Stable Fluorinated Antimicrobial Coatings
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Virginia Commonwealth University VCU Scholars Compass Theses and Dissertations Graduate School 2012 Stable Fluorinated Antimicrobial Coatings Asima Chakravorty Virginia Commonwealth University Follow this and additional works at: https://scholarscompass.vcu.edu/etd Part of the Engineering Commons © The Author Downloaded from https://scholarscompass.vcu.edu/etd/450 This Dissertation is brought to you for free and open access by the Graduate School at VCU Scholars Compass. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of VCU Scholars Compass. For more information, please contact [email protected]. Stable Fluorinated Antimicrobial Coatings A dissertation submitted in partial fulfillment of the requirement for the degree of Doctor of Philosophy at Virginia Commonwealth University by ASIMA CHAKRAVORTY B.TECH (1999), Calcutta University, India B.Sc (Chemisrty) (1996) Calcutta University, India Director: Kenneth J. Wynne, Ph.D. Professor, Department of Chemical and Life Science Engineering Virginia Commonwealth University Richmond, VA December 2012 ACKNOWLEDGEMENTS The author wishes to thank all the people without whose support and understanding this journey would not have been possible. I would like to convey my gratitude to my advisor, Dr Kenneth Wynne for his continuous guidance and support. His constant encouragement and belief in me has helped me overcome the challenges I have faced in my research. I have learnt a lot from him and hope to make him proud in my future endeavors. I would also take this opportunity to thank all members of the Wynne group for their help and cooperation. Their friendship has made the last few years some of the best years of my life. I would also like to thank the members of the Ohman group for their help and the National Science Foundation (NSF) and Virginia Commonwealth University for providing financial support for this project. None of this would have been possible without my wonderful family – my husband and son who have made me laugh even in the toughest situations and my two sets of parents back home in India! I cannot thank my parents enough for their constant encouragement, guidance and unconditional love. Finally, I would like to dedicate my thesis to my granddad (Dadu) who would have been very proud to see this day. ii TABLE OF CONTENTS List of Schemes……………………………………………..……………….………………..…….vi List of Figures…………………………...……………………………………….……..….….…...vii List of Tables………………………………………………………………………..….……….......x Abstract………………………………………………………………………….……….................xi Chapter 1. Introduction – Antimicrobial polymeric surfaces 1.1 Introduction……………………………………………………….....…………….…….1 1.2 Scope of work………………………………………………………..……...……….….9 Chapter 2. Novel Fluorinated polyoxetanes with –CF2H end groups: Synthesis, Characterization and Applications 2.1 Introduction…………………………………………………………….….……..…….16 2.2 Experimental Section…………………………….…….…….……………….…….….17 2.3 Instrumentation…...........................................................................................................23 2.4 Results and Discussion………………………………………….……….……….……24 Modulated Differential Scanning Calorimetry……………….…….………..…….25 AFM………………………………………………………….………….….……...28 XPS……………………………………………………………….…………..……31 Dynamic contact angle contact angles……………………….…….……….….…..36 2.5 Conclusion…………………………………………………………….……..…….……45 Supplemental Information……………………………………………….….……….….…..46 iii Chapter 3. Fluorous/ Quaternary polyurethane modifiers for coatings with enhanced antimicrobial activity 3.1 Introduction…………………………………………………………….…..………48 3.2 Experimental Section...………………………………………………....……..…...56 Synthesis of monomers………………..…………………………….....………56 Synthesis of copolyoxetanes…………………..…………………....……..…...57 Preparation of blends and coatings……………………..…...…………………58 3.3 Instrumentation……………………………………………………………...……..62 3.4 Results and Discussions……………………………………………………...…….67 Modulated Differential Scanning Calorimetry………………………….….….67 XPS………………………………………………..…….……….....…….……70 Wetting behavior…………………………………………..…….…….….……72 Zeta Potential……………………………..………………………….……..….78 AFM…………………………………………………………...……….….…...84 Antimicrobial test…………………………………………...……….…...…….87 3.5 Conclusion…………………………………………………….……….…….….…89 Supplemental Information…………………………………………………..…..….…..90 Chapter 4. Bottle Brush Nano Glass Hybrids with P[AB] copolyoxetanetelechelics 4.1 Introduction…………………………………………………..…………….….…..96 4.2 Experimental Section...…………………………………………….…….…….…100 4.3 Instrumentation…………………………………………………………...…..…..105 4.4 Results and discussions……………………………………………..……..…...…107 XPS…………………………………………………..………………….....…112 iv AFM………………………...…………………………………....….…..…...114 Zeta Potential………………………………..………..…..