Spontaneous desorption and phase transitions of self-assembled alkanethiol and alicyclic thiol monolayers chemisorbed on Au(1 1 1) in ultrahigh vacuum at room temperature

Ito, Eisuke; Kang, Hye Won; Lee, Dongjin; Park, Joon B.; Hara, Masahiko; Noh, Jaegeun

doi:10.1016/j.jcis.2012.12.035

Cited by 45 publications

(55 citation statements)

References 86 publications

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“…61,62,64 In Figure 6 peak (S C(sulfide) ) is observed at a BE of (161.04 ± 0.08) eV (S 2p 3/2 ). Although this doublet has often appeared with alkanethiol SAMs of low molecular density or a disordered phase, 37 it is more likely that the cleavage of C-S bond of the thiol molecules is the responsible of the S-Au sulfide appearance, in agreement with previous reports. 55,78 As already reported in SAMs on Au(111), the atomically adsorbed sulfur can be desorbed completely at higher temperatures.…”

Section: Desorption At Higher Temperatures (Ht)supporting

confidence: 91%

“…35,[42][43][44] On the other hand, recent work demonstrated that SAMs of hexanethiol molecules chemisorbed on Au(111) surfaces desorbs spontaneously in high vacuum (HV) conditions (3x10 -7 Pa) at room 5 temperature (RT) and that van der Waals interactions play an important role in determining their structural stability. 37 In contrast to the extensive study on thermal desorption of SAMs of aliphatic thiol molecules on Au(111) surfaces, much less information can be found for such processes on Au(001) surfaces. It has been reported that physisorbed butanethiol on Au(001)-(5×20) desorbs molecularly at ~138 K using TPD.…”

Section: Introductionmentioning

confidence: 99%

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Thermal Stability of Self-Assembled Monolayers of n-Hexanethiol on Au(111)-(1 × 1) and Au(001)-(1 × 1)

et al. 2017

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The thermal desorption in ultra-high vacuum of n-hexanethiol (C6T) self-assembled monolayers (SAMs) prepared from ethanolic solutions on Au(111) and Au(001) unreconstructed surfaces was investigated by X-ray photoelectron spectroscopy. The SAMs desorption was performed from room temperature (RT) to 380 K. We reported that the hexanethiolate surface saturation coverage is bigger (∼ 0.4 ML) for the SAM on Au(001) than on Au(111) (∼ 0.33 ML). We identified a greater stability for C6T SAMs on Au(001). Large amounts of physisorbed species was found on preferred oriented (111) polycrystalline Au at the low coverage regime at RT, while the SAM on the Au(001) single-crystal at this conditions desorbs at a steady pace. At 340 K, both SAMs remain stable at the coverage expected for the lying-down phases that maximizes the van der Waals interactions. We observed that at higher temperatures the carbon alpha-sulfur bond cleavages producing free S on both gold surfaces.

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Section: Desorption At Higher Temperatures (Ht)supporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Thermal Stability of Self-Assembled Monolayers of n-Hexanethiol on Au(111)-(1 × 1) and Au(001)-(1 × 1)

et al. 2017

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“…Ultrahigh vacuum studies showed that thiols desorbed significantly from flat Au at room temperature, in a 7 days time lap. 16 Desorption of linear alkanethiols from flat Au is significant also when surfaces are dipped in hexadecane at 83°C…”

Section: Introductionmentioning

confidence: 99%

Thermal and Chemical Stability of Thiol Bonding on Gold Nanostars

et al. 2015

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The stability of thiol bonding on the surface of star-shaped gold nanoparticles was studied as a function of temperature in water and in a set of biologically relevant conditions. The stability was evaluated by monitoring the release of a model fluorescent dye, Bodipy-thiol (BDP-SH), from gold nanostars (GNSs) cocoated with poly(ethylene glycol) thiol (PEG-SH). The increase in the BDP-SH fluorescence emission, quenched when bound to the GNSs, was exploited to this purpose. A maximum 15% dye release in aqueous solution was found when the bulk temperature of gold nanostars solutions was increased to T = 42 °C, the maximum physiological temperature. This fraction reduces 3-5% for temperatures lower than 40 °C. Similar results were found when the temperature increase was obtained by laser excitation of the near-infrared (NIR) localized surface plasmon resonance of the GNSs, which are photothermally responsive. Besides the direct impact of temperature, an increased BDP-SH release was observed upon changing the chemical composition of the solvent from pure water to phosphate-buffered saline and culture media solutions. Moreover, also a significant fraction of PEG-SH was released from the GNS surface due to the increase in temperature. We monitored it with a different approach, that is, by using a coating of α-mercapto-ω-amino PEG labeled with tetramethylrhodamine isothiocyanate on the amino group, that after heating was separated from GNS by ultracentrifugation and the released PEG was determined by spectrofluorimetric techniques on the supernatant solution. These results suggest some specific limitations in the use of the gold-thiolate bond for coating of nanomaterials with organic compounds in biological environments. These limitations come from the duration and the intensity of the thermal treatment and from the medium composition and could also be exploited in biological media to modulate the in vivo release of drugs.

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“…Structure of Single Crystal Surfaces, Adsorptions and Self-Assembly of Molecules The formation of self-assembled monolayers (SAM) 25 or self-organizing molecules are natural and spontaneous process that plays vital role in bottom-up strategies in the development of molecular electronic devices, biorecognition and biosensors. Mostly, thiols immobilized on gold (Au) electrodes are extensively studied and explored their properties in various conditions such as ultrahigh vacuum, 26 air 27 and in solution state. 28 Several studies were conducted to examine the SAM properties such as their adsorption, electrical and electrochemical properties, thermal and chemical stabilities, however to understand the morphology of the SAM molecules, SPM were considered to analyze the single molecular structures.…”

Section: Electrochemistry With Scanning Tunneling Microscopymentioning

confidence: 99%

Electrochemical Scanning Tunneling Microscopy Analysis on Protein Based Electronic Devices

Yagati¹,

Lee²,

Nam³

et al. 2017

sci adv mater

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Scanning probe microscopy (SPM) techniques demonstrate one of the most promising tools to investigate the physical and chemical properties of materials at nanoscale and become the most common and important characterization tools in the field of nanotechnology. Among many SPM methods electrochemical scanning tunneling microscopy (EC-STM) technique is one technique that directly provides three-dimensional real-space images with in-situ interfacial electrochemical studies and allows locally measured properties of nanostructured materials at atomic resolution. Furthermore, EC-STM based studies provides information on solution covered areas of electrode surfaces, metal deposition, charge transfer, potential-dependent surface morphology, corrosion, semiconductors, and various applications such as protein conductance measurements in nanobioelectronics. Therefore, in this review, we summarize the electrochemical scanning tunneling microscopic investigation on protein based electrode structures and their applications towards novel bioelectronic devices along with recent developments in ECSTM techniques with future prospects in the field of nanobiotechnology.

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Spontaneous desorption and phase transitions of self-assembled alkanethiol and alicyclic thiol monolayers chemisorbed on Au(1 1 1) in ultrahigh vacuum at room temperature

Cited by 45 publications

References 86 publications

Thermal Stability of Self-Assembled Monolayers of n-Hexanethiol on Au(111)-(1 × 1) and Au(001)-(1 × 1)

Thermal Stability of Self-Assembled Monolayers of n-Hexanethiol on Au(111)-(1 × 1) and Au(001)-(1 × 1)

Thermal and Chemical Stability of Thiol Bonding on Gold Nanostars

Electrochemical Scanning Tunneling Microscopy Analysis on Protein Based Electronic Devices

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