Development of a Starch-Based Mussel-Mimetic Adhesive Polymer

186 Pages·2017·3.12 MB·English

Purdue University
Purdue e-Pubs
Open Access Theses Theses and Dissertations
2013
Development of a Starch-Based Mussel-Mimetic
Adhesive Polymer
Jeffrey Kazimir de Kozlowski
Purdue University, [email protected]
Follow this and additional works at:https://docs.lib.purdue.edu/open_access_theses
Part of theBiochemistry Commons
Recommended Citation
de Kozlowski, Jeffrey Kazimir, "Development of a Starch-Based Mussel-Mimetic Adhesive Polymer" (2013).Open Access Theses. 7.
https://docs.lib.purdue.edu/open_access_theses/7
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Graduate School ETD Form 9
(Revised 12/07)
PURDUE UNIVERSITY
GRADUATE SCHOOL
Thesis/Dissertation Acceptance
This is to certify that the thesis/dissertation prepared
By JeffreydeKozlowski
Entitled
DevelopmentofaStarch-BasedMussel-MimeticAdhesivePolymer
MasterofScience
For the degree of
Is approved by the final examining committee:
BernardTao

Chair
JonathanWilker

NathanMosier

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Copyright Disclaimer (Graduate School Form 20), this thesis/dissertation adheres to the provisions of
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BernardTao
Approved by Major Professor(s): ____________________________________
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Approved by: BernieEngel 10/11/201 3
Head of the Graduate Program Date
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DEVELOPMENT OF A STARCH-BASED MUSSEL-MIMETIC ADHESIVE
POLYMER
A Thesis
Submitted to the Faculty
of
Purdue University
by
Jeffrey Kazimir de Kozlowski
In Partial Fulfillment of the
Requirements for the Degree
of
Master of Science
December 2013
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Purdue University
West Lafayette, Indiana
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To Amanda,

I know it was not easy for you to move with me to Indiana without the guarantee of a job.
The past two years have brought us closer than I imagined and in the meantime you
discovered your true professional aspirations. I am so happy that things worked out for
the best and I thank you for putting up with the frustrations of my life as a graduate
student. This thesis represents the time and commitment you deserve every day. I love
you.

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ACKNOWLEDGEMENTS
I would like to first thank my advisor Dr. Bernie Tao for his support throughout my
graduate career. I have learned immensely from him educationally, professionally, and
personally through conversations and advice. I am extremely grateful for his guidance
throughout my project and towards my professional goals. I am glad to have worked
with him.
Next, I would like to thank the Indiana and Iowa Corn Growers Associations for making
this project possible. Thank you for your patience and support throughout this project.
I want to thank my committee member Dr. John Wilker for his insights into this project
and for allowing me to use his organic chemistry lab. Additionally, I owe extreme
gratitude to the Wilker lab group, especially Jess Roman, Cori Jenkins, Heather Meredith,
and Michael North for their unwavering assistance in the lab and for helpful discussions.
I would also like to thank Lisa Mauer, Brad Reuhs, Anton Terekov, and the entire
Whistler Center for their assistance with NMR and IR spectroscopy and for allowing me
to use their labs. A special thanks to Anton Terekov for training me on NMR and other
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equipment.
I owe thanks to many members of the Hamaker lab including Madhuvanti Kale and
Byung-Hoo Lee for their patience and knowledge in HPLC analysis of polysaccharides.
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Thank you to Karl Wood for his timely assistance with mass spectrometry and general
knowledge in analytical chemistry.
Thank you to my committee member Dr. Nate Mosier and to Dr. Michael Ladisch for
their mentorship and support in my professional and academic goals.
To the faculty and staff of ABE and Food Science, thank you for everything you have
done for me and other graduate students. Without your commitment, graduate school
would be a nightmare.
Thanks to Dr. Bruce Applegate for my cat and his vaccinations, and interesting
conversations.
Thank you to Dr. Yuan Yao and Dr. Susan Nielson for allowing me to attend the food
science tour of China. It was a once-in-a-lifetime experience that I will never forget. I
want to especially thank Dr. Yao for his guidance on the trip, for helpful discussions
regarding starch and carbohydrate chemistry, and his friendship.
Finally, I want to thank my family and friends for their support. You are my motivation
and backbone.
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TABLE OF CONTENTS
Page
LIST OF TABLES .............................................................................................................. x
LIST OF FIGURES ........................................................................................................... xi
LIST OF ABBREVIATIONS .......................................................................................... xiv
ABSTRACT ............................................................................................................ xvi
CHAPTER 1. INTRODUCTION ................................................................................. 1
1.1 Objectives ...................................................................................................1
1.2 Organization ...............................................................................................1
CHAPTER 2. LITERATURE REVIEW ...................................................................... 3
2.1 Adhesives ...................................................................................................3
2.1.1 Introduction .........................................................................................3
2.1.2 Motivation for Green Adhesives .........................................................4
2.1.3 Concepts ..............................................................................................5
2.1.4 Mechanisms of Adhesion ....................................................................7
2.1.4.1 Mechanical Adhesion .............................................................................7
2.1.4.2 Chemical Adhesion ................................................................................7
2.1.5 Adhesion in Nature – Mussel Adhesion..............................................8
2.2 DOPA Chemistry .....................................................................................11 v

