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Li Zheng 201511 Msc Thesis.Pdf INVESTIGATION OF DEEP EUTECTIC SOLVENTS AND THEIR DERIVATIVES FOR PHARMACEUTICAL APPLICATIONS by Zheng Li A thesis submitted in conformity with the requirements for the degree of Master of Science Graduate Department of Pharmaceutical Sciences University of Toronto c Copyright 2015 by Zheng Li Abstract Investigation of Deep Eutectic Solvents and Their Derivatives for Pharmaceutical Applications Zheng Li Master of Science Graduate Department of Pharmaceutical Sciences University of Toronto 2015 Deep eutectic solvent (DES) is a liquid typically formed by mixing two solids, such as a quaternary ammonium salt (QAS) and a hydrogen bond donor (HBD). It was found that the melting point de- pression can be statistically correlated with the Hansen solubility parameters of the HBD. It was also discovered that DES derivative (DESD) formed by glycolic acid and choline chloride shows a wide range of enhancement on the solubility of selected weakly basic poorly water-soluble drugs. Furthermore, a new ternary DESD based on choline chloride, glycolic acid, and oxalic acid remark- ably increased the solubility of itraconazole to 5.36 mg/mL (a 53600-fold increase). Subsequently, DESD containing itraconazole was used as a topical formulation to deliver itraconazole through bovine hoof membranes. Overall, the development of the ternary DESDs has tremendously in- creased the solubility of itraconazole, and DESD has displayed great potential as a formulation vehicle for transungual drug delivery. ii Acknowledgements Firstly, I would like to express my sincere gratitude and earnest respect to my supervisor Professor Ping I. Lee. I am thankful for his kind heart of offering me an opportunity at a low point in my life, for his acceptance of me as an international student against all odds, for his endless patience in carrying me through frustration and difficulties, for his unconditional supportiveness of encouraging me to pursue my dreams, for his parent-like strictness that is only possible in a person who truly cares, and for him being a role model who demonstrates how to be respectful, hardworking, humble, considerate, selfless, grateful, and professional. This thesis could have never been completed without his immense knowledge and patient guidance. It is my great honour to be his student. I also want to thank my wife Yiqun Song, who has been wholeheartedly supporting and taking care of me since we met in our hometown high school 10 years ago. She always builds a harbour for me that I know where to dock, no matter what happens and where I sail. I would like to extend my appreciation to my co-supervisor, Professor Sandy Pang, and my advisory committee members, Professor Tigran Chalikian, and Professor Edgar Acosta for their critical and insightful suggestions on my research. I thank Professor James Wells and Dr. David Dubins for the priceless teaching opportunities, which were some of the best experiences in my graduate school. My gratitude also goes to Dr. Dajun Sun, who tremendously helped me with the transition from an outsider to our laboratory, and to Dr. Hongliang Jiang, Dr. Xiping Huang, Dr. Yanhong Luo, Giovanna Schver, Joy Yang, Andrew Ojo, and too many to be named here, for making my graduate school an everlasting memory. Last, but not least, I want to thank my parents and families who worked so hard to make all the aforementioned possible. iii Contents Abstract ii Acknowledgements iii List of Tables vii List of Figures viii List of Symbols xi Acronyms xv 1 Introduction to Deep Eutectic Solvents 1 1.1 History of Room Temperature Ionic Liquids . 1 1.2 Emergence of Deep Eutectic Solvents . 2 1.3 Properties of Deep Eutectic Solvents . 2 1.4 Applications of Deep Eutectic Solvents . 3 1.5 Overview of the M.Sc. Research . 4 1.5.1 Hypothesis . 4 1.5.2 Research Objectives . 5 2 Using Solubility Parameters to Predict Properties of DES 6 2.1 Introduction to Solubility Parameters . 6 2.1.1 Hildebrand Solubility Parameters . 6 2.1.2 Hansen Solubility Parameters . 7 2.2 Solubilities in Deep Eutectic Solvents . 8 iv 2.2.1 DES as a Novel Solvent . 8 2.2.2 Experimentals . 9 Preparation of Deep Eutectic Solvents . 9 Preparation of Saturated Solutions . 