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Novel Porous Films from Functional and Biocompatible Linear-Dendritic Hybrids
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In the last decades, the fabrication of ordered nano- and microporous structures has attracted increasing interest due to their specific properties and multiple possible applications in electronics, as templates or in the biological field. The development of such materials has been favored by the introduction of the simple breath-figure templating method in the 1990’s. In order to fully exploit the potential of these porous materials, the use of advanced functional molecules as precursors is essential. One suitable class of molecules is the well-defined linear-dendritic hybrids (LD hybrids) family. The structural variations, multiple end-groups and possible amphiphilicity of these molecules are significant advantages that could lead to highly sophisticated functional materials with potential usage in biology. Therefore, this project was directed towards the synthesis of advanced LD hybrids and the evaluation of their ability to form ordered functional porous films.

A degradation and toxicity study was initially conducted on polyester-based 2,2-bis(methylol)propionic acid (bis-MPA) dendrimers under physiological conditions to support the potential usage of these molecules for biological purposes. The materials were found to undergo a relatively fast depolymerization process at pH 7.5. Moreover, the initial dendrimer and its decomposition products were proven to be non-toxic for immune competent cells, allowing for the utilization of these molecules for biological applications.

A linear-dendritic-linear hybrid library was successfully synthesized from biocompatible poly(ethylene glycol) (PEG), poly(ε-caprolactone) (PCL) and bis-MPA building blocks using a combination of ring-opening polymerization (ROP)and copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The materials, consisting of one long PEG block connected to the focal point of the dendron and several PCL arms attached at its periphery, were used to construct ordered porous films using the breath figure method. The polymeric architecture strongly affected the ordering of the films with a more regular morphology obtained from a more flexible polymer. Changing the semi-crystalline PCL to amorphous polylactide (PLA) also permitted the formation of porous arrays. Interestingly, films obtained from inverted structures possessing one long PCL block and several short PEG chains, also presented a regular morphology. Moreover they could be activated to exhibit multiple surface hydroxyl groups.

To increase the number of orthogonal synthetic methodologies available for the preparation of advanced macromolecules, high molecular weight dendritic macrothiols were synthesized. These molecules were efficiently coupled to a number of core molecules via thiol-ene coupling, generating a comprehensive library of dendritic materials. This approach represents an attractive alternative to the commonly used, but potentially toxic, CuAAC.

Exploiting the obtained results, a final LD hybrid was synthesized from atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate (HEMA) derivatives and thiol-ene coupling (TEC) with macrothiols. This macromolecule was successfully utilized to form functional ordered porous arrays and the availability of peripheral alkyne functional groups was demonstrated by efficient coupling with fluorescent Rhodamine-B. The HEMA-backbone allowed for the introduction of cross-linkable azide groups that were used to significantly improve the thermal stability of the films from 50 °C to 200 °C. These materials have the potential to be used in applications such as catalysis, in medicine and as sensors.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. , 62 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2013:15
Keyword [en]
poly(ethylene glycol), poly(caprolactone), linear-dendritic hybrid; click chemistry, CuAAC, thiol-ene chemistry, amphiphilic polymer, honeycomb film, isoporous film, thiol, dendrimer
National Category
Polymer Technologies
Identifiers
URN: urn:nbn:se:kth:diva-119985ISBN: 978-91-7501-691-7 (print)OAI: oai:DiVA.org:kth-119985DiVA: diva2:613040
Public defence
2013-04-19, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council
Note

QC 20130327

Available from: 2013-03-27 Created: 2013-03-26 Last updated: 2013-03-27Bibliographically approved
List of papers
1. Stability and biocompatibility of a library of polyester dendrimers in comparison to polyamidoamine dendrimers
Open this publication in new window or tab >>Stability and biocompatibility of a library of polyester dendrimers in comparison to polyamidoamine dendrimers
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2012 (English)In: Biomaterials, ISSN 0142-9612, E-ISSN 1878-5905, Vol. 33, no 7, 1970-1981 p.Article in journal (Refereed) Published
Abstract [en]

