• Bulletin of the Korean Chemical Society
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• v.6 no.1
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• pp.23-29
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• 1985

The charge-transfer complexing properties of 1-methyl nicotinamide (MNA), an acceptor, and adenine, a donor, were investigated in water and SDS micellar solutions in relation to the intramolecular interaction in nicotinamide adenine dinucleotide ($NAD^+$). The spectral and thermodynamic parameters of MNA-indole and methyl viologen-adenine complex formations were determined, and the data were utilized to evaluate the charge-transfer abilities of MNA and adenine. The electron affinity of nicotinamide was estimated to be 0.28 eV from charge-transfer energy $of{\sim}300$ nm for MNA-indole. The large enhancement of MNA-indole complexation in SDS solutions by entropy effect was attributed to hydrophobic nature of indole. The complex between adenine and methyl viologen showed an absorption band peaked near 360 nm. The ionization potential of adenine was evaluated to be 8.28 eV from this. The much smaller enhancement of charge-transfer interaction involving adenine than that of indole in SDS solutions was attributed to weaker hydrophobic nature of the donor. The charge-transfer energy of 4.41 eV (280 nm) was estimated for nicotinamide-adenine complex. The spectral behaviors of $NAD^+$ were accounted to the presence of intramolecular interaction in $NAD^+$, which is only slightly enhanced in SDS solutions. The replacement of nicotinamide-adenine interaction in $NAD^+$ by intermolecular nicotinamide-indole interaction in enzyme bound $NAD^+$, and guiding role of adenine moiety in $NAD^+$ were discussed.

• Bulletin of the Korean Chemical Society
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• v.10 no.5
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• pp.418-422
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• 1989

Cadmium-doped indium sesquioxide systems with a variety of CdO mol % were prepared to investigate the effect of doping on the electrical properties of indium sesquioxide. The electrical conductivities of pure $In_2O_3$ and Cd-doped $In_2O_3$ systems were measured in the temperature range from 25 to $1200^{\circ}C$ and $P_O_2$ range from $10^{-7}$ to $10^{-1}$ atm, and the thermoelectric power was measured in the same temperature range. The electrical conductivity and thermopower decreased with increasing CdO mol % indicating that all the samples are n-type semiconductors. The electrical conductivities of pure $In_2O_3$ and lightly doped $In_2O_3$ were considerably affected by the chemisorption $O_2$ at temperatures of 400 to $560^{\circ}C$ and then gaseous oxygen was reversibly chemisorbed at the temperature. The predominant defects in $In_2O_3$ are believed to be triply-charged interstitial indiums at temperatures above $560^{\circ}C$ and oxygen vacancies below $560^{\circ}C$. In Cd-doped $In_2O_3$ systems, cadmium acts as an electron acceptor and inhibits the transfer of lattice indium to interstitial sites, which give rise to the decrease of the electrical conductivity.

• Journal of Soil and Groundwater Environment
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• v.24 no.5
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• pp.42-54
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• 2019

Biodegradation of an explosive compound, glyceryl trinitrate (GTN), was studied with a denitrifying microbial culture grown in a sequencing batch reactor and a GTN acclimated denitrifying culture. The GTN acclimated culture, which were fed on GTN for 1 month, degraded GTN regioselectively via denitration on C1 position as compared to C2 position denitration by denitrifying culture that has never been exposed to GTN. Accumulation of two isomeric glyceryl dinitrates (GDNs) in both culture medium suggests that GDN denitration is the rate-limiting step in GTN biodegradation. The first order GTN degradation rate normalized to cell concentration of the acclimated culture was calculated to be 0.045 (${\pm}0.002$) L/g-hr. Increasing concentration of electron acceptor(nitrate) resulted in discouraged GTN degradation. According to microbial community analysis, prolonged GTN exposure resulted in 25% increase in the genus level of the GTN acclimated culture with the disappearance of two dominating denitrifying microbial species of Methyloversatilis universalis and Hyphomicrobium zavarzinii in the denitrifying culture.

