Quantitative evaluation of perfluorinated alkanethiol molecular order on gold surfaces

Gamble, Lara J.; Radford, David; Grainger, David W.; Castner, David G.

doi:10.1116/6.0002720

Quantitative evaluation of perfluorinated alkanethiol molecular order on gold surfaces

Journal Article · Mon May 01 04:00:00 EDT 2023 · Biointerphases

DOI:https://doi.org/10.1116/6.0002720· OSTI ID:2425495

; ; ;

Self-assembled monolayers (SAMs) of perfluoroalkanethiols [CF3(CF2)xCH2CH2SH (x = 3, 5, 7, and 9)] on gold were characterized by x-ray photoelectron spectroscopy (XPS), near edge x-ray absorption fine structure (NEXAFS), and static time-of-flight secondary ion mass spectrometry (ToF-SIMS). Perfluoroalkanethiols of several chain lengths were synthesized using a known hydride reduction method for transforming commercially available perfluoroalkyliodides to corresponding perfluoroalkanethiols. This strategy provides improved product yields compared to other known routes based on hydrolysis from the common thioacetyl perfluoroalkyl intermediate. Angle-dependent XPS analysis revealed that CF3(CF2)xCH2CH2SH (x = 5, 7, and 9; F6, F8, and F10, respectively) SAMs on gold exhibited significant enrichment of the terminal CF3 group at the outer monolayer surface with the sulfur present as a metal-bound thiolate located at the monolayer-gold interface. XPS of the CF3(CF2)3CH2CH2SH (F4) monolayer revealed a thin film with a significant (>50%) amount of hydrocarbon contamination consistent with poorly organized monolayers, while the longest thiol (F10) showed XPS signals attributed to substantial ordering and anisotropy. ToF-SIMS spectra from all four SAMs contained molecular ions representative of the particular perfluorinated thiol used to prepare the monolayer. NEXAFS methods were used to determine degrees of ordering and average tilt for molecules comprising monolayers. The SAMs prepared from the longest (F10) thiols exhibited the highest degree of ordering with the molecular axis nearly perpendicular to the gold surface. The degree of ordering decreased significantly with decreasing length of the perfluorocarbon tail.

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: SC0012704

OSTI ID:: 2425495

Journal Information:: Biointerphases, Journal Name: Biointerphases Journal Issue: 3 Vol. 18; ISSN 1934-8630

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

References (66)

