Antimicrobial Copper Iodide Materials Item Type text; Electronic Dissertation Authors Krasnow, Nicholas Riordan Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 04/10/2021 06:29:51 Link to Item http://hdl.handle.net/10150/612146 ANTIMICROBIAL COPPER IODIDE MATERIALS by Nicholas Riordan Krasnow __________________________ Copyright © Nicholas R. Krasnow 2016 A Dissertation Submitted to the Faculty of the DEPARTMENT OF MATERIALS SCIENCE AND ENGINEERING In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 2016 1 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE As members of the Dissertation Committee, we certify that we have read the dissertation prepared by Nicholas R. Krasnow, titled Antimicrobial Copper Iodide Materials and recommend that it be accepted as fulfilling the dissertation requirement for the Degree of Doctor of Philosophy. _______________________________________________________________________ Date: 04/25/2016 Donald Uhlmann _______________________________________________________________________ Date: 04/25/2016 Anoop Agrawal _______________________________________________________________________ Date: 04/25/2016 Srini Raghavan _______________________________________________________________________ Date: 04/25/2016 Manish Keswani Final approval and acceptance of this dissertation is contingent upon the candidate’s submission of the final copies of the dissertation to the Graduate College. I hereby certify that I have read this dissertation prepared under my direction and recommend that it be accepted as fulfilling the dissertation requirement. ________________________________________________ Date: 04/25/2016 Dissertation Director: Donald Uhlmann 2 STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of the requirements for an advanced degree at the University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that an accurate acknowledgement of the source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the copyright holder. SIGNED: Nicholas R. Krasnow 3 ACKNOWLEDGMENTS I would like to acknowledge the enduring support and guidance I have received from my committee members and mentors, Dr. Donald Uhlmann, Dr. Anoop Agrawal, Dr. Srini Raghavan, and Dr. Manish Keswani. I have to give special thanks to Dr. John Cronin, Lori Adams, and Shri Parikh to whom I will be forever indebted to for their daily teachings and support. Additional thanks should be extended to Dr. Jason Torrey and their colleagues for an enduring commitment and cooperation on this project. To the myriad of other teachers, professors, researchers, industrialists, manufacturers, consultants, and football coaches whose names would require too many reams of paper to list; and whom have helped me with everything, thank you. 4 DEDICATION To Mom. 5 TABLE OF CONTENTS Chapter 1.! Introduction ................................................................................... 11! 1.1.! Motivations .............................................................................................. 11! 1.2.! Materials Solutions in Infection Control ................................................. 28! 1.3.! Antimicrobial Agents .............................................................................. 32! 1.4.! Select Antimicrobial Pesticides ............................................................... 40! 1.5.! Testing of Antimicrobial Pesticides and Materials .................................. 49! 1.6.! Objectives and Structuring of this Dissertation ....................................... 52! 1.7.! Literature Cited in Chapter 1 ................................................................... 54! Chapter 2.! Copper Iodide Small Particles as an Antimicrobial Agent ........ 60! 2.1.! Comparative Antimicrobial Properties of Several Metal Compounds .... 60! 2.2.! Antimicrobial Efficacy of Variously Sized CuI Small Particles ............. 77! 2.3.! Confirmatory Experiments on the Usefulness of CuI Small Particles .... 88! 2.4.! CuI Small Particles Versus Small Particles of Other Materials .............. 98! 2.5.! Chapter 2 Conclusions ........................................................................... 103! 2.6.! Literature Cited in Chapter 2 ................................................................. 104! Chapter 3.! CuI Small Particle Production Through Wet Media Milling .. 106! 3.1.! Motivation and Wet Media Milling ....................................................... 107! 