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Designing Polymers for Biological Interfaces - From Antifouling to Drug Delivery
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Unspecific interactions, at the interface between a synthetic material and an aqueous biological environment, leading to irreversible protein adsorption can cause to undesired consequences. These include fouling of a boat hull or a triggered immune response. Thus, stealthy materials are a topic that has generated a great deal of interest in the scientific community. This work deals with the design of networks, nanoparticles, and surfaces containing poly(ethylene glycol) (PEG), known for its resistance to protein adsorption and non-toxic nature. Initially, PEG-based networks, hydrogels, were synthesized using photoinduced thiol-ene chemistry in order to afford coatings targeted for marine antifouling applications. By varying the length of the PEG chain, curing chemistry, cross-linker as well as hydrolytical stability, a library of hydrogel coatings was produced. The coatings were subsequently characterized with respect to curing efficiency, thermal and mechanical properties, and aqueous stability. Furthermore, the antifouling properties of coatings were evaluated using in vitro tests with proteins, marine bacteria, and diatoms. As a final test the coatings were evaluated in a four month field test. It was found that coatings comprising longer PEG chains displayed enhanced antifouling performance, compared to shorter PEGs. In addition, the choice of cross-linker, curing chemistry, and hydrolytical stability also affected the properties to a great extent. This thesis further deals with the design of amphiphilic linear dendritic hybrids, with PEG as the hydrophilic block. Using non-toxic 2,2-bis(methylol) propionic acid (bis-MPA) based dendrons, bearing click functional cores (alkyne or allyl) and peripheral hydroxyl groups, as macrointitiators for ring-opening polymerization of ε-caprolactone, a library of star branched materials was afforded. As a final step, click functional (azide or thiol) PEGs were attached using copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) or thiol-ene click chemistry. The size of the dendrons was varied from generation 0-4, along with variation of both poly(ε-caprolactone) (PCL) length and PEG length. The materials were designed in order to allow a study of the impact of the dendron generation. Finally, the hybrid materials were used for the preparation of micelles, as well as for the formation of honeycomb membranes. The micelles critical micelle concentration, size and drug loading capacity were shown to be highly dependent on the generation of the dendron. The generation of the dendron also had a profound effect on the ability of the hybrid materials to form ordered honeycomb membranes, and hybrid materials of the 3rd generation yielded the most highly ordered membranes.

Abstract [sv]

Ickespecifika interaktioner vid gränsytan, mellan ett syntetiskt material och en vattenbaserad biologisk miljö, kan leda till irreversibel adsorption av proteiner. Detta kan i sin tur leda till oönskade följdeffekter, såsom beväxning på båtskrov eller trigga en immunologisk reaktion. För att motverka dessa effekter har forskare utvecklat så kallade smygmaterial. Denna avhandling behandlar design av nätverk, nanopartiklar och ytor innehållande poly(etylenglykol) (PEG), som är känt för sina smygegenskaper och för att vara icke-toxiskt. Initialt behandlar avhandlingen PEG-baserade nätverk, hydrogeler, syntetiserade med fotoinitierad tiol-enekemi, för användning som beväxningsavvisande beläggningar för marina applikationer. Genom att variera olika parametrar, såsom längden på PEG-kedjan, härdningskemin, tvärbindaren samt den hydrolytiska stabiliteten, byggdes ett bibliotek av hydrogelbeläggningar upp. Hydrogelbeläggningarna karaktäriserades sedan med avseende på härdningseffektivitet, termiska och mekaniska egenskaper, samt hydrolytisk stabilitet. Vidare studerades beläggningarnas avvisande förmåga mot proteiner, bakterier samt kiselalger. Slutligen studerades ytbeläggningarna i ett fyra månader långt fälttest. Av testerna framgick att längre PEG-kedjor gav beläggningar med bättre avvisande förmåga. Dessutom framgick att valet av tvärbindare, härdningskemi samt hydrolytisk stabilitet var av betydelse för beläggningarnas effektivitet. Denna avhandling behandlar vidare design av amfifila linjära dendritiska hybridmaterial, med PEG som den hydrofila delen. Genom att använda icke-toxiska 2,2-bis(metylol)propionsyrabaserade dendroner, med en klickfunktionalitet i kärnan (alkyne eller allyl) och perifera hydroxylgrupper, som makroinitiatorer för ringöppningspolymerisation av ε-kaprolakton byggdes ett bibliotek av material upp. För att göra materialen amfifila, kopplades klickfunktionella PEG-kedjor (azid eller tiol) till kärnan med koppar(I)-katalyserad azid-alkyn cykloadditionskemi alternativt tiol-enekemi. Storleken på dendronerna varierades från generation 0-4, dessutom varierades längden på både poly(ε-kaprolakton)- och PEG-kedjorna. Materialen designades så att inverkan av dendrongenerationen kunde studeras. Slutligen användes dessa hybridmaterial för att framställa miceller samt isoporösa filmer. Micellernas kritiska micellbildningskoncentration, storlek samt förmåga att laddas med läkemedel visade sig vara mycket beroende av dendrongenerationen. Dendrongenerationen visade sig vidare även ha stor inverkan i hybridmaterialens förmåga att självorganisera sig till en isoporös struktur och material av tredje generationen gav de mest välordnade filmerna.

