Formation and removal of alkylthiolate self-assembled monolayers on gold in aqueous solutions.

We report the development of novel reagents and approaches for generating recyclable biosensors. The use of aqueous media for the formation of protein binding alkylthiolate monolayers on Au surfaces results in accelerated alkylthiolate monolayer formation and improvement in monolayer integrity as visualized by fluorescence microscopy and CV techniques. We have also developed an electrocleaning protocol that is compatible with microfluidics devices, and this technique serves as an on-chip method for cleaning Au substrates both before and after monolayer formation. The techniques for the formation and dissociation of biotinylated SAMs from aqueous solvents reported here may be applied towards the development of Au-based sensor devices and microfluidics chips in the future. A potential use of these devices includes the specific capture and triggered release of target cells, proteins, or small molecules from liquid samples.

[1]  G. Whitesides,et al.  Solvent compatibility of poly(dimethylsiloxane)-based microfluidic devices. , 2003, Analytical chemistry.

[2]  Milan Mrksich,et al.  Electrochemical desorption of self-assembled monolayers noninvasively releases patterned cells from geometrical confinements. , 2003, Journal of the American Chemical Society.

[3]  J. Zak,et al.  Voltammetric reductive desorption characteristics of alkanethiolate monolayers at single crystal Au(111) and (110) electrode surfaces , 1997 .

[4]  D E Ingber,et al.  Using microcontact printing to pattern the attachment of mammalian cells to self-assembled monolayers of alkanethiolates on transparent films of gold and silver. , 1997, Experimental cell research.

[5]  K. Stevenson,et al.  ELECTROCHEMICAL MEASUREMENT OF THE FREE ENERGY OF ADSORPTION OF N-ALKANETHIOLATES AT AG(111) , 1998 .

[6]  M. Mrksich,et al.  Biomolecular Surfaces that Release Ligands under Electrochemical Control , 2000 .

[7]  K. Maex,et al.  In-situ cleaning and passivation of oxidized Cu surfaces by alkanethiols and its application to wire bonding , 2004 .

[8]  K. Nelson,et al.  Surface Characterization of Mixed Self-Assembled Monolayers Designed for Streptavidin Immobilization , 2001 .

[9]  M. Porter,et al.  The electrochemical desorption of n-alkanethiol monolayers from polycrystalline Au and Ag electrodes , 1991 .

[10]  Guohua Yang,et al.  Molecular-level approach to inhibit degradations of alkanethiol self-assembled monolayers in aqueous media. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[11]  M. Mrksich,et al.  Diels-Alder Reaction for the Selective Immobilization of Protein to Electroactive Self-Assembled Monolayers , 1999 .

[12]  S. Fraser,et al.  New syntheses for 11-(mercaptoundecyl)triethylene glycol and mercaptododecyltriethyleneoxy biotin amide , 2005 .

[13]  T. Ishida,et al.  Adsorption Processes of Self-Assembled Monolayers Made from Terphenyl Thiols , 2001 .

[14]  D. Kolb,et al.  In Situ Characterization of Self-Assembled Butanethiol Monolayers on Au(100) Electrodes , 2003 .

[15]  Ulrich J. Krull,et al.  Self-assembly of short and long-chain n-alkyl thiols onto gold surfaces: A real-time study using surface plasmon resonance techniques , 1996 .

[16]  R. Glockshuber,et al.  Immobilization of the enzyme beta-lactamase on biotin-derivatized poly(L-lysine)-g-poly(ethylene glycol)-coated sensor chips: a study on oriented attachment and surface activity by enzyme kinetics and in situ optical sensing. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[17]  G. Whitesides,et al.  Formation of monolayer films by the spontaneous assembly of organic thiols from solution onto gold , 1989 .

[18]  M. Grunze,et al.  Temperature Dependence of the Protein Resistance of Poly- and Oligo(ethylene glycol)-Terminated Alkanethiolate Monolayers , 2001 .

[19]  Ralph G. Nuzzo,et al.  Fundamental studies of microscopic wetting on organic surfaces. 1. Formation and structural characterization of a self-consistent series of polyfunctional organic monolayers , 1990 .

[20]  J. M. Harris,et al.  Poly(Ethylene Glycol) Chemistry Biotechnical and Biomedical Applications , 1992 .

[21]  H. Usui,et al.  Voltammetric Properties of the Reductive Desorption of Alkanethiol Self-Assembled Monolayers from a Metal Surface , 2002 .

[22]  K. Uosaki,et al.  SOLVENT EFFECT ON THE STRUCTURE OF THE SELF-ASSEMBLED MONOLAYER OF ALKANETHIOL , 1999 .

[23]  M. Brust,et al.  The fate of sulfur-bound hydrogen on formation of self-assembled thiol monolayers on gold: (1)H NMR spectroscopic evidence from solutions of gold clusters. , 2002, Journal of the American Chemical Society.

[24]  M. Morin,et al.  Electrochemical Desorption and Adsorption of Nonyl Mercaptan at Gold Single Crystal Electrode Surfaces , 1996 .

[25]  J. Delplancke,et al.  Analytical application of self assembled monolayers on gold electrodes: critical importance of surface pretreatment , 1995 .

