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Old Ex Marischal College Paper on Water Structure

Old Ex Marischal College Paper on Water Structure

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The supramolecular structure of liquid water is probably of critical importance to the existence of life.
This review article although written some time ago is thought to remain of topical interest
The supramolecular structure of liquid water is probably of critical importance to the existence of life.
This review article although written some time ago is thought to remain of topical interest

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Published by: Newdeersci on Jul 19, 2010
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This document is thought to be of continued interest to the scientific community.

It is a literature survey drafted in 1992, but remained unpublished because of laboratory closure. Other related articles D Grant, WF Long & FB Williamson which were published at the time of writing are listed at web.abdn.ac.uk/~bch118/publications2003march.doc,

The Structure of Water and Hydrates- Its Importance to Biology
D. Grant, Department of Molecular & Cell Biology Marischal College University of Aberdeen Aberdeen AB9 1AS Scotland , UK (Drafted by D.G. in 1991, transferred to modern electronic format 18/4/08)

Water is, by far, the most abundant molecular component of biological cells and, it may be argued, it’s a pre-requisite for life is a likely requirement for pre-biotic evolution (Stillinger 1980). Those polymeric systems which have the ability to form a range of highly hydrated gels such as amorphous silicas may have been critical components of such evolution (Grant et al. 1992). Water structure and water activity and their alteration by physiologically-active substances may therefore have a fundamental importance to biological function; a corollary to this is that those agents which have a special influence upon water structure may also be active physiologically. Thus physiological metal ions, nucleotides and biopolymers such as glycosaminoglycans, proteins and polyamines inter alia are expected to have important effects on water structure. Alteration of water structure associated with glycosaminoglycans has also been suggested (Grant et al. 1985, 1992a) to be implicated in cellular transformation in cancer and during cell division in mitosis and to be involved in cellular adherence (Grant et al 1985, Curtis et al. 1988, Grant et al. 1992b) including in the mechanism of cellular adherence to substrates (Curtis et al, 1989) as indicated by a dependence of adherence of BHK cells on growth surface hydroxyl group spacing. Anti-inflammatory drugs were suggested (Warner 1973) to possess key functional groups positioned in such a way as to

interlock with the crystal structure of ice as is the case with hydrocortisone, aspirin, indomethacin , flufenisal and naproxen; water molecules in cell membranes were also believed to be similarly ordered. The discontinuity in water associated molecules detectable by near i.r. spectroscopy at near 37C (Luck, 1964) may suggest that this is common homo-isothermal temperature is used by many species allowing advantage to be taken by them of a rapid change in water structure in this temperature region perhaps finding use for this in anti-microbial defence. Biopolymers, including nucleic acids, proteins and glycosaminglycans are highly hydrated ; such coordinated water molecules may be important for stabilising conformations and for the modulation of the reactivity of these molecules. In the cases of the glycosaminoglycans, the anionic groups display different water binding tendencies, that of the -SO3- group being especially high (cf. Zundel & Murr, 1969; Atkins, 1974). Hydrating water molecules may be highly mobile, rapid reorientation typically being about an order of magnitude slower than the corresponding process in bulk water (Piculell, 1985). Organic solvent water mixtures contain water monomer dimer, timer or tetramer and in some cases where water could bind to phosphoryl groups, high polymer equilibria involving water ; organic solvents with a single base site were believed to stabilise a cyclic water trimer (cf. Johnson et al, 1967). The unusual behaviour of water towards non-polar solutes and non-polar side groups attached to biopolymers has long been recognised (Stillinger, 1980) and termed “the hydrophobic bond”. Typical non-polar solutes which can induce hydrophobic bonding are the noble gases and hydrocarbons; none of these molecules can hydrogen-bond to water and all are sparingly soluble in water but dissolved in water they cause water “structure making” between the water molecules by reorganising the random hydrogen-bonding network of liquid water; computer modelling shows that insertion of inert space-filling entities in liquid water

