• Bulletin of the Korean Chemical Society
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• v.23 no.9
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• pp.1229-1258
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• 2002

This paper reports the photochemical reduction of benzil 1 to benzoin 2 and the reduction of 2 to hydrobenzoin 4 in deoxygenated solvents in the presence of triethylamine (TEA) and/or TiO2. Without TEA or TiO2, the photolysis of 1 resulted in very low yield of 2. The presence of TEA or TiO2 increased the rate of disappearance of 1 and the yield of 2, which were further increased considerably by the presence of water. The photoreduction of 1 to 2 proceeds through an electron transfer to 1 from TEA or hole-scavenged excited TiO2 followed by protonation. In the reaction medium of 88 : 7 : 2 : 3 CH3CN/CH3OH/H2O/TEA with 2.5 $㎎/m{\ell}$ of TiO2, the yield of 2 was as high as 85 % at 50 % conversion of 1. The photolysis of 2 in homogeneous media resulted in photo-cleavage to benzoyl and hydroxybenzyl radicals, which are mostly converted to benzaldehyde. The reduction product 4 is formed in low yield through the dimerization of hydroxybenzyl radicals. The addition of TEA increased the conversion rate of 2 and the yield of 4 significantly. This was attributed to the scavenging effect of TEA for benzoyl radical to produce N,N-diethylbenzamide and the photoreduction of benzaldehyde in the presence of TEA. The ratio of $(\pm)$ and meso isomers of 4 obtained from the photochemical reaction is about 1.1. This ratio is the same as that from the photochemical reduction of benzaldehyde in the presence of TEA. In the TiO2-sensitized photochemical reduction of 2, meso-4 was obtained in moderate yield. The reduction of 2 to 4 proceeds through two consecutive electron/proton transfer processes on the surface of the photocatalyst without involvement of ${\alpha}-cleavage$. The radical 11 initially formed from 2 by one electron/proton process can also combine with hydroxy methyl radical, which is generated after hole trapping of excited TiO2 by methanol, to produce 1,2-diphenylpropenone after dehydration reaction.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3681-3689
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• 2013

This study explored a direct SET-photochemical strategy to construct a new family of thioene conjugated-naphthalamide fluorophore based lariat-crown ethers which show strong binding properties towards heavy metal ions. Irradiations of designed nitrogen branched (trimethylsilyl)methylthio-terminated polyethylenoxy-tethered naphthalimides in acidic methanol solutions have led to highly efficient photocyclization reactions to generate naphthalamide based lariat type thiadiazacrown ethers directly in chemo- and regio-selective manners which undergo very facile secondary dehydration reactions during separation processes to produce their corresponding amidoenethio ether cyclic products tethered with electron donating diethyleneoxy- and diethyenethio-side arm chains. Fluorescence and metal cation binding properties of the lariat type enamidothio products were examined. The photocyclized amidoenethio products, thioene conjugated naphthalamide fluorophore containing lariat-thiadiazacrowns exhibited strong fluorescence emissions in region of 330-450 nm along with intramolecular exciplex emissions in region of 450-560 nm with their maxima at 508 nm. Divalent cation $Hg^{2+}$ and $Pb^{2+}$ showed strong binding to sulfur atom(s) in side arm chain and atoms in enethiadiazacrown ether rings which led to significant enhancement of fluorescence from its chromophore singlet excited state and concomitant quenching of exciplex emission. The dual fluorescence emission responses towards divalent cations might provide a new guide for design and development of fluorescence sensors for detecting those metals.

