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

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

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Type
Article
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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.

Publication Date
2019-01
Online Publication Date
2018-07-25
Acceptance Date
2018-07-17
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
Journal ISSN
0022-3549
1520-6017
Volume Title
108
Publisher
Elsevier BV
Sponsorship
EPSRC (1198)
EPSRC EP/N022769/1