• Bulletin of the Korean Chemical Society
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• v.34 no.5
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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.

• Horticultural Science & Technology
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• v.30 no.6
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• pp.734-742
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• 2012

To compare RNA interference-mediated gene silencing technique and T-DNA integration for gene function analysis in Chinese cabbage, BrSAMS-knockout (KO) line and BrSAMS-knockdown (KD) line were used. The KO line had lost the function of a Brassica rapa S-adenosylmethionine synthetase (BrSAMS) gene by T-DNA insertion and the KD line had shown down-regulated BrSAMS genes' expression by dsRNA cleavage. From microarray results of the KO and KD lines, genes linked to SAMS such as sterol, sucrose, homogalacturonan biosynthesis and glutaredoxin-related protein, serine/threonine protein kinase, and gibberellin-responsive protein showed distinct differences in their expression levels. Even though one BrSAMS gene in the KO line was broken by T-DNA insertion, gene expression pattern of that line did not show remarkable differences compared to wild type control. However, the KD line obtained by RNAi technique showed prominent difference in its gene expression. Besides, change of polyamine and ethylene synthesis genes directly associated with BrSAMS was displayed much more in the KD line. In the microarray analysis of the KO line, BrSAMS function could not be clearly defined because of BrSAMS redundancy due to the genome triplication events in Brassicaceae. In conclusion, we supposed that gene knock-down method by RNAi silencing is more effective than knock-out method by T-DNA insertion for gene function analysis of polyploidy crops such as Chinese cabbage.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.26-26
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• 2011

Self-assembled monolayers (SAMs) prepared by sulfur-containing organic molecules on metal surfaces have drawn much attention for more than two decades because of their technological applications in wetting, chemical and biosensors, molecular recognition, nanolithography, and molecular electronics. In this talk, we will present self-assembly mechanism and two-dimensional (2D) structures of various organic thiol SAMs on Au(111), which are mainly demonstrated by molecular-scale scanning tunneling microscopy (STM) observation. In addition, we will provide some idea how to control 2D molecular arrangements of organic SAMs. For instance, the formation and surface structure of pentafluorobenzenethiols (PFBT) self-assembled monolayers (SAMs) on Au(111) formed from various experimental conditions were examined by means of STM. Although it is well known that PFBT molecules on metal surfaces do not form ordered SAMs, we clearly revealed for the first time that adsorption of PFBT on Au(111) at $75^{\circ}C$ for 2 h yields long-range, well-ordered self-assembled monolayers having a $(2{\times}5\sqrt{13})R30^{\circ}$ superlattice. Benzenethiols (BT) SAMs on gold usually have disordered phases, however, we have clearly demonstrated that the displacement of preadsorbed cyclohexanethiol self-assembled monolayers (SAMs) on Au(111) by BT molecules can be a successful approach to obtain BT SAMs with long-range ordered domains. Our results will provide new insight into controlling the structural order of BT or PFBT SAMs, which will be very useful in precisely tailoring the interface properties of metal surfaces in electronic devices.

• Bulletin of the Korean Chemical Society
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• v.30 no.11
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• pp.2549-2554
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• 2009

The structures of 1,n-alkanedithiol (n = 2, 4, 6, 8, 10) self-assembled monolayers (SAMs) on a Au(111) substrate were investigated by electrochemical measurements and theoretical calculations. The results of the experimental techniques indicated that the dithiols, except n = 2, showed an upright molecular structure in the SAMs, in which alkanedithiols were bound to the Au surface via only one thiol functionality and the other one faced up to the air. The results also suggested that the formed dithiol SAMs were densely packed and highly oriented. Except ethanedithiol, which was thought to form a bilayer, the reductive desorption peak potentials of 1,n-alkanedithiol (n = 4, 6, 8, 10) SAMs were more negative than those of the corresponding monothiol ones in 0.1 M KOH solutions. This illustrates that the dithiol SAMs had higher stability than the corresponding monothiol ones. The major part of the high stability may be attributed to the van der Waals interaction among the sulfur atoms on top of the dithiol SAMs. The molecular modeling calculation showed that the structures of dithiol SAMs were similar to those of the corresponding monothiol SAMs and that all the dithiol SAMs, except ethanedithiol, were more stable than the corresponding monothiol SAMs. The calculated energy differences between dithiol and monothiol SAMs decreased with the increment of alkyl-chain length.

• Bulletin of the Korean Chemical Society
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• v.29 no.6
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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.

