• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.275-275
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• 2013

Formation and characterization of self-assembled monolayers (SAMs) on various surfaces are the essential basis for many other applications, including molecular switches, biosensors, microfluidics, and fundamental studies in surfaces and interfaces. To improve the performance at these applications, it is a key to control the quantity of each molecule in various mixed SAMs on the surface. In this study, using mixed SAM of carbamate-based hydroquinone (HQ)-PhBr and11-mercaptoundecanol, the quantitative mass spectrometric method of mixed SAM was developed based on comparison study with XPS and FT-IR methods. In addition, our method was applied to another mixed SAM of biotinylated PEG alkane thiol and 11-mercaptoundecanol for verification purpose. Time-of-flight secondary mass spectrometry (ToF-SIMS) analysis was performed to identify and quantify each molecule of mixed SAM along with principal component analysis (PCA). Since there is no matrix effect in the X-ray photoelectron spectroscopy (XPS) and Fourier transform-infrared (FT-IR) techniques, we compared ToF-SIMS results with XPS and FT-IR results. Because PCA results from ToF-SIMS analysis are well matched with XPS and FT-IR results from both mixed SAMs, we are expecting that our method will be useful to identify and quantify each molecule in various mixed SAMs.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
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• pp.208-209
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• 2011

In this work, we developed self-assembled monolayers (SAMs) of alkanethiols on gold that can release amine groups, when an electrical potential was applied to the gold. The strategy was based on the introduction of the electroactive carbamate group, which underwent the two-electron oxidation with simultaneous release of the amine molecules, to alkanethiols. The synthesis of the designed thiol compounds was achieved by coupling isocyanate-containing compound with hydroquinone. The electroactive thiols were mixed with hydroxyl-containing alkanethiol [$HS(CH_2)_{11}OH$] to form mixed monolayers, and cyclic votammetry was used for the characterization of the release. The mixed SAMs showed a first oxidation peak at +540 mV (versus Ag/AgCl reference electrode), demonstrating irreversible conversion from carbamate to hydroqinone with simultaneous release of the amine groups. The second and third cycles showed typical reversible redox reaction of hydroquinone and quione: the oxidation and reduction occurred at +290 mV and -110 mV, respectively. The measurement of ToF-SIMS further indicates that electrochemical-assisted chemical reaction successfully released amine groups. This new SAM-based electrochemistry would be applicable for direct release of biologically active molecules that contain amine groups.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.601-604
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• 2014

Two classes of morpholino-substitued thioacetate have been successfully synthesized and their electrochemical properties of self-assembled monolayers (SAMs) on Au electrode are measured by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The barrier property of the SAMs-modified surfaces is evaluated by using potassium ferro/ferri cyanide. The results suggest that the arenethioacetate forms higher-quality close-packed blocking monolayers in comparison with alkanethioacetate. Furthermore, it has shown that the barrier properties of these monolayers can be significantly improved by mixed SAMs formation with decanethiol. From our experimental results we find that the electron transfer reaction of $[Fe(CN)_6]^{3/4-}$ redox couple occurs predominantly through the pinholes and defects present in the SAM and both SAMs show a good and fast capacity in recognition for $Ag^+$. The morphological and elementary composition have also been examined by scanning electron microscope (SEM) and energy dispersive spectrometer (EDS).

• 한국윤활학회:학술대회논문집
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• 한국윤활학회 2002년도 proceedings of the second asia international conference on tribology
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• pp.55-56
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• 2002

Nanotribological characteristics of hydrophobic surfaces were studied experimentally using an atomic force microscope (AFM). Two kinds of thiolic self-assembled monolayers (SAM) having different spacer chains and their mixture were deposited onto gold-coated mica, where the deposited SAM resulted in the hydrophobic nature. Results showed that the mixed thiolic SAMs resulted in low adhesion and friction in nano-scale contact. It was argued that the water wetting characteristics played a central role on nano-scale adhesion and friction. Also the effect of mixing the thiolic SAMs were discussed on the basis of real area on contact and the stiffness of the SAM layers.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제40회 동계학술대회 초록집
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• pp.27-27
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• 2011

For the design of real applicable molecular devices, current-voltage properties through molecular nanostructures such as metal-molecule-metal junctions (molecular junctions) have been studied extensively. In thiolate monolayers on the gold electrode, the chemical bonding of sulfur to gold and the van der Waals interactions between the alkyl chains of neighboring molecules are important factors in the formation of well-defined monolayers and in the control of the electron transport rate. Charge transport through the molecular junctions depends significantly on the energy levels of molecules relative to the Fermi levels of the contacts and the electronic structure of the molecule. It is important to understand the interfacial electron transport in accordance with the increased film thickness of alkyl chains that are known as an insulating layer, but are required for molecular device fabrication. Thiol-tethered RuII terpyridine complexes were synthesized for a voltage-driven molecular switch and used to understand the switch-on mechanism of the molecular switches of single metal complexes in the solid-state molecular junction in a vacuum. Electrochemical voltammetry and current-voltage (I-V) characteristics are measured to elucidate electron transport processes in the bistable conducting states of single molecular junctions of a molecular switch, Ru(II) terpyridine complexes. (1) On the basis of the Ru-centered electrochemical reaction data, the electron transport rate increases in the mixed self-assembled monolayer (SAM) of Ru(II) terpyridine complexes, indicating strong electronic coupling between the redox center and the substrate, along the molecules. (2) In a low-conducting state before switch-on, I-V characteristics are fitted to a direct tunneling model, and the estimated tunneling decay constant across the Ru(II) terpyridine complex is found to be smaller than that of alkanethiol. (3) The threshold voltages for the switch-on from low- to high-conducting states are identical, corresponding to the electron affinity of the molecules. (4) A high-conducting state after switch-on remains in the reverse voltage sweep, and a linear relationship of the current to the voltage is obtained. These results reveal electron transport paths via the redox centers of the Ru(II) terpyridine complexes, a molecular switch.