Nandika Priyantha Bandara

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Nandika Priyantha Bandara Nanoengineered and Biomimetic Protein-derived Adhesives with Improved Adhesion Strength and Water Resistance by Nandika Priyantha Bandara A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Food Science and Technology Department of Agricultural, Food and Nutritional Science University of Alberta © Nandika Priyantha Bandara, 2017 ABSTRACT The oilseed industry generates a great deal of meal after oil extraction. Soy meal has a number of value added applications while canola meal is used mainly as a low-value animal feed. There is a growing interest on value addition of meal beyond feed uses. Canola and soy meal contain ~ 33-37% and 43-47% (w/w on DM basis) of protein, respectively. As protein-rich biomass, there is a potential to develop protein-based adhesives as an alternative to petrochemical based adhesives. However, protein based adhesives suffer from weak water resistance and adhesion that limit their widespread commercial applications. Nanomaterials are widely used in composite research to improve flexural strength, elasticity, and thermal stability, while biomimetics are used in biomedical field to develop improved materials by mimicking natural materials as a model. Therefore, the overall objective of this research was to develop protein based adhesive with improved adhesion and water resistance using oilseed proteins via nanotechnological and biomimetic approaches. Two hypotheses were tested in this research: (1) exfoliating nanomaterials in canola protein and preparing hybrid adhesives with chemically modified canola protein will improve adhesion and water resistance; (2) biomimetic modification of soy protein to impart 3,4- dyhydroxyphenylalanine groups will improve adhesion and water resistance. In the first study, exfoliating nanomaterials in canola protein at 1% (w/w) increased the dry, wet and soaked adhesion strengths from 6.38 ± 0.84, 1.98 ± 0.22, and 5.65 ± 0.46 MPa (control sample) to 10.37 ± 1.63, 3.57 ± 0.57, and 7.66 ± 1.37 MPa (nanocrystalline cellulose - NCC) and 8.14 ± 0.45, 3.25 ± 0.36, and 7.76 ± 0.53 MPa (graphite oxide - GO) respectively. Nanomaterial induced increase in thermal stability, exposed hydrophobic groups due to secondary structural changes, and nanomaterial induced cohesion were responsible for the ii improved adhesion. In the second study, effect of different oxidation levels of GO on adhesion was studied. Increasing oxidation time decreased C/O ratio while relative proportion of C-OH, and C=O groups initially increased up to 2 h of oxidation, but reduced upon further oxidation. Canola protein-GO hybrid adhesive (CPA-GO – with 1% GO (w/w) addition) prepared with 2 h oxidized GO increased (p < 0.05) dry, wet and soaked strength to 11.67 ± 1.00, 4.85 ± 0.61, and 10.73 ± 0.45 MPa respectively. Improved exfoliation of GO, improved adhesive and cohesive interactions, increased hydrogen and hydrophobic interactions and improved thermal stability of CPA-GO contributed towards the improved adhesion. In the third study chemically modified canola protein-nanomaterial (CMCP-NM) hybrid wood adhesives were developed. Modifying canola protein with ammonium persulphate (1% w/w APS/protein) significantly improved (p < 0.05) adhesion to 10.47 ± 1.35, 4.12 ± 0.64 and 9.39 ± 1.20 MPa for dry, wet and soaked strength respectively. Exfoliating 1% NCC into CMCP further improved adhesion to 12.50 ± 0.71, 4.79 ± 0.40, and 10.92 ± 0.75 MPa while 1% GO increased the adhesion to 11.82 ± 1.15, 4.99 ± 0.28, and 10.74 ± 0.72 MPa for dry, wet and soaked strength respectively. In the fourth study randomly oriented strand boards (ROSB) were produced using nanoengineered canola protein adhesive (CPA) at pilot scale. The mechanical performances, bond durability and water resistance were not affected by CPA addition up to a level of 40%, compared to commercial LPF adhesives. Mechanical performance of all ROSB panels exceeded the acceptable minimum standards specified by CSA O437.0-93 standards; therefore it can be used in commercial ROSB production, either as 100% resin for interior application or up to 40% replacement of LPF for exterior applications. In the fifth study, mussel inspired biomimetic soy protein adhesive was developed by converting inherent amino acids tyrosine into 3,4-dihydroxyphenylalanine (DOPA) by reacting iii with tyrosinase followed by adding NaOH and FeCl3. Adhesion was significantly increased from 4.97 ± 0.94, 1.79 ± 0.52, and 5.62 ± 0.65 MPa to 13.21 ± 1.58, 3.93 ± 0.21, and 12.10 ± 0.46 MPa for dry, wet and soaked strength respectively, mainly due to DOPA mediated polymerization and crosslinking, increased cohesive interactions, and hydrophobic interactions with wood surface. In addition, prepared adhesive showed acceptable