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Hydrophobic Hydration: A Theoretical Investigation of Structure and Dynamics

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Abstract

The presence of external solutes alters the local structures, and dynamics of water. The nature and extent of these structural modifications depend on several factors. Particularly, the chemical nature of the solute is very crucial. The alteration of water structure and dynamics in the presence of hydrophobic substances draws considerable attention in biological systems. The present work is focused on exploring the microscopic arrangement of solvation shells of tiny hydrophobic solute methane. We explore the tetrahedral order, local structural index, and van Hove self-correlation function to get a quantitative understanding. We observe a slight increase in the structural order of water molecules in methane’s first solvation shell, similar to that of the low-temperature water. We also find that water facing the methane have lower structural order than bulk water. Furthermore, the water molecules in the first solvation shell around methane show relatively slower orientational relaxation.

Graphical Abstract

The hydrophobicity-induced alterations of water structural and dynamical properties are investigated using solvation shell decomposition. We observe the slower relaxation of selected water molecules staying longer time in methane first solvation shell. We find enhanced structural order in the methane first solvation shell and some dangling water molecules.

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References

  1. Bagchi B 2013 Water in Biological and Chemical Processes: From Structure and Dynamics to Function (Cambridge: Cambridge University Press)

    Book  Google Scholar 

  2. Bakulin A A, Pshenichnikov M S, Bakker H J and Petersen C 2011 Hydrophobic Molecules Slow Down the Hydrogen-Bond Dynamics of Water J. Phys. Chem. A 115 1821

    Article  CAS  Google Scholar 

  3. Wiggins P M 1997 Hydrophobic hydration, hydrophobic forces and protein folding Physica A 238 113

  4. Chandler D 2005 Interfaces and the driving force of hydrophobic assembly Nature 437 640

    Article  CAS  Google Scholar 

  5. Huang D M and Chandler D 2000 Temperature and length scale dependence of hydrophobic effects and their possible implications for protein folding 2000 Proc. Natl. Acad. Sci. U.S.A. 97 8324

    Article  CAS  Google Scholar 

  6. Galamba M 2013 Water’s Structure around Hydrophobic Solutes and the Iceberg Model J. Phys. Chem. B 117 2153

    Article  CAS  Google Scholar 

  7. Galamba M 2014 Water Tetrahedrons, Hydrogen-Bond Dynamics, and the Orientational Mobility of Water around Hydrophobic Solutes J. Phys. Chem. B 118 4169

    Article  CAS  Google Scholar 

  8. Reddy K D and Biswas R 2020 Theoretical spectroscopy of isotopically dilute water and hydrophobicity J. Chem. Phys. 153 094501

    Article  CAS  Google Scholar 

  9. Reddy K D, Joy A and Biswas R 2021 Effects of hydrophobic solute on water normal modes Chem. Phys. 550 111303

    Article  CAS  Google Scholar 

  10. Godec A ž, Smith J C and Merzel F 2011 Increase of both Order and Disorder in the First Hydration Shell with Increasing Solute Polarity Phys. Rev. Lett. 107 267801

  11. Houry W, Rothwarf D and Scheraga A 1995 The nature of the initial step in the conformational folding of disulphide-intact ribonuclease Nat. Struct. Mol. Biol. 2 495

    Article  CAS  Google Scholar 

  12. Gessner A, Waicz R, Lieske A, Paulke B, Mäder K and Müller R H 2000 Nanoparticles with decreasing surface hydrophobicities: influence on plasma protein adsorption Int. J. Pharm. 196 245

    Article  CAS  Google Scholar 

  13. Dyson H J, Wright P E and Scheraga H A 2006 The role of hydrophobic interactions in initiation and propagation of protein folding Proc. Natl. Acad. Sci. U.S.A. 103 13057

