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Properties of a water layer on hydrophilic and hydrophobic self-assembled monolayer surfaces: A molecular dynamics study

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Abstract

The microscopic behaviors of a water layer on different hydrophilic and hydrophobic surfaces of well ordered self-assembled monolayers (SAMs) are studied by molecular dynamics simulations. The SAMs consist of 18-carbon alkyl chains bound to a silicon(111) substrate, and the characteristic of its surface is tuned from hydrophobic to hydrophilic by using different terminal functional groups (-CH3, -COOH). In the simulation, the properties of water membranes adjacent to the surfaces of SAMs were reported by comparing pure water in mobility, structure, and orientational ordering of water molecules. The results suggest that the mobility of water molecules adjacent to hydrophilic surface becomes weaker and the molecules have a better ordering. The distribution of hydrogen bonds indicates that the number of water-water hydrogen bonds per water molecule tends to be lower. However, the mobility of water molecules and distribution of hydrogen bonds of a water membrane in hydrophobic system are nearly the same as those in pure water system. In addition, hydrogen bonds are mainly formed between the hydroxyl of the COOH group and water molecules in a hydrophilic system, which is helpful in understanding the structure of interfacial water.

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References

  1. Ball P. Water as an active constituent in cell biology. Chem Rev, 2008, 108: 74–108

    Article  CAS  Google Scholar 

  2. Sedlmeier F, Janecek J, Sendner C, Bocquet L, Netz RR, Horinek D. Water at polar and nonpolar solid walls. Biointerphases, 2008, 3: FC23–FC39

    Article  Google Scholar 

  3. Gordon E, Brown J. How minerals react with water. Science, 2001, 294: 67–70

    Article  Google Scholar 

  4. Pratt LR, Pohorille A. Hydrophobic effects and modeling of biophysical aqueous solution interfaces. Chem Rev, 2002, 102: 2671–2692

    Article  CAS  Google Scholar 

  5. Petersen PB, Saykally RJ. On the nature of ions at the liquid water surface. Annu Rev Phys Chem, 2006, 57: 333–364

    Article  CAS  Google Scholar 

  6. Jungwirth P, Tobias DJ. Specific ion effects at the air/water interface. Chem Rev, 2006, 106: 1259–1281

    Article  CAS  Google Scholar 

  7. Wang JW, Kalinichev AG, Kirkpatrick RJ. Effects of substrate structure and composition on the structure, dynamics, and energetics of water at mineral surfaces: A molecular dynamics modeling study. Geochim Cosmochim Acta, 2006, 70: 562–582

    Article  CAS  Google Scholar 

  8. Szöri M, Tobias DJ, Roeselová M. Microscopic wetting of mixed self-assembled monolayers: A molecular dynamics study. J Phys Chem B, 2009, 113: 4161–4169

    Article  Google Scholar 

  9. Stevens MJ, Grest GS. Simulations of water at the interface with hydrophilic self-assembled monolayers. Biointerphases, 2008, 3: FC13–FC22

    Article  CAS  Google Scholar 

  10. Schreiber F. Structure and growth of self-assembling monolayers. Prog Surf Sci, 2000, 65:151–256

    Article  CAS  Google Scholar 

  11. James M, Darwish TA, Ciampi S, Sylvester SO, Zhang ZM, Ng A, Gooding JJ, Hanley TL. Nanoscale condensation of water on self-assembled monolayers. Soft Matter, 2011, 7: 5309–5318

    Article  CAS  Google Scholar 

  12. James M, Ciampi S, Darwish TA, Hanley TL, Sylvester SO, Gooding JJ. Nanoscale water condensation on click-functionalized self-assembled monolayers. Langmuir, 2011, 27: 10753–10762

    Article  CAS  Google Scholar 

  13. Ruan CY, Lobastov VA, Vigliotti F, Chen SY, Zewail AH. Ultrafast electron crystallography of interfacial water. Science, 2004, 304: 80–84