causes the hydrogen bond network to rearrange to form a local clatharate-like, imperfect-convex-cage; another aspect of the hydrophobic interaction concerns the orientation preference of water molecules next to a non-polar solute - the water molecules tend to straddle the inert solute, pointing two or three tetrahedral directions tangential to the surface of the occupied space and forming water cluster polyhedra like those present in supercooled water (Stillinger, 1980). Pairs of non-polar solutes in water experience an entropy-driven net attraction for one another (part of the origin of the hydrophobic bond) which may determine the native conformation of biopolymers. For water at around room temperature and below, it has been demonstrated by computer simulation (Geiger et al, 1979; Stillinger, 1980) that the liquid lies above the “critical percolation threshold” for hydrogen-bonding; i.e. any macroscopic sample of the liquid will inevitably will have un-interrupted hydrogen-bond paths running in all directions, spanning the entire volume of the sample, being analogous to a gel point. These network pathways, which are random, but with a local preference for tetrahedral geometry, but containing a large proportion of strained and broken bonds, provide natural routes for rapid transport of H+ and OH- (a proton hole) ions by a directed sequence of exchange hops; the strained hydrogen-bonds appear to be more reactive and to be important kinetically (Stillinger, 1980). Studies of supercooled water by Angell et al. (1980) suggested that an anomaly occurs at –45C which is somewhat below the experimental limit of supercooling attainable easily, but this indicates the working of a structural order-disorder phenomenon in the hydrogen-bonded network of supercooled water; it was thought that the unusual properties of supercooled water were mainly caused by the concentration and spatial distribution of the relatively unstrained and hence bulky hydrogen-bond polyhedra embedded within and linked to the random network, possibly including an octameric unit similar to that which occurs in hexagonal ice. These polyhedra were thought to share edges without the introduction of mutual strain, consequently they are able to link up with one another more

readily than a strained and an unstrained polyhedron can, so that the ideal unstrained structures find it advantageous to clump together. At temperatures close to 0C the infrequent unstrained polyhedra can form a dilute “gas” dispersed throughout the predominantly strained and defective network, but as the temperature declines, the polyhedra become more and more frequent since they incorporate stronger hydrogen-bonds, the cluster sizes evidently diverge as the T approaches –45C. Study of the OH-stretching region of the Raman spectrum of aqueous solutions provides a sensitive method of detecting of structure –breaking and structure making effects of solutions when compared to pure water. The 3650cm-1 region of the spectrum of liquid water is considered to be due to nonhydrogen-bonded OH oscillators and the region near 3250cm-1 to OH oscillators vibrating in phase and involved in a fully hydrogen-bonded tetrahedral assembly of five H2O molecules. Loss of intensity in this region is observed for aqueous sugar solutions relative to pure water, indicating a decreases in the the concentration of OH oscillators involved in such an in-plane motion. ClO4- which does not form H-bonds, has an opposite effect to sugars on the water structure (Walrafen & Fischer, 1986); ClO4- efficiently breaks up water structure as confirmed by the increase in the intensity of the absorption due to dangling OH oscillations at 3570cm-1. Luck (1966) studied fundamental, combination and overtone vibrations of water molecules in clusters and estimated the proportion of free OH groups as a function of temperature up to the critical point. The results suggested that the extent of the hydrogen-bonding systems in the neighbourhood of the melting point amounted to several hundred H2O molecules. The υ 1 of H2O in monomer, dimer, trimer, tetramer and polymer was suggested to be 3725, 3700, 3545, 3510, 33980 and 3355cm-1 respectively. The angular dependence of the shift caused by hydrogen-bonding in the H2O, H-O fundamental vibration frequency was also reported by Luck. Free OH, in un-bonded H2O absorbs at 8748cm-1, free OH in H2O molecules with one

