• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.317-317
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• 2010

This paper reports syntheses of $TiO_2$ nanocubes and theirs application to DSSC. We synthesized $TiO_2$ nanocubes via solvothermal method using titanium isopropoxide (TTIP) and tetramethylammoiumhydroxide (TMAH). By adding longer alkyl chain ammonium hydroxide that slowed down the growth rate of the crystal, $TiO_2$ nanocubes were obtained with average particle size in the range of 40 nm to 70 nm. By TEM investigation, each particle was found to be single crystal of anatase having six-faces of (001) and {100} crystallographic planes truncated by {101} series of planes, which are clearly distinguishable from spherical nanoparticles. Among various application, utilizing nanocubes as photo-electrode in dye-sensitized solar cell, we investigated photo-electron conversion performances in comparison with spherical shaped $TiO_2$ nanoparticles by I-V characteristics and IPCE measurements, etc.. Photocurrent-transient analysis revealed that $TiO_2$ nanocubes have a higher transient electron transfer rate by more than 10 times compared with spherical particles of similar size. Fast electron transport along the cube edges having small curvature was suggested as a plausible origin of high diffusion coefficient of electron in nanocube $TiO_2$.

• Bulletin of the Korean Chemical Society
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• v.15 no.9
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• pp.752-758
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• 1994

Several one-electron reduction products of ${\gamma}$(1,2)-[$H_nSiV_2W_{10}O_{40}]^{(6-n)-}$ were separated by precipitating or coprecipitating with diamagnetic host compounds at different pH. Mono-and diprotonated species, 1 and 2, in powder samples exhibit aPR spectra characteristic of a mononuclear oxovanadium species, indicating that the unpaired electron is trapped at one vanadium atom. The EPR spectrum of the unprotonated species 0 shows 15 parallel lines, indicating that the unpaired electron interacts equally with two vanadium atoms. While different species were precipitated depending upon the pH of the solution and the charge of the host anion, only one species 1' was formed in the frozen solutions at pH 3.2-4.7. The EPR spectrum of 1' indicates that the unpaired electron is trapped at one vanadium atom and 1/16 of the spin density is delocalized onto the second vanadium atom. The species 1' is probably another form of the monoprotonated species. The EPR spectra show that some of 2 transform into 1 and some of 0 transform into 1' in the solid state at low temperatures. It is suggested that proton transfer between the heteropolyanion and water molecues in the solid state is involved in these transformations.

• Journal of Photoscience
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• v.10 no.1
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• pp.9-20
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• 2003

Recent studies on the photoreactivity of l,4-unsaturated systems have changed some ideas that were firmly established in this area of research for many years. Thus, we have described the first examples of 2-aza-di-$\pi$-methane (2-ADPM) rearrangements promoted by triplet-sensitization and by single electron transfer (SET) using electron-acceptor sensitizers. These reactions afford N-vinylaziridine and cyclopropylimine photoproducts in the first examples of di-$\pi$-methane processes that yield three-membered ring heterocycles. l-Aza-1,4-dienes also undergo SET-promoted l-aza-di-$\pi$-methane (l-ADPM) rearrangements via radical-cation intermediates using electron acceptor sensitizers. In some cases, alternative cyclizations yielding different carbocycles and heterocycles have been observed. The l-ADPM and di-$\pi$-methane (DPM) reactions also occur via radical-anion intermediates on irradiation using electron donor sensitizers. On the other hand, the photoreactivity reported for $\beta$,${\gamma}$-unsaturated aldehydes for many years was decarbonylation to the corresponding alkenes. However, our studies demonstrate that these compounds undergo the oxa-di-$\pi$-methane (ODPM) rearrangement with high chemical and quantum efficiency. A comparison of the photochemical reactivity of $\beta$,${\gamma}$-unsaturated aldehydes and corresponding methyl ketones has shown that the ketones do not undergo the ODPM rearrangement while the corresponding aldehydes are reactive by this pathway. Monosubstituted $\beta$,${\gamma}$-unsaturated aldehydes at C-2 undergo the ODPM rearrangement yielding the corresponding cyclopropane carbaldehydes diastereoselectively. Finally, we have described the first examples of reactions, similar to the well know Norrish Type I process, which take place in the triplet excited state of $\beta$,${\gamma}$-unsaturated carbonyl compounds by excitation of the C-C double bond instead of the carbonyl group.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.33 no.5
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• pp.360-366
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• 2020