    Article  CAS  Google Scholar 

  14. Cheng Y K and Rossky P J 1998 Surface topography dependence of biomolecular hydrophobic hydration Nature 392 696

    Article  CAS  Google Scholar 

  15. Lum K, Chandler D and Weeks J D 1999 Hydrophobicity at small and large length scales J. Phys. Chem. B 103 4570

    Article  CAS  Google Scholar 

  16. Kauzmann W 1959 Some Factors in the Interpretation of Protein Denaturation Adv. Protein Chem. 14 1-63

    Article  CAS  Google Scholar 

  17. Pratt D R and Chandler D 1977 Theory of the hydrophobic effect J. Chem. Phys. 67 3683

    Article  CAS  Google Scholar 

  18. Pratt L R 1985 Theory of Hydrophobic Effects Annu. Rev. Phys. Chem. 36 433

    Article  CAS  Google Scholar 

  19. Charles T 1978 The Hydrophobic Effect and the Organization of Living Matter Science 200 1012

    Article  Google Scholar 

  20. Laage D, Stirnemann G and Hynes J T 2009 Why water reorientation slows without iceberg formation around hydrophobic solutes J. Phys. Chem. B 113 2428

    Article  CAS  Google Scholar 

  21. Rossato L, Rossetto F and Silvestrelli P L 2012 Aqueous Solvation of Methane from First Principles J. Phys. Chem. B 116 4552

    Article  CAS  Google Scholar 

  22. Guillot B, Guissani Y and Bratos S 1991 A computer-simulation study of hydrophobic hydration of rare gases and of methane. I. Thermodynamic and structural properties J. Chem. Phys. 95 3643

  23. Rossky P J and Zichi D A 1982 Molecular librations and solvent orientational correlations in hydrophobic phenomena Faraday Symp. Chem. Soc. 17 69

    Article  Google Scholar 

  24. Hummer G, Garde S, García A E, Paulaitis M E and Pratt L R 1998 Hydrophobic Effects on a Molecular Scale J. Phys. Chem. B 102 10469

    Article  CAS  Google Scholar 

  25. Huang X, Margulis C J and Berne B J 2003 Do Molecules as Small as Neopentane Induce a Hydrophobic Response Similar to That of Large Hydrophobic Surfaces? J. Phys. Chem. B 107 11742

    Article  CAS  Google Scholar 

  26. Lazaridis T and Paulaitis M E 1992 Entropy of hydrophobic hydration: a new statistical mechanical formulation J. Phys. Chem. 96 3847

    Article  CAS  Google Scholar 

  27. Montagna M, Sterpone F and Guidoni L 2012 Structural and Spectroscopic Properties of Water around Small Hydrophobic Solutes J. Phys. Chem. B 116 11695

    Article  CAS  Google Scholar 

  28. Grdadolnik J, Merzel F and Avbelj F 2017 Origin of hydrophobicity and enhanced water hydrogen bond strength near purely hydrophobic solutes Proc. Natl. Acad. Sci. U.S.A. 114 322

    Article  CAS  Google Scholar 

  29. Frank H S and Evans M W 1945 Free Volume and Entropy in Condensed Systems III. Entropy in Binary Liquid Mixtures; Partial Molal Entropy in Dilute Solutions; Structure and Thermodynamics in Aqueous Electrolytes J. Chem. Phys. 13 507

  30. De Jong P H K, Wilson J E, Neilson G W and Buckingham A D 1997 Hydrophobic hydration of methane Mol. Phys. 91 99

    Article  Google Scholar 

  31. Buchanan P, Aldiwan N, Soper A K, Creek J L and Koh C A 2005 Decreased structure on dissolving methane in water Chem. Phys. Lett. 415 89

    Article  CAS  Google Scholar 

  32. Strazdaite S, Versluis, J, BackusmEllen H G and Bakker H J 2014 Enhanced ordering of water at hydrophobic surfaces J. Chem. Phys. 140 054711

    Article  Google Scholar 

  33. Rankin B M, Ben-Amotz D, van der Post, Sietse T and Bakker H J 2015 Contacts Between Alcohols in Water Are Random Rather than Hydrophobic J. Phys. Chem. Lett. 6 688

    Article  CAS  Google Scholar 

  34. Qvist J and Halle B 2008 Thermal Signature of Hydrophobic Hydration Dynamics J. Am. Chem. Soc. 130 10345

    Article  CAS  Google Scholar 

  35. Ishihara Y, Okouchi S and Uedaira H 1997 Dynamics of hydration of alcohols and diols in aqueous solutions J. Chem. Soc. Faraday Trans. 93 3337

