Surface-Enhanced Raman Scattering Study of the Kinetics of Self-Assembly of Carboxylate-Terminated n-Alkanethiols on Silver

Ma, Chaoxiong; Harris, Joel M.

doi:10.1021/la2037444

Surface-Enhanced Raman Scattering Study of the Kinetics of Self-Assembly of Carboxylate-Terminated n-Alkanethiols on Silver

Journal Article · Fri Jan 20 00:00:00 EST 2012 · Langmuir

DOI:https://doi.org/10.1021/la2037444· OSTI ID:2480877

Ma, Chaoxiong ^[1]; Harris, Joel M. ^[1]

University of Utah, Salt Lake City, UT (United States)

Adsorption of 11-mercaptoundecanoic acid (MUA) on silver from methanol and aqueous solutions was monitored in situ by surface-enhanced Raman scattering (SRES) spectroscopy. While adsorption of MUA from methanol is a one-step formation of a thiol-bound monolayer, SERS spectra reveal that monolayer formation from aqueous solution involves interactions of both carboxylate and thiol groups of MUA with the silver surface. Several Raman scattering bands, including the ν(C–S), ν_s(COO^–), and ν(C–C), were used to investigate the evolution of the structure of adsorbed MUA on silver surfaces. The time-dependent profiles of these bands for assembly from aqueous solution indicate a multistep process, which is initiated by the binding of both carboxylate and thiol groups to silver, producing a mixture of gauche and trans conformations. In a subsequent step, the COO–Ag interactions are displaced by stronger S–Ag bonds, leading to ordering of the resulting monolayer with formation of a complete SAM with all-trans conformations. The results also showed that the adsorption process depended strongly on the solution pH and surface potential of the metal. Furthermore, these factors can significantly affect the participation and displacement of –COO^– during self-assembly of MUA from aqueous solution.

View Accepted Manuscript (DOE)

Research Organization:: University of Utah, Salt Lake City, UT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG03-93ER14333

OSTI ID:: 2480877

Journal Information:: Langmuir, Journal Name: Langmuir Journal Issue: 5 Vol. 28; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (63)