    Article  CAS  Google Scholar 

  14. Grigera JR, Kalko SG. Wall-water interface. A molecular dynamics study. Langmuir, 1996, 12: 154–158

    Article  CAS  Google Scholar 

  15. Xu Z, Song K, Yuan SL, Liu CB. Microscopic wetting of self-assembled monolayers with different surfaces: A combined molecular dynamics and quantum mechanics study. Langmuir, 2011, 27: 8611–8620

    Article  CAS  Google Scholar 

  16. Szöri M, Roeselová M, Jedlovszky P. Surface hydrophilicity-dependent water adsorption on mixed self-assembled monolayers of C7-CH3 and C7-COOH residues. A grand canonical Monte Carlo simulation study. J Phys Chem, 2011, 115: 19165–19177

    Google Scholar 

  17. Leung K, Luzar A, Bratko D. Dynamics of capillary drying in water. Phys Rev Lett, 2003, 90: 65502(1–4)

    Google Scholar 

  18. Jensen TR, Østergaard JM, Reitzel N, Balashev K, Peters GH, Kjaer K, Bjørnholm T. Water in contact with extended hydrophobic surfaces: Direct evidence of weak dewetting. Phys Rev Lett, 2003, 90: 086101(1–4)

    Article  Google Scholar 

  19. Brovchenko I, Geiger A, Oleinikova A. Water in nanopores: II. The liquid-vapour phase transition near hydrophobic surfaces. J Phys Condens Matter, 2004, 16:S5345

    Article  CAS  Google Scholar 

  20. Leng YS, Cummings PT. Fluidity of hydration layers nanoconfined between mica surfaces. Phys Rev Lett, 2005, 94: 026101 (1–4)

    Article  Google Scholar 

  21. Li JY, Liu T, Li X, Ye L, Chen HJ, Fang HP, Wu ZH, Zhou RH. Hydration and dewetting near graphite-CH3 and graphite-COOH plates. J Phys Chem B, 2005, 109: 13639–13648

    Article  CAS  Google Scholar 

  22. Huang XH, Zhou RH, Berne BJ. Drying and hydrophobic collapse of paraffin plates. J Phys Chem B, 2005, 109: 3546–3552

    Article  CAS  Google Scholar 

  23. Gordillo MC, Nagy G, Martí J. Structure of water nanoconfined between hydrophobic surfaces. J Chem Phys, 2005, 123: 54707(1–9)

    Article  Google Scholar 

  24. Choudhury N, Pettitt BM. On the mechanism of hydrophobic association of nanoscopic solutes. J Am Chem Soc, 2005, 127: 3556–3567

    Article  CAS  Google Scholar 

  25. Leng YS, Cummings PT. Hydration structure of water confined between mica surfaces. J Chem Phys, 2006, 124: 074711(1–4)

    Google Scholar 

  26. Giovambattista N, Debenedetti PG, Rossky PJ. Hydration behavior under confinement by nanoscale surfaces with patterned hydrophobicity and hydrophilicity. J Phys Chem C, 2007, 111: 1323–1332

    Article  CAS  Google Scholar 

  27. Yuan SL, Cai ZT, Jiang YS. Molecular simulation study of alkyl monolayers on the Si(111) surface. New J Chem, 2003, 27: 626–633

    Article  CAS  Google Scholar 

  28. Berendsen HJC, Postma JPM, Gunsteren WFV, Hermans J. Interaction models for water in relation to protein hydration. In: Pullman B, Ed. Intermolecular Forces. Dordrecht: Reidel, 1981. 331–342

    Chapter  Google Scholar 

  29. Rivera JL, McCabe C, Cummings PT. Molecular simulations of liquid-liquid interfacial properties: Water-n-alkane and water-methanol-n-alkane systems. Phys Rev E, 2003, 67: 011603(1–10)

    Article  Google Scholar 

  30. Jang SS, Lin ST, Maiti PK, Blanco M, Goddard III WA, Shuler P, Tang YC. Molecular dynamics study of a surfactant-mediated decane-water interface: Effect of molecular architecture of alkyl benzene sulfonate. J Phys Chem B, 2004, 108: 12130–12140

