title: Correlation between chemical reactivity and the Hammett acidity function in amorphous solids using inversion of sucrose as a model reaction.
abstract: The goal was to evaluate the effects of acidity, expressed as the Hammett acidity function, on chemical reactivity in freeze-dried materials (lyophiles). Dextran-sucrose-citrate and polyvinyl pyrrolidone (PVP)-sucrose-citrate aqueous solutions, adjusted to pH values of 2.6, 2.8, and 3.0 were freeze dried, and characterized by X-ray powder diffractometry, DSC, isothermal microcalorimetry, and Karl Fischer titrimetry. Lyophiles were also prepared from identical solutions but containing bromophenol blue (BB). Diffuse reflectance-visible spectroscopy was used to measure the extent of BB protonation from which the Hammett acidity functions were determined. The stability studies were performed at 60 degrees C. All the freeze-dried samples were observed to be X-ray amorphous with <0.15% w/w water content. The T(g) of dextran lyophiles were approximately 20 degrees C higher than that of PVP lyophiles whereas enthalpy relaxation rates at 60 degrees C were similar. The Hammett acidity functions were significantly lower (i.e., higher acidity) for dextran systems (<2.2-2.6) when compared with PVP systems (3.3-3.9). The rate of sucrose inversion was significantly (an order of magnitude) higher in dextran lyophiles. This study showed that in amorphous matrices with comparable water content and structural relaxation times, chemical reactivity could be significantly different depending on the matrix "acidity".
authors.affiliation: College of Pharmacy, 308, Harvard St. S.E., University of Minnesota, Minneapolis, MN 55455, USA.
authors.forename: Koustuv
authors.initials: K
authors.lastname: Chatterjee
authors.forename: Evgenyi Y
authors.initials: EY
authors.lastname: Shalaev
authors.forename: Raj
authors.initials: R
authors.lastname: Suryanarayanan
authors.forename: Ramprakash
authors.initials: R
authors.lastname: Govindarajan
mesh_terms: D000143:Acids / Q000737:chemistry; D000465:Algorithms; D001978:Bromphenol Blue; D002152:Calorimetry, Differential Scanning; D002626:Chemistry, Pharmaceutical / Q000379:methods*; D004396:Coloring Agents; D005612:Freeze Drying; D005947:Glucose / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008956:Models, Chemical; D011108:Polymers / Q000737:chemistry; D012996:Solutions; D013056:Spectrophotometry, Ultraviolet; D013395:Sucrose / Q000737:chemistry*; D014867:Water / Q000032:analysis; D014961:X-Ray Diffraction