Repository logo
 

Freezing of Aqueous Solutions and Chemical Stability of Amorphous Pharmaceuticals: Water Clusters Hypothesis.

Accepted version
Peer-reviewed

Type

Article

Change log

Authors

Shalaev, Evgenyi 
Soper, Alan 
Zeitler, J Axel 
Ohtake, Satoshi 
Roberts, Christopher J 

Abstract

Molecular mobility has been traditionally invoked to explain physical and chemical stability of diverse pharmaceutical systems. Although the molecular mobility concept has been credited with creating a scientific basis for stabilization of amorphous pharmaceuticals and biopharmaceuticals, it has become increasingly clear that this approach represents only a partial description of the underlying fundamental principles. An additional mechanism is proposed herein to address 2 key questions: (1) the existence of unfrozen water (i.e., partial or complete freezing inhibition) in aqueous solutions at subzero temperatures and (2) the role of water in the chemical stability of amorphous pharmaceuticals. These apparently distant phenomena are linked via the concept of water clusters. In particular, freezing inhibition is associated with the confinement of water clusters in a solidified matrix of an amorphous solute, with nanoscaled water clusters being observed in aqueous glasses using wide-angle neutron scattering. The chemical instability is suggested to be directly related to the catalysis of proton transfer by water clusters, considering that proton transfer is the key elementary reaction in many chemical processes, including such common reactions as hydrolysis and deamidation.

Description

Keywords

amorphism, chemical stability, deamidation, freeze-drying, lyophilization, protein formulation(s), solid-state, stability, structure, water sorption, Chemical Phenomena, Chemistry, Pharmaceutical, Drug Stability, Freeze Drying, Freezing, Hydrolysis, Solutions, Temperature, Water

Journal Title

J Pharm Sci

Conference Name

Journal ISSN

0022-3549
1520-6017

Volume Title

108

Publisher

Elsevier BV
Sponsorship
EPSRC (1198)
EPSRC EP/N022769/1