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Subcritical Water As a Tunable Solvent for Particle Engineering

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Subcritical Water As a Tunable Solvent for Particle Engineering SUBCRITICAL WATER AS A TUNABLE SOLVENT FOR PARTICLE ENGINEERING By Adam Carr, B.E. (Chemical Engineering) A thesis submitted to the School of Chemical Engineering in partial fulfillment of the requirements of the degree: Doctor of Philosophy (PhD) The University of New South Wales May 2010 ABSTRACT In the research described in this thesis, an environmentally friendly technique for engineering the morphology of particles was developed. Active pharmaceutical ingredients (APIs) were used as model compounds to explore the potential of the new particle engineering technology. APIs were chosen because tuning the size and shape of drug particles can have pharmacokinetic benefits. The new technology used subcritical water (SBCW) as a solvent to dissolve APIs. By rapidly cooling a SBCW-API solution, the dissolved drug was rapidly precipitated, often with a narrow particle size distribution. Furthermore, it was shown that the morphology of the precipitated particles can be changed by altering several process variables. In order to develop a new precipitation technology, fundamental solubility data were required. Solubility data were collected for the model APIs; budesonide, griseofulvin, naproxen and pyrimethamine in SBCW from 100°C to 200°C. To ensure that the solubility results were reliable, data were also collected for anthracene, which were compared to published SBCW solubility data. The solubility of budesonide in SBCW was low. Organic solvents were added to the SBCW-budesonide solution to increase the solubility of the API. A model that correlated the solubility of the solute in SBCW with the dielectric constant of the solvent was developed. Model outputs were within 5% of the experimental solubility values. The solubilities of the APIs were also modelled using a state of the art model available in the published literature. The Modified UNIversal Functional Activity Coefficient (M-UNIFAC) model was used to predict the solubility of budesonide, griseofulvin, naproxen and pyrimethamine in SBCW. It was shown that some of the parameters in literature were not sufficient to describe the data. Model error is reduced significantly when the model parameters were optimized. The potential of the SBCW micronization process to produce particles for drug delivery via inhalation has been assessed. Budesonide was micronized under a model precipitation condition, the suspension of API in water was then spray dried, and the aerodynamic particle size was established using an Anderson Cascade Impactor. It has been shown that, when coupled with an effective drying process, particles suitable for inhalable drug delivery may be produced. i “I keep asking that the God of our Lord Jesus Christ, the glorious Father, may give you the Spirit of wisdom and revelation, so that you might know Him better.” Ephesians 1:17 “I, wisdom, dwell together with prudence; I possess both knowledge and discretion” Proverbs 8:12 For my father and mother ii ACKNOWLEDGEMENTS AND THANKS I wish to thank my principle academic supervisor, Professor Neil Foster, for his guidance and support throughout my PhD. He has been very generous with his professional and personal time, and has encouraged me to grow as a researcher through many different hurdles. His ability to see opportunity in what most people would see as a dead end continues to surprise and inspire me. I would also like to thank my co-supervisor, Dr. Raffaella Mammucari. Her day-to-day insight, knowledge and critical thinking kept me on my toes, and helped me to develop many of the research skills I now possess. Perhaps most of all, I have enjoyed the way that Raffaella has made herself available to chat about both academic and personal matters at any time of the day, making working in the lab a delight. I would like to thank all of my lab colleagues; particularly Roshan, Danh and Wendy. Their friendship through what can often be a tough environment has been liberating and very much appreciated. Roshan’s good humor was especially appreciated, particularly when the outlook seemed bleak. I would very much like to thank my family: Greg, Lynda, Jason and Brittany and my fiancée Jessica for both the emotional and directional support that they have given me throughout the course of my PhD. A special thanks goes to my mother for praying for me continually, and my father whose wisdom guided me into doing a PhD in the first place. Finally, I would like to thank my God and Heavenly Father, who has directed me onto a path I would never have thought likely, and for blessing me with this insight into His creation. I thank him for the hope that He gives me through my Lord Jesus Christ, which enables me to overcome barriers and hardships, to endure suffering, and to continue to walk on the road He has laid before my feet. iii LIST OF PUBLICATIONS Patents Subcritical water Processing of Hydrophobic Pharmaceuticals, Combined patent with Professor Neil Foster and Dr. Raffaella Mammucari (Filed for provisional patent on 25th March 2010) Articles Carr, A., Mammucari, R. and N. Foster, The Solubility and Micronization of Griseofulvin using Subcritical Water. Industrial & Engineering Chemistry Research, 2010 (accepted February 2010) Carr, A., Mammucari, R., and N. Foster, The Solubility, Solubility Modeling and Precipitation of Naproxen from a Subcritical Water Solution. Industrial & Engineering Chemistry Research, 2010 (Accepted August 2010) Carr, A., Mammucari, R., and N. Foster, The Solubility and Solubility Modelling of Budesonide in Pure and Alcohol-Modified Subcritical Water Solutions, Journal of Supercritical Fluids, 2010 (Accepted July 2010) Carr, A., Mammucari, R., and N. Foster, Micronization of Budesonide using Pure and Alcohol Modified Subcritical Water Solutions, (Submitted to the Journal of Pharmaceutical Science, August 2010) Carr, A., Mammucari, R., and N. Foster, Subcritical Water as a Tunable Solvent for Organic Compounds (Submitted to the Journal of Chemical Reviews, August 2010) Conference Papers Adam G. Carr, R. Mammucari, N.R. Foster, “Subcritical Water as a Universal Solvent and Antisolvent for Active Pharmaceutical Ingredients”, International Symposium of Supercritical Fluids, Arcachon, France, May 2009 Adam G. Carr, R. Mammucari, N.R. Foster, “Subcritical water as an Innovative Green Fluid for Manufacturing Micronized Biomaterials”, ICONN 2008 meeting, Melbourne, Australia, January 2008 Adam G. Carr, R. Mammucari, N.R. Foster, “Subcritical Water as a Novel Fluid for Pharmaceutical Processing Medium”, AICHE Annual Meeting, Salt Lake City, Utah, USA, Nov. 2007 iv TABLE OF CONTENTS Abstract ..................................................................................................................................................................................i Acknowledgements and Thanks ............................................................................................................................... iii List of Publications .......................................................................................................................................................... iv 1. Thesis Introduction ................................................................................................................................................ 1 1.1. The Pharmacokinetics and Therapeutic Action of Selected APIs .............................................. 2 1.1.1. Pharmaceutical Action and Micronization ................................................................................ 2 1.2. Micronization Techniques ......................................................................................................................... 5 1.2.1. ‘Top-down’ Methods........................................................................................................................... 5 1.2.1. ‘Bottom-up’ Methods .......................................................................................................................... 7 1.2.2. Supercritical Fluid Micronization ................................................................................................. 8 1.2.3. Limitations of Rapid Precipitation Techniques ....................................................................... 9 1.2.4. Subcritical Water as an Alternative Solvent for Micronization ..................................... 10 1.3. Summary ........................................................................................................................................................ 11 1.4. References ..................................................................................................................................................... 12 2. Water as a Tunable Solvent for Hydrophobic Organic Compounds ............................................... 16 2.1. Introduction ................................................................................................................................................. 17 2.2. The Solubility of Organic Compounds in Subcritical Water ..................................................... 19 2.2.1. The Influence of Solvent Conditions ......................................................................................... 22 2.2.2. The Influence of the Solute ........................................................................................................... 24 2.3. Modeling the Solubility of Organic Compounds in Subcritical Water .................................. 30 2.3.1. Empirical Models .............................................................................................................................
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