free OH group, OH group in a hydrogen-bond in a cyclic double bridge between two H2O molecules having bond angle of 109o. Water bridges may interlink basic amino acids resides with heparin (Grant et al, 1991) and have relevance for glycosaminoglycan-protein binding, particularly in a pericellular environment. It should be noted that water has a number of unusual properties with anomalies in practically every single one of its physical properties; e.g. it increases in volume on freezing, it has a density maximum at 4C, an isothermal compressibility minimum at 46C, has a high dielectric constant, anomalously high melting, boiling and critical temperatures, shows increasing liquid fluidity with increasing pressure, the heat of melting is only 13% of the sublimation energy of the solid and has a high mobility for transport of H+ and OH- ions (Stillinger, 1980) and has a highly anomalous surface tension, attributable to a highly preferential internal orientation of the hydrogen bonds (Bernal, 1965). It might have been expected on comparison with H2S that water would have been a gas at room temperature; indeed H2S, on account of its greater molecular weight, might have been expected to have a more coherent structure. A consideration of complex dimensionality of the crystalline state as discussed by Bernal suggests that while liquid water possess a lower degree of order than allowed for in traditional crystallography, the structure of water may, however, be conceived as having crystallinity in the sense that liquid water is a state of ordered matter, demonstrating a gradation between the three-dimensional crystalline state and the liquid state which under ideally limiting conditions would exhibit a nodimensional-order (exemplified by liquid mercury); biological membranes also possess a type of crystallinity less than three dimensional in this case they contain two-dimensional crystallike order. Water molecule aggregates, evidently up to several

100A in size, might also be considered to be a branch of colloidal science (Bernal, 1965) cf., also Stillinger’s (1980) discussion of supercooled water. The sort of order apparent in “ amorphous” silicates, e.g., as suggested by 29Si nmr spectra of sodium silicate and possibly capable of nucleating similar ordered “amorphous” particles (Grant et al. 1992) may be in some way analogous to the type of ordered structures present in liquid water. When units have low symmetry, whether intrinsically or by random movement, or made random by relatively rapid structure alterations, it is impossibly to obtain regular three-dimension arrangements over time scales required for diffraction measurements of crystallinity (Bernal, 1965); the possibility of nucleation of low-order crystal aggregate structures in liquid water, should be considered; particular nucleating agents might have the property of nucleating slightly different distribution of water aggregates, at least on a short enough time scale which retain physiological activities; convincing experimental methods for the detection of such possibilities have evidently yet to be developed. Possible nmr evidence for water aggregates similar to those in amorphous silicates (detectable by high resolution 29Si nmr) comes form the coalesced proton average nmr spectrum of water molecules in hydrocarbon mixtures which showed different chemical shifts and peak widths for water aggregates composed of in differently shaped micelles containing different quantities of stabilising oil and surfactant molecules (Shah & Hamlin, 1971). Long-range, thermodynamically metastable, but with long term stability quasi-periodic order is exhibited by quasicrystals with crystallographically-forbidden symmetries (cf. Fujiwara & Ogawa, 1990). New theories of crystallinity of which the fivefold rotational symmetry may be but one facet, may have some relevance for random assemblage of low order aggregates of crystallite-like water structures. Benveniste (cf Davenas et al. 1988) suggested the existence of “ghost”, putative water-memory-structures in very dilute