Dendrimers can be designed for several biomedical applications due to their well-defined structure, functionality and dimensions. The present study focused on the in vitro biocompatibility evaluation of a library of aliphatic polyester dendrimers based on 2,2-bis(methylol)propionic acid (bis-MPA) with an overall diameter of 0.5-2 nm. In addition, dendrimers with two different chemical surfaces (neutral with hydroxyl end group and anionic with carboxylic end group) and dendrons corresponding to the structural fragments of the dendrimers were evaluated. Commercial polyamidoamine dendrimers (PAMAM) with cationic (amine) or neutral (hydroxyl) end group were also included for comparison. Cell viability studies were conducted in human cervical cancer (HeLa) and acute monocytic leukemia cells (THP.1) differentiated into macrophage-like cells as well as in primary human monocyte-derived macrophages. Excellent biocompatibility was observed for the entire hydroxyl functional bis-MPA dendrimer library, whereas the cationic, but not the neutral PAMAM exerted dose-dependent cytotoxicity in cell lines and primary macrophages. Studies to evaluate material stability as a function of pH, temperature, and time, demonstrated that the stability of the 4th generation hydroxyl functional bis-MPA dendrimer increased at acidic pH. Taken together, bis-MPA dendrimers are degradable and non-cytotoxic to human cell lines and primary cells.

Keyword
Dendrimer, Biocompatibility, Cytokine secretion, Macrophage, Degradation
National Category
Cell and Molecular Biology Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-87615 (URN)10.1016/j.biomaterials.2011.11.054 (DOI)000300473900002 ()22177621 (PubMedID)2-s2.0-84855729574 (Scopus ID)
Funder
EU, FP7, Seventh Framework ProgrammeSwedish Research Council
Note
QC 20120402Available from: 2012-02-14 Created: 2012-02-14 Last updated: 2017-12-07Bibliographically approved
2. 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
3. A one component methodology for the fabrication of honeycomb films from biocompatible amphiphilic block copolymer hybrids: a linear-dendritic-linear twist
Open this publication in new window or tab >>A one component methodology for the fabrication of honeycomb films from biocompatible amphiphilic block copolymer hybrids: a linear-dendritic-linear twist
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2013 (English)In: Polymer Chemistry, ISSN 1759-9954, Vol. 4, no 9, 2680-2690 p.Article in journal (Refereed) Published
Abstract [en]

The development of a facile method for the fabrication of breath figure (BF) films from hydrophobic polymers is gaining significant importance for their accessibility as templates in fields ranging from electronics and cell culturing to sensing and catalysis. By introducing polyester-based dendritic linkers, a library of micrometre sized honeycomb structures was successfully fabricated from amphiphilic linear-dendritic-linear hybrids comprising hydrophobic PCL or PLA and hydrophilic PEG blocks. From the array of produced films, the incorporation of a third generation dendritic linker was found to generate well-ordered honeycomb films in the several hundreds of micrometre range. This one component approach minimizes the number of unknown parameters and represents a fully reliable methodology for the fabrication of functional BFs from challenging and biocompatible polymers.

Keyword
Porous Polymer-Films, Water-Assisted Formation, Breath Figures, Morphology Control, Microporous Films, Membranes, Patterns, Adhesion, Growth, Cells
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-119933 (URN)10.1039/C3PY00053B (DOI)000316965200007 ()2-s2.0-84875818911 (Scopus ID)
Funder
Swedish Research Council, 2011-4477 2010-453
Note

QC 20130514

Available from: 2013-03-26 Created: 2013-03-26 Last updated: 2013-05-14Bibliographically approved
4. Novel Macrothiols for the Synthesis of a Structurally Comprehensive Dendritic Library using Thiol-Ene Click Chemistry
Open this publication in new window or tab >>Novel Macrothiols for the Synthesis of a Structurally Comprehensive Dendritic Library using Thiol-Ene Click Chemistry
2011 (English)In: Journal of Polymer Science Part A: Polymer Chemistry, ISSN 0887-624X, E-ISSN 1099-0518, Vol. 49, no 13, 2990-2995 p.Article in journal (Refereed) Published
Abstract [en]

The authors are grateful to the Swedish Research Council (VR) for its financial support (grants 2008-5609, 2006-3617, and 2009-3259).

Keyword
click chemistry, dendrimers, dendritic-linear hybrids, dendronized polymer, macromonomers, polyesters, thiols
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-35128 (URN)10.1002/pola.24742 (DOI)000291363200026 ()2-s2.0-79957958713 (Scopus ID)
Note
QC 20110623 Available from: 2011-06-23 Created: 2011-06-20 Last updated: 2017-12-11Bibliographically approved
5. Thermally stable and functional honeycomb films from linear dendritic hybrids derived from HEMA and Bis-MPA
Open this publication in new window or tab >>Thermally stable and functional honeycomb films from linear dendritic hybrids derived from HEMA and Bis-MPA
(English)Manuscript (preprint) (Other academic)
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-119934 (URN)
Funder
Swedish Research Council
Note

QS 2013

Available from: 2013-03-26 Created: 2013-03-26 Last updated: 2013-03-27Bibliographically approved

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