• Korean Journal of Materials Research
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• v.16 no.10
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• pp.619-623
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• 2006

Selective vapor deposition of conductive poly(3,4-ethylenedioxythiophene) (PEDOT), thin films has been carried out on self assembled monolayers patterned oxide substrate. Since the 3,4-ethylenedioxythiophene(EDOT) monomer can be polymerized only in the presence of oxidant such as $FeCl_3$, the PEDOT thin film is selectively deposited on patterned $FeCl_3$, which only adsorbs on the partly removed SAMs region due to the inability of $FeCl_3$ to adsorb on SAMs. Therefore, the partly removed SAMs can act as an adsorption layer for the $FeCl_3$ and also as a glue layer for the deposition of PEDOT, resulting in the significantly increased adhesion of PEDOT to $SiO_2$ substrate. The use of UV lithography and Cr patterned quartz mask provided the formation of SAMs patterns on oxide substrates, which allowed for the selective deposition of conductive PEDOT thin films.$^{oo}The$ new process was successfully developed for the selective deposition of PEDOT thin films on SAMs patterned oxide substrate, providing a new way for the patterning of vapor phase deposition of PEDOT thin films with accurate alignment and addressing the inherent adhesion issues between PEDOT and dielectrics.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.402-402
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• 2012

Bundles of single-walled carbon nanotube (SWCNTs) were grown using catalytic layer supported by self-assembled monolayers (SAMs). Amine-SAMs were introduced on SiO2/Si substrate (SAMs/Si) there then iron nanoclusters solution was dropped on it through spin-coating (Fe/SAMs/Si). This catalytic template was used to grow CNTs and the synthesized carbon material was confirmed the bundles of dense SWCNTs with incorporation of ca.1% nitrogen. The SAMs has played an active role to support catalytic layer and also acted as a source of N-dope onto SWCNTs in CVD.

• Polymer(Korea)
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• v.28 no.1
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• pp.3-9
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• 2004

Silane modified perfluoropolyethers (SPFPE) was synthesized as a self-assembled mono-layers (SAMs) thin film for micro-electro mechanical system (MEMS). SPFPE was compared to the Perfluoropolyethers (PFPE) as well as octadecyltrichlorosilane (OTS) and perfluorooctyltrichlorosilane (FOTS) with respect to the development of hydrophobicity in the SAMs surface. SPFPE shows less hydrophobicity than those of OTS and FOTS. Thermal annealing of SPFPE SAMs resulted in the enhancement of hydrophobicity as much as those of OTS and FOTS. The SAMs formed from SPFPE were found to be similar as OTS and FOTS SAMs with smooth R$\sub$a/ values of 0.3 nm. However, the flexible chain mobility of SPFPE resulted in 50% reduction as much as the fiction force in OTS.

• Proceedings of the Korea Concrete Institute Conference
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• 1996.10a
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• pp.546-550
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• 1996

The personal-computer software program named SAMS(Structural Aging Management System) was developed for the concrete structure of NPP(Nuclear Power Plant). SAMS is constituted of three part, detabase system containing various inspection data, operation program for standard input/output of the inspection data, and application program for efficient operation of database system. Using the SAMS, the field engineers can easily acquire the information about the various inspection data, repair and accidental histories of NPP structures. SAMS will contribute to the effcient maintenance of NPP structures.

• Bulletin of the Korean Chemical Society
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• v.32 no.4
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• pp.1253-1257
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• 2011

The surface structures, adsorption conditions, and thermal desorption behaviors of cyclopentanethiol (CPT) self-assembled monolayers (SAMs) on Au(111) were investigated by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). STM imaging revealed that although the adsorption of CPT on Au(111) at room temperature generates disordered SAMs, CPT molecules at $50^{\circ}C$ formed well-ordered SAMs with a $(2{\surd}3{\times}{\surd}5)R41^{\circ}$ packing structure. XPS measurements showed that CPT SAMs at room temperature were formed via chemical reactions between the sulfur atoms and gold surfaces. TDS measurements showed two dominant TD peaks for the decomposed fragments ($C_5H_9^+$, m/e = 69) generated via C-S bond cleavage and the parent molecular species ($C_5H_9SH^+$, m/e = 102) derived from a recombination of the chemisorbed thiolates and hydrogen atoms near 440 K. Interestingly, dimerization of sulfur atoms in n-alkanethiol SAMs usually occurs during thermal desorption and the same reaction did not happen for CPT SAMs, which may be due to the steric hindrance of cyclic rings of the CPT molecules. In this study, we demonstrated that the alicyclic ring of organic thiols strongly affected the surface structure and thermal desorption behavior of SAMs, thus providing a good method for controlling chemical and physical properties of organic thiol SAMs.