Pentafluoro-λ⁶-sulfanyl-Terminated Chlorosilanes: New SF₅-Containing Films and Polysiloxane Materials Nixon, Paul G.; Winter, Rolf; Castner, David G. Chemistry of Materials, Vol. 12, Issue 10 https://doi.org/10.1021/cm000339k	journal	September 2000
How perfluoroalkyl substances modify fluorinated self-assembled monolayer architectures: An electrochemical and computational study Moro, Giulia; Dongmo Foumthuim, Cedrix J.; Spinaci, Marco Analytica Chimica Acta, Vol. 1204 https://doi.org/10.1016/j.aca.2022.339740	journal	April 2022
Photopolymerized Epoxide Copolymer Thin Films with Surfaces Highly Enriched with Sulfonyl Fluoride Groups Schnurer, A. U.; Holcomb, N. R.; Gard, G. L. Chemistry of Materials, Vol. 8, Issue 7 https://doi.org/10.1021/cm960049x	journal	January 1996
Langmuir–Blodgett Monolayers of Partially Fluorinated Ionic Liquids as Two-Dimensional, More Sustainable Functional Materials and Coatings Sieling, Thorben; Christoffers, Jens; Brand, Izabella ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 13 https://doi.org/10.1021/acssuschemeng.9b01496	journal	May 2019
Burying the Inverted Surface Dipole: Self-Assembled Monolayers Derived from Alkyl-Terminated Partially Fluorinated Alkanethiols Marquez, Maria D.; Zenasni, Oussama; Rodriguez, Daniela Chemistry of Materials, Vol. 32, Issue 3 https://doi.org/10.1021/acs.chemmater.9b02887	journal	December 2019
Microstructure, Wettability, and Thermal Stability of Semifluorinated Self-Assembled Monolayers (SAMs) on Gold Fukushima, H.; Seki, S.; Nishikawa, T. The Journal of Physical Chemistry B, Vol. 104, Issue 31 https://doi.org/10.1021/jp0003499	journal	August 2000
Self-Assembled Monolayers of Symmetrical and Mixed Alkyl Fluoroalkyl Disulfides on Gold. 2. Investigation of Thermal Stability and Phase Separation Schönherr, H.; Ringsdorf, H.; Jaschke, M. Langmuir, Vol. 12, Issue 16 https://doi.org/10.1021/la9601420	journal	January 1996
Studies of Molecular Orientation and Order in Self-Assembled Semifluorinated n-Alkanethiols: Single and Dual Component Mixtures Tsao, M. -W.; Hoffmann, C. L.; Rabolt, J. F. Langmuir, Vol. 13, Issue 16 https://doi.org/10.1021/la970293i	journal	August 1997
Structural Investigation of Molecular Organization in Self-Assembled Monolayers of a Semifluorinated Amidethiol Lenk, T. J.; Hallmark, V. M.; Hoffmann, C. L. Langmuir, Vol. 10, Issue 12 https://doi.org/10.1021/la00024a037	journal	December 1994
Perfluorinated polymer surfaces comprising SF5-terminated long-chain perfluoroacrylate Winter, R.; Nixon, P. G.; Terjeson, R. J. Journal of Fluorine Chemistry, Vol. 115, Issue 2 https://doi.org/10.1016/S0022-1139(02)00008-8	journal	June 2002
Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV Scofield, J. H. Journal of Electron Spectroscopy and Related Phenomena, Vol. 8, Issue 2 https://doi.org/10.1016/0368-2048(76)80015-1	journal	January 1976
Control strategies for atmospheric pressure plasma polymerization of fluorinated silane thin films with antiadhesive properties Laghi, Giulia; Franco, Domenico; Condorelli, Guglielmo Guido Plasma Processes and Polymers, Vol. 20, Issue 4 https://doi.org/10.1002/ppap.202200194	journal	December 2022
Terminally perfluorinated long-chain alkanethiols Graupe, Michael; Koini, Thomas; Wang, Vincent Y. Journal of Fluorine Chemistry, Vol. 93, Issue 2 https://doi.org/10.1016/S0022-1139(98)00284-X	journal	February 1999
Chemical functionality in self-assembled monolayers: structural and electrochemical properties Chidsey, Christopher E. D.; Loiacono, Dominic N. Langmuir, Vol. 6, Issue 3 https://doi.org/10.1021/la00093a026	journal	March 1990
Time-of-flight secondary ion mass spectrometry: techniques and applications for the characterization of biomaterial surfaces Belu, Anna M.; Graham, Daniel J.; Castner, David G. Biomaterials, Vol. 24, Issue 21 https://doi.org/10.1016/S0142-9612(03)00159-5	journal	September 2003
Polarized NEXAFS studies on the mechanical rubbing effect of poly(tetrafluoroethylene) oligomer and its model compound Nagayama, K.; Sei, M.; Mitsumoto, R. Journal of Electron Spectroscopy and Related Phenomena, Vol. 78 https://doi.org/10.1016/S0368-2048(96)80102-2	journal	May 1996
The effect of sulfur–metal bonding on the structure of self-assembled monolayers Zharnikov, M.; Frey, S.; Rong, H. Physical Chemistry Chemical Physics, Vol. 2, Issue 15 https://doi.org/10.1039/b004232n	journal	January 2000