3.2.! Experimental Set Up .............................................................................. 140! 3.3.! Preliminary Grinding Experiments ........................................................ 147! 3.4.! Production of PVP-NaI Stabilized CuI Small Particles ......................... 172! 3.5.! Literature Cited in Chapter 3 ................................................................. 181! Chapter 4.! CuI Small Particles with Modified Surface Chemistry ........... 183! 4.1.! CuI Small Particles Using Vinyl-Acetate-PVP ..................................... 183! 4.2.! Functionalized CuI Small Particles with Other Copolymers ................. 184! Chapter 5.! Applications of Surface Modified CuI Small Particles ............ 190! 5.1.! Antimicrobial Coatings .......................................................................... 190! 5.2.! Antimicrobial Wound Coverings ........................................................... 192! 5.3.! CuI Based Wound Cream ...................................................................... 194! 5.4.! Antimicrobial Surface Cleaners with Residual Disinfecting Films ....... 195! Chapter 6.! Summary and Outlook ................................................................ 197! 6.1.! Summary ................................................................................................ 197! 6.2.! Outlook .................................................................................................. 199! References ........................................................................................................... 200! 6 LIST OF FIGURES Figure 2.1 – Cuprous oxide, cupric oxide, and silver with biomolecules [Sunada et al.] 63! Figure 2.2 – Antibacterial Activity of Cu2O and CuO [Sunada et al.] 64! Figure 2.3 – Antimicrobial Efficacy of Various Cu and Ag Compounds 70! Figure 2.4 – CuCl and AgCl on an E. coli inoculated Mueller Hinton Agar Plate 71! Figure 2.5 – Example CuI/PVP Particles Prepared by the “Acetonitrile Method” 81! Figure 2.6 – CuI used to prepare the CuI-PVP-MMPs and CuI-PVP-LMPs 83! Figure 2.7 – Qualitative Measure of Growth in Antimicrobial Suspension Test 85! Figure 3.1 – Horizontal Wet-Media Mill Schematic 119! Figure 3.2 – Good and poor quality grinding media [Adapted from Weber et al.] 121! Figure 3.3 – Left, Rotating Gap Separator & Right, Cartridge Screen Separator 123! Figure 3.4 – Schematic of Double Mechanical Seal 124! Figure 3.5 – Rapid Settling of <10µ CuI Particles 129! Figure 3.6 – Active Volume Between Grinding Media 134! Figure 3.7 – Reduced Stress Number (SNr) vs. Product Size [Kwade et al.] 136! Figure 3.8 – SEGM vs. Product Size vs. Em 138! Figure 3.9 – Sample DLS/SLS measurement for Monodispersed Particles 143! Figure 3.10 – Sample DLS/SLS measurement for Polydispersed Particles 144! Figure 3.11 – DLS Measurement with “Optimal” or “Maximum” Peak Resolution 145! Figure 3.12 – Settling of CuI Processed without Dispersant 148! Figure 3.13 – Difference between processing routes of CuI/PVP formulation 150! Figure 3.14 – Proposed physicochemical differences between CuI/PVP particles 150! Figure 3.15 – Bimodal Distribution for grinding CuI/SLS 153! Figure 3.16 – Example DLS measurement to explain Figure 3.15. 154! Figure 3.17 – Scanning Electron Micrograph of CuI milled with SLS for 24 hours 154! Figure 3.18 – Mechanical integrity of CuI/SDS powder coatings 159! Figure 3.19 – Antimicrobial CuI Powder Coatings with Cleaning and Abrasion 161! Figure 3.20 – Cross Section of 3% Cu Containing Powder Coating 161! Figure 3.21 – S. aureus on Powder Coatings 162! Figure 3.22 – AFM Analysis of CuI Powder Coatings 163! Figure 3.23 – SEM and EDS Analysis of Failed CuI Based Polyester Thermoplastic 164! Figure 3.24 – Cratering in Solvent Based Acrylic Coating Due to Poor Dispersal 165! Figure 3.25 – Proposed intermediate between CuI and PVP to improve stability 167! Figure 3.26 – Particle Size Distributions for Grinding of CuI-PVP-NaI 168! Figure 3.27 – SEM/STEM of 50%CuI, 2% NaI, and 48% PVP (600 minutes) 169! Figure 3.28 – CuI Fracture surface from two different CuI sources 174! Figure 3.29 – Electron Micrograph of CuI particles at 100µ/4000RPM/6 hours 176! Figure 3.30 – Electron Micrograph of CuI particles at 300µ/2000RPM/6 hours 178! Figure 3.31 – Electron Micrograph of CuI particles at 100µ/1000RPM/24hours 179! LIST OF TABLES Table 1.1 – Cu or Ag Compounds against QB bacteriophages [Sunada et al.] 47! Table 1.2 – MIC and MBC for silver or copper nanoparticles