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Advanced Functional Thin Films and Networks towards Biological Applications
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Functional polymeric scaffolds have been employed in biological applications as several utilities, from nano-sized drug delivery systems to concrete implants. The progression in biological fields essentially relies on finding an appropriate material to fulfil the critical requirements for various types of applications with great potential for tuning functionality and mechanical properties. Therefore, the generation of new materials in extensive libraries is desirable for researchers. In this thesis, two main varieties of functional scaffolds have been constructed; these include i) periodic structure isoporous membranes and ii) three dimension (3D) crosslinked networks with programmable functionalities and mechanical properties. In the first case, a library of linear dendritic (LD) block copolymers was synthesised from biocompatible 2,2-bis(methylol)propionic acid (bis-MPA) dendrons and 2- hydroxyethyl methacrylate (HEMA) derivatives. These materials were successfully employed for the fabrication of isoporous membranes via the facile Breath Figure (BF) method. The dendritic periphery end groups control the manipulation of film morphology, as well as introduction of desired functionalities, either pre- or post- film formation. The introduction of azide functional group along the polymer backbone allows crosslinking reaction, which enhances the stability of the isoporous films. The stability towards temperature was improved from around its glass transition temperature (Tg) to 400 °C after crosslinking; simultaneously the porosity is maintained after immersion in the whole range of pH (1-14). These materials show great potential use as high performance isoporous membranes in futuristic applications such as micro-reactors, sensors and cell patterning platforms. In the second case, the facile fabrication of functional networks employs off-stoichiometric crosslinking, which resulted in residual reactive functional groups after film formation and networks with different crosslinking density. This straightforward off-stoichiometric concept is applied with commercially available materials and well-controlled dendritic-linear-dendritic (DLD) hybrid polymers, generating functional networks with different properties from high stiffness film to soft hydrogels. The network post-modification can be performed topologically and throughout the scaffold. Several crosslinking chemistries were employed for construction of hydrogels from DLD hybrid polymers. The Copper(I) Catalysed Azide-Alkyne Cycloaddition (CuAAC) click reaction results in hydrogels with higher compressive modulus compared to other hydrogels constructed from thiol-ene, thiol-yne and amine-N-hydroxysuccinimide (NHS) esters coupling methods with similar building blocks. These functional crosslinked networks are suitable for numerous applications including fabrication of microfluidic devices, cell culture platforms and bone adhesives.

 

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. , 72 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:23
National Category
Polymer Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-166600ISBN: 978-91-7595-552-0 (print)OAI: oai:DiVA.org:kth-166600DiVA: diva2:811610
Public defence
2015-06-05, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
VINNOVA
Note

QC 20150520

Available from: 2015-05-20 Created: 2015-05-12 Last updated: 2015-05-20Bibliographically approved
List of papers
1. Functional porous membranes from amorphous linear dendritic polyester hybrids
Open this publication in new window or tab >>Functional porous membranes from amorphous linear dendritic polyester hybrids
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2015 (English)In: Polymer Chemistry, ISSN 1759-9954, E-ISSN 1759-9962, Vol. 6, no 13, 2390-2395 p.Article in journal (Refereed) Published
Abstract [en]

By combining ATRP, dendrimer chemistry and 'click' reactions, a library of novel linear dendritic block copolymers (hybrids) was successfully synthesized. The isolated polymers displayed hydrophilic alkyne groups and T-g's ranging from 14 degrees C to 67 degrees C. A T-g threshold of 39 degrees C was found necessary for straightforward porous membrane fabrication via the breath figure method. Exploiting the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, a robust and benign protocol was identified enabling surface functionalization under aqueous conditions. Such manipulations included the introduction of fluorescent rhodamine for thorough assessment by confocal fluorescence microscopy as well as polyethylene glycol chains or perfluorinated groups for tuning the membrane wettability. Finally, with the initial indication of being nontoxic to human dermal fibroblasts (hDF) and osteoblast-like MG63, the porous membranes can potentially find use in the field of controlled cell culture such as patterning of cell growth.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-164488 (URN)10.1039/c4py01803f (DOI)000351493500004 ()2-s2.0-84925004535 (Scopus ID)
Note

QC 20150420

Available from: 2015-04-20 Created: 2015-04-17 Last updated: 2017-12-04Bibliographically approved
2. Beyond state of the art honeycomb membranes: High performance ordered arrays from multi-programmable linear-dendritic block copolymers
Open this publication in new window or tab >>Beyond state of the art honeycomb membranes: High performance ordered arrays from multi-programmable linear-dendritic block copolymers
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2015 (English)In: Advanced Functional Materials, ISSN 1616-301X, E-ISSN 1616-3028, Vol. 25, no 30Article in journal (Refereed) Published
Abstract [en]