• Bulletin of the Korean Chemical Society
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• v.18 no.3
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• pp.318-323
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• 1997

ο-(2-Vinyloxyethoxy)benzylidenemalononitrile (3a) and methyl ο-(2-vinyloxyethoxy)-benzylidenecyanoacetate (3b), m-(2-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl m-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b) were prepared by the condensation of ο-(2-vinyloxyethoxy)benzaldehyde (1) and m-(2-vinyloxyethoxy)benzaldehyde (2) with malononitrile or methyl cyanoacetate, respectively. Bifunctional vinyl ether monomers 3a and 3b polymerized quantitatively with radical initiators in γ-butyrolactone solution at 65 ℃, while meta-isomers 4a and 4b gave lower yields of polymers under the same conditions. The polymers 5-6 obtained from the monomers 3-4 were insoluble in common solvents due to cross-linking. Under the same polymerization conditions ethyl vinyl ether polymerized well with model compounds ο-methoxybenzylidenemalononitrile 7a, methyl ο-methoxybenzylidenecyanoacetate 7b, m-methoxybenzylidenemalononitrile 8a, and methyl m-methoxybenzylidenecyanoacetate 8b, respectively, to give 1:1 alternating copolymers 9-10 in high yields. Cross-linked polymers 5-6 showed a thermal stability up to 300 ℃, and showed a double phase degradation pattern in their TGA thermograms. Polymers 5-6 showed broad endothermic bands around 75-110 ℃ without any characteristic Tg peaks in DSC thermograms. Alternating copolymers 9-10, except copolymer 9b were soluble in common organic solvents. The inherent viscosities of polymer 9-10 were in the range of 0.35-0.62 dL/g. Polymer films cast from acetone solution were cloudy and tough and Tg values obtained from DSC thermograms were in the range of 118-165 ℃.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.12
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• pp.1298-1304
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• 2005

This study was performed to evaluate the characteristics of the competition between two electron acceptors, perchlorate and nitrate, with Citrobacter Amalonaticus strain JB101. In addition, the applicability of membrane bioreactor(MBR) for perchlorate removal was evaluated. The maximum growth rate of strain JB101 on perchlorate and nitrate are 0.27 and 0.58 $hr^{-1}$, and maximum substrate utilization rates were 35.1 mg $ClO_4^-/g$ protein-day and 45.6 mg $NO_3^-/g$ protein-day, respectively. Nitrate was a competitive inhibitor for perchlorate, and strain JB101 prefer nitrate to perchlorate as electron acceptor. Complete removal of perchlorate could be achieved up to the surface leading rate of 4.6 g $ClO_4^-/m^2-day$ with the MBR fed with 20 mg $ClO_4^-/L$(HCMBR). When 5 mg/L of nitrate was added to the same influent, perchlorate removal efficiency decreased to 96.5%, while nitrate was completely removed. For the MBR fed with 0.7 mg/L of perchlorate (LCMBR), the maximum perchlorate removal efficiency was 100% up to the loading rate of 0.23 g $ClO_4^-/m^2-day$. Membrane fouling was found to be a problem at high leading rate for both MBRs. The acetate consumption ratio per perchlorate was $13.7{\sim}51.7\;e^-eq./e^-eq.$ in LCMBR, while the value was $2.5{\sim}3.6\;e^-eq./e^-eq.$ in HCMBR. This difference could be related to the acetate consumption with oxygen as electron acceptor. Therefore, the amount of acetate addition must be determined considering the concentrations of other electron acceptors in the influent.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.9 no.2
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• pp.197-206
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• 1999