aqueous solutions of physiologically active agents by using immunological methods (the procedure employed in these experiments has, however been vigorously criticized). The numerous crystalline polymorphs of solid water, at least nine in number, include some that form at elevated pressure (Stillinger,1980) seem to lend weight to possibilities that liquid water could contain perhaps under different stimuli, a variety of different low order metastable crystalline structures which might nevertheless be capable of different physiological interactions. The properties of water depend on how far the hydrogen is form the oxygen, i.e., the acidity of the medium. At low pH the hydrogen moves out from the oxygen as far as 1.05A; at high pHs it moves to 0.85A, in neutral water it is at 0.96A (Bernal, 1965). The results of quantum mechanical studies lend support to a notion, that of Frank and Wen (1957) and Frank (1958), that hydrogen bonding in water is “cooperative” (Stillinger, 1980); the hydrogen bonds mutually reinforce each other, encouraging chains of hydrogen-bonds to form. A calculated hydrogen-bond pair occurrence potential as a function of pair potential at different temperatures indicates an invariant point at –4kcal/mol , suggesting that a thermally activation bond breakage occurs which transfers pairs across this invariant point as the temperature rises (Stillinger, 1980). Water is known to possess unusual proton transfer properties which are of importance to its chemistry. The symmetrical hydrogen-bonded H5O2+ and H5O2+(H2O)4 studied by ab initio calculations by Muniz et al (1985) suggested that the energy minimum of the former cation in which the proton is located midway between the two hydrogen atoms is broken down by solvation into two minima corresponding to structures with unsymmetric hydrogen-bonds. When considering an adiabatic transfer model, solvation parameters were suggested to take part

in the reaction coordinate of the proton-transfer model, the inversion of solvation distances produces spontaneous proton transfer, the proton adjusting its position to the changes in solvation. Given that there is an unsymmetrical contracted hydration shell around the H3O+ unit, and an expanded one around the H2O part of the cation, the symmetry of the energetic profile was suggested to be destroyed if solvent relaxation was not allowed, this being supposed to prevent proton tunnelling from taking place; in order for this to occur, the symmetry of the energy profile had to be re-established by means of solvent movement to make the hydration shells around the two water molecules between which the proton is transferred, identical. Ling (1973) has stressed the role of “ structured” water in cellular phenomena, e.g. on the permeability properties of natural membranes which are extremely permeable to water molecules in disagreement with a hydrocarbon solubility theory of permeability. A possible model for the water permeability was considered to be cellulose acetate film, where gaps between the cellulose acetate fibres are filled with water channels in which the water occurs as a polarised multilayer structure (cf. Anon. 1973). High and low density forms of liquid water can be shown to exist in cellulose acetate and in gels (Wiggins, 1995); the low density form of water exists at weakly hydrogen-bonding or hydrophobic surfaces; both high and low density forms can coexist in polyelectrolyte solutions as well as in gels. The formation of different kinds of water can explain the hydrophobic interaction, the attractive hydration force and the mechanisms of the high and low temperature denaturation of proteins. Such structural water channels in polysaccharide gels and effects of cations on them, may be probed by X-ray diffraction analysis of oriented hydrated fibres (Arnott, 1989). Similar studies carried out with glycosaminoglycans (Atkins, 1974)

showed that the conformation of the polysaccharide and the degree of hydration may be dependent on the cations present. Aspects of such hydrated gel structures are relevant to an understanding of biological tissue both multi-cellular extracellular and cytosolic. The arrays of microtubules which are arranged in parallel arrays in axon, cilia, mitotic spindle and other cellular formations participate in many cellular processes, including directed division, exitability etc., and show a dependence on the electric events occurring at the level of the cell surface or cytoplasmic organelles, naturally occurring fields in the range 20-500mV/cm have been implicated (Jaffe & Nucitelli, 1977). Microtubules were found to align in parallel arrays and may be involved in the mechanism of the action of electromagnetic fields on some bio-molecular processes (Vassilev et al. 1982). The Hofmeister series ranks the potency of aqueous soloutions of ions for the denaturation of proteins. The molecular origin of the series is not known but it is believed to be related to the water structuring ability of the ions. Geometric molecular structure of water & related (e.g. the Frank &Wen, Bernal & Fowler and Pauling Models) The detailed molecular structure of water is as outline above is essentially unknown; one suggested model of liquid water is that flickering clusters (Frank & Wen, 1957) in which individual molecular aggregates are held together by hydrogenbonds continually rearranging, the precise arrangements and rate of interchange can be conceived as being alterable by solutes. The presence of water molecule aggregates of a quartz-like structure was proposed for liquid water by Bernal & Fowler (1933) based on the known crystalline ice structures, and 46 molecule aggregate of poly-pentagonal dodecahedral structures, by Pauling (1959); these structures were based on atomic radial distribution curves determined by X-ray diffraction, there is a problem of accomodating various fixed structures of aggregates

