• 전기화학회지
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• 제2권1호
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• pp.27-30
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• 1999

Self-Assembled monolayers of carboxyl-terminated alkanethiols, which is negatively charged in pH 7.0, were usually used to facilitate the electron transfer between the positively charged protein and the electrode. In case of L-cysteine, as it has both positive and negative group, it can be a candidate for a new modifier to facilitate positively charged protein or negatively charged protein. Our investigation of L-cysteine shows that the electron transfer occurs successfully to both cytochrome c (cyt. c) and pyrroloquinoline quinone (PQQ). By using 1-ethyl-3-(3-dime-thlyaminopropyl) carbodiimide (EDC), we made a covalent bond between cyt. c and monolayer. Then PQQ was electrostatically adsorbed to the same monolayer. Cyclic voltammograms show that both molecules do not interfere each other and electron transfer is appreciable.

• Journal of Electrochemical Science and Technology
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• 제10권2호
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• pp.170-176
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• 2019

Alkanethiol self-assembled monolayers (SAMs) and partially ferrocene (Fc) modifications were applied to the Au ultramicroelectrode (UME) rather than to standard sized electrodes with dimension of millimeters. The electron transfer mediation of the SAMs and Fc modified Au UME was investigated by using a p-aminophenol (p-AP) oxidation reaction via cyclic voltammetry. The electrocatalytic p-AP oxidation at the SAMs and Fc modified Au UME showed a much larger electrocatalytic current density than that at the standard sized electrode due to the fast mass transfer rate at the UME.

• Bulletin of the Korean Chemical Society
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• 제27권3호
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• pp.403-406
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• 2006

The surface structure and electrochemical behavior of self-assembled monolayers (SAMs) formed by aromatic thiols on Au(111) were investigated by scanning tunneling microscopy (STM) and cyclic voltammetry. Benzenethiol (BT) forms disordered phases on Au(111) which are composed of many bright domains, while benzyl mercaptan (BM), with a methylene unit between the aromatic group and sulfur atom, forms twodimensional ordered SAMs on Au(111). In addition, two phase-separated domains consisting of disordered and ordered phases were observed in binary SAMs formed from a 1 : 1 mixed ethanol solution of BT and BM. From STM and CV measurements, we found that the blocking efficiency of aromatic thiol SAMs coated on an Au(111) electrode for an electron transfer reaction decreases as the structural order of the SAMs increases. Molecular-scale STM and CV results obtained here will be very useful in designing functional SAMs for further applications, such as the improvement of corrosion passivation of Au(111) on an aromatic thiolmodified Au(111) surface.

• Bulletin of the Korean Chemical Society
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• 제29권6호
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• pp.1229-1232
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• 2008

The surface structure, electrochemical behavior, and wetting property of self-assembled monolayers (SAMs) formed by dioctyl diselenide (DODSe) on Au(111) were investigated by scanning tunneling microscopy (STM), cyclic voltammetry (CV), and contact angle measurements. In contrast to the formation of well-ordered SAMs by octanethiol on Au(111), the SAMs formed by DODSe have a disordered phase and many unusual vacancy islands (VIs). In addition, the formation of DODSe SAMs is largely influenced by the solution concentration used. DODSe SAMs formed in 5 $\mu$ M and 50 $\mu$ M solutions have two mixed domains consisting of missing-row ordered phases and disordered phases, while DODSe SAMs formed in 1 mM and 5 mM solutions have only disordered phases with an abnormally high VI fraction of 22-24%. We also found that the wetting property and electrochemical behavior of DODSe SAMs on Au(111) are markedly influenced by the formation of ordered SAMs and the density of VIs.

• 대한기계학회논문집A
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• 제28권9호
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• pp.1270-1275
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• 2004

Standard positive photoresist techniques were adapted to generate nano-scale patterns of gold substrate using self-assembled monolayers (SAMs) and femtosecond laser. SAMs formed by the adsorption of alkanethiols onto gold substrate are employed as very thin photoresists, Alkanethiolates formed by the adsorption of alkanethiols are oxidized on exposure to UV light in the presence of air to alkylsulfonates. Specifically, it is known that deep UV light of wavelength less than 200nm is necessary for oxidation to occur. In this study, ultrafast laser of wavelength 800nm and pulse width 200fs is applied for photolithography. Results show that ultrafast laser of visible range wavelength can replace deep UV laser source for photo patterning using thin organic films. Femtosecond laser coupled near-field scanning optical microscopy facilitates not only the patterning of surface chemical structure, but also the creation of three-dimensional nano-scale structures by combination with suitable etching methods.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2445-2448
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• 2007

Self-assembled monolayers (SAMs) were formed by adsorption of thioacetyl-terminated tolanethioacetate (TTA) on Au(111) in a 0.5-mM ethanol solution after one day immersion at room temperature. Molecular-scale STM imaging revealed that the TTA SAMs were composed of two mixed phases; an ordered phase with small domains describing a ( × 2 )R30° structure and a disordered phase. Interestingly, after annealing the precovered TTA SAMs on Au(111) at 90 °C for 1 h, the small ordered domains grew unidirectionally, resulting in the formation of unique rod-like domains, which were assigned a ( × 2 )R7° structure. These results will be very useful in understanding the formation and thermal behavior of TTA SAMs on gold surfaces.

