Ambient Surface Analysis of Organic Monolayers using Direct Analysis in Real Time Orbitrap Mass Spectrometry

R.K. Manova, S. Joshi, A. Debrassi, N.S. Bhairamadgi, E. Roeven, J. Gagnon, M.N. Tahir, F.W. Claassen, L.M.W. Scheres, T. Wennekes, C.G.P.H. Schroën, T.A. van Beek, H. Zuilhof, M.W.F. Nielen

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Abstract

A better characterization of nanometer-thick organic layers (monolayers) as used for engineering surface properties, biosensing, nanomedicine, and smart materials will widen their application. The aim of this study was to develop direct analysis in real time high-resolution mass spectrometry (DART-HRMS) into a new and complementary analytical tool for characterizing organic monolayers. To assess the scope and formulate general interpretation rules, DART-HRMS was used to analyze a diverse set of monolayers having different chemistries (amides, esters, amines, acids, alcohols, alkanes, ethers, thioethers, polymers, sugars) on five different substrates (Si, Si3N4, glass, Al2O3, Au). The substrate did not play a major role except in the case of gold, for which breaking of the weak Au–S bond that tethers the monolayer to the surface, was observed. For monolayers with stronger covalent interfacial bonds, fragmentation around terminal groups was found. For ester and amide-terminated monolayers, in situ hydrolysis during DART resulted in the detection of ions characteristic of the terminal groups (alcohol, amine, carboxylic acid). For ether and thioether-terminated layers, scission of C–O or C–S bonds also led to the release of the terminal part of the monolayer in a predictable manner. Only the spectra of alkane monolayers could not be interpreted. DART-HRMS allowed for the analysis of and distinction between monolayers containing biologically relevant mono or disaccharides. Overall, DART-HRMS is a promising surface analysis technique that combines detailed structural information on nanomaterials and ultrathin films with fast analyses under ambient conditions.
Original languageEnglish
Pages (from-to)2403-2411
JournalAnalytical Chemistry
Volume86
Issue number5
DOIs
Publication statusPublished - 2014

Fingerprint

Surface analysis
Mass spectrometry
Monolayers
Alkanes
Sulfides
Amides
Amines
Esters
Alcohols
Medical nanotechnology
Intelligent materials
Ethers
Ultrathin films
Disaccharides
Substrates
Carbon Monoxide
Carboxylic Acids
Nanostructured materials
Sugars
Gold

Keywords

  • self-assembled monolayers
  • tof-sims
  • static sims
  • gold
  • silicon
  • biofunctionalization
  • functionalization
  • fragmentation
  • biosensors
  • layer

Cite this

Manova, R.K. ; Joshi, S. ; Debrassi, A. ; Bhairamadgi, N.S. ; Roeven, E. ; Gagnon, J. ; Tahir, M.N. ; Claassen, F.W. ; Scheres, L.M.W. ; Wennekes, T. ; Schroën, C.G.P.H. ; van Beek, T.A. ; Zuilhof, H. ; Nielen, M.W.F. / Ambient Surface Analysis of Organic Monolayers using Direct Analysis in Real Time Orbitrap Mass Spectrometry. In: Analytical Chemistry. 2014 ; Vol. 86, No. 5. pp. 2403-2411.
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abstract = "A better characterization of nanometer-thick organic layers (monolayers) as used for engineering surface properties, biosensing, nanomedicine, and smart materials will widen their application. The aim of this study was to develop direct analysis in real time high-resolution mass spectrometry (DART-HRMS) into a new and complementary analytical tool for characterizing organic monolayers. To assess the scope and formulate general interpretation rules, DART-HRMS was used to analyze a diverse set of monolayers having different chemistries (amides, esters, amines, acids, alcohols, alkanes, ethers, thioethers, polymers, sugars) on five different substrates (Si, Si3N4, glass, Al2O3, Au). The substrate did not play a major role except in the case of gold, for which breaking of the weak Au–S bond that tethers the monolayer to the surface, was observed. For monolayers with stronger covalent interfacial bonds, fragmentation around terminal groups was found. For ester and amide-terminated monolayers, in situ hydrolysis during DART resulted in the detection of ions characteristic of the terminal groups (alcohol, amine, carboxylic acid). For ether and thioether-terminated layers, scission of C–O or C–S bonds also led to the release of the terminal part of the monolayer in a predictable manner. Only the spectra of alkane monolayers could not be interpreted. DART-HRMS allowed for the analysis of and distinction between monolayers containing biologically relevant mono or disaccharides. Overall, DART-HRMS is a promising surface analysis technique that combines detailed structural information on nanomaterials and ultrathin films with fast analyses under ambient conditions.",
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author = "R.K. Manova and S. Joshi and A. Debrassi and N.S. Bhairamadgi and E. Roeven and J. Gagnon and M.N. Tahir and F.W. Claassen and L.M.W. Scheres and T. Wennekes and C.G.P.H. Schro{\"e}n and {van Beek}, T.A. and H. Zuilhof and M.W.F. Nielen",
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Manova, RK, Joshi, S, Debrassi, A, Bhairamadgi, NS, Roeven, E, Gagnon, J, Tahir, MN, Claassen, FW, Scheres, LMW, Wennekes, T, Schroën, CGPH, van Beek, TA, Zuilhof, H & Nielen, MWF 2014, 'Ambient Surface Analysis of Organic Monolayers using Direct Analysis in Real Time Orbitrap Mass Spectrometry', Analytical Chemistry, vol. 86, no. 5, pp. 2403-2411. https://doi.org/10.1021/ac4031626

