Thermodynamic and Kinetic Studies of Nucleation

Crystallization from solution is an important industrial separation and purification process.  The goal of the crystallization process is the control of crystal size distribution, crystal shape, and crystal solid form.  The first step in the crystallization process is the birth of the new phase which is known as nucleation.  Experimental studies of the thermodynamics and kinetics of nucleation processes are difficult because of the role of surfaces and impurities in aiding the nucleation process.  To eliminate these effects and get precise information,  studies of nucleation are conducted by the electrodynamic levitation of single solution droplets without a container.  This method allows precise study of thermodynamic properties of supersaturated solutions and through measurement of nucleation induction times, the kinetics of the process.  Current work is focused on these measurements in several different types of materials including proteins. 

Molecular Modeling

Molecular modeling employs inter-atomic potential functions to calculate interactions between atoms and molecules.  When applies to crystalline materials molecular modeling can yield interesting insights and results which cannot otherwise easily be obtained.  Current work employs molecular modeling for the study of impurity crystal interactions and their effect on crystal morphology, for the analysis of materials and methods which can be used to template crystallization  and for the identification and potential prediction of polymorphs of organic materials.  In addition,  molecular dynamic simulations are used to examine the mechanism by which additives are used as nucleating agents in polymers. 

Laser-induced Nucleation

Recent work has revealed that high intensity, non-absorbing laser pulses can induce nucleation in supersaturated aqueous solutions of organic materials.  Work in this area is focused on understanding the mechanism by which the laser aids in the nucleation process and as a probe for understanding the fundamentals of nucleation. 

Crystal Growth on Self-assembled Monolayers

It has been shown that self assembled monolayers can be used to template crystal growth by providing a surface which will aid in the formation of a particular crystal face or polymorph.  Work in this area is focused on the ability to predict in advance the properties of a particular monolayer and the likely crystal morphology and/or phase which will result from its use.

Park, K., Evans, M.B.J. and Myerson, A.S. (2003).  Determination of Solubility of Polymorphs Using Differential Scanning Calorimetry. Crystal Growth & Design, 3, 991-995.

Knezic, D., Zaccaro, J. and Myerson, A.S. (2004).  Thermodynamic Properties of Supersaturated Protein Solutions.  Crystal Growth & Design, 4, 199-208.

Devarakonda, S., Evans, M.B.J., Lee, A.Y., and Myerson, A.S. (2004).  Molecular dynamics study of the interactions of ice inhibitors on the ice {001} surface.  Langmuir, 20, 5353-5357.

Devarakonda, S., Evans, M.B.J., and Myerson, A.S. (2004).  Impact of ultrasonic energy on the flow crystallization of dextrose monohydrate.  Crystal Growth & Design, 4, 687-690.

Knezic, D., Zaccaro, J. and Myerson, A.S. (2004).  Nucleation induction time in levitated droplets.  J. Physical Chemistry B, 108, 10672-10677.

Chattopadhyay, S., Erdemir, D., Evans, J.M.B., Ilavsky, J., Amenitsch, H., Segre, C.U., and Myerson, A.S. (2005). SAXS Study of the Nucleation of Glycine Crystals from a Supersaturated Solution. Crystal Growth & Design,5, 523-527.

Hu, Y., Liang, J.K., Myerson, A.S., and Taylor, L.S. (2005). Crystallization Monitoring by Raman Spectroscopy: Simultaneous Measurement of Desupersaturation Profile and Polymorphic Form in Flufenamic Acid Systems. Industrial and Engineering Chemistry Research,44, 1233-1240.

134. Aber, J.E., Arnold, S., Garetz, B.A., and Myerson, A.S. (2005). Strong dc Electric Field Applied to Supersaturated Aqueous Glycine Solution Induces Nucleation of the γ Polymorph. Physical Review Letters, 94, 145503.

Mukuta, T., Lee, A.Y., Kawakami, T., and Myerson, A.S. (2005). Influence of Impurities on the Solution-Mediated Phase Transformation of an Active Pharmaceutical Ingredient. Crystal Growth & Design, 5, 1429-1436.

Yi, Y., Hatziavramidis, D., Myerson, A.S., Waldo, M., Beylin, V.G., and Mustakis, J. (2005). Development of a Small-Scale Automated Solubility Measurement Apparatus. Industrial Engineering Chemistry Research, 44, 5427-5433.

Matic, J., Sun, X., Garetz, B.A., and Myerson, A.S. (2005). Intensity, Wavelength, and Polarization Dependence of Nonphotochemical Laser-Induced Nucleation in Supersaturated Aqueous Urea Solutions. Crystal Growth & Design, 5, 1565-1567.

Lee, A.Y., Lee, I., Dette, S.S., Boerner, J. and Myerson, A.S. (2005). Crystallization on Confined Engineered Surfaces: A Method to Control Crystal Size and Generate Different Polymorphs. Journal of the American Chemical Society, 127, 14982-14983.

Sun, X., Garetz, B.A., Myerson, A.S. (2006). Supersaturation and Polarization Dependence of Polymorph Control in the Nonphotochemical Laser-Induced Nucleation (NPLIN) of Aqueous Glycine Solutions. Crystal Growth & Design, 6, 684-689.

Lee, A.Y., Lee, I.S., Myerson, A.S. (2006). Factors Affecting the Polymorphic Outcome of Glycine Crystals Constrained on Patterned Substrates. Chemical Engineering & Technology, 29, 281-285.