Controlled Switchable Surface Liu, Ying; Mu, Li; Liu, Baohong Chemistry - A European Journal, Vol. 11, Issue 9 https://doi.org/10.1002/chem.200400931	journal	April 2005
Surface‐enhanced Raman scattering of 3‐mercaptopropionic acid adsorbed on a colloidal silver surface Castro, J. L.; López‐Ramírez, M. R.; Arenas, J. F. Journal of Raman Spectroscopy, Vol. 35, Issue 11 https://doi.org/10.1002/jrs.1247	journal	September 2004
Raman study on the structure of adlayers formed on silver from mixtures of 2-aminoethanethiol and 3-mercaptopropionic acid Wrzosek, Beata; Bukowska, Jolanta; Kudelski, Andrzej Journal of Raman Spectroscopy, Vol. 36, Issue 11 https://doi.org/10.1002/jrs.1403	journal	January 2005
Determination of specific adsorption of some simple anions at a polycrystalline silver-aqueous interface using differential capacitance and kinetic probe techniques Larkin, D.; Guyer, Kendall L.; Hupp, Joseph T. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 138, Issue 2 https://doi.org/10.1016/0022-0728(82)85091-2	journal	September 1982
Self-assembled and Langmuir—Blodgett stearic acid monolayers on silver: a comparative reflection—absorption Fourier transform infrared spectroscopic study Jung Ahn, Sang; Hee Son, Dong; Kim, Kwan Journal of Molecular Structure, Vol. 324, Issue 3 https://doi.org/10.1016/0022-2860(94)08315-0	journal	August 1994
A generalized treatment of the dynamics of the adsorption of Langmuirian systems at stationary or rotating disk electrodes Bhugun, Iqbal; Anson, Fred C. Journal of Electroanalytical Chemistry, Vol. 439, Issue 1 https://doi.org/10.1016/S0022-0728(97)00366-5	journal	December 1997
Diffuse reflectance infrared spectra of stearic acid self-assembled on fine silver particles Lee, Seung Joon; Kim, Kwan Vibrational Spectroscopy, Vol. 18, Issue 2 https://doi.org/10.1016/S0924-2031(98)00086-1	journal	December 1998
Self assembly of 16-mercapto-1-hexadecanol on gold: surface characterization and kinetics Pan, Sheng; Belu, Anna M.; Ratner, Buddy D. Materials Science and Engineering: C, Vol. 7, Issue 1 https://doi.org/10.1016/S0928-4931(99)00002-8	journal	May 1999
Adsorption of mercaptopropionic acid onto Au(1 1 1) Petri, Marc; Kolb, Dieter M.; Memmert, Ulrich Electrochimica Acta, Vol. 49, Issue 1 https://doi.org/10.1016/j.electacta.2003.07.010	journal	December 2003
Electrochemical and infrared spectroscopy studies of 4-mercaptobenzoic acid SAMs on gold surfaces Rosendahl, Scott M.; Burgess, Ian J. Electrochimica Acta, Vol. 53, Issue 23 https://doi.org/10.1016/j.electacta.2007.11.020	journal	October 2008
Patterning self-assembled monolayers Smith, Rachel K.; Lewis, Penelope A.; Weiss, Paul S. Progress in Surface Science, Vol. 75, Issue 1-2 https://doi.org/10.1016/j.progsurf.2003.12.001	journal	June 2004
Intracellular pH Sensors Based on Surface-Enhanced Raman Scattering Talley, Chad E.; Jusinski, Leonard; Hollars, Christopher W. Analytical Chemistry, Vol. 76, Issue 23, p. 7064-7068 https://doi.org/10.1021/ac049093j	journal	December 2004
Electron-Transfer Processes of Cytochrome c at Interfaces. New Insights by Surface-Enhanced Resonance Raman Spectroscopy Murgida, Daniel H.; Hildebrandt, Peter Accounts of Chemical Research, Vol. 37, Issue 11 https://doi.org/10.1021/ar0400443	journal	September 2004
Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology Love, J. Christopher; Estroff, Lara A.; Kriebel, Jennah K. Chemical Reviews, Vol. 105, Issue 4 https://doi.org/10.1021/cr0300789	journal	April 2005
Vibrational Spectroscopic Investigation of Benzoic Acid Adsorbed on Silver Kwon, Yong Joon; Son, Dong Hee; Ahn, Sang Jung The Journal of Physical Chemistry, Vol. 98, Issue 34 https://doi.org/10.1021/j100085a030	journal	August 1994
Test of surface selection rules for surface-enhanced Raman scattering: the orientation of adsorbed benzene and monosubstituted benzenes on gold Gao, Xiaoping.; Davies, John P.; Weaver, Michael J. The Journal of Physical Chemistry, Vol. 94, Issue 17 https://doi.org/10.1021/j100380a059	journal	August 1990
