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University Microfilms, Inc., Ann Arbor. Michigan a COMPARATIVE STUDY of PHEOPHYTIN a and of PHEOPHYTIN B MONOLAYERS

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University Microfilms, Inc., Ann Arbor. Michigan a COMPARATIVE STUDY of PHEOPHYTIN a and of PHEOPHYTIN B MONOLAYERS This dissertation has bean I microfilmed exactly as received ^7-16,272 DITMARS Jr., Walter Earl, 1923- A COMPARATIVE STUDY OF PHEOPHYTIN a AND OF PHEOPHYTIN b MONOLAYERS. The Ohio State University, Ph.D., 1967 Chemistry, plysical University Microfilms, Inc., Ann Arbor. Michigan A COMPARATIVE STUDY OF PHEOPHYTIN a AND OF PHEOPHYTIN b MONOLAYERS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University by Walter Earl Ditmars Jr., B*Sc., M,Sc, The Ohio State University 1967 Approved by r Adviser Department of Chemistry ACKNOWLEDGMENTS I wish to thank my adviser, Professor Quentin Van Vifinkle, for his continued interest and support in initiating and bringing to fruit the research reported herein. It is an understatement to say that without his unusual courage of moral conviction and high standards for academic performance this work could not have come into being. I wish to acknowledge the assistance of the members of the Chemistry Department Machine and Glassblowers Shops in construc­ tion of various pieces of apparatus used in the research. I am indebted to H.F. Blanck Jr., P. Kullavanijaya, and J, Larry for assistance in calculations of the osciallator and dipole strengths of the visible and ultraviolet light absorption of the chlorophylls and several of their derivatives, I wish to thank H.F. Blanck Jr., and J. Larry for as­ sistance in performing the work on the spectroscopic and stability studies, and for many stimulating discussions. I am especially appreciative for the support my family has given me, and for the patience shown in the hardships endured to accomplish this work. This work was generously supported by grants from the National Science Foundation and the National Institutes of Health, 111 VITA June 6, 1 9 2 3 Born - Boston, Massachusetts 1 9 4 5........ 1 9 4 5 -1 9 4 6. Research Chemist, Mass. Inst, Tech, Cambridge, Mass. 1 9 4 9........ M.Sc. , University of Conn., Storrs, Conn. 1 9 4 9 -1 9 5 2 . • # Research Associate, The Ohio State University, Columbus, Ohio 1 9 5 2 -1 9 5 7 * * # • Principal Chemist, Battelle Memorial Inst., Columbus, Ohio 1 9 5 7 -1 9 6 6. # m Research Associate, The Ohio State University, Columbus, Ohio 1 9 6 6-Present. « • Principal Abstractor, Chemical Abstracts Service, Columbus, Ohio PUBLICATIONS "The Vapor Pressure of Inorganic Substances VII. Iron between 1 3 5 6°K and 1 5 1 9^K and cobalt between 1 3 Ô3°K and 1 3 2 2 *K." J.ÏÏ. “Edwards, H.L. Johnston, and VV.E* Ditmars, Jr. JACS 73 4729 C195I). "The Vapor Pressure of Inorganic Substances X, Dissociation Pressures of lithium hydroxide between 650° and 800°K," V/.E. Ditmars, Jr. and H.L. Johnston. JACS 75 I 8 3O (1955)* "The Vapor Pressures of Inorganic Substances II. Titanium between 158?° and 1764°K and copper between 1143° and 1292°K," J.VV, Edwards, H.L. Johnston, and W.E. Ditmars, Jr. JACS 75 2467 (1 9 5 3). XV PUBLICATIONS "Current generator cell," J, McCallum, T,B. Johnson, W.E, Ditmars, Jr., and L.D, McGraw, U.S. 2,979»553» April 11, 1 9 6 1. "Alkaline Voltaic Cells having anodes of Nb, V, or Mo." J. McCallum and W.E. Ditmars, Jr. U.S. 2,936,592, May 30» 1961. "Electrical Concurrent Generating Cells." J. McCallum, T.B. Johnson, VV.E. Ditmars, Jr., and L.D. McGraw. U.S. 3,033,910, May 8, 1 9 6 2. "Current Generator Cell." J, McCallum, T.B. Johnson, VV.E. Ditmars, Jr., and L.D, McGraw. U.S. 3,093,512, U.S. 3 ,0 9 3,5 1 3 , U.S. 3 ,0 9 3,5 1 4, June 11, I9 6 3. "Heterogeneity of the interaction of DNA (deoxyribonucleic acid) with acrif lavine. " R.K. Tubbs, VV.E, Ditmars, Jr., and Q, Van Winkle. J. Mol. Biol. 9 545-57 (1964). "A Comparative Study of Pheophytin a and Pheophytin b Mono­ layers." VV.E. Ditmars, Jr. and Q. Van Winkle, submitted to the Journal of Physical Chemistry, 1967. FIELDS OF STUDY Major Fields; Undergraduate: Chemistry, Mathematics Graduate: Physical Chemistry Surface Chemistry Professor Quentin Van Winkle CONTENTS ACKNOWLEDGMENTS...................................... il VITA ............................................... iv TABLES •••...••••••••••••••••••• viii ILLUSTRATIONS. .................................. xi ABBREVIATIONS AND SYMBOLS............................ xii Page INTRODUCTION .......................................... 1 The Chlorophylls in V i v o ...................... 1 Statement of Problem ....................... 4 LITERATURE SURVEY. .................................... 7 EXPERIMENTAL.......................................... 1? Reagents, General Procedures, and General Facilities. , .................. 17 Preparation of the Chlorophylls and their Derivatives ............... 