University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Fall 2018 OPTICAL PROPERTIES OF THE PIGMENTS FROM CEPHALOPOD CHROMATOPHORES: SOLUTION AND PARTICLE DETERMINATION Sean Ryan Dinneen University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Dinneen, Sean Ryan, "OPTICAL PROPERTIES OF THE PIGMENTS FROM CEPHALOPOD CHROMATOPHORES: SOLUTION AND PARTICLE DETERMINATION" (2018). Doctoral Dissertations. 2423. https://scholars.unh.edu/dissertation/2423 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. OPTICAL PROPERTIES OF THE PIGMENTS FROM CEPHALOPOD CHROMATOPHORES: SOLUTION AND PARTICLE DETERMINATION BY SEAN R. DINNEEN B.S., Eastern Nazarene College, 2014 DISSERTATION Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemistry September, 2018 This dissertation has been examined and approved in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry by: Dr. Margaret E. Greenslade, Associate Professor of Chemistry Dr. Leila F. Deravi, Assistant Professor of Chemistry and Materials Science, Northeastern University Dr. Sterling A. Tomellini, Professor of Chemistry Dr. Arthur Greenberg, Professor of Chemistry Dr. Richard M. Osgood III, Research Physicist, US Army Natick Soldier RD&E Center Defended On May 25th, 2018 Original approval signatures are on file with the University of New Hampshire Graduate School Dinneen | ii This dissertation is dedicated to my wife, Melanie Catherine Dinneen. In a world where people often camouflage themselves, my true colors are brighter when we’re together Dinneen | iii ACKNOWLEDGMENTS I would like to thank my fellow members of the Greenslade group and the Deravi group for their support. I specifically acknowledge Tyler Galpin for assistance with the RI and CRD experiments, Jillian Morang for assistance with the CRD experiments, Brent Lawson for assistance with the collection of aerosols, and Christopher DiBona for moral support. I acknowledge the University Instrumentation Center for their assistance with SEM sample preparation, and J. Michel Flores for sharing the refractive index retrieval program. Thanks to Cindi Rohwer and Laura Bicknell for logistical support and scheduling. Thanks to the UNH facilities and custodial staff for keeping our buildings and equipment running smoothly, allowing us to focus on our science. I would also like to acknowledge my graduate committee members Sterling Tomellini, Arthur Greenberg, Richard Osgood III, and former member Marc Boudreau. This work was supported by the UNH Department of Chemistry, Northeastern University Department of Chemistry and Chemical Biology, and the Army Research Office (W911NF-16-1- 0455). Finally, I would like to acknowledge Dr. Margaret Greenslade and Dr. Leila Deravi for being the best co-advisers a graduate student could ask for. Thank you for your support, for giving me unique opportunities and experiences, and for continuing to deal with me even when I don’t respond to emails consistently. Dinneen | iv TABLE OF CONTENTS COMMITTEE PAGE……………………………………………………………… . ii DEDICATION………………………………………………………………………. iii ACKNOWLEDGEMENTS…………………………………………………………. iv LIST OF TABLES……………………………...…………………………………… vii LIST OF FIGURES……………………………………………..…………………… viii ABSTRACT…………………………………………………………………………. ix CHAPTER PAGE I. INTRODUCTION TO BIOINSPIRED COLORATION SYSTEMS……… 1 Structural coloration…………………………………………………… 2 Pigmented coloration………………………………………………….. 10 Pigmentary and structural coloration in cephalopods…..……………… 14 Bioinspired technologies……..………………………………………… 16 Dissertation aims……………………………………………………….. 23 II. EXPERIMENTAL CONSIDERATIONS………………………………….. 24 Squid dissection and tissue digestion…………………………………… 24 Pigment variability……………………………………………………… 27 Refractometry…………………………………………………………… 29 Cavity ring-down spectroscopy…………………………………………. 30 Experimental vs. calculated extinction values………………………….. 32 III. COLOR RICHNESS IN CEPHALOPOD CHROMATOPHORES ORIGINATING FROM HIGH REFRACTIVE INDEX BIOMOLECULES…………………………………………………………. 33 Dinneen | v Abstract………………………………………………………………… 33 Introduction…………………………………………………………….. 33 Discussion……………………………………………………………… 35 Experimental…………………………………………………………… 45 IV. OPTICAL EXTINCTION OF SIZE-CONTROLLED AEROSOLS GENERATED FROM SQUID CHROMATOPHORE PIGMENTS………………………………………………………………… 48 Abstract………………………………………………………………… 48 Introduction……………………………………………………………. 48 Results and Discussion………………………………………………… 49 V. AN ITERATIVE CORRECTION APPROACH USED TO RETRIEVE THE REFRACTIVE INDEX OF SQUID PIGMENT AEROSOLS…………… 59 Abstract……………………………………………………………….. 