• 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.

• Journal of Embryo Transfer
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• v.25 no.1
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• pp.35-42
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• 2010

Many studies propose that dysfunction of mitochondrial proton-translocating NADH-ubiquinone oxidoreductase (complex I) is associated with neurodegenerative disorders, such as Parkinson's disease and Huntington's disease. Mammalian mitochondrial proton-translocating NADH-quinone oxidoreductase (complex I) consists of at least 46 different subunits. In contrast, the NDI1 gene of Saccharomyces cerevisiae is a single subunit rotenone-insensitive NADH-quinone oxidoreductase that is located on the matrix side of the inner mitochondrial membrane. With a recombinant adeno-associated virus vector carrying the NDI1 gene (rAAV-NDI1) as the gene delivery method, we were able to attain high transduction efficiencies even in the human epithelial cervical cancer cells that are difficult to transfect by lipofection or calcium phosphate precipitation methods. Using a rAAV-NDI1, we demonstrated that the Ndi1 enzyme is successfully expressed in HeLa cells. The expressed Ndi1 enzyme was recognized to be localized in mitochondria by confocal immunofluorescence microscopic analyses and immunoblotting. Using digitonin-permeabilized cells, it was shown that the NADH oxidase activity of the NDI1-transduced HeLa cells were not affected by rotenone which is inhibitor of complex I, but was inhibited by flavone and antimycin A. The NDI1-transduced cells were able to grow in media containing rotenone. In contrast, control cells that did not receive the NDI1 gene failed to survive. In particular, in the NDI1-transduced cells, the yeast enzyme becomes integrated into the human respiratory chain. It is concluded that the NDI1 gene provides a potentially useful tool for gene therapy of mitochondrial diseases caused by complex I deficiency.

• Membrane Journal
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• v.20 no.1
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• pp.1-7
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• 2010

A graft copolymer, i.e. poly(vinylidene fluoride-co-chlorotrifluoroethylene )-g-poly(styrene sulfonic acid) (P(VDF-co-CTFE)-g-PSSA) with 47 wt% of PSSA was synthesized via atom transfer radical polymerization (ATRP). This copolymer was combined with titanium isopropoxide (TTIP) to produce graft copolymer/$TiO_2$ nanocomposite membranes via sol-gel process. $TiO_2$ precursor (TTIP) was selectively incorporated into the hydrophilic PSSA domains of the graft copolymer and grown to form $TiO_2$ nanoparticles, as confirmed by FT-IR and UV-visible spectroscopy. Water uptake and ion exchange capacity (IEC) decreased with TTIP contents due to the decrease in number of sulfonic acid in the membranes. At 5 wt% of TTIP, the mechanical properties of membranes increased while maintaining the proton conductivity.

• Applied Chemistry for Engineering
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• v.16 no.1
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• pp.153-157
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• 2005

4-(Dimethylamino)pyridinium dichromate was synthesized by the reaction of 4-(dimethylamino)pyridine with chromium(VI)trioxide in $H_2O$, and characterized by IR, EA and ICP. The oxidation of benzyl alcohol using 4-(dimethylamino)pyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexen < chloroform < acetone < N,N-dimethylformamide. In the presence of hydrochloric acid(HCl), 4-(dimethylamino)pyridinium dichromate oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) smoothly in N,N-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron-withdrawing groups retarded the reaction. The Hammett reaction constant($\rho$) was -0.70 at 303K. The observed experimental data have been rationalized as follows: the proton transfer occurs after the prior formation of a chromate ester in the rate-determining step.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.13 no.1
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• pp.462-469
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• 2012

Cr(VI)-4,4'-bipyridine complex(4,4'-bipyridinium dichromate) was synthesized by the reaction of 4,4'-bipyridine with chromium trioxide in H2O, and characterized by IR, ICP. The oxidation of benzyl alcohol using 4,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene$CH_3$, H, m-Br, m-$NO_2$) smoothly in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.63(303K). The observed experimental data have been rationalized as follows; the proton transfer occurs after the prior formation of a chromate ester in the rate determining step.