22 Spectroscopic Measurements ....................... 30 Oscillator Strengths..................... 31 Constituent Analysis ..... ............. 32 Monolayer Apparatus ................. ..... 39 Monolayer Procedures ............... 4$ Experimental Accuracy - Spectroscopic Data........................................ 32 Experimental Accuracy - Monolayer Data............................ 67 RESULTS AND DISCUSSION ................................ 76 Monolayer Stability. ................... 76 Surfaces Pressures and Surface Potentials. .... 83 Monolayer Model.................................. 96 vi CONTENTS (Contd.) Page SUMMARY........... 122 APPENDIX A. CHEMICAL AND PHOTOCHEMICAL STABILITY TESTS OF THE CHLOROPHYLLS AMD SEVERAL DERIVATIVES IN VARIOUS SOLVENTS.......... 127 INTRODUCTION .................................. 128 EXPERIMENTAL .................................. 129 RESULTS AND DISCUSSION ........................ 155 Chemical Stability ......... 135 Photochemical Stability, 145 sm m A R Y . .................................... 174 APPENDIX B. VISIBLE ABSORPTION SPECTRA OF THE CHLOR­ OPHYLLS AlU) SEVERAL DERIVATIVES IN VARIOUS SOLVENTS ..................... l80 INTRODUCTION .................................. l8l RESULTS AND DISCUSSION ........................ l86 Table 2 7 .................................. I87 Table 2 8 .................................. 198 Tables 29, 30, and 31....................... 20? Tables 32, 33, 34, and 35................. 241 Table 3 6 .................................. 261 SUMMARY ........................................ 271 BIBLIOGRAPHY ........................................ 277 V I 1 TABLES Table Page 1. Comparison of the Spectral Parameters of this Research With Those of the Chlor­ ophyll Derivatives of Holt, 28 2. Optical Density Values and Wavelengths for the 0,99 X 10 Solutions, and Values of the Denomlnator"T)etermlnants Used for Component Correlation 33 5, Comparison of the Visible Absorption Parameters of the Chlorophylls In Ethyl Ether. 5^ 4, Visible Absorption Parameters of the Pheophytlns 60 5, Estimated Uncertainties In Band Peak Positions and Band Cut-Offs 63 6, Estimated Errors In Oscillator and Dipole Strengths Arising from Uncertainties In Choice of Band Cut-Offs 66 7, Procedural Errors In the Area Per Molecule , ,, . 70 8, Percentage Variations In o calculated from Observed Variations In AV 74 9, Stability Tests on Chlorophyll a Monolayers, • , , 77 10. Stability Tests on Pheophytin Monolayers at Air-Water Interfaces, ............ 8o 11, Surface Pressure and Surface Potential Values for Pheophytin a and b at pH = 4,0 and pH 3.0. 84 12, Average Compressibilities of ph a, ph b, chi a, and chi b Monolayers ...T., 89 1 3 . Effect of pH on (p,/D) cos 9 for pha.,,,,., 91 vlll TABLES (Contd,) Table Page 14. Variation of Monolayer Molecule Characteristics With Angle of Tilt (6)...................... 109 1 5. Areas Per Molecule and Free Areas Per Monolayer Unit at the Start of Transition «••••••• 115 1 6. Initial Energy Absorption of Solutions in the Photochemical Experiments ........... •..* 131 1 7. Description of the Systems in Chemical Stability Tests . ......... 136 1 8. Chemical Stability of Chlorophyll a in Benzene Solutions ......... 139 1 9. Chemical Stability of the Chlorophylls and the Pheophytins in Various Solvents ...... l4o 20. Systems Used in Low Light Intensity Photobleaching Tests ................... 146 21. Photobleaching Behavior at Low Light Intensities, chi a, chi b , al chi a, al ph a, and ph a . 149 22. Photobleaching Behavior at Low Light Intensities, chi a ...................................... 152 2 3 . Systems Used in High Light Intensity Photo­ bleaching Tests ....... ............. 156 24. Photobleaching Behavior at High Light Intensities. Benzene Solutions ............... I61 2 5. Photobleaching Behavior at High Light Intensities, Solvents Different than Benzene ............. 162 2 6. Apparent Quantum Yield in the Initial Period of Photodecomposition ...... 167 2 7. Band Peak Wavelengths and Wave Numbers of the Chlorophylls and Several Derivatives in Various Solvents. .................. I88 ix TABLES (Contd.) Table Page 2 8. The Change of Band Peak Wave Numbers With Change of Solvent in Reference to Ethyl Ether. 199 2 9. Oscillator Strengths of the Chlorophylls and Several Derivatives in Various Solvents . , . 208 30. Dipole Strengths of the Chlorophylls and Several Derivatives in Various Solvents • • • « 220 3 1 . Changes in Oscillator and Dipole Strengths With Change of Solvent in Reference to Ethyl Ether 229 3 2 . Spectroscopic Parameters of the Chlorophylls and Several Derivatives in Various Solvents • • 242 33. Ratios of Peak Absorbances* Oscillator Strengths, and Dipole Strengths ......... 244 3 4 . The Change of Band Peak Wave Numbers With Change of Substituent in the Same Solvent. 248 35. Changes in Oscillator and Dipole Strengths With Change
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