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Anomalies of water and its solutions, and the problem of sudden
nucleation in the phenomenology of biopreservation.
C. Austen Angell,
Dept. of Chemistry and Biochemistry, Arizona State University, Tempe, AZ85287-1604
Abstract
The formation of crystals during cooling of simple liquids is normally a mild process, as
metastability is relieved by a process of nucleation (usually heterogeneous and random) and the
growth of a modest number of separate crystals. However, there are cases in which it can be
sudden and explosive (Ref. 1, p.3)1 and if this would be the case for biological tissues being
processed for preservation, it would obviously be a very bad thing. Unfortunately, water and its
solutions provide one of the examples where this behavior may be encountered. We discuss the
background to the sudden nucleation phenomenon2,3, observed long ago without proper
understanding in concentrated ionic solutions4, describe other examples (never published) of an
exaggerated form of the same phenomenon when the initial vitrification was carried out under
pressure, and explain its relation to the famous anomalies of water. These we will link to
observations in related cases like the crystallization of liquid silicon, and the occurrence of nanodroplets of pure silica in many binary silicate glass systems. Finally, we will discuss the possible
relevance of some recent observations on benign interactions of biomaterials with certain
hydrated ionic liquids5, to a new "cryo-ionic" approach to biopreservation. (replace water by
gdm+ talk to zuofeng).
References.
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Angell, C. A. Liquid Fragility and the Glass Transition in Water and Aqueous solutions. Chem.
Rev. 102, 2627-2649 (2002).
MacFarlane, D. R., K., k. R. & Angell, C. A. "Direct Observation of Time-TemperatureTransforma-tion Curves for Crystallization of Ice from Solutions by a Homogeneous
Mechanism," D. R. MacFarlane, R. K. Kadiyala, and C. A. Angell, J. Phys. Chem., 87, 1094
(1983). J. Phys. Chem. 87, 1094-1097 (1983).
MacFarlane, D. R., Kadiyala, K. & and Angell, C. A. Homogeneous Nucleation and Growth of Ice
from Solutions: TTT Curves, the Nucleation Rate and the Stable Glass Criterion. J. Chem. Phys.
79, 3921 (1983).
Angell, C. A. & Sare, E. J. Liquid-Liquid Immiscibility in Common Aqueous Salt Solutions at
Low Temperatures,. J. Chem. Phys. 49, 4713 (1968 (1968).
Byrne, N., Wang, L.-M., Belieres, J.-P. & Angell, C. A. Reversible folding-unfolding aggregation
protection, and multi-year stabilisation, in high concentration protein solutions, using ionic
liquids Chemistry Communications, 2714 (2007).