59 Introduction…………………………………………………………… 60 Methods………………………………………………………………. 62 Results………………………………………………………………… 65 Discussion……………………………………………………………. 69 VI. CONCLUSIONS…………………………………………………………. 72 LIST OF REFERENCES…………………………………………………………….. 75 Dinneen | vi LIST OF TABLES Table 1.1 Natural pigment characteristics and properties…………………………. 13 Table 3.1 Extrapolated refractive indices of four solvent systems………………… 36 Table 4.1 Size selected and experimentally measured particle diameters with calculated extinction cross-sections……………………………….. 56 Table 4.2 Comparing measured extinction to Mie calculated extinction………….. 57 Table 5.1 Maxwell-Garnett input and output with error…………………………… 68 Dinneen | vii LIST OF FIGURES Figure 1.1 Thin-film interference diagrams………………………………………… 2 Figure 1.2 Parotia lawesii iridescent feathers and melanosome TEM images…….. 4 Figure 1.3 Sapphirina metallina guanine crystals and reflectivity spectra………… 6 Figure 1.4 Hibiscus trionum petal structural ridges………………………………… 7 Figure 1.5 Beetle Pachyrhynchus argus photonic crystal scales…………………… 9 Figure 1.6 Common ommochromes and ommochrome precursors………………… 11 Figure 1.7 Pentanin and magnesium-coordinated chlorin of chlorophyll…...……... 12 Figure 1.8 Doryteuthis pealeii optical organ hierarchy…………………………….. 14 Figure 1.9 Doryteuthis pealeii pigments, granules, and absorption……...….......…. 15 Figure 1.10 Multilayer synthetic melanin nanoparticle films………………………... 17 Figure 1.11 Charidotella egregia humidity-based metallic gold to red transition…… 18 Figure 1.12 Inkjet printed mesoporous silica nanoparticle photonic crystals……….. 20 Figure 1.13 Infrared-reflecting reflectin protein-based films………………………… 21 Figure 1.14 Biomimetic squid granule thin films……………………………………. 22 Figure 2.1 Extracted pigment absorption and TLC separated band absorption……. 26 Figure 2.2 Ommochrome variability and maturity in dragonflies species…………. 28 Figure 2.3 CRD (τ vs. time) and CPC (number concentration vs. time) raw data…. 31 Figure 3.1 Actuation of squid dorsal mantle chromatophores……………………… 35 Figure 3.2 Xanthommatin and decarboxylated xanthommatin…………………….. 36 Figure 3.3 Pigment refractive index as a function of mass fraction of sample…….. 37 Figure 3.4 Pigment imaginary refractive index as a function of wavelength………. 38 Figure 3.5 Scattering and absorption cross-sections of squid pigment…………….. 39 Figure 3.6 FDTD calculated scattering and absorption cross-sections…………….. 40 Figure 3.7 Optical cross sections calculated at different wavelengths for k……….. 41 Figure 3.8 Optical cross sections calculated with ±10% on n and k……………….. 42 Figure 3.9 Optical cross sections calculated over an extended size range…………. 43 Figure 3.10 Compared optical cross sections of squid pigment and melanin……….. 44 Figure 4.1 Atomization scheme and experimental setup for CRD analysis………... 50 Figure 4.2 Particle size distributions for squid pigment aerosols…………………... 51 Figure 4.3 Aerosol collection setup and SEM size analysis………………………... 53 Figure 4.4 Optical extinction of squid pigment versus number concentration……... 55 Figure 4.5 Extinction cross section versus particle diameter for squid pigment…… 57 Figure 5.1 Flow chart describing the iterative doublet correction process…………. 64 Figure 5.2 Mie corrected and uncorrected Qext versus size parameter……………… 66 Figure 5.3 Mie corrected data with Mie traces using n = 1.92 and 1.5606…………. 67 Figure 5.4 Mie corrected data using n = 1.5606 and the percent difference of Mie traces using n = 1.5606 and n = 1.59……………………………. 68 Dinneen | viii ABSTRACT OPTICAL PROPERTIES OF THE PIGMENTS FROM CEPHALOPOD CHROMATOPHORES: SOLUTION AND PARTICLE DETERMINATION By Sean R. Dinneen University of New Hampshire, September, 2018 Cephalopods are arguably one of the most photonically sophisticated marine animals, as they can rapidly adapt their dermal color and texture to their surroundings using both structural and pigmentary coloration. Their chromatophore organs facilitate this process, but the molecular mechanism potentiating color change is not well understood. The central hypothesis of this work is that the pigments, which are localized within nanostructured granules in the chromatophore, enhance the scattering of light within the dermal tissue. To test this, phenoxazone-based pigments were first extracted from the chromatophore and their complex refractive index (RI) from experimentally determined real and approximated imaginary portions of the RI were extrapolated. Mie theory was used