Drost-Hansen temperatures, 182

It has been suggested from time to time that the properties of water undergo more or less sudden transitions at several discrete temperatures. Mention of this phenomenon in the literature is quite scattered, however, and until recently, fairly little attention has been paid to these anomalies. Dorsey (26) has indicated the possible existence of anomalies in water properties while other authors have discussed one or more specific examples of unexpected temperature dependences. More recently, Drost-Hansen and co-workers (28, 29, 30, 31, 32, 33, 34, 35) have compiled examples of these anomalies and attempted to explain their origin qualitatively in terms of higher-order phase transitions in the structure of water. 

Unexpected but often abrupt changes in the properties of aqueous interfacial systems with temperature constitute one of the unique characteristics of vicinal water. Attention has already been drawn to the anomalies observed by Etzler in the specific heat values of vicinal water. Evidence of abrupt changes in the properties of both pure water and aqueous solutions have been studied in the past, but it was not until 1968 that it became clear that although unusual changes in some aqueous properties do indeed occur, they are associated only with interfacial water and not bulk water or bulk aqueous solutions (see Drost-Hansen, 1965, 1968, 1969). 

Thermal anomalies in water near surfaces as diverse as diamond, glass, quartz, clays, mica, fatty acids, chondroitin 4-sulfate, polystyrene, polyvinyl acetate, cellulose, gelatin, and other biomacromolecules (such as enzymes and other proteins) in solution are known to occur close to the critical temperatures. Tj has also been shown to be unaffected by the concentration of electrolytes in solution. The concentrations of alkali chlorides (Li% Na", K, Rb and Cs" ) were varied by a factor of ICf with no detectable systematic effects on Tj (Drost-Hansen, 1985). However, the evidence for the paradoxical effect does not rely solely on the substrate independence of Tjj. 

It is clear that the evidence for vicinal hydration of macromolecules in solution may be indirect or circumstantial, but it cannot be readily dismissed. A vast literature exists on the effects of temperature on rates of enzymatic reactions. It is our view that in many cases, where sufficiently closely spaced data are available, distinct changes in the rate of enzymatic reactions occur at or very near 15°, 30°, 45°, and 60°C. It thus seems reasonable to assume that vicinal water is present and manifests its existence by affecting the rates of the reactions. For a fuller discussion of the evidence for the occurrence of kinks in enzymatic rate data, see Drost-Hansen (1971, 1973) and Etzler and Drost-Hansen (1979). 

Drost-Hansen, W. (1973a). Aspects of the relationship between temperature and aquatic chemistry (with special reference to biological problems). U.S. Senate Committee on effects and methods of control of thermal discharges. Part II, Serial 93-14, November 1973, pp. 847-1140. Available from U.S. Government Printing Office, Washington, DC. 

Drost-Hansen, W. Neill, H. W. (1955). Temperature anomalies in the properties of liquid water. Phys. Rev. 1(X), 1600. 

Drost-Hansen, W. Lavergne, M. (1956). Discontinuities in slope of the temperature dependence of the thermal expansion of water. Naturwissenschaften 43,511. 

There is a surprising paucity of data relating to the effects of temperature oh simple membrane systems. In our laboratory (Drost-Hansen, 1970), we have... 

Figure 6. Potential difference across cell wall in the (large) green photosynthesizing alga Valonia utricularis as a function of temperature. Note abrupt changes near 15° and 29°C. (From Drost-Hansen and Thorhaug, 1967).

Based on surface tension measurements using the rise height of water in narrow capillaries and then obtaining the entropy term by numerical differentiation of the data, Drost-Hansen (1965) found a large peak in entropy of surface formation near 30 C. This is taken to mean that vicinal water is disorganized at 30°C (see also Drost-Hansen, 1973). Another example is provided by the data of Wershun (1967), who studied the effects of temperature on chromosome aberration rate in the broad-leaf bean Viciafaba. As shown in Figure 7, a notable peak occurs at 30°C. 

Figure 7. Rate of chromosome aberration in the broad leaf bean V/c/a iaba as a function of temperature. Note sharp peak near 30 C. (From Wersuhn, 1967 see also Drost-Hansen, 1981).

Figure 8. Percentage survival of the alga Valonia ventricosa after 3 days of exposure to various temperatures. Note changes near 15-16 and 31-32 C. (From Thorhaug, 1976 see also Drost-Hansen, 1981).

Drost-Hansen, W. (1981). Gradient device for the study of temperature effects on biological systems. J. Wash. Acad. Sci. 71, 187-201. 

Drost-Hansen, W. Thorhaug, A. (1967). Temperature effects in membrane phenomena. Nature 215, 506-508. 

Oppenheinier, C. H. Drost-Hansen, W. (1960). A relationship between multiple temperature optima for biological systems and the properties of water. J. Bacteriol. 80,21-24. 

The results agree with the notion of the microcavity (voids, pockets) structure of protein molecules (Kraivyaryainen 1980) according to which the protein molecule may be represented as an entity of spatially separated hydrophobic, hydrophilic, and mosaic cavities. Organic substances concentrated in such cavities behave like a liquid in a confined volume for which in a number of cases a rise in the temperature of freezing of water has been recorded (Drost-Hansen and Etzler 1989). 

Drost-Hansen, W. Temperature effects on cell-functioning—a critical role for vicinal water. Cell Mol. Biol. (Noisy-le-grand). 2001,47, 865—883. 

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