[26]  A. Kell,et al.  Selective reductive desorption of a SAM-coated gold electrode revealed using fluorescence microscopy. , 2004, Journal of the American Chemical Society.

[27]  G. Whitesides,et al.  Self-assembled monolayers of thiolates on metals as a form of nanotechnology. , 2005, Chemical reviews.

[28]  R. Georgiadis,et al.  In situ kinetics of self-assembly by surface plasmon resonance spectroscopy , 1996 .

[29]  M. Grunze,et al.  Investigation of intermediate steps in the self-assembly of n-alkanethiols on gold surfaces by soft X-ray spectroscopy , 1993 .

[30]  Tetsuya Osaka,et al.  Detection of biomolecular interaction between biotin and streptavidin on a self-assembled monolayer using magnetic nanoparticles. , 2004, Biotechnology and bioengineering.

[31]  J. Meléndez,et al.  Detection of DNA hybridization using the TISPR-1 surface plasmon resonance biosensor. , 1999, Analytical biochemistry.

[32]  F. Schreiber Structure and growth of self-assembling monolayers , 2000 .

[33]  D. Yan,et al.  Formation of n-Alkanethiolate Self-Assembled Monolayers onto Gold in Aqueous Micellar Solutions of n-Alkyltrimethylammonium Bromides , 2003 .

[34]  Ruedi Aebersold,et al.  Microspotting streptavidin and double-stranded DNA arrays on gold for high-throughput studies of protein-DNA interactions by surface plasmon resonance microscopy. , 2004, Analytical chemistry.

[35]  George M. Whitesides,et al.  Molecular Conformation in Oligo(ethylene glycol)-Terminated Self-Assembled Monolayers on Gold and Silver Surfaces Determines Their Ability To Resist Protein Adsorption , 1998 .

[36]  M. Grunze,et al.  LOW-ENERGY CONFIGURATIONS OF METHOXY TRIETHYLENE GLYCOL TERMINATED ALKANETHIOL SELF-ASSEMBLED MONOLAYERS AND THEIR RELEVANCE TO PROTEIN ADSORPTION , 1998 .

[37]  B. Liedberg,et al.  Functionalized Surfaces of Mixed Alkanethiols on Gold as a Platform for Oligonucleotide Microarrays , 2002 .

[38]  T. Schneider,et al.  Electrochemical quartz crystal microbalance studies of adsorption and desorption of self-assembled monolayers of alkyl thiols on gold , 1993 .

[39]  E. Aydil,et al.  Polyethylene glycol-coated biocompatible surfaces. , 2000, Journal of biomedical materials research.

[40]  M. Grunze,et al.  Electrokinetic Characterization of Oligo- and Poly(ethylene glycol)-Terminated Self-Assembled Monolayers on Gold and Glass Surfaces , 2003 .

[41]  M. Grunze,et al.  Probing resistance to protein adsorption of oligo(ethylene glycol)-terminated self-assembled monolayers by scanning force microscopy , 1999 .

[42]  M. Morin,et al.  Vibrational Study of the Fast Reductive and the Slow Oxidative Desorptions of a Nonanethiol Self-Assembled Monolayer from a Au(111) Single Crystal Electrode , 1997 .

[43]  M. Grunze,et al.  Factors that determine the protein resistance of oligoether self-assembled monolayers --internal hydrophilicity, terminal hydrophilicity, and lateral packing density. , 2003, Journal of the American Chemical Society.

[44]  Michael Himmelhaus,et al.  Covalent Coupling of Antibodies to Self-Assembled Monolayers of Carboxy-Functionalized Poly(ethylene glycol): Protein Resistance and Specific Binding of Biomolecules† , 2003 .

[45]  George M. Whitesides,et al.  Formation of monolayers by the coadsorption of thiols on gold: variation in the head group, tail group, and solvent , 1989 .

[46]  Christian Grunwald,et al.  Double-wavelength technique for surface plasmon resonance measurements: basic concept and applications for single sensors and two-dimensional sensor arrays. , 2005, Analytical chemistry.

[47]  B. Liedberg,et al.  Self-Assembled Monolayers of Oligo(ethylene glycol)-Terminated and Amide Group Containing Alkanethiolates on Gold , 1999 .

[48]  M. Porter,et al.  Reductive desorption of alkanethiolate monolayers at gold: a measure of surface coverage , 1991 .

[49]  D. Allara,et al.  Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry , 1987 .

[50]  V. Lakshminarayanan,et al.  A study of the hydrophobic properties of alkanethiol self-assembled monolayers prepared in different solvents , 2004 .

[51]  P. E. Laibinis,et al.  In situ studies of thiol self-assembly on gold from solution using atomic force microscopy , 1998 .

[52]  Milan Mrksich,et al.  A surface chemistry approach to studying cell adhesion , 2000 .

[53]  M. Mrksich,et al.  Design of self-assembled monolayers that release attached groups using applied electrical potentials , 1997 .

[54]  J. White,et al.  Crystalline structures of pristine and hydrated mercaptohexanol self‐assembled monolayers on Au(111) , 1996 .