NUCLEATION AND GROWTH-KINETICS OF BIOCHEMICALS MEASURED AT HIGH SUPERSATURATIONS

被引:65
作者
MAHAJAN, AJ [1 ]
KIRWAN, DJ [1 ]
机构
[1] UNIV VIRGINIA, CTR BIOPROC DEV, DEPT CHEM ENGN, CHARLOTTESVILLE, VA 22903 USA
关键词
D O I
10.1016/0022-0248(94)90468-5
中图分类号
O7 [晶体学];
学科分类号
0702 ; 070205 ; 0703 ; 080501 ;
摘要
A grid mixer device (characteristic micromixing time < 3 ms) was successfully used to measure both nucleation and growth kinetics of lovastatin in 60 vol% methanol and asparagine monohydrate in 50 vol% 2-propanol at 23 degrees C at high supersaturations but in the absence of mixing limitations. The supersaturation ratios investigated were in the range 1.25-8.8 for the lovastatin system and 1.17-4.1 for the asparagine system. When plotted according to primary nucleation theory, the induction time and nucleation rate measurements for both systems exhibited a homogeneous nucleation region at high supersaturations and a heterogeneous nucleation region at low supersaturations. The values of interfacial free energy extracted from these measurements for lovastatin (1.4-1.6 mJ/m(2)) and asparagine (4.5-6.1 mJ/m(2)) were an order-of-magnitude lower than those for inorganic salts reflecting the weaker intermolecular bonding in such biochemical solutes. The measured crystal growth rates for both solutes over the entire range of supersaturation could be represented with a power law dependence on chemical potential driving force. The kinetic orders of crystal growth were found to be 6.7 and 2.9 for lovastatin and asparagine, respectively. These unusually high kinetic orders could be represented by a polynuclear surface nucleation growth mechanism. The activation energy for the growth of lovastatin was measured as 280 kJ/mol.
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页码:281 / 290
页数:10
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