The stochiometric mixture of evaporating materials for the $AgInSe_2$single crystal thin films were prepared from horizontal furnace. Using extrapolation method of X-ray diffraction patterns for the $AgInSe_2$polycrystal, it was found tetragonal structure whose lattice constant $a_0$ and $C_0$ were 6.092 $\AA$ and 11.688 $\AA$, respectively. To obtain the single crystal thin films of AgInSe$_2$, the mixed crystal was deposited on thoroughly etched semi-insulator GaAs(100) substrate by HWE system. The source and substrate temperature were fixed to $610^{\circ}C$ and $450^{\circ}C$ respectively, and the thickness of the single thin films was obtained to 3.8 $\mu\textrm{m}$. The crystallization of single crystal thin films was investigated by the photoluminescence (PL) and double crystal X-ray dirrfaction (DCXD). The Hall effect was measured by the method of van der Pauw and carrier density and mobility dependence on temperature were studied. The carrier density and mobility of $AgInSe_2$single crystal thin films deduced from Hall data are $9.58{\times}10^{22} electron/m^3,\; 3.42{\times}10^{-2}m^2/V{\cdot}s$ at 293 K, respectively. From the photocurrent spectrum by illumination of perpendicular light on the c-axis of the $AgInSe_2$single crystal thin film, the spin orbit coupling $\Delta$So and the crystal field splitting $\Delta$Cr were obtained to 0.29 eV and 0.12 eV at 20 K respectively. From PL peaks measured at 20 K, 881.1 nm (1.4071 eV) and 882.4 nm (1.4051 eV) mean $E_x^U$ the upper polariton and $E_x^L$ the lower polariton of the free exciton $(E_x)$, also 884.1 nm (1.402 eV) express $I_2 peak of donor-bound exciton emission and 885.9 nm (1.3995 Ev) emerges $I_1$ peak of acceptor-bound exciton emission. In addition, the peak observed at 887.5 nm (1.3970 eV) was analyzed to be PL peak due to DAP.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.505-512
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• 2014

A new donor-accepter-donor-accepter-donor (D-A-D-A-D) type 2,1,3-benzothiadiazole-thiophene-based acceptor unit 2,5-di(4-(5-bromo-4-octylthiophen-2-yl)-2,1,3-benzothiadiazol-7-yl)thiophene ($DTBTTBr_2$) was synthesized. Copolymerized with fluorene and indeno[1,2-b]fluorene electron-rich moieties, two alternating narrow band gap (NBG) copolymers PF-DTBTT and PIF-DTBTT were prepared. And two copolymers exhibit broad and strong absorption in the range of 300-700 nm with optical band gap of about 1.75 eV. The highest occupied molecular orbital (HOMO) energy levels vary between -5.43 and -5.52 eV and the lowest unoccupied molecular orbital (LUMO) energy levels range from -3.64 to -3.77 eV. Potential applications of the copolymers as electron donor material and $PC_{71}BM$ ([6,6]-phenyl-$C_{71}$ butyric acid methyl ester) as electron acceptors were investigated for photovoltaic solar cells (PSCs). Photovoltaic performances based on the blend of PF-DTBTT/$PC_{71}BM$ (w:w; 1:2) and PIF-DTBTT/$PC_{71}BM$ (w:w; 1:2) with devices configuration as ITO/PEDOT: PSS/blend/Ca/Al, show an incident photon-to-current conversion efficiency (IPCE) of 2.34% and 2.56% with the open circuit voltage ($V_{oc}$) of 0.87 V and 0.90 V, short circuit current density ($J_{sc}$) of $6.02mA/cm^2$ and $6.12mA/cm^2$ under an AM1.5 simulator ($100mA/cm^2$). The photocurrent responses exhibit the onset wavelength extending up to 720 nm. These results indicate that the resulted narrow band gap copolymers are viable electron donor materials for polymer solar cells.

• Journal of the Korean Chemical Society
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• v.18 no.2
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• pp.85-96
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• 1974

Extended H ckel Theory and CNDO/2 MO calculation methods have been applied to $C_6H_5YCH_2Cl$(Y = None, -$CH_2$-, -O-, -S-, -CO-, -$SO_2$-). It has been shown that charge distributions in molecules are mainly controlled by the migration of valence inactive electron, giving the order of ${\sigma}$-acceptor and ${\pi}$-donor effects -O- > -S- > -$CH_2$- > -$SO_2$-. The -CO- group exceptionally acts as ${\sigma}$-donor and ${\pi}$-acceptor. It was also predicted that, $S_N2$ reactivities of C$C_6H_5YCH_2Cl$ would be in the order of -O-${\thickapprox}$-CO- >>-S-${\thickapprox}$None > -$CH_2$-, neglecting solvent effect. From the results of our studies, we conclude that the structural factors influencing 의 $S_N$ reactivities will be: (1) positive charge developments on reaction center carbon atom (2) energy level of ${\sigma}$-antibonding unoccupied MO with respect to C-Cl bond. (3) ${\sigma}$-antibonding strength of C-Cl bond at that level.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.89.1-89.1
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• 2010