Ambient Surface Analysis of Organic Monolayers using Direct Analysis in Real Time Orbitrap Mass Spectrometry. / Manova, R.K.; Joshi, S.; Debrassi, A.; Bhairamadgi, N.S.; Roeven, E.; Gagnon, J.; Tahir, M.N.; Claassen, F.W.; Scheres, L.M.W.; Wennekes, T.; Schroën, C.G.P.H.; van Beek, T.A.; Zuilhof, H.; Nielen, M.W.F.

In: Analytical Chemistry, Vol. 86, No. 5, 2014, p. 2403-2411.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Ambient Surface Analysis of Organic Monolayers using Direct Analysis in Real Time Orbitrap Mass Spectrometry

AU - Manova, R.K.

AU - Joshi, S.

AU - Debrassi, A.

AU - Bhairamadgi, N.S.

AU - Roeven, E.

AU - Gagnon, J.

AU - Tahir, M.N.

AU - Claassen, F.W.

AU - Scheres, L.M.W.

AU - Wennekes, T.

AU - Schroën, C.G.P.H.

AU - van Beek, T.A.

AU - Zuilhof, H.

AU - Nielen, M.W.F.

PY - 2014

Y1 - 2014

N2 - A better characterization of nanometer-thick organic layers (monolayers) as used for engineering surface properties, biosensing, nanomedicine, and smart materials will widen their application. The aim of this study was to develop direct analysis in real time high-resolution mass spectrometry (DART-HRMS) into a new and complementary analytical tool for characterizing organic monolayers. To assess the scope and formulate general interpretation rules, DART-HRMS was used to analyze a diverse set of monolayers having different chemistries (amides, esters, amines, acids, alcohols, alkanes, ethers, thioethers, polymers, sugars) on five different substrates (Si, Si3N4, glass, Al2O3, Au). The substrate did not play a major role except in the case of gold, for which breaking of the weak Au–S bond that tethers the monolayer to the surface, was observed. For monolayers with stronger covalent interfacial bonds, fragmentation around terminal groups was found. For ester and amide-terminated monolayers, in situ hydrolysis during DART resulted in the detection of ions characteristic of the terminal groups (alcohol, amine, carboxylic acid). For ether and thioether-terminated layers, scission of C–O or C–S bonds also led to the release of the terminal part of the monolayer in a predictable manner. Only the spectra of alkane monolayers could not be interpreted. DART-HRMS allowed for the analysis of and distinction between monolayers containing biologically relevant mono or disaccharides. Overall, DART-HRMS is a promising surface analysis technique that combines detailed structural information on nanomaterials and ultrathin films with fast analyses under ambient conditions.

AB - A better characterization of nanometer-thick organic layers (monolayers) as used for engineering surface properties, biosensing, nanomedicine, and smart materials will widen their application. The aim of this study was to develop direct analysis in real time high-resolution mass spectrometry (DART-HRMS) into a new and complementary analytical tool for characterizing organic monolayers. To assess the scope and formulate general interpretation rules, DART-HRMS was used to analyze a diverse set of monolayers having different chemistries (amides, esters, amines, acids, alcohols, alkanes, ethers, thioethers, polymers, sugars) on five different substrates (Si, Si3N4, glass, Al2O3, Au). The substrate did not play a major role except in the case of gold, for which breaking of the weak Au–S bond that tethers the monolayer to the surface, was observed. For monolayers with stronger covalent interfacial bonds, fragmentation around terminal groups was found. For ester and amide-terminated monolayers, in situ hydrolysis during DART resulted in the detection of ions characteristic of the terminal groups (alcohol, amine, carboxylic acid). For ether and thioether-terminated layers, scission of C–O or C–S bonds also led to the release of the terminal part of the monolayer in a predictable manner. Only the spectra of alkane monolayers could not be interpreted. DART-HRMS allowed for the analysis of and distinction between monolayers containing biologically relevant mono or disaccharides. Overall, DART-HRMS is a promising surface analysis technique that combines detailed structural information on nanomaterials and ultrathin films with fast analyses under ambient conditions.

KW - self-assembled monolayers

KW - tof-sims

KW - static sims

KW - gold

KW - silicon

KW - biofunctionalization

KW - functionalization

KW - fragmentation

KW - biosensors

KW - layer

U2 - 10.1021/ac4031626

DO - 10.1021/ac4031626

M3 - Article

VL - 86

SP - 2403

EP - 2411

JO - Analytical Chemistry

JF - Analytical Chemistry

SN - 0003-2700

IS - 5

ER -