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By Harry Darrow Brown

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This problem is far from resolved and a possible alternative to the simple notion of epitaxy has been presented by the present author. " I n this new (very tentative) hypothesis it is proposed t h a t nucleating agents are capable of inducing a rigid structure of water adjacent to the sub­ strate, b u t this structure is significantly different from the bulk structure. I n the transition zone between the two aqueous structures (the stabilized, vicinal structures and the bulk structure) m a y possibly exist a layer of enhanced disorder—the disordered layer in the the three-layer model of vicinal water (see Section I I I , D ) .

Recently, the present author has added to this t y p e of evidence an additional, independent set of arguments for demonstrating the probable structuring of w a t e r n e a r interfaces. C . EVIDENCE FOR VICINAL ORDERING BASED ON THERMAL ANOMALIES 1. Illustrative Examples T h e new evidence is based on the existence of t h e r m a l anomalies in t h e properties of vicinal water. I t appears t h a t these anomalies can best be in­ terpreted as manifestations of cooperative phenomena (order-disorder p h e n o m e n a ) , requiring t h e stabilization of structures which form co­ operative, large-scale entities among t h e molecules involved.

Finally, a v a s t literature exists on t h e polypeptides and proteins, b u t these systems are poor as model systems insofar as vicinal water structures are concerned because of the intrinsic complications which derive from the larger size of t h e solutes, the simultaneous presence of nonpolar, polar, and ionic groups, and conforma­ tional changes. 3. "Ice-Likeness" of Vicinal Water As discussed in various papers by the present author, it appears likely t h a t I c e - I h - l i k e structures m a y not play an i m p o r t a n t role in t h e structure of bulk (pure) water nor m a y such I c e - I h - l i k e structured units be present in ordinary solutions.

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