ph responsive, adhesive hydrogels based on reversible catechol

124 Pages·2017·4.65 MB·English

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Dissertations, Master's Theses and Master's Dissertations, Master's Theses and Master's
Reports - Open Reports
2015
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Ameya Ravindra Narkar
Michigan Technological University
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Part of the Biomedical Engineering and Bioengineering Commons
Copyright 2015 Ameya Ravindra Narkar
RReeccoommmmeennddeedd CCiittaattiioonn
Narkar, Ameya Ravindra, "PH RESPONSIVE, ADHESIVE HYDROGELS BASED ON REVERSIBLE CATECHOL -
BORONIC ACID COMPLEXATION", Master's Thesis, Michigan Technological University, 2015.
https://doi.org/10.37099/mtu.dc.etds/1002
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Part of the Biomedical Engineering and Bioengineering Commons
PH RESPONSIVE, ADHESIVE HYDROGELS BASED ON REVERSIBLE
CATECHOL - BORONIC ACID COMPLEXATION
By
Ameya Ravindra Narkar
A THESIS
Submitted in partial fulfillment of the requirements for the degree of
MASTER OF SCIENCE
In Biomedical Engineering
MICHIGAN TECHNOLOGICAL UNIVERSITY
2015
(cid:0) 2015 Ameya Ravindra Narkar

This thesis has been approved in partial fulfillment of the requirements for the Degree
of MASTER OF SCIENCE in Biomedical Engineering.
Department of Biomedical Engineering
Thesis Advisor: Dr. Bruce P. Lee
Committee Member: Dr. Jingfeng Jiang
Committee Member: Dr. Patricia A. Heiden
Department Chair: Dr. Sean Kirkpatrick

Contents
List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xvii
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xix
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxi
List of Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxiii
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxv
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Synthesis of hydrogel . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3 Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1 FTIR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2 Equilibrium swelling tests . . . . . . . . . . . . . . . . . . . . . . . 12
v
3.3 Rheometry tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.4 Contact mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.5 Reversibility swelling and Rheometry studies . . . . . . . . . . . . . 16
3.6 Statistical analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.1 FTIR Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.2 Swelling ratio tests . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.3 Rheological analyses . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.4 Relation between the swelling and rheometry tests: Justification for
stitching together the evidence from swelling and rheometry . . . . 32
4.5 Contact mechanics tests . . . . . . . . . . . . . . . . . . . . . . . . 38
4.6 Reversibility studies . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.6.1 Swelling studies results . . . . . . . . . . . . . . . . . . . . . 54
4.6.2 Rheological analyses . . . . . . . . . . . . . . . . . . . . . . 56
4.6.3 Lack of enough evidence to prove reversibility using swelling
and rheometry . . . . . . . . . . . . . . . . . . . . . . . . . 58
5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
7 Future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
vi
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
A Protocols for manufacture of supporting materials and addistional
information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
A.1 Silane coating borosilicate glass slides . . . . . . . . . . . . . . . . . 73
A.2 Acidic and basic pH buffer solutions . . . . . . . . . . . . . . . . . . 75
A.3 Significance of the reacting components . . . . . . . . . . . . . . . . 76
B Compilation of images . . . . . . . . . . . . . . . . . . . . . . . . . . 83
B.1 Additional information for polymer structures . . . . . . . . . . . . 83
B.2 Contact mechanics images . . . . . . . . . . . . . . . . . . . . . . . 83
B.3 Images of the hydrogel discs . . . . . . . . . . . . . . . . . . . . . . 88
B.4 Additional information for rheological analyses . . . . . . . . . . . . 89
C Letters of Permission . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
vii

List of Figures
1.1 (a)The interaction of the catecholic functional groups with glass at pH
3, (b)formation of o-quinone, a deterrent to adhesive interactions . . 4
1.2 An overview of the study: (a) A mussel attached to a clay slab via
byssal threads. After synthesis, the hydrogel adhesives were immersed
in(b)apH3bufferedsolutionwhichcausesthehydrogelstoshrinkand
(c) a pH 9 buffered solution in which the hydrogels exhibit swelling be-
havior. They were further characterized using (d) Rheological analyses
to probe their viscoelastic properties, (e) ATR- FTIR to determine the
presence of desired functional groups, and (f) contact mechanics test
setuptodeterminetheinterfacialbindingofthehydrogeladhesivesand
(g) results comparing the elevated and reduced adhesive interaction, of
DMA and AAPBA (10mol%DMA+10 mol%AAPBA=D10B10) con-
taining hydrogels [in contarst to control (0mol%DMA and 0 mol%
AAPBA black)=D0B0], with a borosilicate glass substrate in pres-
ence of acidic (blue) and basic (grey) pH environments. Mussel photo
courtesy Mr. Zhao Quin [1] C. . . . . . . . . . . . . . . . . . . . . . 6
ix