• Bulletin of the Korean Chemical Society
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• 제32권8호
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• pp.2623-2627
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• 2011

We investigated the surface structure and wetting behavior of octaneselenolate self-assembled monolayers (SAMs) on Au(111) formed in a 50 ${\mu}M$ ethanol solution according to immersion time, using scanning tunneling microscopy (STM) and an automatic contact angle (CA) goniometer. Closely-packed, well-ordered alkanethiol SAMs would form as the immersion time increased; unexpectedly, however, we observed the structural transition of octaneselenolate SAMs from a molecular row phase with a long-range order to a disordered phase with a high density of vacancy islands (VIs). Molecularly resolved STM imaging revealed that the missing-row ordered phase of the SAMs could be assigned as a $(6{\times}{\surd}3)R30^{\circ}$ superlattice containing three molecules in the rectangular unit cell. In addition, CA measurements showed that the structural order and defect density of VIs are closely related to the wetting behaviors of octaneselenolate SAMs on gold. In this study, we clearly demonstrate that interactions between the headgroups and gold surfaces play an important role in determining the physical properties and surface structure of SAMs.

• Bulletin of the Korean Chemical Society
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• 제32권1호
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• pp.281-285
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• 2011

We investigated the effects of tunneling current on scanning tunneling microscopy (STM) images of 1-octanethiol (OT) and 1-decanethiol (DT) self-assembled monolayers (SAMs). At a low tunneling current, the domain boundaries and ordered alkanethiol molecules were clearly resolved. As the tunneling current was increased at a constant bias voltage, however, the STM images showed disordered structures of the OT and DT SAMs. As the tunneling current was reduced back to low values, the ordered structures of the alkanethiol molecules reappeared. The reversibility of the process suggests that the sulfur head groups did not rearrange under any of the tunneling current conditions. On the basis of our observations, which are inconsistent with the standard model for STM imaging of molecules on metal surfaces, we consider the STM imaging mechanism in terms of a two-region tunneling junction model.

• Bulletin of the Korean Chemical Society
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• 제30권2호
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• pp.441-444
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• 2009

The formation and structure of self-assembled monolayers (SAMs) by the adsorption of acetyl-protected octylthioacetate (OTA) on Au(111) in a catalytic tetrabutylammonium cyanide (TBACN) solution were examined by means of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV). Molecular-scale STM imaging revealed that OTA molecules on Au(111) in a pure solvent form disordered SAMs, whereas they form well-ordered SAMs showing a c(4 × 2) structure in a catalytic TBACN solution. XPS and CV measurements also revealed that OTA SAMs on Au(111) formed in a TBACN solution have a stronger chemisorbed peak in the S 2p region at 162 eV and a higher blocking effect compared to OTA SAMs formed in a pure solvent. In this study, we clearly demonstrate that TBACN can be used as an effective deprotecting reagent for obtaining well-ordered SAMs of thioacetyl-protected molecules on gold.

• Bulletin of the Korean Chemical Society
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• 제34권5호
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• pp.1383-1387
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• 2013

The surface structure and electrochemical behavior of self-assembled monolayers (SAMs) prepared from benzenethiol (BT), cyclohexanethiol (CHT), and cyclopentanethiol (CPT) on Au(111) surface were examined by scanning tunneling microscopy (STM) and cyclic voltammetry (CV) to understand the influence of thiol molecular backbone structure on the formation and reductive desorption behavior of SAMs. STM imaging showed that BT and CPT SAMs on Au(111) surface formed at room temperature were mainly composed of disordered domains, whereas CHT SAMs were composed of well-ordered domains with three orientations. From these STM results, we suggest that molecule-substrate interaction is a key parameter for determining the structural order and disorder of simple aromatic and alicyclic thiol SAMs on Au(111). In addition, the reductive desorption peak potential for BT SAMs with aromatic rings was observed at a less negative potential of -566 mV compared to CHT SAMs (-779 mV) or CPT SAMs (-775 mV) with aliphatic cyclic rings. This reductive desorption behavior for BT SAMs is due to the presence of p-orbitals on the aromatic rings, which promote facile electron transfer from the Au electrode to BT as compared to CHT and CPT. We also confirmed that the reductive desorption behavior for simple alicyclic thiol SAMs such as CHT and CPT SAMs on Au electrodes was not significantly influenced by the degree of structural order.