Research article Topical Sections

Hydrophilic surfaces via the self-assembly of nitrile-terminated alkanethiols on gold

  • Received: 12 December 2017 Accepted: 22 February 2018 Published: 06 March 2018
  • A series of CN-terminated alkanethiols were synthesized and used to generate self-assembled monolayers (SAMs) on gold. The SAMs were characterized using ellipsometry, contact angle goniometry, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). The SAMs were compared to those derived from a series of analogous CH3-terminated alkanethiols. The CN-terminated SAMs exhibited lower film thicknesses than the CH3-terminated SAMs, which was largely due to their greater tilt angle on the surface. Additionally, the CN-terminated SAMs form well-ordered films on flat gold surfaces with relative packing densities being indistinguishable from the CH3-terminated SAMs. The CN-terminated SAMs exhibited a less hydrophobic character than the SAMs derived from CH3-terminated adsorbates, which was attributed to the dipole moment of the terminal group as well as the lone pair of the nitrogen atom of the CN-terminal group.

    Citation: Chul Soon Park, Oussama Zenasni, Maria D. Marquez, H. Justin Moore, T. Randall Lee. Hydrophilic surfaces via the self-assembly of nitrile-terminated alkanethiols on gold[J]. AIMS Materials Science, 2018, 5(2): 171-189. doi: 10.3934/matersci.2018.2.171

    Related Papers:

  • A series of CN-terminated alkanethiols were synthesized and used to generate self-assembled monolayers (SAMs) on gold. The SAMs were characterized using ellipsometry, contact angle goniometry, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). The SAMs were compared to those derived from a series of analogous CH3-terminated alkanethiols. The CN-terminated SAMs exhibited lower film thicknesses than the CH3-terminated SAMs, which was largely due to their greater tilt angle on the surface. Additionally, the CN-terminated SAMs form well-ordered films on flat gold surfaces with relative packing densities being indistinguishable from the CH3-terminated SAMs. The CN-terminated SAMs exhibited a less hydrophobic character than the SAMs derived from CH3-terminated adsorbates, which was attributed to the dipole moment of the terminal group as well as the lone pair of the nitrogen atom of the CN-terminal group.