Focused electron beams with high energy acceleration are versatile probes. Focused electron beams can be used for high-resolution imaging and multi-mode nanofabrication, in combination with, molecular precursor delivery, in an electron microscopy environment. A high degree of control with atomic-to-microscale resolution, a focused electron beam allows for precise engineering of a graphene-based field-effect transistor (FET). In this study, the effect of electron irradiation on a graphene FET was systematically investigated. A separate evaluation of the electron beam induced transport properties at the graphene channel and the graphene-metal contacts was conducted. This provided on-demand strategies for tuning transfer characteristics of graphene FETs by focused electron beam irradiation.

• Journal of Photoscience
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• v.7 no.4
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• pp.143-148
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• 2000

Studies have been conducted to explore single electron transfer(SET) promoted photocyclization of ($\omega$-phthalimidoalkoxy)acetic acids(alkoxy=ethoxy, n-propoxy and n-butyloxy). Photocyclizations occur in methanol or acetone in high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the carboxylic group. These photocyclizations are thought to proceed through pathways involving intramolecular SET from oxygen in the $\alpha$-carboxymethoxy groups to the singlet excited state phthalimide moieties followed by decarboxylation of the intermediate $\alpha$-carboxymethoxy cation fadicals and cyclizations by radical coupling. The photocyclizations occur ca. three times faster in both methanol or acetone with one equivalent of sodium hydroxide added to the reactions and occur slower in acetone than in methanol. The efficient and regiselective cyclization reactions observed for photolyses in methanol represent synthetically useful processes for construction of heterocyclic compounds.

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3233-3240
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• 2012

We demonstrated the combined applications of online protein digestion using trypsin immobilized enzyme reactor (IMER) and dual tandem mass spectrometry with collisionally activated dissociation (CAD) and electron transfer dissociation (ETD) for tryptic peptides eluted through the trypsin-IMER. For the trypsin-IMER, the organic and inorganic hybrid monolithic material was used. By employing the trypsin-IMER, the long digestion time could be saved with little or no sacrifice of the digestion efficiency, which was demonstrated for standard protein samples. For three model proteins (cytochrome c, carbonic anhydrase, and bovine serum albumin), the tryptic peptides digested by the IMER were analyzed using LC-MS/MS with the dual application of CAD and ETD. As previously shown by others, the dual application of CAD and ETD increased the sequence coverage in comparison with CAD application only. In particular, ETD was very useful for the analysis of highly-protontated peptide cations, e.g., ${\geq}3+$. The combination approach provided the advantages of both trypsin-IMER and CAD/ETD dual tandem mass spectrometry applications, which are rapid digestion (i.e., 10 min), good digestion efficiency, online coupling of trypsin-IMER and liquid chromatography, and high sequence coverage.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.375.1-375.1
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• 2016

Polymerase chain reaction (PCR) has revolutionized genetics and become one of the most popular techniques in modern biological and medical sciences. It can be used not only as an in vitro DNA amplification method but also used in many bioassay applications. The PCR can be used to exponentially produce a large number of DNA copies from a small quantity of DNA molecules in a few hours. However, as unwanted DNA fragments are also often manufactured, the amplification efficiency of PCR is decreased. To overcome this limitation, several nanomaterials have been employed to increase the specificity of the PCR reaction. Recently, graphene has attracted a great interest for its excellent electron transfer, thermal and biocompatibility. Especially, gold nanoparticle-coated graphene oxide (GO/AuNPs) led to enhance electron and thermal transfer rate and low-charge transfer resistance. Therefore, we report the development of a demonstration for the PCR efficiency using a large-scale production of the GO and combination of gold nanoparticles. Because a thermal conductivity is an important factor for improving the PCR efficiency in different DNA polymerases and different size samples. When PCR use GO/AuNPs, the result of transmission electron microscopy and real-time quantitative PCR (qPCR) showed an enhanced PCR efficiency. We have demonstrated that GO/AuNPs would be simply outperformed for enhancing the specificity and efficiency of DNA amplification procedure.