A new generation of honeycomb membranes is herein described from a novel library of multipurpose linear-dendritic block copolymers. These are accomplished by combining atom transfer radical polymerization together with dendrimer chemistry and click reactions. The resulted amorphous block copolymers, with T-g between 30 and 40 degrees C, display three important functions, i.e., pore generating aromatic groups, crosslinking azides, and multiple dendritic functional groups. All block copolymers enable the successful fabrication of honeycomb membranes through the facile breath figure method. The peripheral dendritic functionality is found to influence the porous morphologies from closed pored structure with pore size of 1.12 mu m(2) to open pore structure with pore size 10.26 mu m(2). Facile UV crosslinking of the azides yields membranes with highly durable structural integrity. Upon crosslinking, the pH and thermal stability are extended beyond the noncrosslinked membranes in which the porous integrity is maintained up to 400 degrees C and pH 1-14. Taking into account the straightforward and cost-efficient strategy to generate ordered, functional, and structurally stable honeycomb membranes on various solid substrates, it is apparent that these multipurpose block copolymers may unlock future applications including use as molds for soft lithography.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-166861 (URN)10.1002/adfm.201501643 (DOI)000359381300010 ()2-s2.0-84938973586 (Scopus ID)
Note

Updated from manuscript to article.

QC 20150909

Available from: 2015-05-20 Created: 2015-05-20 Last updated: 2017-12-04Bibliographically approved
3. UV initiated thiol-ene chemistry: a facile and modular synthetic methodology for the construction of functional 3D networks with tunable properties
Open this publication in new window or tab >>UV initiated thiol-ene chemistry: a facile and modular synthetic methodology for the construction of functional 3D networks with tunable properties
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2013 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 1, no 44, 13732-13737 p.Article in journal (Refereed) Published
Abstract [en]

A facile methodology for the fabrication of functional crosslinked three dimensional (3D) networks has herein been explored via the benign and UV initiated thiol-ene coupling (TEC) chemistry. The careful selection of monomers or polymers and their feed ratio resulted in straightforward design of organic, inorganic and hydrogel networks with readily available alkenes or thiol functional groups. All crosslinked networks were fabricated within 1 second of UV exposure at wavelengths of 320-390 nm and generally exhibited excellent gel fractions around 90%. By introducing off-stoichiometric thiol and ene (OSTE) monomer feed ratios the window of mechanical properties could be manipulated. For the organic triazine system, the Young's modulus was altered from 780 MPa at an equimolar monomer ratio to soft 106 kPa for 2.5 equiv. with excess of thiol compared to enes. Postfunctionalizations with hydrophilic polyethylene glycols or acrylic acid and hydrophobic heneicosa-fluorododecyl acrylate were explored for the manipulation of functional networks. In this case, the rigid networks with excess of thiols were used as model substrates of which the initial contact angle (CA) of 60 degrees was decreased to 43 degrees by the introduction of acrylic acid and increased to 140 degrees by successful attachment of fluorinated molecules. Finally, amalgamating micropatterning strategy with simple postfunctionalizations of hydrophobic groups resulted in superhydrophobic rigid surfaces with a CA of 173 degrees.

Keyword
Microfluidic Devices, Poly(Dimethylsiloxane), Strategies
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-136533 (URN)10.1039/c3ta12963b (DOI)000326463400005 ()2-s2.0-84886447725 (Scopus ID)
Funder
Swedish Research Council, 2010-453
Note

QC 20131209

Available from: 2013-12-09 Created: 2013-12-05 Last updated: 2017-05-30Bibliographically approved
4. Dendritic hydrogels: From exploring various crosslinking chemistries to introducing functions and naturally abundant resources
Open this publication in new window or tab >>Dendritic hydrogels: From exploring various crosslinking chemistries to introducing functions and naturally abundant resources
2015 (English)In: Journal of Polymer Science Part A: Polymer Chemistry, ISSN 0887-624X, E-ISSN 1099-0518, Vol. 53, no 21, 2431-2439 p.Article in journal (Refereed) Published
Abstract [en]

Dendritic hydrogels from dendritic-linear-dendritic (DLD) block copolymers based on PEG and bis-MPA dendrons were constructed via UV-initiated thiol-ene, thiol-yne, CuAAC, and amine-NHS crosslinking chemistries. Stoichiometric ratio manipulations, prior to film formation, resulted in functional hydrogels with tuneable compressive moduli. The highest gel fractions for all networks were obtained at off-stoichiometric ratios with surplus of DLDs. Finally, sustainable networks were fabricated by amalgamating DLD, naturally abundant cellulose nanocrystal, and protein-based bovine serum albumin.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-166862 (URN)10.1002/pola.27750 (DOI)000362372700001 ()2-s2.0-84941803770 (Scopus ID)
Note

Updated from manuscript to article.

QC 20151021

Available from: 2015-05-20 Created: 2015-05-20 Last updated: 2017-12-04Bibliographically approved

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