………….…...….115 Antimicrobial test…………………………..……………..…..……....……..119 Swell test………………………………………………..…….………....…..124 4.5 Conclusion………………..……………………..……….…….….….………….124 Chapter 5. Kill kinetics of biocides 5.1 Introduction……………………………………....……….………….…….….….127 5.2 Experimental Section...…………………...…………………..……….….……....134 5.3 Test procedure………………………………...……………….…….….…….......136 5.4 Results and discussion……………………………..……..…………..….…….....137 5.5 Conclusion……………………………..……………..………………….…...…..138 Chapter 6. Conclusion and Future work…………………..……..………….…….…...……..….141 References…………………………………..……………………………………….......….....…146 Vita…………………………………..……………………………………..…..…..…..…..…….158 v LIST OF SCHEMES Scheme 2.1. Synthesis of 4F(x=1) and 8F(x=3) monomers……………………………..………..20 Scheme 2.2. Synthesis of P[4F] and P[8F] diols…………………………………………..……...21 Scheme 2.3 End-group functionalization with TFA……………………………………….……..26 Scheme 3.1 Preparation of base polyurethane……………………………………………..……...61 Scheme 3.2 Aerosol spray test…………………………………………………………….……...66 Scheme 4.1 Preparation of U-4F/C12-SiO1.5…………………………………………….……...101 vi LIST OF FIGURES Figure 1.1 Biocide releasing polymers……………………………………………………….……3 Figure 1.2. N-chloramine biocidal silicone………………………………………………………..4 Figure 1.3. Bacterial Cell Wall…………………………………………...…………….………….6 Figure 1.4. Surface modification techniques: A. Plasma/ radiation surface treatments, B. Chemical methods- grafting onto treated surfaces, C. Painting, drip coating, D. Polymeric blends…...........................................................................10 Figure 1.5 Depiction of polyurethane solid state morphology........................................................11 Figure 1.6. TM-AFM phase image of base polyurethane. Scan size 500×500nm; Setpoint ratio (Asp/Ao)=0.9………………………………………………………………………………….....…12 Figure 1.7. Model for surface modification of base polyurethane...…………………………..…..15 Figure 2.1. Schematic of near surfacepolyurethane morphology…………………….….…….….18 Figure 2.2. 1H-NMR spectrum of 4F, P[4F-10] diol and P[4F-10]-TFA (end group peaks circled)……………………………………………………….………….…..….27 Figure 2.3. Thermograms for polyurethanes and precursor polyols…………………...……….…29 Figure 2.4. 10 X 10 µm TM-AFM images at rsp=0.7 for U[4F-10]: a, 2D Height (x= 500 nm) b, phase; U[8F-9.8]: c, 2D Height (x= 500 nm); d, phase…………….…….…....….32 Figure 2.5. 1 X 1 µm TM-AFM images at rsp=0.7 for U[4F-10]: a, 2D Height (x= 500 nm) b, phase; U[8F-9.8]: c, 2D Height (x= 500 nm); d, phase………………….…….….33 Figure 2.6. Model for surface nanoscale phase separation for the fluorous soft blocks….….....…34 Figure 2.7. High resolution C1S spectra for P-4F-10 and P-8F-9.8…………………….……..…..37 Figure 2.8. Dynamic contact angle force distance curves for A)U[3F-3.4], B) U[4F-10], C) U[8F-9.8]; solid line: 1st cycle, dashed line: 5th cycle………………………..…….43 vii Figure 2.9. Wetting models for dry (d) and immersed (i) surfaces……………….…….….……..44 Figure 3.1. Schematic for a conventional polyurethane (soft block, solid line) modified with a PSM having a copolymer soft block (dashed line) with A and B side chains (one set shown)…..………………………………………………………….…..……50 Figure 3.2. Components of HMDI-BD(30)-P[(3FOx)(C12)-86:13-Mn], U-1 and P[AB] soft block………………………………………..…………………………..……………..51 Figure 3.3. Components of matrix polyurethane………………………………………….………52 Figure 3.4. Streaming potentials vs. pumping cycle (20 sec/cycle) for: A, neat P[(3FOx)(C12)] modifier and B, 2 wt%.........................................................................................54 Figure 3.5. Polyurethane surface modifier with P[(4F)(C12)-p:(1-p)] soft block……..….…..…..60 Figure 3.6. Schematic of the Clamping cell…………………………………….………..……….64 Figure 3.7. Thermal analysis of soft block and polyurethane……………………….………..…..69 Figure 3.8 High resolution N1s peaks for modified base polyurethane ……………..…………...73 Figure 3.9. N1s spectra for 2 wt% blend after 30 scans……………………….………….….…...74 Figure 3.10. C1s spectra for 0.5, 1 and 2 wt% blends………………………….………….…...…75 Figure 3.11. Static contact angle by Sessile drop…………………………….…………….……..77 Figure 3.12. Schematic of the Microfluidic capillary method…………………….……….…...…81 Figure 3.13. Zeta potential of blends within 1 week of coating…………….………..…….……..82 Figure 3.14. Zeta potential of blends after 4 weeks of coating…………….………….………….83 Figure 3.15. Phase and 3D Height images of blends with varying percentages of polymer surface modifier-within 1 wk of coating......…………………………….……………..85 Figure 3.16. Phase and 3D Height images of blends with varying percentages of polymer surface modifier after 4 weeks of coating.………………………………….……….….86 Figure S3.1 NMR spectra for mole ratio and molecular weight calculation…………….….……91 Figure S3.2. NMR spectra for P[(4F)(C12)-66:34]…………………………………….…….…..92