Surface selection rules for surface-enhanced Raman spectroscopy: calculations and application to the surface-enhanced Raman spectrum of phthalazine on silver Moskovits, M.; Suh, J. S. The Journal of Physical Chemistry, Vol. 88, Issue 23 https://doi.org/10.1021/j150667a013	journal	November 1984
Surface Raman scattering of self-assembled monolayers formed from 1-alkanethiols at silver [electrodes] Bryant, Mark A.; Pemberton, Jeanne E. Journal of the American Chemical Society, Vol. 113, Issue 10 https://doi.org/10.1021/ja00010a001	journal	May 1991
Thermodynamically controlled electrochemical formation of thiolate monolayers at gold: characterization and comparison to self-assembled analogs Weisshaar, Duane E.; Lamp, Brian D.; Porter, Marc D. Journal of the American Chemical Society, Vol. 114, Issue 14 https://doi.org/10.1021/ja00040a058	journal	July 1992
Conformation of mono- and dicarboxylic acids adsorbed on silver surfaces Moskovits, M.; Suh, J. S. Journal of the American Chemical Society, Vol. 107, Issue 24 https://doi.org/10.1021/ja00310a014	journal	November 1985
Chain Length Dependence and Sensing Capabilities of the Localized Surface Plasmon Resonance of Silver Nanoparticles Chemically Modified with Alkanethiol Self-Assembled Monolayers Malinsky, Michelle Duval; Kelly, K. Lance; Schatz, George C. Journal of the American Chemical Society, Vol. 123, Issue 7, p. 1471-1482 https://doi.org/10.1021/ja003312a	journal	February 2001
Proton-Coupled Electron Transfer of Cytochrome c Murgida, Daniel H.; Hildebrandt, Peter Journal of the American Chemical Society, Vol. 123, Issue 17 https://doi.org/10.1021/ja004165j	journal	April 2001
Control of Alkanethiolate Monolayer Structure Using Vapor-Phase Annealing Donhauser, Zachary J.; Price, David W.; Tour, James M. Journal of the American Chemical Society, Vol. 125, Issue 38 https://doi.org/10.1021/ja035036g	journal	September 2003
Structure and Dynamics in Alkanethiolate Monolayers Self-Assembled on Gold Nanoparticles: A DSC, FT-IR, and Deuterium NMR Study Badia, Antonella; Cuccia, Louis; Demers, Linette Journal of the American Chemical Society, Vol. 119, Issue 11 https://doi.org/10.1021/ja963571t	journal	March 1997
Electrochemical Oxidative Adsorption of Ethanethiolate on Ag(111) Hatchett, David W.; Stevenson, Keith J.; Lacy, William B. Journal of the American Chemical Society, Vol. 119, Issue 28 https://doi.org/10.1021/ja964396j	journal	July 1997
Electrochemical Measurement of the Free Energy of Adsorption of n-Alkanethiolates at Ag(111) Hatchett, David W.; Uibel, Rory H.; Stevenson, Keith J. Journal of the American Chemical Society, Vol. 120, Issue 5 https://doi.org/10.1021/ja972617v	journal	January 1998
In Situ Investigation of Molecular Adsorption on Au Surface by Surface-Enhanced Infrared Absorption Spectroscopy Imae, Toyoko; Torii, Hiroyuki The Journal of Physical Chemistry B, Vol. 104, Issue 39 https://doi.org/10.1021/jp001592a	journal	September 2000
Metal Film over Nanosphere (MFON) Electrodes for Surface-Enhanced Raman Spectroscopy (SERS): Improvements in Surface Nanostructure Stability and Suppression of Irreversible Loss Dick, Lisa A.; McFarland, Adam D.; Haynes, Christy L. The Journal of Physical Chemistry B, Vol. 106, Issue 4 https://doi.org/10.1021/jp013638l	journal	January 2002
Coupling to Lysine-13 Promotes Electron Tunneling through Carboxylate-Terminated Alkanethiol Self-Assembled Monolayers to Cytochrome c Niki, Katsumi; Hardy, W. Reef; Hill, Michael G. The Journal of Physical Chemistry B, Vol. 107, Issue 37 https://doi.org/10.1021/jp035392l	journal	August 2003
Vibrational Spectra and Structural Transitions of Potassium Caprate A-Form Crystal Ishioka, Tsutomu; Wakisaka, Hiroyuki; Saito, Takuya The Journal of Physical Chemistry B, Vol. 102, Issue 27 https://doi.org/10.1021/jp980668o	journal	June 1998