Place, publisher, year, edition, pages
Stockholm: KTH , 2010. , 69 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2010:50
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-26413ISBN: 978-91-7415-802-1 (print)OAI: oai:DiVA.org:kth-26413DiVA: diva2:372425
Public defence
2010-12-10, F3, Lindstedtsvägen 26 entréplan, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council, 2009-3259
Note
QC 20101125Available from: 2010-11-25 Created: 2010-11-25 Last updated: 2010-11-25Bibliographically approved
List of papers
1. Poly(ethylene glycol)-Based Thiol-ene Hydrogel Coatings-Curing Chemistry, Aqueous Stability, and Potential Marine Antifouling Applications
Open this publication in new window or tab >>Poly(ethylene glycol)-Based Thiol-ene Hydrogel Coatings-Curing Chemistry, Aqueous Stability, and Potential Marine Antifouling Applications
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2010 (English)In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 2, no 3, 903-912 p.Article in journal (Refereed) Published
Abstract [en]

Photocured thiol-ene hydrogel coatings based on poly(ethylene glycol) (PEG) were investigated for marine antifouling purposes. By varying the PEG length, vinylic end-group, and thiol cross-linker, a library of hydrogel coatings with different structural composition was efficiently accomplished, with or without ester linkages. The thiol-methacrylate and thiol-allyl systems were evaluated with respect to curing, degradation, as well as antifouling properties. Moth acrylate-based systems exhibited homopolymerization, whereas allyl-based systems reacted more selectively through thiol-ene couplings reaction. The ester-free hydrogels elucidated higher hydrolytic stability whereas longer PEG chains accelerated the degradation process. The antifouling properties were evaluated by protein adsorption With Bovine serum albumin (BSA) and bioassays with the marine bacteria, Cobetia marina, and the marine diatom, Amphora coffeaeformis; in all tests, longer PEG lengths improved the antifouling properties.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2010
Keyword
thiol-ene chemistry, photocuring, hydrogels, degradation, antifouling, bioassays, click chemistry, terminal alkynes, efficient, networks, surfaces, photopolymerization, future, azides
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-19329 (URN)10.1021/am900875g (DOI)000275825700045 ()20356297 (PubMedID)2-s2.0-77952295264 (Scopus ID)
Note

QC 20100525

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
2. Poly(ethylene glycol)-based thiol-ene hydrogels evaluated for their potential as antifouling coatings: Field studies and mechanical properties
Open this publication in new window or tab >>Poly(ethylene glycol)-based thiol-ene hydrogels evaluated for their potential as antifouling coatings: Field studies and mechanical properties
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(English)Article in journal (Other academic) Submitted
Identifiers
urn:nbn:se:kth:diva-26389 (URN)
Note
QS 20120328Available from: 2010-11-25 Created: 2010-11-25 Last updated: 2012-03-28Bibliographically approved
3. Linear dendritic polymeric amphiphiles with intrinsic biocompatibility: synthesis and characterization to fabrication of micelles and honeycomb membranes
Open this publication in new window or tab >>Linear dendritic polymeric amphiphiles with intrinsic biocompatibility: synthesis and characterization to fabrication of micelles and honeycomb membranes
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2011 (English)In: Polymer Chemistry, ISSN 1759-9954, Vol. 2, 394-402 p.Article in journal (Refereed) Published
Abstract [en]

Linear dendritic hybrid materials enable a range of architectural variations which offers novel possibilities in the tailoring of polymeric materials. In this study dendrons based on the 2,2-bis(methylol)propionic acid (bis-MPA) building block, bearing click chemistry moieties in the core and peripheral hydroxyl functionalities, have been used as macroinitiators for ring opening polymerization of ε-caprolactone. A library of star branched polymers with poly(ε-caprolactone) chains was initially constructed using dendrons up to 4th generation. In a second step, the popular CuAAC or thiol–ene click reaction was efficiently used to attach poly(ethylene glycol) chains of different lengths to the core. Potential applications of the resulted amphiphilic linear dendritic hybrids were investigated. Both self-assembled micelles loaded with doxorubicin anticancer drug and ordered honeycomb membranes with enhanced surface area were successfully fabricated and characterized.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-26392 (URN)10.1039/C0PY00258E (DOI)000286327400019 ()2-s2.0-78751533187 (Scopus ID)
Funder
Swedish Research Council, 2009-3259Swedish Research Council, 2006-3617Knut and Alice Wallenberg Foundation
Note
QC 20101125Available from: 2010-11-25 Created: 2010-11-25 Last updated: 2013-03-27Bibliographically approved
4. Honeycomb films from amphiphilic linear-dendritic-linear hybrids: effect of branching and of the block length
Open this publication in new window or tab >>Honeycomb films from amphiphilic linear-dendritic-linear hybrids: effect of branching and of the block length
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(English)Manuscript (preprint) (Other academic)
National Category
Polymer Chemistry Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-26395 (URN)
Note

QC 20101125

Available from: 2010-11-25 Created: 2010-11-25 Last updated: 2016-04-18Bibliographically approved

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