Old Ex Marischal College Paper on Water Structure

8/9/2019 Old Ex Marischal College Paper on Water Structure

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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thought to be of continued interest to the scientific community.It is a literature survey drafted in 1992, but remained unpublished because of laboratory closure.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 BiologyD. Grant, Department of Molecular & Cell BiologyMarischal 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, its a pre-requisite for lifeis 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 tothis 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 andduring 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) topossess key functional groups positioned in such a way as to


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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 andglycosaminglycans 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 slowerthan 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


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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 rapidtransport 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 ofsupercooled 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


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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 non-hydrogen-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 meltingpoint amounted to several hundred H2O molecules. The 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


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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 compressibilityminimum 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 H2Sthat 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, beconceived 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 no-

dimensional-order (exemplified by liquid mercury); biological

membranes also possess a type of crystallinity less than three

dimensional in this case they contain two-dimensional crystal-

like order. Water molecule aggregates, evidently up to several


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100A in size, might also be considered to be a branch of

colloidal science (Bernal, 1965) cf., also Stillingers (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 aggregatestructures 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 thecoalesced 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 withcrystallographically-forbidden symmetries (cf. Fujiwara &

Ogawa, 1990). New theories of crystallinity of which the five-

fold 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


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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 highpHs 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, encouragingchains 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 propertieswhich 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 un-

symmetric hydrogen-bonds. When considering an adiabatic

transfer model, solvation parameters were suggested to take part


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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 thehydrophobic 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)


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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 extra-

cellular 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 eventsoccurring 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 ofelectromagnetic 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 hydrogen-

bonds continually rearranging, the precise arrangements and rateof 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


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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 un-

bonded 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 andpressure 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-H-

bonded 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 freeOH 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 extentis 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


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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 byLima 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.


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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 bacterialErwina 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 allowsilica 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) polymer-polymer 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+]


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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 containe.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 seemspossible 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


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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 of18O(-H2O) compared

with 16O-(-H2O) when observed for water which is hydrogen-

bonded 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 aqueoussolutions 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 biologicalprocesses.

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 interactionbetween 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


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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, theglycosaminoglycans 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 long-

ranged. 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 wouldoperate 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-PHOP bonds (Schioberg & Zundel,

1976) as well as by their degree of hydration (Carmona &


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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. JRHaris, 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, 515-

Bonner OR Curry JD (1970) Infrared Physics 10 91-94


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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 247 481-

Frank 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, MiePrefecture, Japan, 14-19 November 1989, Springer-Verlag,

Berlin, Heidelberg, New York, Paris, Tokyo, Hong Kong,

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Geiger A Stillinger FH Rahman J Chem Phys 70, 4185

DATA


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Grant D Long WF Williamson FB (1985) Biochem Soc Trans

13 389

Grant D Long WF Williamson FB (1991) Biochem J 277 569-

571

Grant D Long WF Wiliamson FB (1992) Med Hypoth 38 46-

48

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

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Documents

Old Ex Marischal College Paper on Water Structure