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Design, Synthesis, and Evaluation of Innovative BODIPY-Peptidic Conjugates for Biological Application

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Design, Synthesis, and Evaluation of Innovative BODIPY-Peptidic Conjugates for Biological Application Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School 2017 Design, Synthesis, and Evaluation of Innovative BODIPY-Peptidic Conjugates for Biological Application Tyrslai Menyaee Williams Louisiana State University and Agricultural and Mechanical College, [email protected] Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_dissertations Part of the Chemistry Commons Recommended Citation Williams, Tyrslai Menyaee, "Design, Synthesis, and Evaluation of Innovative BODIPY-Peptidic Conjugates for Biological Application" (2017). LSU Doctoral Dissertations. 4327. https://digitalcommons.lsu.edu/gradschool_dissertations/4327 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Doctoral Dissertations by an authorized graduate school editor of LSU Digital Commons. For more information, please [email protected]. DESIGN, SYNTHESIS, AND EVALUATION OF INNOVATIVE BODIPY-PEPTIDIC CONJUGATES FOR BIOLOGICAL APPLICATION A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Tyrslai Menyaeé Williams B.S., Southern University A&M College Baton Rouge, LA, 2011 August 2017 To my guardian angels Jency Williams, Libby Thompson, and Ann Glover we did it! To my heartbeats’ Marleigh Wright and Daviah Glover your unconditional love motivates me daily. ii ACKNOWLEDGEMENTS The impeccable journey of achieving my Doctorate of Philosophy in organic chemistry has been one of continuous learning and growth as a scientist and more importantly a woman. I would first like to thank God for being my light and salvation in everything that I do. I know that I am nothing without you, and pray you always get the glory in all I do. I am very thankful for the opportunity he has given me to encounter a great mentor and advisor, the sweetest person I’ve ever met, Professor M. Graça H. Vicente. Dr. Vicente not only took me into her group and allowed me to develop my foundation as a scientist. But she has been a true mentor to me over the years. The critical and independent thinking skills I have developed under her leadership are etched in my mind, and I will definitely apply them to my next chapter in life. She has been a pillar of encouragement uplifting me through all areas of my life, especially when I doubted myself. Words cannot express the level of adoration I have for her, thank you Professor M. Graça H. Vicente. I would also like to thank my dissertation committee members, Professor Kevin M. Smith, Professor Isiah Warner, and Professor Marcia Newcomer for their continued support and advice during this journey. A special thank you to my committee member Dr. Warner, over the years you have encouraged me in many ways said and unsaid, and it has been an honor to have you serve as one of my mentors. Your contribution to the world of science is ever-growing, however it never seems to shield the devotion you have for the minority students here at LSU. We are forever indebted to you. I would also like to thank Ms. Connie David for her advice and guidance in using MALDI- TOF-TOF analyses; Dr. Thomas Weldeghiorghis in the LSU NMR Facility for training me on various NMR techniques; Dr. Seetharama Jois at the University of Louisiana at Monroe for his guidance in developing peptide sequences; and Dr. Martha Sibrian-Vazquez none of this work would be possible without you. You are truly talented and very much appreciated. Thank you to the past and present members of the Vicente and Smith research groups: Dr. Krystal Fontenot Dr. Alecia M. McCall, Dr. Jaime Gibbs, Dr. Dinesh Bhupathiraju, Dr. Moses Ihachi, Dr. Benson Ongorora, Dr. Haijun Wang, Dr. Timsy Uppal, Dr. Waruna Jindasa, Dr. Ning iii Zhao, Dr. Sunting Xuan, Dr. Alex Ngyuen, Elizabeth Okoth, Qianli Meng, Daniel LaMaster, Maodie Wang, Guangyu Zhang, Dr. Liqiang Luan, and Nichole E Kaufman. A special thank you to Zehua Zhou for all of her expertise in cell studies; Dr. Mathis for his patience and time with mice studies; and Dr. Caitlin Ayala, for being a devoted friend and support system regardless of the miles between us. Words cannot express how grateful I am to my exceptional family. To my mother, thank you for your many sacrifices, hard-work, and dedication to my siblings and I. Words can never express how much I appreciate your devotion to being a good mother, provider, and person over the years. The unwavering love and support you have offered over me has always lifted me up during this process. To my grandmother, your constant prayers, livelihood, and dedication throughout this process. Your love has kept me grounded and humble. Thank you will never indicate just how much you mean to me. To my brilliant brother and marvelous sister, I hope that this journey sparks a light in you to pursue your wildest dreams. You two are capable of anything and I will forever support you as you have supported me. Finally to my fiancé, Keyala S. Carter, thank you for always being my biggest cheerleader, my rock, my partner, and most importantly my purifier through it all, I truly appreciate your commitment to this process and me. You manage to always guide me to the light at the end of the tunnel no matter what the situation looks like. Enduring these difficult times has not been easy, but there is no one else I would rather share these tender moments with than you. I am truly thankful for your commitment and love during these years, and allowing me to be vulnerable with you. Because of you I now know what it means to be whole. Thank you all for every seed you have sown in me. My only wish is that I affect change in others the way you all have done so for me. iv TABLE OF CONTENTS ABBREVIATIONS ....................................................................................................................... vii ABSTRACT ................................................................................................................................... ix CHAPTER 1. Introduction to methods of targeting Colorectal Cancer for In Vivo Imaging ........ 1 1.1 Colorectal Cancer (CRC) ...................................................................................................... 1 1.2 Methods for Detecting Colorectal Cancer ............................................................................. 5 1.3 Photodynamic Therapy as a method of treatment for CRC .................................................. 9 1.4 Epidermal Growth Factor Receptor .................................................................................... 11 1.5 BODIPY Dyes and Applications to In Vivo Imaging ......................................................... 14 1.6 Research Focus ................................................................................................................... 21 1.7 References ........................................................................................................................... 22 CHAPTER 2. Design and Synthetic Strategies for Peptides that Target EGFR ........................... 34 2.1 Introduction to EGFR-L1 and EGFR-L2 ............................................................................ 34 2.2 Results and Discussion........................................................................................................ 35 2.3 Derivatives of EGFR-L1 and EGFR-L2 ............................................................................. 42 2.4 Characterization of Peptides ............................................................................................... 51 2.5 Conclusions ......................................................................................................................... 56 2.6 Experimental ....................................................................................................................... 57 2.7 References ........................................................................................................................... 62 CHAPTER 3. Design and Synthetic Strageties for BODIPY-Peptidic Conjugates for Diagnosis of CRC via Peptide Linkages............................................................................................................. 67 3.1 Introduction ........................................................................................................................ 67 3.2 Results and Discussion....................................................................................................... 69 3.3 Characterization of BODIPY-Peptide Conjugates .............................................................. 88 3.3 Conclusion ........................................................................................................................ 101 3.4 Experimental ..................................................................................................................... 102 3.5 References ......................................................................................................................... 109 CHAPTER 4. Design and Synthetic Strageties for BODIPY-Peptidic Conjugates for Diagnosis of CRC via Isothiocyanate Chemistry ............................................................................................... 67 4.1 Introduction .....................................................................................................................
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