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    [1] Nuzzo RG, Allara DL (1983) Adsorption of bifunctional organic disulfides on gold surfaces. J Am Chem Soc 105: 4481–4483. doi: 10.1021/ja00351a063
    [2] Whelan CM, Kinsella M, Carbonell L, et al. (2003) Corrosion inhibition by self-assembled monolayers for enhanced wire bonding on Cu surfaces. Microelectron Eng 70: 551–557. doi: 10.1016/S0167-9317(03)00283-1
    [3] Ostuni E, Chapman RG, Liang MN, et al. (2001) Self-assembled monolayers that resist the adsorption of proteins and the adhesion of bacterial and mammalian cells. Langmuir 17: 6336–6343. doi: 10.1021/la010552a
    [4] Pham T, Lai D, Ji D, et al. (2004) Well-ordered self-assembled monolayer surfaces can be used to enhance the growth of protein crystals. Colloid Surface B 34: 191–196.
    [5] Shakiba A, Patil SL, Zenasni O, et al. (2017) DNA loading and release using custom-tailored poly(L-lysine) surfaces. ACS Appl Mater Interfaces 9: 23370–23378. doi: 10.1021/acsami.7b05024
    [6] Nuzzo RG, Dubois LH, Allara DL (1990) Fundamental studies of microscopic wetting on organic surfaces. 1. formation and structural characterization of a self-consistent series of polyfunctional organic monolayers. J Am Chem Soc 112: 558–569.
    [7] Kim HI, Graupe M, Oloba O, et al. (1999) Molecularly specific studies of the frictional properties of monolayer films: a systematic comparison of CF3-, (CH3)2CH-, and CH3-terminated Films. Langmuir 15: 3179–3185. doi: 10.1021/la981497h
    [8] Love JC, Estroff LA, Kriebel JK, et al. (2005) Self-assembled monolayers of thiolates on metals as a form of nanotechnology. Chem Rev 105: 1103–1169. doi: 10.1021/cr0300789
    [9] Chinwangso P, Lee HJ, Jamison AC, et al. (2017) Structure, wettability, and thermal stability of organic thin-films on gold generated from the molecular self-assembly of unsymmetrical oligo(ethylene glycol) spiroalkanedithiols. Langmuir 33: 1751–1762. doi: 10.1021/acs.langmuir.6b03803
    [10] Marquez MD, Zenasni O, Jamison AC, et al. (2017) Homogeneously mixed monolayers: emergence of compositionally conflicted interfaces. Langmuir 33: 8839–8855. doi: 10.1021/acs.langmuir.7b00755
    [11] Rittikulsittichai S, Park CS, Jamison AC, et al. (2017) Bidentate aromatic thiols on gold: new insight regarding the influence of branching on the structure, packing, wetting, and stability of self-assembled monolayers on gold surfaces. Langmuir 33: 4396–4406. doi: 10.1021/acs.langmuir.7b00088
    [12] Park CS, Lee HJ, Jamison AC, et al. (2016) Robust thick polymer brushes grafted from gold surfaces using bidentate thiol-based atom-transfer radical polymerization initiators. ACS Appl Mater Interfaces 8: 5586–5594. doi: 10.1021/acsami.5b11305
    [13] Schreiber F (2000) Structure and growth of self-assembling monolayers. Prog Surf Sci 65: 151–257. doi: 10.1016/S0079-6816(00)00024-1
    [14] Chen S, Zheng J, Li L, et al. (2005) Strong resistance of phosphorylcholine self-assembled monolayers to protein adsorption:  insights into nonfouling properties of zwitterionic materials. J Am Chem Soc 127: 14473–14478. doi: 10.1021/ja054169u
    [15] Arima Y, Iwata H (2007) Effect of wettability and surface functional groups on protein adsorption and cell adhesion using well-defined mixed self-assembled monolayers. Biomaterials 28: 3074–3082. doi: 10.1016/j.biomaterials.2007.03.013
    [16] Nanda D, Varshney P, Satapathy M, et al. (2017) Self-assembled monolayer of functionalized silica microparticles for self-cleaning applications. Colloid Surface A 529: 231–238. doi: 10.1016/j.colsurfa.2017.06.007
    [17] Laibinis PE, Whitesides GM, Allara DL, et al. (1991) Comparison of the structures and wetting properties of self-assembled monolayers of n-alkanethiols on the coinage metal surfaces, copper, silver, and gold. J Am Chem Soc 113: 7152–7167. doi: 10.1021/ja00019a011
    [18] Colorado R, Lee TR (2000) Physical organic probes of interfacial wettability reveal the importance of surface dipole effect. J Phys Org Chem 13: 796–807. doi: 10.1002/1099-1395(200012)13:12<796::AID-POC317>3.0.CO;2-#
    [19] Baghbanzadeh M, Simeone FC, Bowers CM, et al. (2014) Odd-even effects in charge transport across n-alkanethiolate based SAMs. J Am Chem Soc 136: 16919–16925. doi: 10.1021/ja509436k
    [20] Lee S, Puck A, Graupe M, et al. (2001) Structure, wettability, and frictional properties of phenyl-terminated self-assembled monolayers on gold. Langmuir 17: 7364–7370. doi: 10.1021/la0111497
    [21] Graupe M, Koini T, Kim HI, et al. (1999) Self-assembled monolayers of CF3-terminated alkanethiols on gold. Colloid Surface A 154: 239–244. doi: 10.1016/S0927-7757(98)00902-9