• Transactions of the Korean Society of Automotive Engineers
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• v.21 no.1
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• pp.99-106
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• 2013

DME (Di-Methyl Ether) is synthetic product that is produced through dehydration of methanol or a direct synthesis from syngas. And it is able to save fossil fuel and reduce pollutants of emission such as PM and $CO_2$. In spite of its advantages it is difficult to design DME fuelled engine system because DME fuel may cause to severely generate cavitation and corrosion in fuel delivery system due to physical properties of DME. Therefore, in this study three-dimensional internal flow characteristics with consideration of cavitation were predicted in the DME injector using diesel and DME fuel. Moving grid technique was employed to describe needle motion and 1-D hydraulic simulation of injector was also simulated to obtain transient needle motion profiles. The results of simulation show that cavitations was generated at the inlet of nozzle near high velocity region both diesel and DME. And mass flow rate of DME is reduced by 4.73% compared to that of diesel at maximum valve lift because cavitation region of DME is much more larger. To increase flow rate of DME injector, internal flow simulation has been conducted to investigate the nozzle hole inner R-cut effect. The flow rates of diesel and DME increase as R-cut increases, and flow coefficient of DME fuel injector was increased by 6.3% on average compared with diesel fuelled injector. Finally, optimum shape of DME injector nozzle is suggested through the comparison of flow coefficient with variation of nozzle hole inner R-cut.

• Korean Chemical Engineering Research
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• v.47 no.4
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• pp.446-452
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• 2009

The behavior of a one-step fixed bed reactor which directly synthesizes dimethyl ether(DME) from Natural Gas was simulated. In the reactor, the prevention of the occurrence of hot spots which can cause deactivation of catalysts is pivotal, since methanol synthesis and dehydration reaction involved in the synthesis of DME are highly exothermic. Therefore, we simulated and compared performance of the reactor with counter-current cooling and pool boiling system that can be applied to a commercial plant. As a result, we found that counter-current cooling system is more effective in terms of CO conversion and DME productivity. However, pool boiling system can operate in a small temperature gradient that can decrease problems caused by hot spot. And, the system can operate in a safer range.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.249-249
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• 2013

Surface-enhanced Raman spectroscopy (SERS) is a sensitive approach to detect and to identify a variety of molecules. To enhance the Raman signal, optimization of the gap between nanostructures is quite important. One-dimensional materials such as nanowires, nanotubes, and nanograsses have great potential to be used in SERS due to their unique sizes and shape dependent characteristics. In this study we investigate a simple way to fabricate SERS substrates based on randomly grown copper oxide (CuO) nanowires. CuO nanograss is fabricated on pre-cleaned Cu foils. Cu oxidized in an ammonium ambient solution of 2.5 M NaOH and 0.1 M $(NH_4)_2S_2O_8$ at $4^{\circ}C$ for 10, 30, and 60 minutes. Then, Cu(OH)2 nanostructures are formed and dried at $180^{\circ}C$ for 2 h. With the drying process, the Cu(OH)2 nanostructure is transformed to CuO nanograss by dehydration reaction. CuO nanograss are grown randomly on Cu foil with the average length of 10 ${\mu}m$ and the average diameter of a 100 nm. CuO nanograsses are covered by Ag with various thicknesses from 10 to 30 nm using a thermal evaporator. Then, we immerse uncoated and Ag coated CuO nanowire samples of various oxidation times in a 0.001M methanol-based 4-mercaptopyridine (4-Mpy) in order to evaluate SERS enhancement. Raman shift and SERS enhancement are measured using a Raman spectrometer (Horiba, LabRAM ARAMIS Spectrometer) with the laser wavelength of 532 nm. Raman scattering is believed to be enhanced by the interaction between CuO nanograss and Ag island film. The gaps between Ag covered CuO nanograsses are diverse from <10 nm at the bottom to ~200 nm at the top of nanograsses. SERS signal are improved where the gaps are minimized to near 10s of nanometers. There are many spots that provide sufficiently narrow gap between the structures on randomly grown CuO nanograss surface. Then we may find optimal enhancement of Raman signal using the mapping data of average results. Fabrication of CuO nanograss based on a solution method is relatively simple and fast so this result can potentially provide a path toward cost effective fabrication of SERS substrate for sensing applications.