Determination of the Distance Dependence and Experimental Effects for Modified SERS Substrates Based on Self-Assembled Monolayers Formed Using Alkanethiols Kennedy, B. J.; Spaeth, S.; Dickey, M. The Journal of Physical Chemistry B, Vol. 103, Issue 18 https://doi.org/10.1021/jp984454i	journal	May 1999
Silver Nanoparticles Capped by Long-Chain Unsaturated Carboxylates Wang, Wei; Chen, Xiao; Efrima, Shlomo The Journal of Physical Chemistry B, Vol. 103, Issue 34 https://doi.org/10.1021/jp991101q	journal	August 1999
Self-Assembly of n -Alkanethiol Monolayers. A Study by IR−Visible Sum Frequency Spectroscopy (SFG) Himmelhaus, M.; Eisert, F.; Buck, M. The Journal of Physical Chemistry B, Vol. 104, Issue 3 https://doi.org/10.1021/jp992073e	journal	January 2000
Synthesis and characterization of simple self-assembling, nanoporous monolayer assemblies: a new strategy for molecular recognition Chailapakul, Orawon; Crooks, Richard M. Langmuir, Vol. 9, Issue 4 https://doi.org/10.1021/la00028a002	journal	April 1993
Kinetics of carboxylic acid surface displacement reactions: a coupled surface plasmon and surface Raman scattering investigation Siirila, A. R.; Bohn, P. W. Langmuir, Vol. 7, Issue 10 https://doi.org/10.1021/la00058a036	journal	October 1991
Zwitterionic SAMs that Resist Nonspecific Adsorption of Protein from Aqueous Buffer Holmlin, R. Erik; Chen, Xiaoxi; Chapman, Robert G. Langmuir, Vol. 17, Issue 9 https://doi.org/10.1021/la0015258	journal	May 2001
Controlling the Adsorption of Single Poly(styrenesulfonate) Sodium on NH ₃ ⁺ -Modified Gold Surfaces on a Molecular Scale Zhu, M.; Schneider, M.; Papastavrou, G. Langmuir, Vol. 17, Issue 21 https://doi.org/10.1021/la001605b	journal	October 2001
Synthesis and Characterization of Amine-Terminated Self-Assembled Monolayers Containing Diethylene Glycol Linkages Chirakul, Panadda; Pérez-Luna, Victor H.; Owen, Hang Langmuir, Vol. 18, Issue 11 https://doi.org/10.1021/la015703o	journal	May 2002
In-Situ Investigation of Binary-Component Self-Assembled Monolayers: A SERS-Based Spectroelectrochemical Study of the Effects of Monolayer Composition on Interfacial Structure Oklejas, Vanessa; Harris, Joel M. Langmuir, Vol. 19, Issue 14 https://doi.org/10.1021/la020916e	journal	June 2003
Electric Field Driven Protonation/Deprotonation of Self-Assembled Monolayers of Acid-Terminated Thiols Burgess, Ian; Seivewright, Brian; Lennox, R. Bruce Langmuir, Vol. 22, Issue 9 https://doi.org/10.1021/la052767g	journal	April 2006
Assembly Dynamics and Detailed Structure of 1-Propanethiol Monolayers on Au(111) Surfaces Observed Real Time by in situ STM Zhang, Jingdong; Ulstrup, Jens Langmuir, Vol. 22, Issue 14 https://doi.org/10.1021/la0605891	journal	July 2006
Reactivity of Acid Fluoride-Terminated Self-Assembled Monolayers on Gold Chi, Young Shik; Lee, Kyung-Bok; Kim, Yongseong Langmuir, Vol. 23, Issue 3 https://doi.org/10.1021/la061878s	journal	December 2006
Surface-Enhanced Raman Spectroscopy Investigation of the Potential-Dependent Acid−Base Chemistry of Silver-Immobilized 2-Mercaptobenzoic Acid Ma, Chaoxiong; Harris, Joel M. Langmuir, Vol. 27, Issue 7 https://doi.org/10.1021/la1044859	journal	March 2011
Kinetics of Alkanethiol Adsorption on Gold Pan, W.; Durning, C. J.; Turro, N. J. Langmuir, Vol. 12, Issue 18 https://doi.org/10.1021/la9408634	journal	January 1996
Defect Pinning in Monolayer Films by Highly Controlled Graphite Defects: Molecule Corrals Patrick, David L.; Cee, Victor J.; Purcell, Timothy J. Langmuir, Vol. 12, Issue 7 https://doi.org/10.1021/la950354h	journal	January 1996
In Situ Kinetics of Self-Assembly by Surface Plasmon Resonance Spectroscopy Peterlinz, Kevin A.; Georgiadis, R. Langmuir, Vol. 12, Issue 20 https://doi.org/10.1021/la9508452	journal	January 1996
In Situ Scanning Tunneling Microscopy Observation of the Self-Assembly Process of Alkanethiols on Gold(111) in Solution Yamada, Ryo; Uosaki, Kohei Langmuir, Vol. 14, Issue 4 https://doi.org/10.1021/la970974d	journal	January 1998