to the density, dispersion of dielectric constant and the known structure of ice, which has several forms). Leyendekkers (1985) explained the anomalies in the heat capacities and acoustic characteristics of water in terms of unbonded and singly bonded water molecules attached to aggregates, the transitions of these special water molecule environments probably were the critical factor underlying the anomalous properties of water and an activation mechanism of an equilibrium involving their rearrangements governing gas phase transition of “the second kind”. The experimental values of un-bonded water molecules used in these calculations (for H2O) at different temperature and pressure was reported by Luck (1980) from the near i.r. (NIR) spectrum of water. Luck (e.g.1975) reported the i.r. spectra of H2O in the temperature region from -50C to 400C showing that H2O , as well as CH3OH and C2H5OH , possessed less non-Hbonded OH groups than most theories of liquids claimed. An exact interpretation of the i.r. spectra was not possible, but the model of the structure of liquid water which was adopted had flickering clusters possessing fissure planes consisting of free OH groups dividing groups with closed H-bonds in ice-like structures. The smaller proton mobility in liquid water in comparison with that in ice had to conform with the presence of large clusters. The mobility of the cluster surfaces was believed to determine mobility in the liquid state. Long range order The origin of this order was far form clear and its spatial extent is a matter for controversy (Franks 1979). The degree of orientation of water on extended surfaces varies considerably. Near the surface, up to 10-20A distant, water is believed to be bound in the form of ice. Beyond that, up to 100A or so, the water is less tightly bonded and is able to accommodate ions, though with restricted possibilities of movement. This is about the limit to which the structure of water itself is liable to be affected by hydrophilic surfaces. However beyond that there is

an influence exerted thought water for quite great distances, measured up to 4000A but probably further (cf. a colloidal sol, long range force, cf. the co-acervate phenomenon (Bernal, 1965). Bernal hypothesised that in other than very primitive cells, there was an almost complete lack of spherical organelles; water in contact with the rough side of the endoplasmic reticulum and the cristae of the mitochondria was more viscous being in a partly gel-like state than water on the smooth side named by him the endolymph) which was seen to communicate with the extracellular water, even when the membrane is continuous, by a process of forming and separating of small globules of liquid (micro-pinocytosis). No part of the cell except that in the interior of vesicles was at a distance of more than a few hundred A from some other part of the membrane and consequently a force should always act between them producing interacted water molecules.

The rate-determining processes in crystallization from aqueous solutions of Ca salts such as CaCO3, are likely to involve water molecules in the transition states of the rate determining reactions, since these ions are hydrated in solution but become dehydrated in the insoluble salt crystalline forms. CaCO3 exists in many forms, the nucleation of which demonstrated the “non-genetic inheritance of form” as was ponted out by Lima de Faria (1986) this may provide a clue about the fundamental processes inherent in both crystal and cells about which, e g. for the molecular mechanism of crystallization and nucleation, little is known, but which if understood, might shed further light on the still less understood biological non-genetic determined processes. Of these, aspects of water structuring may be involved in the control of crystallization from aqueous solution.

