼합되지 않는 다른 액체의 미립자를 유화제의 도움을 받아 안정하게 분산시킨 것 Liposome–인지질을 물에 현탁시킨 2분자막의 폐쇄 소포 Advantage–high biocompatibilityDrawback–stability Application–drug delivery, biosensor etc. Polymerized liposome Langmuir 1998, 14, 1974-1976 Introduction Advantage : physical stability, durability during chemical modification System Diacetylen functionalized lipid ------ Form conjugated system (blue)-------- Perturbation of  orbital overlap (red color) Uv light Binding Virus,toxin

  9. : -amino acid residue 가 아미드결합된 거대 생체분자 protein • 단백질의 구조 • Primary structure : 아미노산 잔기의 결합서열 • Secondary structure • driving force : hydrogen bond 약 5kcal/mol • Tertiary sturcture • driving force : 탄화수소 곁사슬의 소수성 상호작용 • cyteine잔기사이에 이황화물 다리의 형성, hydrogen bond, salt bridge 등 Polymer Matrials Lab. 피브로인의  병풍구조 케라틴의  나선형 구조

  10. Aminoic acid 미오글로블린의 2차및 3차구조

  11. Polymer Matrials Lab. Surface modification with protein • Nylon –polyamide, interchain hydrogen • bonding • Macromolecules 1998, 31, 8540-8548 • Polymerization • diacid + diamine • amino acid • ring opening of lactam • structure Langmuir 1997, 13, 6485-6490 Advantage : improve wettability and biocompatiblity Method Physical : hydrophobic or electrostatic interaction reversible  buffer, detergent, other protein Chemical : covalent bonding irreversible, more popular • odd (b) even number of methylenes • in the diamine unit

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