Since Gratzel and co-workers developed a new type of solar cell based on the nanocrystalline $TiO_2$ electrode, dye-sensitized solar cells (DSSCs) have attracted considerable attention on account of their high solar energy-to-conversion efficiencies (11%), their easy manufacturing process with low cost production compared to conventional p-n junction solar cells. The mechanism of DSSC is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline $TiO_2$. The oxidized dye is reduced by the hole injection process from either the hole counter or electrolyte. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO gap, of dye molecule in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. To date, high performance and good stability of DSSC based on Ru-dyes as a photosensitizer had been widely addressed in the literatures. DSSC with Ru-bipyridyl complexes (N3 and N719), and the black ruthenium dye have achieved power conversion efficiencies up to 11.2% and 10.4%, respectively. However, the Ru-dyes are facing the problem of manufacturing costs and environmental issues. In order to obtain even cheaper photosensitizers for DSSC, metal-free organic photosensitizers are strongly desired. Metal-free organic dyes offer superior molar extinction coefficients, low cost, and a diversity of molecular structures, compared to conventional Ru-dyes. Recently, novel photosensitizers such as coumarin, merocyanine, cyanine, indoline, hemicyanine, triphenylamine, dialkylaniline, bis(dimethylfluorenyl)-aminophenyl, phenothiazine, tetrahydroquinoline, and carbazole based dyes have achieved solar-to-electrical power conversion efficiencies up to 5-9%. On the other hand, organic dye molecules have large ${\pi}$-conjugated planner structures which would bring out strong molecular stacking in their solid-state and poor solubility in their media. It was well known that the molecular stacking of organic dyes could reduce the electron transfer pathway in opto-electronic devices, significantly. In this paper, we have studied on synthesis and characterization of dendritic organic dyes with different number of electron acceptor/anchoring moieties in the end of dendrimer. The photovoltaic performances and the incident photon-to-current (IPCE) of these dyes were measured to evaluate the effects of the dendritic strucuture on the open-circuit voltage and the short-circuit current.

• Journal of the Mineralogical Society of Korea
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• v.15 no.3
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• pp.231-240
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• 2002

Microbial metal reduction influences the biogeochemical cycles of carbon and metals as well as plays an important role in the bioremediation of metals, radionuclides, and organic contaminants. The use of bacteria to facilitate the production of magnetite nanoparticles and the formation of carbonate minerals may provide new biotechnological processes for material synthesis and carbon sequestration. Metal-reducing bacteria were isolated from a variety of extreme environments, such as deep terrestrial subsurface, deep marine sediments, water near Hydrothemal vents, and alkaline ponds. Metal-reducing bacteria isolated from diverse extreme environments were able to reduce Fe(III), Mn(IV), Cr(VI), Co(III), and U(VI) using short chain fatty acids and/or hydrogen as the electron donors. These bacteria exhibited diverse mineral precipitation capabilities including the formation of magnetite ($Fe_3$$O_4$), siderite ($FeCO_3$), calcite ($CaCO_3$), rhodochrosite ($MnCO_3$), vivianite [$Fe_3$($PO_4$)$_2$ .$8H_2$O], and uraninite ($UO_2$). Geochemical and environmental factors such as atmospheres, chemical milieu, and species of bacteria affected the extent of Fe(III)-reduction as well as the mineralogy and morphology of the crystalline iron mineral phases. Thermophilic bacteria use amorphous Fe(III)-oxyhydroxide plus metals (Co, Cr, Ni) as an electron acceptor and organic carbon as an electron donor to synthesize metal-substituted magnetite. Metal reducing bacteria were capable of $CO_2$conversion Into sparingly soluble carbonate minerals, such as siderite and calcite using amorphous Fe(III)-oxyhydroxide or metal-rich fly ash. These results indicate that microbial Fe(III)-reduction may not only play important roles in iron and carbon biogeochemistry in natural environments, but also be potentially useful f3r the synthesis of submicron-sized ferromagnetic materials.