9 Measurement of Solubility in DES . 10 Selection of Descriptors of the Solubility Correlation . 12 Estimation of Entropy of Melting . 14 Estimation of Enthalpy of Melting . 16 Estimation of Molar Volume of Solids . 18 Data Handling . 20 2.2.3 Results and Discussion . 20 Correlation of Solubility in DES . 20 Discussion . 23 2.3 Prediction of Melting Point Depression of a ChCl Based Binary DES . 24 2.3.1 Normalization of Melting Points . 24 Statistical Regression . 26 2.3.2 Quantitative Statistical Correlation . 26 3 Hansen Solubility Parameter and Aqueous Solubility 29 3.1 Introduction . 29 3.2 Methods . 30 3.2.1 Data Collection . 30 3.3 Results and Discussion . 30 3.3.1 Correlation Based on All 273 Data . 30 3.3.2 Data Mining: Effect of Compound Phases and Source of HSP . 31 3.3.3 Comparison with General Solubility Equation . 32 4 Solubility Enhancement by Using Derivatives of Deep Eutectic Solvent 35 4.1 Background . 35 4.2 Drug Solubility Enhancement in DES of ChCl and Glycolic Acid . 36 4.2.1 Introduction . 36 4.2.2 Methods . 36 v Preparation of New DESD . 36 4.2.3 Results and Discussion . 37 Discovery of ChCl and Glycolic Acid as a DESD Pair . 37 4.3 Drug Solubility Enhancement in DESD of Choline Chloride and Glycolic Acid . 39 4.3.1 Method . 39 Drug Solubilization . 39 4.3.2 Drug Solubility in DESD . 39 4.4 Drug Solubility Enhancement in Ternary DESD . 40 4.4.1 Introduction . 40 4.4.2 Methods . 40 4.4.3 Results and Discussion . 41 4.5 Supersaturation Generated by the Addition of DESD . 43 4.5.1 Introduction . 43 Supersaturation Maintained by DESD-Containing Medium . 43 Supersaturation Generated by DESD-Containing Formulation . 44 5 Topical Delivery for Nail Fungal Infection 47 5.1 Introduction . 47 5.2 Methods . 48 5.2.1 Permeation Experiment Setup . 48 5.3 Results and Discussion . 49 5.3.1 Second-Derivative Method in UV-Vis Spectroscopy . 49 5.3.2 Permeation Profile . 51 5.3.3 Measurement of Partition Coefficients . 52 Estimation of Kh .................................. 53 Estimation of K0 .................................. 55 5.3.4 Transport Equations . 56 Lag Time and Diffusion Coefficient . 59 5.4 Conclusion . 59 6 Summary and Future Directions 61 6.1 Summary . 61 vi 6.2 Future Directions . 62 Appendices 64 A Solubility Data Used in Thesis 65 B SPSS Options and Output 75 B.1 SPSS Options and Output for MPD Regression . 76 B.2 SPSS Options and Output for Aqueous Solubility Regression . 80 Bibliography 84 vii List of Tables 2.1 HPLC methods to measure compound solubility in ChCl and urea DES . 11 2.2 Group contribution for Hoftyzer and van Krevenlen’s method . 13 2.3 Group contribution values for estimation of enthalpy of melting . 17 2.4 Volume increments for common elements in a crystal . 19 2.5 The molecular volume increments of 1,2,4,5-tetrabromobenzene, C6H2Br4 . 20 2.6 Solubility of 24 compounds in DES of ChCl and urea . 21 2.7 Melting point depression of hydrogen bond donors . 25 3.1 Statistical summary of aqueous solubility models . 32 4.1 Properties of four drugs and their solubility in two DESDs . 40 4.2 Itraconazole solubility in ternary DESDs . 41 4.3 pKa of five polyprotic carboxylic acids used as the third component . 43 5.1 Itraconazole concentrations of partition coefficient measurements . 54 5.2 Final distribution of itraconazole in the permeation experiment apparatus . 58 5.3 Lag time analysis of the permeation profile . 59 A.1 Aqueous solubility data used in aqueous solubility models . 65 A.2 HPLC-measured solubility of 25 compounds in DES of ChCl and glycolic acid . 74 viii List of Figures 1.1 Phase diagram of urea and choline chloride . 3 1.2 Common deep eutectic pairs . 4 2.1 Chemical structure of diacetone alcohol . 14 2.2 Chemical structure of phenylacetic acid . 15 2.3 Chemical structure of 1,2,4,5-tetrabromobenzene . 19 2.4 Solubility correlation of acids and non-acids in DES . 23 2.5 Dependence of estimated melting point depression values on the difference between δh and δp .......................................... 27 2.6 Accuracy of predicted melting point depression . 28 3.1 Semi-empirical correlation of aqueous solubility of 273 compounds . 31 3.2 Comparison between HSP model with GSE . 34 4.1 Deep eutectic solvent-like mixture of ChCl and glycolic.
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