Publisher Summary This chapter describes many of the techniques employed to study water–macromolecules interactions, their general usefulness, points out areas of mutual support and contradiction. The chapter also presents hydration of other macromolecules and the hydration of small molecules. Four broadly based approaches to operational definitions of hydration include—(1) preferential hydration, (2) hydrodynamic hydration, (3) structural hydration, and (4) low temperature hydration. The use of high resolution X-ray and neutron diffraction data on protein crystals provides an independent approach for estimation of hydration. The chapter presents several proposals for predicting protein hydration based on the amino acid composition of the protein; however, the two main questions concerned include—whether ionic groups are more hydrated than other polar groups, and whether the amide and peptide functions are hydrated or not. Low pH, and to a much smaller degree, high pH should dehydrate proteins. Intermolecular association via ionic mechanisms should be strongly dehydrating; whereas hydrophobic interactions should not have much effect on hydration levels. Although, there is a presumption that both the enthalpy and the entropy are negative for the process of adding water molecules to isolated proteins, which are maintained in their native conformations, but there is no unequivocal evidence for this.

Hydration of Proteins and Polypeptides

Reaction of water vapor with α-Al2O3(0001) and α-Fe2O3(0001) surfaces : synchrotron X-ray photoemission studies and thermodynamic calculations

We have investigated hydroxylation and water adsorption on α Fe 2O3(0001) at water vapor pressures up to 2 Torr and temperatures ranging from 277 to 647 K (relative humidity (RH) < 34%) using ambient-pressure X-ray photoelectron spectroscopy (XPS). Hydroxylation occurs at the very low RH of 1 × 10-7 % and precedes the adsorption of molecular water. With increasing RH, the OH coverage increases up to one monolayer (ML) without any distinct threshold pressure. Depth profiling measurements showed that hydroxylation occurs only at the topmost surface under our experimental conditions. The onset of molecular water adsorption varies from ∼2 ×10-5 to ∼4 ?10-2 % RH depending on sample temperature and water vapor pressure. The coverage of water reaches 1 ML at ∼15% RH and increases to 1.5 ML at 34% RH.

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E McCafferty

Papers

Entropy of adsorption and the mobility of water vapor on α-Fe2O3