Modulated r.f./microwave fields modify calcium binding at cell surfaces and modulate a host of calcium dependent intracellular enzyme mechanisms which regulate the flow of intracellular messages (protein kinases), cell metabolites and cell growth; the use of imposed fields might reveal the essential importance of biological organization at the atomic rather than the molecular level and in physical rather than chemical terms; with coherent states between adjacent molecular electric charges and enormous co-operativity in energy release by very weak triggers as the physical essence of living matter (Adey, 1988). Nucleation of ice crystal formation is more directly involved with ice nucleation bacterial Erwina ananas, which was increased with increasing supercooling and required the presence of a water glass interface; the nucleation was inhibited by sugar (Watanabe & Arai , 1987). Silica is formed of joined tetrahedra in a similar fashion to joined hydrogen-bonded water tetrahedra; this appears to allow silica gels and water structures to be mutually accommodating. Similar considerations apply to sugars and polysaccharides cf., the water structuring properties of glycosaminolycan-rich extracellular space and to such materials as polyacrylamide gels; phase transitions occur in these latter materials, considered (Tanaka et al. 1982) to be as a consequence of change in the balance between three classes of forces which contribute to the osmotic pressure in the gel viz., 1) rubber elasticity, 2) polymerpolymer affinity and 3) the hydrogen ion pressure (Tanaka et al. 1982); drastic changes in the state of a gel can be brought about by small changes in the external conditions (e.g. temperature, pH, ionic conditions or solvent). Gels share mathematics with other critical processes (chaotic processes-the possibility that at least some biological control mechanisms may straddle potential chaotic systems of such water-rich gel systems might be worth considering, e.g. the effect of small changes in ionic [e.g. Ca2+]

concentrations); in the gels fluctuations create local variations in the density of the polymer networks so that small aggregations of polymer are constantly forming and disintegrating ; a divergence of scattered light occurs at the critical point where the polymer network becomes infinitely compressible; this can be considered in terms of phase transitions and critical phenomena. The Rees (1968) hypothesis of polysaccharide gels gives an equivalent model of a similar phenomenon where the points involving the cooperative association of long regions of m polymer chains occur, so that sol-gel transformation may involve a conformational change (Bryce et al. 1974). Various gel-like mixtures (electro-rheological [ER] fluids ) may contain e.g. silica, water and polyelectrolytes (however although systems without water have been described particularly good ER systems contain water) which exhibit applied-voltage-dependent gel formation, have been formulated by empirical methods (Webb, 1990). ER fluids are able to convert rapidly (millisecond) and repeatedly between a fluid and a solid when an electric field is applied or removed (of interest for mechanism (such as clutches etc. in robotic systems). It seems possible that alteration of gelation by modulation of hydrogen-bonding arrangements in H2O polyhedra or related hydrogen-bonded clusters, is the basis of the mechanism of action of these fluids; lack of understanding of the molecular origin of these phenomena has, however, apparently severely limited the development of ER fluids for engineering use. Vibrational spectroscopy, especially near i.r. spectroscopy, gives insight into water structure (cf Luck, loc cit; Symons, 1989). Whilst the band positions observed are known to correspond to combination and overtone bands, the causes of relative intensities in the near i.r. are less understood. There is an apparent lack of any direct correlation between hydrogen-bond strength and water structure from consideration of i.r. spectra of H2O and D2O (Bonner & Curry, 1970). Consideration of the

expected effects of hydrogen-bonding, however, seems to suggest more complex than-hitherto-appreciated aspects of water structures, cf. the much greater than expected observed difference between the n.m.r. signals of 18O(-H2O) compared with 16O-(-H2O) when observed for water which is hydrogenbonded to organic molecules (Pinchas & Meshulam, 1970). The enthalpies and entropies of transfer of non-electrolytes and individual ions from H2O to D2O show linear correlation (compensation effect). These results were interpreted as indicating that “ there seems to be a wide variety of perturbations of liquid water which evoke the same type of response in water”. Even for relatively strong aqueous solutions there is evidence for structural arrangements characteristic of the bulk structure of water which are unaffected by the presence of the solute, even in rather high concentrations of electrolytes (Drost-Hansen, 1971). The factors giving rise to entropy-enthalpy change correlations as well as the detailed structure of water have not been established , but it is evident that such knowledge, if achieved, might aid a fuller understanding of fundamental biological processes. Plasma membrane lipid head groups are hydrated and this is believed to be involved in their phase transitional behaviour. This phenomenon can be studied in a water-tetradecane solvent system (Rand et al. 1990) where inverse hexagonal phases containing cylindrical water cores can be detected. It was necessary to take into account two modes of interaction between lipid polar groups and molecules, one mode of interaction being of a “ normal” solvation (solvent affinity type, due to hydrogen bonding of the solute with water) and the other (a mode of interaction resulting from the geometrical properties of lipid bilayers when large amounts of water molecules are taken up by them [“non-local” solvation] which was thought to arise when a spontaneous curvature of the lipid mono-layers creates a free-energy minimum in a type of geometry which is

