Weakly hydrated surfaces and the binding interactions of small biological solutes

Brady, John W.; Tavagnacco, Letizia; Ehrlich, Laurent; Chen, Mo; Schnupf, Udo; Himmel, Michael E.; Saboungi, Marie‐Louise; Cesàro, Attilio

doi:10.1007/s00249-011-0776-2

Cited by 16 publications

(19 citation statements)

References 49 publications

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“…The behavior of water is complicated: it is a good solvent for monomers and oligosaccharides inasmuch it is able to compete with the specific inter and intramolecular hydrogen bond network (Talon et al 2004;Brady et al 2010). In many cases it is the thermodynamic stability of the solid-state form which protects the solute molecules from being solubilized (Cesàro 1986).…”

Section: Polysaccharide Conformation and Dynamics In Solutionsmentioning

confidence: 99%

Biophysical functionality in polysaccharides: from Lego-blocks to nano-particles

2011

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The objective of the paper is to show the very important biophysical concepts that have been developed with polysaccharides. In particular, an attempt will be made to relate "a posteriori" the fundamental aspects, both experimental and theoretical, with some industrial applications of polysaccharide-based materials. The overview of chain conformational aspects includes relationships between topological features and local dynamics, exemplified for some naturally occurring carbohydrate polymers. Thus, by using simulation techniques and computational studies, the physicochemical properties of aqueous solutions of polysaccharides are interpreted. The relevance of conformational disorder-order transitions, chain aggregation, and phase separation to the underlying role of the ionic contribution to these processes is discussed. We stress the importance of combining information from analysis of experimental data with that from statistical-thermodynamic models for understanding the conformation, size, and functional stability of industrially important polysaccharides. The peculiar properties of polysaccharides in industrial applications are summarized for the particularly important example of nanoparticles production, a field of growing relevance and scientific interest.

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Section: Polysaccharide Conformation and Dynamics In Solutionsmentioning

confidence: 99%

Biophysical functionality in polysaccharides: from Lego-blocks to nano-particles

2011

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“…However, as the spatial dimensions of hydrophobic species grow larger, it becomes impossible for water molecules to straddle the hydrophobic surface and still make hydrogen bonds to other water molecules off to its sides. 8–12 Under these conditions, the water molecules point one hydrogen atom or lone pair directly at the non-hydrogen-bonding surface, since the resulting loss of one hydrogen bond is nevertheless energetically better than the loss of the two to three hydrogen bonds that would result if they adopted the orientation of waters adjacent to a methane molecule. 3,8,9,12,13 The aggregation of such extended surfaces in aqueous solution would then be enthalpically-dominated, since the pairing of two such surfaces would allow the liberated water molecules to regain their lost hydrogen bonds.…”

Section: Introductionmentioning

confidence: 99%

Water structuring above solutes with planar hydrophobic surfaces

Schnupf

Brady

2017

Phys. Chem. Chem. Phys.

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Many important biological solutes possess not only polar and hydrogen bonding functionalities, but also weakly-hydrating, or hydrophobic, surfaces. Theories of the hydration of such surfaces predict that their solvent interactions will change from a wetting type interaction to a dewetting regime as a function of the solute size, with a gradual transition in behavior taking place around characteristic lengths of ~ 1 nm. Aggregations of non-polar species over this size range will undergo a transition from being dominated by entropy to being dominated by enthalpy. These transitions can be understood in part in terms of the geometries required of the solvating water molecules. We report here a series of simulations in aqueous solution of organic molecules with planar faces of increasing size, ranging from cyclopropane to circumcircumcoronene, in order to explore the transition in behavior for such solutes as their size increases. For this series, the dewetting transition occurred gradually, converging asymptotically to a limiting separation value for first layer water molecules of around 3.3 Å, while the transition in hydrogen bonding orientational structure occurred between cyclopropane and cyclopentadene. Water immediately adjacent to the largest planar hydrophobic surfaces oriented in ways that resembled on average the structural organization of the basal planes of ice.

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“…6 When a solute molecule is present in aqueous environment, its functional groups must interact with the surrounding water, and its presence can impose a structuring pattern on the adjacent solvent molecules, which differs from that of pure bulk water. 7,8 These solutes may self-aggregate in aqueous medium depending on the interaction of these solutes with water.…”

Section: Introductionmentioning

confidence: 99%

“…However, in case of extended hydrophobic surface, water structural reorganization at the solute surface is required, as it becomes impossible for water molecules to straddle the surface and still forms hydrogen bonds to other water molecules off to its side. 6,10 Therefore, to maximize the total interaction, a water molecule prefers to sacrifice one possible bonding interaction by pointing one hydrogen atom or lone pair directly at the non-hydrogen bonding surface, as the resulting loss of one hydrogen bond is energetically favorable than the loss of three hydrogen bonds that would result if it adopted an orientation of waters as that of adjacent to a methane molecule. 6,[11][12][13] Thus, when such larger hydrophobic solutes aggregate in aqueous solution, these hydrophobically structured water molecules are liberated, as the surface area accessible to water molecules decreases which results in regain of lost hydrogen bonds, and, therefore, aggregation is enthalpy driven.…”

Section: Introductionmentioning

confidence: 99%

“…6,10 Therefore, to maximize the total interaction, a water molecule prefers to sacrifice one possible bonding interaction by pointing one hydrogen atom or lone pair directly at the non-hydrogen bonding surface, as the resulting loss of one hydrogen bond is energetically favorable than the loss of three hydrogen bonds that would result if it adopted an orientation of waters as that of adjacent to a methane molecule. 6,[11][12][13] Thus, when such larger hydrophobic solutes aggregate in aqueous solution, these hydrophobically structured water molecules are liberated, as the surface area accessible to water molecules decreases which results in regain of lost hydrogen bonds, and, therefore, aggregation is enthalpy driven. The aggregation of caffeine molecule in water is very interesting to study because of the simultaneous presence of hydrophobic methyl (-CH 3 ) groups and extended flat hydrophobic faces, as well as three proton acceptor groups (O11, O13, N9).…”

Section: Introductionmentioning

confidence: 99%

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Effects of dilute aqueous NaCl solution on caffeine aggregation

Sharma

Paul

2013

The Journal of Chemical Physics

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The effect of salt concentration on association properties of caffeine molecule was investigated by employing molecular dynamics simulations in isothermal-isobaric ensemble of eight caffeine molecules in pure water and three different salt (NaCl) concentrations, at 300 K temperature and 1 atm pressure. The concentration of caffeine was taken almost at the solubility limit. With increasing salt concentration, we observe enhancement of first peak height and appearance of a second peak in the caffeine-caffeine distribution function. Furthermore, our calculated solvent accessible area values and cluster structure analyses suggest formation of higher order caffeine cluster on addition of salt. The calculated hydrogen bond properties reveal that there is a modest decrease in the average number of water-caffeine hydrogen bonds on addition of NaCl salt. Also observed are: (i) decrease in probability of salt contact ion pair as well as decrease in the solvent separated ion pair formation with increasing salt concentration, (ii) a modest second shell collapse in the water structure, and (iii) dehydration of hydrophobic atomic sites of caffeine on addition of NaCl.

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Weakly hydrated surfaces and the binding interactions of small biological solutes

Cited by 16 publications

References 49 publications

Biophysical functionality in polysaccharides: from Lego-blocks to nano-particles

Biophysical functionality in polysaccharides: from Lego-blocks to nano-particles

Water structuring above solutes with planar hydrophobic surfaces

Effects of dilute aqueous NaCl solution on caffeine aggregation

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