    Article  CAS  Google Scholar 

  31. Wu JR, Berland KM. Propagators and time-dependent diffusion coefficients for anomalous diffusion. Biophys J, 2008, 95: 2049–2052

    Article  CAS  Google Scholar 

  32. Chen W, Sun HG, Zhang XD, Korošak D. Anomalous diffusion modeling by fractal and fractional derivatives. Comput Math Appl, 2010, 59: 1754–1758

    Article  Google Scholar 

  33. Sun HG, Chen W, Sheng H, Chen YQ. On mean square displacement behaviors of anomalous diffusions with variable and random orders. Phys Lett A, 2010, 374: 906–910

    Article  CAS  Google Scholar 

  34. Spoel DVD, Maaren PJV, Berendsen JC. A systematic study of water models for molecular simulation: Derivation of water models optimized for use with a reaction field. J Chem Phys, 1998, 108: 10220–10230

    Article  Google Scholar 

  35. Mark P, Nilsson L. Structure and dynamics of the TIP3P, SPC, and SPC/E water models at 298 K. J Phys Chem A, 2001, 105: 9954–9960

    Article  CAS  Google Scholar 

  36. Hower JC, He Y, Bernards MT, Jiang S. Understanding the nonfouling mechanism of surfaces through molecular simulations of sugar-based self-assembled monolayers. J Chem Phys, 2006, 125: 214704(1–7)

    Article  Google Scholar 

  37. He Y, Hower J, Chen S, Bernards MT, Chang Y, Jiang S. Molecular simulation studies of protein interactions with zwitterionic phosphorylcholine self-assembled monolayers in the presence of water. Langmuir, 2008, 24: 10358–10364

    Article  CAS  Google Scholar 

  38. Impey RW, Madden PA, McDonald IR. Hydration and mobility of ions in solution. J Phys Chem, 1983, 87: 5071–5083

    Article  CAS  Google Scholar 

  39. Zielkiewicz J. Structural properties of water: Comparison of the SPC, SPCE, TIP4P, and TIP5P models of water. J Chem Phys, 2005, 123: 104501–104506

    Article  Google Scholar 

  40. Winter N, Vieceli J, Benjamin I. Hydrogen-bond structure and dynamics at the interface between water and carboxylic acid-functionalized self-assembled monolayers. J Phys Chem B, 2008, 112: 227–231

    Article  CAS  Google Scholar 

  41. Wang JW, Kalinichev AG, Kirkpatrick RJ. Asymmetric hydrogen bonding and orientational ordering of water at hydrophobic and hydrophilic surfaces: A comparison of water/vapor, water/talc, and water/mica interfaces. J Phys Chem C, 2009, 113: 11077–11085

    Article  CAS  Google Scholar 

  42. Janecek J, Netz RR. Interfacial water at hydrophobic and hydrophilic surfaces: Depletion versus adsorption. Langmuir, 2007, 23: 8417–8429

    Article  CAS  Google Scholar 

  43. Trudeau TG, Jena KC, Hore DK. Water structure at solid surfaces of varying hydrophobicity. J Phys Chem C, 2009, 113: 20002–20008

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Key Lab of Colloid and Interface Chemistry, Shandong University, Jinan, 250100, China

    EnZe Li & ShiLing Yuan

  2. China Research Institute of Daily Chemical Industry, Taiyuan, 030001, China

    EnZe Li & ZhiPing Du

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  1. EnZe Li
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  2. ZhiPing Du
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Correspondence to ShiLing Yuan.

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Li, E., Du, Z. & Yuan, S. Properties of a water layer on hydrophilic and hydrophobic self-assembled monolayer surfaces: A molecular dynamics study. Sci. China Chem. 56, 773–781 (2013). https://doi.org/10.1007/s11426-013-4835-7

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  • DOI: https://doi.org/10.1007/s11426-013-4835-7

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