• Journal of Biomedical Engineering Research
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• v.36 no.6
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• pp.241-250
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• 2015

Noninvasive temperature monitoring is feasible with Magnetic Resonance Imaging (MRI) based on temperature sensitive MR parameters such as $T_1$ and $T_2$ relaxation times, Proton Resonance Frequency shift (PRFs), diffusion, exchange process, magnetization transfer contrast, chemical exchange saturation transfer, etc. While the temperature monitoring is very useful to guide the thermal treatment such as RF hyperthermia or thermal ablation, the optimization of the MR thermometry method is essential because the range of temperature measurement depends on the choice of the measurement methods. Useful temperature range depends on the purpose of treatment methods, for example, $42^{\circ}C$ to $45^{\circ}C$ for RF hyperthermia and over $50^{\circ}C$ for thermal ablation. In this paper, MR thermometry methods using $T_1$ and $T_2$ relaxation times and PRFs-based MR thermometry are tried on a 3.0 T MRI system and their results are reported and compared. In addition, the scanning protocol and temperature calculation algorithms from $T_1$ and $T_2$ relaxation times and PRFs are optimized for the different temperature ranges for the purpose of RF hyperthermia and/or thermal ablation.

• Journal of the Korean Chemical Society
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• v.46 no.5
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• pp.432-449
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• 2002

For various oxidoreductases, the optimum pHs of the enzymes can be calculated using the rule based on proton transfer. Relative probability of a certain amino acid side chain to be in the water, or the relative affinity to the water was calculated using Boltzman distribution. Also, the protonated and deprotonated portions of a certain amino acid side chain were calculated using p$K_R$ of that and the effective protonated and deprotonated protions were the product of relative probability and the protonated and deproteonated protions. Where the total effective protonated portion was equal to the effective deprotonated portion of amino acid side chains, it was expected that oxidoreductases have max-imum activities. The optimum pHs calculated by our rule were compared with the experimental results.

• Journal of the Korean Society of Urban Environment
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• v.18 no.4
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• pp.503-509
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• 2018

In this study, a Proton-Transfer Reaction-Time-of-Flight Mass spectrometer (PTR-TOF-MS) was used for the continuous monitoring of Volatile Organic Compounds (VOCs) emitted from semiconductor workplace such as photolithography (PHOTO), flat panel display (FPD), organic light emitting diode (OLED), etching (WET) process. The averaged VOCs mixing ratio in the such workplace, PHOTO was 6.5 ppm, FPH was 6.4 ppm, WET was 2.0 ppm and OLED was 1.3 ppm, respectively. The abundance of VOCs in the workplace were methyl ethyl ketone (MEK) with 2.8 ppm (69%) and acetaldehyde with 0.5 ppm (13.2%). Depending on the semiconductor process characteristics, various VOCs have been observed in the workplace. The VOCs mixing ratio are lower than the workplace regulation standard (TWA), it is necessary to continuously monitor and effectively manage these VOCs.

• Applied Chemistry for Engineering
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• v.30 no.1
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• pp.74-80
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• 2019

$Nafion/TiO_2$ composite membranes were prepared via an in-situ sol-gel process with different immersing periods from 1 day to 7 days for the low humidifying proton exchange membrane fuel cell. As the immersing time increased, the $TiO_2$ content within the Nafion membrane increased. The contact angle decreased with the increased $TiO_2$ content in the composite membrane due to the increased hydrophilicity. The water uptake and proton conductivity reached to the highest level for 4 day immersing period, then decreased as the immersing period increased. A 7 days of immersing time was shown to be too long because too much $TiO_2$ aggregates were formed on the membrane surface as well as interior of the membrane, interfering the proton transfer from anode to cathode. Cell performance results were in good agreement with those of the water uptake and proton conductivity; current densities under a relative humidity (RH) of 40% were 0.54, 0.6, $0.63A/cm^2$ and $0.49A/cm^2$ for the immersing time of 1, 3, 4 and 7 days, respectively at a 0.6 V. The composite membrane prepared via the in-situ sol-gel process exhibited the enhancement in the cell performance under of RH 40% by a maximum of about 66% compared to those of using the recasting composite membrane and Nafion 115.

• Korean Chemical Engineering Research
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• v.51 no.5
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• pp.556-560
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• 2013

Recently, there are many efforts focused on development of more economical non-fluorinated membranes for use in PEMFCs (Proton Exchange Membrane Fuel Cells). In this study, characteristics of poly(arylene ether sulfone)(PAES) were compared with fluorinated membrane at PEMFC operation condition. I-V polarization curve, hydrogen crossover, electrochemical surface area, membrane resistance and charge transfer resistance were measured. PAES membrane showed similar performance compared with fluorinated membrane at 100% relative humidity, but the performance of PAES membrane decreased largely due to low ionic conductivity at low relative humidity.