Surface Analysis – The Principal Techniques Vickerman, John C.; Gilmore, Ian S. John Wiley & Sons, Ltd https://doi.org/10.1002/9780470721582	book	March 2009
Structures of Molecules and Crystals of Fluoro-Carbons Bunn, C. W.; Howells, E. R. Nature, Vol. 174, Issue 4429 https://doi.org/10.1038/174549a0	journal	September 1954
Characterizing protein G B1 orientation and its effect on immunoglobulin G antibody binding using XPS, ToF-SIMS, and quartz crystal microbalance with dissipation monitoring Harrison, Elisa T.; Wang, Yung-Chen; Carter, Lauren Biointerphases, Vol. 15, Issue 2 https://doi.org/10.1116/1.5142560	journal	March 2020
Contrasting Transport and Electrostatic Properties of Selectively Fluorinated Alkanethiol Monolayers with Embedded Dipoles Bruce, Robert C.; You, Lin; Förster, Anja The Journal of Physical Chemistry C, Vol. 122, Issue 9 https://doi.org/10.1021/acs.jpcc.7b11892	journal	February 2018
Influence of Constitution on Adhesion Zisman, W. A. Industrial & Engineering Chemistry, Vol. 55, Issue 10 https://doi.org/10.1021/ie50646a003	journal	October 1963
Formation of monolayer films by the spontaneous assembly of organic thiols from solution onto gold Bain, Colin D.; Troughton, E. Barry; Tao, Yu Tai Journal of the American Chemical Society, Vol. 111, Issue 1, p. 321-335 https://doi.org/10.1021/ja00183a049	journal	January 1989
Lattice Imaging of Self-Assembled Monolayers of Partially Fluorinated Disulfides and Thiols on Sputtered Gold by Atomic Force Microscopy Schönherr, H.; Vancso, G. J. Langmuir, Vol. 13, Issue 14 https://doi.org/10.1021/la960561x	journal	July 1997
Systematic Studies of the Frictional Properties of Fluorinated Monolayers with Atomic Force Microscopy: Comparison of CF ₃ - and CH ₃ -Terminated Films Kim, Hyun I.; Koini, Thomas; Lee, T. Randall Langmuir, Vol. 13, Issue 26 https://doi.org/10.1021/la970539j	journal	December 1997
Surface analysis tools for characterizing biological materials Baio, Joe E.; Graham, Daniel J.; Castner, David G. Chemical Society Reviews, Vol. 49, Issue 11 https://doi.org/10.1039/D0CS00181C	journal	January 2020
Molecular Orientation and Grafting Density in Semifluorinated Self-Assembled Monolayers of Mono-, Di-, and Trichloro Silanes on Silica Substrates Genzer, Jan; Efimenko, Kirill; Fischer, Daniel A. Langmuir, Vol. 18, Issue 24 https://doi.org/10.1021/la025921x	journal	November 2002
Polarized XANES studies of oriented polyethylene and fluorinated polyethylenes Ohta, Toshiaki; Seki, Kazuhiko; Yokoyama, Toshihiko Physica Scripta, Vol. 41, Issue 1 https://doi.org/10.1088/0031-8949/41/1/036	journal	January 1990
Self-assembled monolayers of semifluorinated thiols on electrochemically modified polycrystalline nickel surfaces Tortech, L.; Mekhalif, Z.; Delhalle, J. Thin Solid Films, Vol. 491, Issue 1-2 https://doi.org/10.1016/j.tsf.2005.06.090	journal	November 2005
Structure of self-organizing organic films: A near edge x-ray absorption fine structure investigation of thiol layers adsorbed on gold Hähner, G.; Kinzler, M.; Thümmler, C. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 10, Issue 4 https://doi.org/10.1116/1.577906	journal	July 1992
Multitechnique Characterization of Self-Assembled Carboxylic Acid-Terminated Alkanethiol Monolayers on Nanoparticle and Flat Gold Surfaces Techane, Sirnegeda D.; Gamble, Lara J.; Castner, David G. The Journal of Physical Chemistry C, Vol. 115, Issue 19 https://doi.org/10.1021/jp201213g	journal	April 2011
Assessment of fibronectin conformation adsorbed to polytetrafluoroethylene surfaces from serum protein mixtures and correlation to support of cell attachment in culture Grainger, David W.; Pavon-Djavid, Graciella; Migonney, Veronique Journal of Biomaterials Science, Polymer Edition, Vol. 14, Issue 9 https://doi.org/10.1163/156856203322381456	journal	January 2003
Evaluation of Fluorinated Self‐Assembled Monolayer by Photoelectron and Near Edge X‐Ray Absorption Fine Structure Spectroscopy Haruyama, Yuichi; Okada, Makoto; Nakai, Yasuki Electronics and Communications in Japan, Vol. 98, Issue 11 https://doi.org/10.1002/ecj.11759	journal	October 2015