    Article  CAS  Google Scholar 

  36. Ben-Amotz D 2015 Hydrophobic Ambivalence: Teetering on the Edge of Randomness J. Phys. Chem. Lett. 6 1696

    Article  CAS  Google Scholar 

  37. Chaudhari M I, Rempe S B, Asthagiri D, Tan L and Pratt L R 2016 Molecular Theory and the Effects of Solute Attractive Forces on Hydrophobic Interactions J. Phys. Chem. B 120 1864

    Article  CAS  Google Scholar 

  38. Pattenaude R S, Rankin B M, Mochizuki K and Ben-Amotz D 2016 Water-mediated aggregation of 2-butoxy ethanol Phys. Chem. Chem. Phys. 18 24937

    Article  CAS  Google Scholar 

  39. Duboué-Dijon E and Laage D 2015 Characterization of the Local Structure in Liquid Water by Various Order Parameters J. Phys. Chem. B 119 8406

    Article  Google Scholar 

  40. Abraham M J, Murtola T, Schulz R, P S, Smith J C, Hess B and Lindahl E 2015 Gromacs: High performance molecular simulations through multi-level parallelism from laptops to supercomputers SoftwareX 1-2 19

  41. Jorgensen W L, Maxwell D S and Tirado-Rives J 1996 Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids J. Am. Chem. Soc. 118 11225

    Article  CAS  Google Scholar 

  42. Berendsen H J C, Grigera J R and Straatsma T P 1987 The missing term in effective pair potentials J. Phys. Chem. 91 6269

    Article  CAS  Google Scholar 

  43. Nosé S and Klein M L 1983 Constant pressure molecular dynamics for molecular systems Mol. Phys. 50 1055

    Article  Google Scholar 

  44. Parrinello M and Rahman A. 1981 Polymorphic transitions in single crystals: A new molecular dynamics method J. Appl. Phys. 52 7182

    Article  CAS  Google Scholar 

  45. Hess B, Bekker H, Berendsen H J C and Fraaije J G E M 1997 LINCS: A linear constraint solver for molecular simulations J. Comput. Chem. 18 1463

    Article  CAS  Google Scholar 

  46. Darden T, York D and Pedersen L 1993 Particle mesh Ewald: An N\(^.\) log(N)method for Ewald sums in large systems J. Chem. Phys. 98 10089

  47. Møller K B, Rey R and Hynes J T 2004 Hydrogen Bond Dynamics in Water and Ultrafast Infrared Spectroscopy:A Theoretical Study J. Phys. Chem. A 108 1289

  48. Bagchi B 2012 Molecular Relaxation in Liquids (USA: Oxford University Press)

    Google Scholar 

  49. Petersena C, Tielrooij K -J and Bakker H J 2009 Strong temperature dependence of water reorientation in hydrophobic hydration shells J. Chem. Phys. 130 214511

  50. De Bar and Roger B 1963 Evaluation of the Van Hove Correlation Functions for Certain Physical Systems Phys. Rev. 130 827

    Article  Google Scholar 

  51. Biswas R, Furtado J and Bagchi B 2013 Layerwise decomposition of water dynamics in reverse micelles: A simulation study of two-dimensional infrared spectrum J. Chem. Phys. 139 144906

  52. Errington J R and Debenedetti P G 2001 Relationship between structural order and the anomalies of liquid water Nature 409 318

    Article  CAS  Google Scholar 

  53. Shiratani E and Sasai M 1996 Growth and collapse of structural patterns in the hydrogen bond network in liquid water J. Chem. Phys. 104 7671

    Article  CAS  Google Scholar 

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Acknowledgements

R. B. acknowledges the Indian Institute of Technology Tirupati for their support through the new faculty seed grant (NFSG: CHY1819003NFSGRAJI) and computational support. R. B. also acknowledges support from Science and Engineering Research Board, Department of Science & Technology, Government of India through the core research grant (CRG/2021/003859).

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  1. Department of Chemistry and Center for Atomic, Molecular and Optical Sciences Technologies, Indian Institute of Technology Tirupati, Tirupati, 517619, India

    Kambham Devendra Reddy & Rajib Biswas

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  1. Kambham Devendra Reddy
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  2. Rajib Biswas
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Correspondence to Rajib Biswas.

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Reddy, K.D., Biswas, R. Hydrophobic Hydration: A Theoretical Investigation of Structure and Dynamics. J Chem Sci 135, 5 (2023). https://doi.org/10.1007/s12039-022-02123-4

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