Corrosion Passivation of Gold by n -Alkanethiol Self-Assembled Monolayers: Effect of Chain Length and End Group Zamborini, Francis P.; Crooks, Richard M. Langmuir, Vol. 14, Issue 12 https://doi.org/10.1021/la971121o	journal	June 1998
In Situ Monitoring of Kinetics of Charged Thiol Adsorption on Gold Using an Atomic Force Microscope Hu, Kai; Bard, Allen J. Langmuir, Vol. 14, Issue 17 https://doi.org/10.1021/la971363o	journal	July 1998
Effects of Electrolyte and Potential on the in Situ Structure of Alkanethiol Self-Assembled Monolayers on Silver Schoenfisch, Mark H.; Pemberton, Jeanne E. Langmuir, Vol. 15, Issue 2 https://doi.org/10.1021/la9811618	journal	December 1998
Characterization of Self-Assembled Monolayers for Biosensor Applications Nyquist, R. M.; Eberhardt, A. S.; Silks, L. A. Langmuir, Vol. 16, Issue 4 https://doi.org/10.1021/la990018r	journal	January 2000
Surface-enhanced Raman scattering Campion, Alan; Kambhampati, Patanjali Chemical Society Reviews, Vol. 27, Issue 4 https://doi.org/10.1039/a827241z	journal	January 1998
Distance dependence of surface enhanced Raman scattering probed by alkanethiol self-assembled monolayers Compagnini, Giuseppe; Galati, Clelia; Pignataro, Salvatore Physical Chemistry Chemical Physics, Vol. 1, Issue 9 https://doi.org/10.1039/a901034c	journal	January 1999
Controlled protein assembly on a switchable surfaceElectronic supplementary information (ESI) available: preparation and characterization of LD-MHA-SAM-n and the assembled protein films. See http://www.rsc.org/suppdata/cc/b4/b400776j/ Liu, Ying; Mu, Li; Liu, Baohong Chemical Communications, Issue 10 https://doi.org/10.1039/b400776j	journal	January 2004
Electric field induced switching of poly(ethylene glycol) terminated self-assembled monolayers: A parallel molecular dynamics simulation Vemparala, Satyavani; Kalia, Rajiv K.; Nakano, Aiichiro The Journal of Chemical Physics, Vol. 121, Issue 11 https://doi.org/10.1063/1.1781120	journal	September 2004
Control and placement of molecules via self-assembly Lewis, P. A.; Donhauser, Z. J.; Mantooth, B. A. Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1088/0957-4484/12/3/306	journal	August 2001
A Reversibly Switching Surface Lahann, J. Science, Vol. 299, Issue 5605 https://doi.org/10.1126/science.1078933	journal	January 2003
Growth Processes and Control of Two-Dimensional Structure of Carboxylic Acid-Terminated Self-Assembled Monolayers on Au(111) Noh, Jaegeun; Konno, Kaoru; Ito, Eisuke Japanese Journal of Applied Physics, Vol. 44, Issue 2R https://doi.org/10.1143/JJAP.44.1052	journal	February 2005
Surface-Enhanced Raman Spectroscopy Stiles, Paul L.; Dieringer, Jon A.; Shah, Nilam C. Annual Review of Analytical Chemistry, Vol. 1, Issue 1, p. 601-626 https://doi.org/10.1146/annurev.anchem.1.031207.112814	journal	July 2008
Localized Surface Plasmon Resonance Spectroscopy and Sensing Willets, Katherine A.; Van Duyne, Richard P. Annual Review of Physical Chemistry, Vol. 58, Issue 1 https://doi.org/10.1146/annurev.physchem.58.032806.104607	journal	May 2007
Resolution of Intermediate Adsorbate Structures in the Potential-Dependent Self-Assembly of n-Hexanethiolate on Silver by in situ Surface-Enhanced Raman Spectroscopy Uibel, Rory H.; Harris, Joel M. Applied Spectroscopy, Vol. 58, Issue 8 https://doi.org/10.1366/0003702041655395	journal	August 2004
Adsorption of S—S Containing Proteins on a Colloidal Silver Surface Studied by Surface-Enhanced Raman Spectroscopy Podstawka, Edyta; Ozaki, Yukihiro; Proniewicz, Leonard M. Applied Spectroscopy, Vol. 58, Issue 10 https://doi.org/10.1366/0003702042336073	journal	October 2004
Surface-Enhanced Raman Spectroscopy Studies of Surfactant Adsorption to a Hydrophobic Interface Olson, Lydia G.; Harris, Joel M. Applied Spectroscopy, Vol. 62, Issue 2 https://doi.org/10.1366/000370208783575492	journal	February 2008

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