Hyperbranched polymer

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Hyperbranched polymer Lipid and Protein
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Contents
Hyperbranched polymer Introducton definiton of
terms dendrimer? hyperbranched polymer? ??
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
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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 ? Hyperbranched Polymer? ??
• Dendrimer ??? ??? monodisperse?? ??? ???? ????
  ?? ???? ?
• ??. ???? ???? ??? ????? ???? ???? ??.
• Hyperbranched Polymer ??? ??? monodisperse???
  ??? globular ??? ??
• ? ??? ?? ????? ????. ABx ??? ???? ????
  one-pot??
• ?? ?? ????.

Linear polymers
Log?
Hyperbranched polymers
dendrimers
Log M
The intrinsic viscosity ? of polymers related
to their molecular weight.
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History 1952? Flory? ?? ABx? ??? ?? ??? A 1?,
??? B n(x-1)1? (n???) ?? ???? ??? ?? ??
??. 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
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Chemical shift for model compounds in acetone-d6
For theoritical generation 7 DB 83
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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 ??? ???
?? 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) Consideratio
n 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
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Introduction

• Self-assembly A process in which a Complex
  hierarchical structure is established without
  external intervention.

Lipid
??? ????? ??? ?? ??? ?????? ????
???? ???? ???? ?? ??, ??
?????, ????? Self assembling lipid soap
??? ???? sodium ?? potassium??
??? phospholipid phophoglyceride,
sphingolipid
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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
Liposome?
Result
Various monomeric amphiphilic lipid
Stability of polymeric lipids Cross-linked lipid
more stable with surfactant
polymerization Thermal AIBN polymerization
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Emulsion ?? ?? ? ??? ???? ?? ?? ??? ???? ????
??? ?? ???? ???? ? Liposome
???? ?? ???? 2???? ?? ?? Advantage high
biocompatibility Drawback
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)--------? P
erturbation of ? orbital overlap (red color)
Uv light
Binding Virus,toxin
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???? ? ??? ??
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Aminoic acid
??????? 2?? 3???
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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