Covalent Modification of Nanocellulose Towards Advanced Functional Materials

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School of Chemical Technology | Doctoral thesis (article-based) | Defence date: 2017-08-09
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Author
Date
2017
Department
Biotuotteiden ja biotekniikan laitos
Department of Bioproducts and Biosystems
Major/Subject
Mcode
Degree programme
Language
en
Pages
98 + app. 66
Series
Aalto University publication series DOCTORAL DISSERTATIONS, 116/2017
Abstract
Nanocelluloses including cellulose nanocrystals (CNC), cellulose nanofibrils (CNF) and bacterial cellulose (BNC) display properties that make them suitable for the development of new, advanced materials. They are expected to play key roles in the future bioeconomy, where sustainability and biomass valorization are important concepts. This thesis work mainly focused on proposing and testing effective chemical modification strategies to endow nanocelluloses with new properties and, developing novel hybrid materials. CNF and BNC as well as Carboxymethylated CNF (CM-CNF), TEMPO-oxidized CNF (TO-CNF) and TEMPO-oxidized CNC (TO-CNC) were studied with different microscopies including Atomic Force Microscopy, spectroscopic techniques such as X-ray photoelectron spectroscopy and Fourier Transform-Infrared Spectroscopy and other surface, thermo-mechanical and magnetic instrumentation. In order to prepare the hybrid materials, nanoparticles including gold nanoparticles (Au NP), carbon quantum dots (CQD) and magnetic nanoparticles (Fe3O4 NP) were synthesized. The binding of the respective NP with nanocellulose was accomplished by using Ethylcarbodiimide hydrochloride/N-hydroxysuccinimide (EDC/NHS) and Azide-alkyne Huisgen cycloaddition (CuAAC click coupling). In turn, the NP assemblies that were installed on the surface made the nanocelluloses truly functional. Significantly, the aforementioned reactions were performed in aqueous media under relatively mild reaction conditions. Several applications of the synthesized nanoparticle-nanocellulose hybrids were demonstrated. For instance, CQD-functionalized nanocellulose was utilized for preparing luminescent nanopaper and as cytocompatible probes for bio-imaging. Magnetically responsive hybrids were designed for protein separation and an impressive separation capacity was realized for isolation of lysozyme from egg white. As very important forms of nanocellulose networks, films and nanopapers were developed as alternatives to plastics made from non-renewable carbon sources. To this end, the change of the inherent hydrophilic character of the cellulosic materials was addressed by using different strategies. For example, photo-induced (thiol-ene and thiol-yne) click reactions were demonstrated to tailor the surface wettability of films and nanopapers. The reactions were shown to be scalable and effective and can be completed within ten minutes. The developed approaches facilitated the generation of properties that are otherwise not possible for unmodified nanocelluloses. For example, CNF films with patterned surface designs and super-slippery properties were developed, making them suitable for applications relevant to drug screening, cell culture, diagnostics, anti-fouling, etc. Overall, this thesis demonstrates a body of work that expands the possible utilization of nanocelluloses in advanced materials.
Description
Supervising professor
Rojas, Orlando J., Prof., Aalto University, Department of Bioproducts and Biosystems, Finland
Thesis advisor
Filpponen, Ilari, Dr., Auburn University, USA and Aalto University, Finland
Keywords
nanocellulose, covalent modificaiton, nanoparticles, functionalization
Other note
Parts
  • [Publication 1]: Junka K., Guo J., Filpponen I., Laine J., Rojas O.J. (2014) Modification of cellulose nanofibrils with luminescent carbon dots. Biomacromolecules 15(3), 876-881.
    DOI: 10.1021/bm4017176 View at publisher
  • [Publication 2]: Guo J., Filpponen I., Su P., Laine J., Rojas O.J. (2016) Attachment of gold nanoparticles on cellulose nanofibrils via click reactions and electrostatic interactions. Cellulose 23, 3065-3075.
    DOI: 10.1007/s10570-016-1042-7 View at publisher
  • [Publication 3]: Guo J., Liu D., Filpponen I., Johansson L., Malho J. M., Quraishi S., Liebner F., Santos H., Rojas O.J. (2017) Photoluminescent Hybrids of Cellulose Nanocrystals and Carbon Quantum Dots as Cytocompatible Probes for in vitro Bio-imaging. Accepted to Biomacromolecules.
    DOI: 10.1021/acs.biomac.7b00306 View at publisher
  • [Publication 4]: Guo J., Filpponen I., Johansson L. S., Mohammadi P., Latikka M., Linder M., Ras R., Rojas O.J. (2017) Complexes of Magnetic Nanoparticles with Cellulose Nanocrystals as Regenerable, Highly Efficient, and Selective Platform for Protein Separation. Biomacromolecules 18(3), 898-905.
    DOI: 10.1021/acs.biomac.6b01778 View at publisher
  • [Publication 5]: Guo J., Fang W., Welle A., Feng W., Filpponen I., Rojas O. J., Levkin P. (2016) Superhydrophobic and slippery lubricant-infused flexible transparent nanocellulose films by photo-induced thiolene functionalization. ACS Appl. Mater. Interfaces 30, 34115-3122.
    DOI: 10.1021/acsami.6b11741 View at publisher
  • [Publication 6]: Guo J.,Filpponen I., Johansson L. S., Heiβler S., Li L., Levkin P., Rojas O.J. (2017) Micro-patterns on nanocellulose films and paper by photo-induced thiol-yne click coupling: a facile method toward wetting with spatial resolution. Submitted.
Citation
Permanent link to this item
https://urn.fi/URN:ISBN:978-952-60-7489-4
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[diss] Kemian tekniikan korkeakoulu / CHEM