adhesion to mica, glass and polystyrene surfaces as well. The findings of this thesis provide evidence on the potential of nanotechnological and biomimetic methods to develop protein based adhesives with improved adhesion and water resistance. iv PREFACE This thesis contains original research work done by Nandika Priyantha Bandara and has been written according to the guidelines for a paper format thesis of the Faculty of Graduate Studies and Research at the University of Alberta. The concept of the thesis was originated from my PhD supervisor Dr. Jianping Wu and the research was funded by grants received from Alberta Innovates Biosolutions (ALBIO) and Alberta Livestock and Meat Agency (ALMA) to Dr. Jianping Wu; and scholarship funds received from Alberta Innovates Technology Futures (AITF) doctoral scholarship, Queen Elizabeth II (QE II) doctoral scholarship, Mitacs Accelerate Internship, and Agricultural Institute of Canada Foundation (AICF) Karl Iverson Award to myself. The thesis consists of eight chapters. Chapter 1 provides a general introduction and the objectives of the thesis. Chapter 2 provides a detailed literature review regarding the agricultural and oilseed industry byproducts, oilseed industry byproduct value addition, wood adhesion, wood adhesive and current innovations in biobased wood adhesives. Chapter 3 has been published as “Exfoliating nanomaterials in canola protein derived adhesive improves strength and water resistance” in RSC Advances [2017, 7(11), 6743-6752], chapter 4 entitled as “Graphite oxide improves adhesion and water resistance of canola protein–graphite oxide hybrid wood adhesive” has been submitted for consideration to Scientific Reports. Chapter 5 entitled as “Chemically Modified Canola Protein-Nanomaterial Hybrid Wood Adhesive Shows Improved Adhesion and Water Resistance” in ready for the submission for publication. Chapter 6 entitled as “Randomly Oriented Strand Board Composites from Nanoengineered Protein Based Wood Adhesive” has been submitted for consideration to Composite Part A – Applied Science and v Manufacturing and chapter 7 entitled as “Biomimetic soyprotein adhesive inspired by mussel adhesion” is ready for submission. Chapter 8 provides an overall conclusions and future recommendations to the thesis. A patent application was filed under the United States Provisional Patent Application Serial No. 62/380,043 – “Improved Protein Based Adhesives” covering all the research findings presented in this thesis from chapter 3 to chapter 7. I was responsible for the literature search relevant to all the chapters above, designing and performing laboratory experiments, data analysis and writing first draft of manuscript, and manuscript revision while Dr. Jianping Wu contributed to experimental design, data interpretation, preparation and submission of manuscripts. Dr. Hongbo Zeng contributed to experimental design, and data interpretation of chapter 7. Mr. Yussef Ezparza contributed to the FTIR and XPS data analysis and interpretation of chapters 4 and 5. Mr. Jiancheng Qi from Agri- Food Discovery Place of University of Alberta contributed in pilot scale canola protein extraction. Dr. Siguo Chen, Mr. Grant Reekie, Mr. David Bilyk, and Mr. Steve Lee from Alberta Innovates Technology Futures contributed in performing pilot scale trails in Chapter 6. vi DEDICATION This thesis is dedicated To my beloved parents A.M. Heenbanda and W.M. Somawasala, who guided me throughout my life, and encouraged me; to my wife Chamila, my lovely kids Chathuli and Navindu…. vii ACKNOWLEDGEMENTS There are countless people who have encouraged and supported me throughout my graduate studies and who I am forever grateful to. First and foremost, I would like to express my heartiest gratitude to my supervisor Dr. Jianping Wu for providing the opportunity to pursue my graduate studies and for his enormous support, encouragement and guidance given throughout the program. I am also very thankful to Dr. Hongbo Zeng and Dr. Lingyun Chen, for their guidance, help and support throughout the graduate program as my PhD supervisory committee members. Their contribution towards designing and executing my research program provided me with a valuable experience in my PhD studies. I would like to express my sincere thanks to Dr. Ning Yan for accepting to be the external examiner for my PhD defense and to Dr. David Bressler for serving as the arm’s length examiner. I would also like to thank Alberta Innovates Biosolutions (ALBIO), and Alberta Livestock and Meat Agency (ALMA) for the financial support provided throughout my doctoral program. In addition, I would like to acknowledge the financial support I received through Alberta Innovates Technology Futures (AITF) doctoral scholarship, Queen Elizabeth II (QE II) doctoral
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