    [22] Krishna DD, Ramakrishnan R, Sundararajan U, et al. (2006) A simple technique to grow polymer brushes using in situ surface ligation of an organometallic initiator. J Am Chem Soc 128: 13040–13041. doi: 10.1021/ja064549v
    [23] Meyerbröker N, Zharnikov M (2012) Modification of nitrile-terminated biphenylthiol self-assembled monolayers by electron irradiation and related applications. Langmuir 28: 9583–9592. doi: 10.1021/la301399a
    [24] Bain CD, Troughton EB, Tao YT, et al. (1989) Formation of monolayer films by the spontaneous assembly of organic thiols from solution onto gold. J Am Chem Soc 111: 321–335. doi: 10.1021/ja00183a049
    [25] Fenter P, Eberhardt A, Liang KS, et al. (1997) Epitaxy and chain length dependent strain in self-assembled monolayers. J Chem Phys 106: 1600–1608. doi: 10.1063/1.473281
    [26] Frey S, Shaporenko A, Zharnikov M, et al. (2003) Self-assembled monolayers of nitrile-functionalized alkanethiols on gold and silver substrates. J Phys Chem B 107: 7716–7725. doi: 10.1021/jp0221690
    [27] Hautman J, Bareman JP, Mar W, et al. (1991) Molecular dynamics investigations of self-assembled monolayers. J Chem Soc Faraday Trans 87: 2031–2037. doi: 10.1039/ft9918702031
    [28] Law KY (2013) Definitions for Hydrophilicity, Hydrophobicity, and Superhydrophobicity: Getting the Basics Right. J Phys Chem Lett 1: 57–58.
    [29] Holmlin RE, Chen X, Chapman RG, et al. (2001) Zwitterionic SAMs that resist nonspecific adsorption of protein from aqueous buffer. Langmuir 17: 2841–2850. doi: 10.1021/la0015258
    [30] Lee HJ, Jamison AC, Lee TR (2015) Boc-protected ω-amino alkanedithiols provide chemically and thermally stable amine-terminated monolayers on gold. Langmuir 31: 2136–2146. doi: 10.1021/la5044359
    [31] Engquist I, Lestelius M, Liedberg B (1997) Microscopic wettability of ester- and acetate-terminated self-assembled monolayers. Langmuir 13: 4003–4012. doi: 10.1021/la9608526
    [32] Allara DL, Nuzzo RG (1985) Spontaneously organized molecular assemblies. 1. Formation, dynamics, and physical properties of n-alkanoic acids adsorbed from solution on an oxidized aluminum surface. Langmuir 1: 45–52.
    [33] Porter MD, Bright TB, Allara DL, et al. (1987) Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry. J Am Chem Soc 109: 3559–3568.
    [34] Snyder RG, Strauss HL, Elliger CA (1982) Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 1. Long, disordered chains. J Phys Chem 86: 5145–5150.
    [35] Sellers H, Ulman A, Shnidman Y, et al. (1993) Structure and Binding of Alkanethiolates on Gold and Silver Surfaces: Implications for Self-Assembled Monolayers. J Am Chem Soc 115: 9389–9401. doi: 10.1021/ja00074a004
    [36] Castner DG, Hinds K, Grainger DW (1996) X-ray photoelectron spectroscopy sulfur 2p study of organic thiol and disulfide binding interactions with gold surfaces. Langmuir 12: 5083–5086. doi: 10.1021/la960465w
    [37] Ågren H, Carravetta V, Vahtras O, et al. (1994) Direct, atomic orbital, static exchange calculations of photoabsorption spectra of large molecules and clusters. Chem Phys Lett 222: 75–81. doi: 10.1016/0009-2614(94)00318-1
    [38] Widrig CA, Chung C, Porter MD, et al. (1991) The Electrochemical desorption of n-alkanethiol monolayers from polycrystalline Au and Ag electrodes. J Electroanal Chem Interfacial Electrochem 310: 335–359. doi: 10.1016/0022-0728(91)85271-P
    [39] Kondoh H, Kodama C, Sumida H, et al. (1999) Molecular processes of adsorption and desorption of alkanethiol monolayers on Au(111). J Chem Phys 111: 1175–1184. doi: 10.1063/1.479302
    [40] Hutt DA, Leggett GJ (1996) Influence of adsorbate ordering on rates of UV photooxidation of self-assembled monolayers. J Phys Chem 100: 6657–6662. doi: 10.1021/jp952734h
    [41] Bain CD, Whitesides GM (1989) Attenuation lengths of photoelectrons in hydrocarbon films. J Phys Chem 93: 1670–1673. doi: 10.1021/j100341a095
    [42] Lee S, Shon YS, Colorado R, et al. (2000) The influence of packing densities and surface order on the frictional properties of alkanethiol self-assembled monolayers (SAMs) on gold: a comparison of SAMs derived from normal and spiroalkanedithiols. Langmuir 16: 2220–2224. doi: 10.1021/la9909345
    [43] Shon YS, Colorado R, Williams CT, et al. (2000) Low-density self-assembled monolayers on gold derived from chelating 2-monoalkylpropane-1,3-dithiols. Langmuir 16: 541–548. doi: 10.1021/la981698l
    [44] Park JS, Smith AC, Lee TR (2004) Loosely packed self-assembled monolayers on gold generated from 2-alkyl-2-methylpropane-1,3-dithiols. Langmuir 20: 5829–5836. doi: 10.1021/la036424z
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