able to create voids or low-density regions in the liquid crystalline structure, voids that are filled with compatible water. Without enough water the hydrophilic cores of the hexagonal II phase was considered to shrink; without enough alkane, the inverse hexagonal phase often simply ceased to exist; curvature energy was evidently important for membrane hydration in the above situations. Crystal deposition diseases of the joints are age-dependent and may be related to parallel age-dependent changes in the joint glycosaminoglycans; highly hydrated joint proteoglycans secreted by chondrocytes occur adjacent to a calcified (hydroxyapatite) zone interlocking with bone, the glycosaminoglycans are predominantly chondritin-6-0-sulphate and keratan sulphate arranged like a bottle –brush on a protein core (cf. Dieppe & Calvert, 1983). Such sulphated polysacharides may be capable of producing both hydrophobic and hydrophilic forces at interfaces. Sequences of hydrophilic and hydropobic regions may also occur in heparan sulphate (more hydrophobic NAc-rich regions occur in blocks). Studies of adsorbed double-chained quaternary ammonium salt on mica indicated that hydrophobic forces are strong and longranged. Similar hydophobic processes may also play a key role in biological self-assembly processes. Long-range forces reflect interactions due to surface-induced water structure and are 10 to 100 times stronger than the van der Waals forces that would operate in the absence of any surface-induced order in water. The situation is in direct contrast with that observed for hydophilic bilayers where the forces have been indicated to be short range (Pashley et al. 1985). Electric fields, e.g., generated by Ca2+, can influence the proton potentials of C-OH…-O-P…HOP bonds (Schioberg & Zundel, 1976) as well as by their degree of hydration (Carmona &

Garcia-Ramos, 1985) and thereby possibly also affect water structures. Bulk diamagnetic susceptibility differences may occur between water spheres, cylinders and lamellae, producing difference in the n.m.r. spectra as well as characteristic electrical and birefringence effects (Shah & Hamlin, 1971). References Adey T (1988) Nature 333, 401 Amost LA (1982) In “Electron Microscopy of Proteins” (Ed. JR Haris, Vol III pp 207-250, Academic New York Angel CA in “Water, a comprehensive treatise” Ed F Franks, Plenum, New York, 1980, cf. Stillinger (1980) Anon (1973) New Scientist 20 September p 670, cf. also ibid., 59, p. 378 Arnott S (1973) Roy Soc Chem Carbohydrate Groups Spring Meeing Cranfiedl p. 29-31 Atkins EDT et al. (19731,) Polymer 15 263-271 Bernal JD (1959) in “Hydrogen bonding, Proc Symp Ljubliana 1959 Ed Hadzi D & Thompson HW, Pergamon Press London, New York Paris & Los Angeles p. 7-22 Bernal JD (1965) Symp Soc Exptl Biol 19 17-32 Bernal JD & Fowler RH (1933) J Chem Phys 1, 515Bonner OR Curry JD (1970) Infrared Physics 10 91-94