Molecular-Level Control over Surface Order in Self-Assembled Monolayer Films of Thiols on Gold Bain, C. D.; Whitesides, G. M. Science, Vol. 240, Issue 4848 https://doi.org/10.1126/science.240.4848.62	journal	April 1988
Quantitative electron spectroscopy of surfaces: A standard data base for electron inelastic mean free paths in solids Seah, M. P.; Dench, W. A. Surface and Interface Analysis, Vol. 1, Issue 1 https://doi.org/10.1002/sia.740010103	journal	February 1979
Self-Assembled Monolayers of Symmetrical and Mixed Alkyl Fluoroalkyl Disulfides on Gold. 1. Synthesis of Disulfides and Investigation of Monolayer Properties Schönherr, H.; Ringsdorf, H. Langmuir, Vol. 12, Issue 16 https://doi.org/10.1021/la9601418	journal	January 1996
Surface analysis: From single crystals to biomaterials Castner, David G. Surface and Interface Analysis, Vol. 50, Issue 11 https://doi.org/10.1002/sia.6422	journal	March 2018
Deposition of Highly Ordered CF₂-Rich Films Using Continuous Wave and Pulsed Hexafluoropropylene Oxide Plasmas Butoi, Carmen I.; Mackie, Neil M.; Gamble, Lara J. Chemistry of Materials, Vol. 12, Issue 7 https://doi.org/10.1021/cm0002416	journal	June 2000
Biomedical surface analysis: Evolution and future directions (Review) Castner, David G. Biointerphases, Vol. 12, Issue 2 https://doi.org/10.1116/1.4982169	journal	June 2017
Mechanisms of Defect Passivation by Fluorinated Alkylthiolates on PbS Quantum Dots Perez, Kaitlyn A.; Lian, Shichen; Kodaimati, Mohamad S. The Journal of Physical Chemistry C, Vol. 122, Issue 25 https://doi.org/10.1021/acs.jpcc.8b01066	journal	December 2017
The impact of fluorination on the structure and properties of self-assembled monolayer films Zenasni, Oussama; Jamison, Andrew C.; Lee, T. Randall Soft Matter, Vol. 9, Issue 28 https://doi.org/10.1039/c3sm00054k	journal	January 2013
Packing and molecular orientation of alkanethiol monolayers on gold surfaces Ulman, Abraham; Eilers, James E.; Tillman, Nolan Langmuir, Vol. 5, Issue 5 https://doi.org/10.1021/la00089a003	journal	September 1989
Evidence for Cleavage of Disulfides in the Self-Assembled Monolayer on Au(111) Ishida, Takao; Yamamoto, Shin'ichi; Mizutani, Wataru Langmuir, Vol. 13, Issue 13 https://doi.org/10.1021/la962022y	journal	June 1997
Self-Assembled Organic Monolayers Terminated in Perfluoroalkyl Pentafluoro-λ⁶-sulfanyl (-SF₅) Chemistry on Gold Winter, R.; Nixon, P. G.; Gard, G. L. Langmuir, Vol. 20, Issue 14 https://doi.org/10.1021/la040011w	journal	June 2004
X-ray Photoelectron Spectroscopy Sulfur 2p Study of Organic Thiol and Disulfide Binding Interactions with Gold Surfaces Castner, David G.; Hinds, Kenneth; Grainger, David W. Langmuir, Vol. 12, Issue 21 https://doi.org/10.1021/la960465w	journal	January 1996
Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry Porter, Marc D.; Bright, Thomas B.; Allara, David L. Journal of the American Chemical Society, Vol. 109, Issue 12 https://doi.org/10.1021/ja00246a011	journal	June 1987
Modification of semifluorinated alkanethiolate monolayers by low energy electron irradiation Frey, S.; Heister, K.; Zharnikov, M. Physical Chemistry Chemical Physics, Vol. 2, Issue 9 https://doi.org/10.1039/a910314g	journal	January 2000
Wettabilities of Self-Assembled Monolayers Generated from CF₃-Terminated Alkanethiols on Gold Miura, Yasuhiro F.; Takenaga, Mitsuru; Koini, Thomas Langmuir, Vol. 14, Issue 20 https://doi.org/10.1021/la980154g	journal	September 1998
Antifouling Coatings Generated from Unsymmetrical Partially Fluorinated Spiroalkanedithiols St. Hill, Lydia R.; Craft, John W.; Chinwangso, Pawilai ACS Applied Bio Materials, Vol. 4, Issue 2 https://doi.org/10.1021/acsabm.0c01409	journal	February 2021
Determination of molecular orientations on surfaces from the angular dependence of near-edge x-ray-absorption fine-structure spectra Stöhr, J.; Outka, D. A. Physical Review B, Vol. 36, Issue 15 https://doi.org/10.1103/PhysRevB.36.7891	journal	November 1987
An unexpected packing of fluorinated n ‐alkane thiols on Au(111): A combined atomic force microscopy and x‐ray diffraction study Liu, Gang‐yu; Fenter, Paul; Chidsey, Christopher E. D. The Journal of Chemical Physics, Vol. 101, Issue 5 https://doi.org/10.1063/1.467479	journal	September 1994
C 1s excitation studies of diamond (111). II. Unoccupied surface states Morar, J. F.; Himpsel, F. J.; Hollinger, G. Physical Review B, Vol. 33, Issue 2 https://doi.org/10.1103/PhysRevB.33.1346	journal	January 1986