• BMB Reports
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• v.31 no.4
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• pp.307-327
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• 1998

Cytochrome c peroxidase (CcP) is a yeast mitochondrial enzyme which catalyzes the reduction of hydrogen peroxide to water using two equivalents of ferrocytochrome c. The CcP/cytochrome c system has many features which make it a very useful model for detailed investigation of heme protein structure/function relationships including activation of hydrogen peroxide, protein-protein interactions, and long-range electron transfer. Both CcP and cytochrome c are single heme, single subunit proteins of modest size. High-resolution crystallographic structures of both proteins, of one-to-one complexes of the two proteins, and a number of active-site mutants are available. Site-directed mutagenesis studies indicate that the distal histidine in CcP is primarily responsible for rapid utilization of hydrogen peroxide implying significantly different properties of the distal histidine in the peroxidases compared to the globins. CcP and cytochrome c bind to form a dynamic one-to-one complex. The binding is largely electrostatic in nature with a small, unfavorable enthalpy of binding and a large positive entropy change upon complex formation. The cytochrome c-binding site on CcP has been mapped in solution by measuring the binding affinities between cytochrome c and a number of CcP surface mutations. The binding site for cytochrome c in solution is consistent with the crystallographic structure of the one-to-one complex. Evidence for the involvement of a second, low-affinity cytochrome c-binding site on CcP in long-range electron transfer between the two proteins is reviewed.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2000.05a
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• pp.108-111
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• 2000

FeS/FeS$_2$ minerals have been known to be potentially useful reductant to the removal of common organic contaminants in groundwater and soil. This research is aimed at improving our understanding of factors affecting the pathways and rates of reductive transformation of Hexachloroethane by catalytical iron minerals in natural system. Hexachloroethane is reduced by FeS/FeS$_2$ minerals under anaerobic condition to tetrachloroethylene and trichloroethylene with pentachloroethyl radical as the intermediate products. The kinetics of reductive transformations of the Hexachloroethane have been investigated in aqueous solution containing FeS, FeS$_2$. The proposed reduction mechanism for the adsorbed nitrobenzene involves the electron donor-acceptor complex as a precursor to electron transfer. The adsorbed Hexachloroethane undergo a series of electron transfer, proton transfer and dehydration to achieve complete reduction. It can be concluded that the reductive transformation reaction takes place at surface of iron-bearing minerals and is dependent on surface area and pH. Nitrobenzene reduction kinetics is affected by reductant type, surface area, pH, the surface site density, and the surface charge. FeS/FeS$_2$-mediated reductive dechlorination may be an important transformation pathway in natural systems.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4247-4252
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• 2011

The porphyrin-incorporated arylether dendrimers ZnP-D1 and ZnP-D4 were investigated to discover the influence of dendritic environments for the axial ligation of pyridine and photoinduced electron transfer by methyl viologen. Absorption and fluorescence spectra of ZnP, ZnP-D1, and ZnP-D4 were measured in dichloromethane with the addition of pyridine or methyl viologen dichloride. Axial ligation of pyridine was confirmed by red-shifted absorption spectrum. The complex formation constants $K_f$ (Table 1) for axial coordination of pyridine on ZnP, ZnP-D1, and ZnP-D4 were estimated to be $4.4{\times}10^3\;M^{-1}$, $3.3{\times}10^3\;M^{-1}$, and $1.7{\times}10^3\;M^{-1}$, respectively. The photoinduced electron transfer to methyl viologen dichloride was confirmed by fluorescence quenching. Stern-Volmer constants Ksv for ZnP, ZnP-D1, and ZnP-D4 were calculated to be $2.6{\times}10^3$, $2.5{\times}10^3$, and $2.1{\times}10^3$, respectively. ZnP-D4 surrounded by 4 aryl ether dendrons shows the smallest $K_f$ and Ksv values, with comparison to ZnP and ZnP-D1.