Bryce TA McKinnon AA Morris ER Rees DA Thom D (1974) Faraday Discuss Chem Soc 57 221-229 Carmona P Garcia-Ramos JV (1985) J Chem Soc Faraday Trans 2 929-935 Curtis ASG et al. (1986) J Cell Sci 86 9-24(1983) j Cell Biol 97 1500-1506 Cf. Curtis ASG McMurray H ibid 86 25-33 Davenas E et al. (1988) Nature 333 816-818 Dieppe P Calvert P (1983) “Crystals and Joint Disease” Chapman & Hall London Drost-Hansen W (1971) in “Structure and Properties of Water at Biological Interfaces” in Chemistry of the Cell Interface Vol 2 p 1-184 (HD Brown Ed) Frank HS (1958) Proc Roy Soc Lond Ser A 247 481Frank HS Wen WY (1957) Discuss Faraday Soc 24 133 Franks F (1979) (Ed.) Water, a comprehensive treatise Vol 6 p.16 Fujiwara T & Ogawas T (Eds.) (1990) Quasicrystals, Proceedings of the 12th Taniguchi Symposium, Shima, Mie Prefecture, Japan, 14-19 November 1989, Springer-Verlag, Berlin, Heidelberg, New York, Paris, Tokyo, Hong Kong, Barcelona Geiger A Stillinger FH Rahman DATA J Chem Phys 70, 4185

Grant D Long WF Williamson FB (1985) Biochem Soc Trans 13 389 Grant D Long WF Williamson FB (1991) Biochem J 277 569571 Grant D Long WF Wiliamson FB (1992) Med Hypoth 38 4648 Grant D Long WF Williamson FB (1992a) (Proc Workshop) “Making Light Work. Advances in Near Infrared Spectroscopy” Ed. Murray I & Cowe IA VCH Weinheim, New York, Basel & Cambridge p. 633-635 Grant D Long WF Williamson FB (1992b) ibid. p. 636-639 Jaffe LF & Nuccitelli R (1977) Ann Rev Biophys Bioeng 6 445-476 Johnson JR Christian SD Affsprung HE J Chem Soc 1967 1924-1928 Leyendekkers JV (1985) J Chem Soc Trans Faraday Soc 81 519-536 Lima-de-Faria A (1988) “Evolution Without Selection-Form and function by autoevolution” Elsevier Amsterdam Ling GN (1973) Biophysical J 13 807 Luck WAP (1963) Ber Bunsenges physik Chem 67 75, 84 Cf ibid (1965) 69 626-637 especially Fig 6 on p 630 Luck WAP (1975) Top Curr Chem 5 115-180 Luck WAP (1980) Angew Chem Int Rd Engl 19 28 DATA Muniz MA Bertran J Andres JL Duran M Lledos A (1985) J Chem Soc Faraday Trans 1, 81, 1547-1554 Pashley RM McGuiggan PM Ninham BW (1985) Science 220 1088-1089

Pauling L (1959) in “ Hydrogen Bonding”, Proc Symp Ljubliana 1957, Ed D Hadzi & HW Thompson, Pergamon Press London New York Paris & Los Angeles p 1-6 Piculell L (1985) Water 17O and 2H spin relaxation in aqueous colloidal systems, Lund, PhD thesis Pinchas S Meshulam E (1970) J Chem Soc Chem Commun 1147 Rand RP Fuller NL Gruner SM Parsegian VA (1990) Biocemistry 29 76-87 Rees DA (1972) Chemistry & Industry 19 August 630-636 Sachi G (1964) Bull Chem Soc Japan 37 1685 Schioberg D Zundel G (1976) Z Phys Chem (Frankfurt) 102 169-174; Canad J Chem 54 2193-2200 Shah DO Hamlin RM (1971) Science 171 483-485 Stillinger FH (1980) Science 209 451-457 Symons M.C.R (1989) Chem Brit May 491-494, 498 Tanaka T Nishio I Sun S-T Ueno-Nishio S (1982) Science 218 467-469 Vassilev PM Dronzine RT Vassileva MP Georgiev GA (1982) Biosci Reports 2 1025-1029 Walrafen GE Fischer MR (1985) in “ Methods in Enzymology” 127 Academic Press 102-105 Watanabe M Arai S (1987) Agric Biol Chem 51 557-563

Warner D (1973) Reported in Chem Week, June 20, p31 Webb N (1990) Chem in Brit 26 338-340 Wiggins PM (1995) Prog Polym Sci 20 1121-1163 (added later) Zundel S Murr A (1969) Journal de Chimie Physique 66 246-249

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