Molecular Orientation of Single and Two-Armed Monodendron Semifluorinated Chains on “Soft” and “Hard” Surfaces Studied Using NEXAFS Genzer, Jan; Sivaniah, Easan; Kramer, Edward J. Macromolecules, Vol. 33, Issue 16 https://doi.org/10.1021/ma991710w	journal	July 2000
Determination of surface structure and orientation of polymerized tetrafluoroethylene films by near-edge x-ray absorption fine structure, x-ray photoelectron spectroscopy, and static secondary ion mass spectrometry Castner, David G.; Lewis, Kenneth B.; Fischer, Daniel A. Langmuir, Vol. 9, Issue 2 https://doi.org/10.1021/la00026a029	journal	February 1993
Hydrophobicity of Self-Assembled Monolayers of Alkanes: Fluorination, Density, Roughness, and Lennard-Jones Cutoffs Carlson, Shane; Becker, Maximilian; Brünig, Florian N. Langmuir, Vol. 37, Issue 47 https://doi.org/10.1021/acs.langmuir.1c02187	journal	November 2021
Biomedical surface science: Foundations to frontiers Castner, David G.; Ratner, Buddy D. Surface Science, Vol. 500, Issue 1-3 https://doi.org/10.1016/S0039-6028(01)01587-4	journal	March 2002
Photopolymerized Acrylate Copolymer Films with Surfaces Enriched in Sulfur Pentafluoride (−SF₅) Chemistry Winter, R.; Nixon, P. G.; Gard, G. L. Chemistry of Materials, Vol. 11, Issue 11 https://doi.org/10.1021/cm981102f	journal	October 1999
X-ray photoelectron spectroscopy of partial and stamped thiol-based self-assembled monolayers Evans, S. D.; Cooper, S. D.; Johnson, S. R. Supramolecular Science, Vol. 4, Issue 3-4 https://doi.org/10.1016/S0968-5677(97)00011-4	journal	September 1997
Longitudinal acoustic modes of polytetrafluoroethylene copolymers and oligomers Rabolt, John F.; Fanconi, Bruno Polymer, Vol. 18, Issue 12 https://doi.org/10.1016/0032-3861(77)90290-7	journal	December 1977
Atomic force microscopic characterization of a fluorinated alkanethiolate monolayer at gold and correlations to electrochemical and infrared reflection spectroscopic structural descriptions Alves, Carla A.; Porter, Marc D. Langmuir, Vol. 9, Issue 12 https://doi.org/10.1021/la00036a027	journal	December 1993
Semifluorinated thiols in Langmuir monolayers – A study by nonlinear and linear vibrational spectroscopies Volpati, Diogo; Chachaj-Brekiesz, Anna; Souza, Adriano L. Journal of Colloid and Interface Science, Vol. 460 https://doi.org/10.1016/j.jcis.2015.08.069	journal	December 2015
Tight binding of albumin to glow discharge treated polymers Kiaei, David; Hoffman, Allan S.; Horbett, Thomas A. Journal of Biomaterials Science, Polymer Edition, Vol. 4, Issue 1 https://doi.org/10.1163/156856292X00286	journal	January 1993
A Neutron Reflectivity Investigation of Surface and Interface Segregation of Polymer Functional End Groups Elman, J. F.; Johs, B. D.; Long, T. E. Macromolecules, Vol. 27, Issue 19 https://doi.org/10.1021/ma00097a013	journal	September 1994
Unsymmetrical Spiroalkanedithiols Having Mixed Fluorinated and Alkyl Tailgroups of Varying Length: Film Structure and Interfacial Properties Chinwangso, Pawilai; St. Hill, Lydia R.; Marquez, Maria D. Molecules, Vol. 23, Issue 10 https://doi.org/10.3390/molecules23102632	journal	October 2018
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
Structure of self‐assembled monolayers of semifluorinated alkanethiols on gold and silver substrates Frey, S.; Heister, K.; Zharnikov, M. Israel Journal of Chemistry, Vol. 40, Issue 2 https://doi.org/10.1560/0K18-2RLA-GAQD-NHRU	journal	October 2000

Similar Records

Rapid Degradation of Alkanethiol-Based Self-Assembled Monolayers on Gold in Ambient Laboratory Conditions

Journal Article · Wed Jul 21 00:00:00 EDT 2004 · Surface Science · OSTI ID:15011515

Near-Edge X-Ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

Journal Article · Tue May 26 00:00:00 EDT 2009 · J. Am. Chem. Soc. 130:10536,2008 · OSTI ID:953607

Characterization of Functionalized Self-Assembled Monolayers and Surface-Attached Interlocking Molecules Using Near-Edge X-ray Absorption Fine Structure Spectroscopy

Thesis/Dissertation · Wed Mar 31 23:00:00 EST 2004 · OSTI ID:15014054

Related Subjects

Biophysics
Materials Science

Quantitative evaluation of perfluorinated alkanethiol molecular order on gold surfaces

Citation Formats

References (66)

Similar Records

Related Subjects