Influence of a Neighboring Charged Group on Hydrophobic Hydration Shell Structure

Davis, Joel G.; Zukowski, Samual R.; Rankin, Blake M.; Ben‐Amotz, Dor

doi:10.1021/jp510641a

Cited by 32 publications

(44 citation statements)

References 33 publications

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“…The broad OH features at ∼3400 cm −1 is due largely to water molecules that are H-bonded to the carboxylate headgroup of C 9 COONa, as evidenced by the appearance of a very similar band in the hydration shell spectrum of sodium formate (HCOONa). 20 In order to suppress the SC OH band arising from the carboxylate headgroup hydration shell, and thus highlight features arising from the hydrophobic hydration shell of the surfactant's tail (C 9 ), we have implemented a Raman-MCR headgroup subtraction procedure by including an equimolar concentration of HCOONa in the solvent reference solution, as previously described. 20 In other words, since the carboxylate headgroup is now present in both the surfactant solution and in the solvent reference solution, the resulting Raman-MCR SC spectrum contains OH features arising primarily from the surfactant's hydrophobic hydration shell.…”

Section: ■ Resultsmentioning

confidence: 99%

“…20 In order to suppress the SC OH band arising from the carboxylate headgroup hydration shell, and thus highlight features arising from the hydrophobic hydration shell of the surfactant's tail (C 9 ), we have implemented a Raman-MCR headgroup subtraction procedure by including an equimolar concentration of HCOONa in the solvent reference solution, as previously described. 20 In other words, since the carboxylate headgroup is now present in both the surfactant solution and in the solvent reference solution, the resulting Raman-MCR SC spectrum contains OH features arising primarily from the surfactant's hydrophobic hydration shell. Figure 2B shows headgroup-subtracted SC spectra obtained in this way, both below (0.05 M, blue) and above (1.0 M, red) the CMC of C 9 COONa (∼0.098 M).…”

Section: ■ Resultsmentioning

confidence: 99%

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Micelle Structure and Hydrophobic Hydration

2015

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Despite the ubiquity and utility of micelles self-assembled from aqueous surfactants, longstanding questions remain regarding their surface structure and interior hydration. Here we combine Raman spectroscopy with multivariate curve resolution (Raman-MCR) to probe the hydrophobic hydration of surfactants with various aliphatic chain lengths, and either anionic (carboxylate) or cationic (trimethylammonium) head groups, both below and above the critical micelle concentration. Our results reveal significant penetration of water into micelle interiors, well beyond the first few carbons adjacent to the headgroup. Moreover, the vibrational C-D frequency shifts of solubilized deuterated n-hexane confirm that it resides in a dry, oil-like environment (while the localization of solubilized benzene is sensitive to headgroup charge). Our findings imply that the hydrophobic core of a micelle is surrounded by a highly corrugated surface containing hydrated non-polar cavities whose depth increases with increasing surfactant chain length, thus bearing a greater resemblance to soluble proteins than previously recognized.

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Section: ■ Resultsmentioning

confidence: 99%

Section: ■ Resultsmentioning

confidence: 99%

Micelle Structure and Hydrophobic Hydration

2015

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“…(55) These results showed that at low temperatures the hydration shells of each class has an enhanced water structure with greater tetrahedral order than the bulk, but for alcohols longer than 10 Å this structure disappeared as temperature increased. Additionally, at high pH onset of the hydration-shell structural transformation was suppressed by the carboxylate.…”

Section: Positive Curvaturementioning

confidence: 88%

Molecular Shape and the Hydrophobic Effect

Hillyer

Gibb

2016

Annu. Rev. Phys. Chem.

116

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This review focuses in papers published since 2000 on the topic of the properties of solutes in water. More specifically, it evaluates the state-of-the-art of our understanding of the complex relationship between the shape of a hydrophobe and the Hydrophobic effect. To highlight this a selection of references covering both empirical and molecular dynamics studies of small (molecular-scale) solutes are presented. These include empirical studies of small molecules, synthetic hosts, crystalline monolayers, and proteins, as well as in silico investigations of entities including idealized hard and soft spheres, small solutes, hydrophobic plates, artificial concavity, molecular hosts, carbon nanotubes and spheres, and proteins. KeywordsWater; non-covalent interactions; supramolecular chemistry; Hydrophobic Effect; hydration ExordiumWater is found in many parts of the universe, but planet Earth truly is a water-world. All four spheres consist to some extent of water: the hydrosphere, biosphere, atmosphere and lithosphere all contain (respectively decreasing) proportions of water. This review pertains to the hydrosphere and biosphere. More specifically, this review concerns the complex relationship between hydrophobic solutes and the solvent of life.(1) For understanding how solute shape and functionality control solvation, and how this solvation folds into measurable spectroscopic and thermodynamic changes, is key to understanding our world.The ubiquity of water is reflected in a massive literature and consequently boundaries must be set for any review. First, although there is a continuum between a hydrophobe and a hard ion, and cases where the Hydrophobic effect (HE) and the Hofmeister effect(2-4) meet,(5; 6) where possible the latter is avoided. Second, this review focuses on the molecular-scale HE(7) and avoids the micro-scale.(8) Third, temperature and pressure can have a considerable effect on the HE,(9) but with only a few exceptions this review concerns ambient conditions. Fourth, bio-membranes are not discussed.(10) Finally, the bulk of this review concerns work performed since 2000.The layout of this review follows the broad types of curvature as defined by mathematics: positive curvature (convex), zero curvature (flat surface) and negative curvature (concave).

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“…The latter influences the pattern of HB network and acts as suppressor of dangling defects. 173 Finally, the waters near addends (ester-and phenyl group of PCBM and charged groups of FP family) build the HB network, which is characterized by a combination of four-and five membered cycles, i.e., network reveals greater tetrahedral ordering.…”

Section: E Dangling-oh Bonds and Hydrogen Bonds Pattern Near A Solutmentioning

confidence: 99%

Water around fullerene shape amphiphiles: A molecular dynamics simulation study of hydrophobic hydration

Varanasi

Guskova

John

et al. 2015

The Journal of Chemical Physics

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Fullerene C60 sub-colloidal particle with diameter ∼1 nm represents a boundary case between small and large hydrophobic solutes on the length scale of hydrophobic hydration. In the present paper, a molecular dynamics simulation is performed to investigate this complex phenomenon for bare C60 fullerene and its amphiphilic/charged derivatives, so called shape amphiphiles. Since most of the unique properties of water originate from the pattern of hydrogen bond network and its dynamics, spatial, and orientational aspects of water in solvation shells around the solute surface having hydrophilic and hydrophobic regions are analyzed. Dynamical properties such as translational-rotational mobility, reorientational correlation and occupation time correlation functions of water molecules, and diffusion coefficients are also calculated. Slower dynamics of solvent molecules—water retardation—in the vicinity of the solutes is observed. Both the topological properties of hydrogen bond pattern and the "dangling" -OH groups that represent surface defects in water network are monitored. The fraction of such defect structures is increased near the hydrophobic cap of fullerenes. Some "dry" regions of C60 are observed which can be considered as signatures of surface dewetting. In an effort to provide molecular level insight into the thermodynamics of hydration, the free energy of solvation is determined for a family of fullerene particles using thermodynamic integration technique.

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Influence of a Neighboring Charged Group on Hydrophobic Hydration Shell Structure

Cited by 32 publications

References 33 publications

Micelle Structure and Hydrophobic Hydration

Micelle Structure and Hydrophobic Hydration

Molecular Shape and the Hydrophobic Effect

Water around fullerene shape amphiphiles: A molecular dynamics simulation study of hydrophobic hydration

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