2.2.2 DOPA in Adhesion ...........................................................................13
2.2.3 DOPA in Cohesion ............................................................................14
2.3 Mussel-Mimetic Adhesive Polymers .......................................................16
2.3.1. Catechol-Functionalized Polymers ..........................................................17
2.3.1.1 Benzotriazoles ......................................................................................17
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2.3.1.2 Carbodiimide ........................................................................................18
2.3.1.3 Schiff Base............................................................................................21
2.3.2 Polymerization of Catechol-Functionalized Monomers ...................22
2.3.2.1 Condensation ........................................................................................22
2.3.2.2 Ring-Opening Addition of N-Carboxyanhydrides ...............................23
2.3.2.3 Reactive Anhydride or Acid Chloride ..................................................24
2.3.2.4 Vinyl Polymerization............................................................................25
2.3.3 Characterizing DOPA-polymer Conjugates ......................................26
2.3.3.1 DOPA Content......................................................................................26
2.3.3.2 Verification of Conjugation ..................................................................27
2.3.4 Performance of Mussel-Inspired Adhesives .....................................28
2.3.5 DOPA for Adhesive Polymer Crosslinking ......................................30
2.3.5.1 Chemical Oxidants ...............................................................................30
2.3.5.2 Metals ...................................................................................................31
2.3.5.3 Enzymes ...............................................................................................32
2.4 Opportunity for Catechol-Functionalized Biopolymers...........................32
2.5 Starch and Starch Adhesives ....................................................................34 v
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2.5.1 Introduction .......................................................................................34
2.5.2 History of Starch Adhesives..............................................................34
2.5.3 Structure ............................................................................................35
2.5.4 Modified Starch .................................................................................37
2.5.5 Carboxymethyl Starch .......................................................................38
2.5.6 CMS Bioconjugates ..........................................................................39
2.6 Future Studies in Mussel-Inspired Biopolymer Adhesives ......................40
CHAPTER 3. MATERIALS AND METHODS ........................................................ 42
3.1 Materials ...................................................................................................42
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3.2 Preparation of Hydrolyzed Non-Granular Starch ....................................44
3.2.1 Enzymatic Hydrolysis Time Study ...................................................44
3.2.2 Gram-Scale Preparation of Non-Granular Hydrolyzed Starch .........46
3.2.2.1 Starch Dissolution ................................................................................46
3.2.2.2 Enzymatic Hydrolysis of Dissolved Starch ..........................................46
3.2.2.3 Starch Recovery....................................................................................47
3.2.3 Molecular Weight Distribution of Hydrolyzed Starch ......................48
3.3 Carboxymethyl Starch ..............................................................................49
3.3.1 Synthesis ...........................................................................................49
3.3.1.1 One-Step Non-Granular CMS ..............................................................49
3.3.1.2 Multi-Step Granular CMS ....................................................................51
3.3.2 Degree of Substitution.......................................................................53
3.4 Starch-Catechol Conjugates .....................................................................54
3.4.1 CMS-Dopamine Synthesis by EDC ..................................................54
3.4.1.1 One-step Reaction ................................................................................54
3.4.1.2 One-Step Anaerobic Reaction ..............................................................55
3.4.1.3 One-Step Reaction with Ascorbic Acid ...............................................56
3.4.1.4 Two-Step Reaction ...............................................................................57 vi
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3.4.2 Starch-Dopamine Synthesis by CDI .................................................60
3.4.2.1 In DMSO ..............................................................................................60
3.4.2.2 In DMF .................................................................................................60
3.4.3 Starch-Benzoic Acid Conjugates ......................................................61
3.4.3.1 Starch-DMBA.......................................................................................61
3.4.3.2 Starch-DHBA .......................................................................................64
3.4.4 Characterization of Catechol-Functionalized Starch Polymers ........66
3.4.4.1 Catechol Content ..................................................................................66
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3.4.4.2 Verification of Conjugation Bond-Type by FTIR ................................70
3.4.4.3 Characterization of Dihydroxybenzoic acid-Phenylboronic acid Esters .
..............................................................................................................70
3.4.5 Lap-Shear Adhesive Test ..................................................................71
CHAPTER 4. RESULTS AND DISCUSSION .......................................................... 72
4.1 Enzymatic Hydrolysis of Hi-Maize® 260 ...............................................72
4.1.1 Enzymatic Hydrolysis Time Study ...................................................74
4.1.2 Gram-Scale Preparation of Hydrolyzed Non-Granular Starch .........75
4.2 Carboxymethylation of Hi-Maize® 260 ..................................................77
4.2.1 One-Step Non-Granular CMS ...........................................................77
4.2.2 Fed-Batch Non-Granular CMS .........................................................78
4.2.2.1 Additional SMCA .................................................................................78
4.2.2.2 Additional SMCA and NaOH ..............................................................79
4.2.3 Single and Multi-step Granular CMS ...............................................79
4.2.3.1 Method 1 ...............................................................................................81
4.2.3.2 Method 2 ...............................................................................................81
4.3 Starch-Catechol Conjugates .....................................................................82
4.3.1 Synthesis of CMS-dopamine by EDC...............................................82 v
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4.3.1.1 One-step Reaction ................................................................................83
4.3.1.2 Two-Step Reaction ...............................................................................90
4.3.1.3 Summary of EDC Reactions ................................................................93
4.3.1.4 FTIR Characterization of CMS-Dopamine ..........................................94
4.3.1.5 Adhesive Strength of CMS-Dopamine .................................................97
4.3.2 Starch-Catechol Conjugates ..............................................................98
4.3.2.1 Starch-DMBA.....................................................................................102
4.3.2.2 Starch-DHBA .....................................................................................109