• Title/Summary/Keyword: oxidative coupling

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A Comparative Study on the Removals of 1-Naphthol by Natural Manganese Oxides and Birnessite (천연망간산화물과 버네사이트에 의한 1-Naphthol의 제거 특성 비교)

  • Lee, Doo-Hee;Harn, Yoon-I;Kang, Ki-Hoon;Shin, Hyun-Sang
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.4
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    • pp.278-286
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    • 2009
  • In this study, four natural Mn oxides ($NMO_1-NMO_4$) was characterized using x-ray diffraction, scanning electron microscopy, and their removal efficiency for 1-naphthol (1-NP) in aqueous phase, using batch reactor, was investigated. The results were compared with one another and a synthetic manganese oxide, birnessite. The NMOs have a various Mn minerals including pyrolusite (${\beta}-MnO_2$), cryptomeltane (${\alpha}-MnO_2$) as well as birnessite (${\delta}-MnO_2$) depending on their sources, which results in different removal efficiencies (removals, kinetics) and reaction types (sorption or oxidative-transformation). The comparative study showed that $NMO_1$ (electrolytic Mn oxide) have a higher removal efficiency for 1-NP via oxidative-transformation compared to birnessite. The 1-NP removals by NMOs were followed by pseudo-first order reaction, and the surface area-normalized specific rate constants ($K_{surf},\;L/m^2$ min) determined were in order of $NMO_1(3.31{\times}10^{-3})$>${\delta}-MnO_2(1.48{\times}10^{-3}){\fallingdotseq}NMO_3(1.46{\times}10^{-3})$>$NMO_2(0.83{\times}10^{-3})$>$NMO_4(0.67{\times}10^{-3})$. From the solvent extraction experiments with the Mn oxide precipitates after reaction, it was observed that the oxidative-transformation rates of 1-NP were in order of $NMO_1{\fallingdotseq}{\delta}-MnO_2$>$NMO_3$>$NMO_4{\gg}NMO_2$ and the analysis of HPLC chromatogram and UV-Vis. absorption ratios ($A_{2/4}$, $A_{2/6}$) on the supernatant confirmed that the reaction products were oligomers formed by oxidative-coupling reaction. Results from this study proved that natural Mn oxide (except $NMO_2$) used in this experiment can be effectively applied for the removal of naphthols in aqueous phase, and the removal efficiencies are depending on the surface characters of the Mn oxides.

Detect of Hypericin (HyH) gene in Hypericum erectum in Korea and Comparison of H. perforatum in Europe (한국내 고추나물의 하이퍼리신 유전자(HyH)의 탐색과 유럽의 서양고추나물과 비교)

  • Huh, Man-Kyu
    • Journal of Life Science
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    • v.17 no.8 s.88
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    • pp.1034-1038
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    • 2007
  • Hypericin (HyH) is a substance which is isolated a medicinal herb, Hypericum perforatum L., commonly known as St. John's Wort. Hypericum erectum is a long-lived herb that is distributed in Korea. Cloned HyH genes H. erectum of were conformed by sequencing. The cDNA Hyp-1 sequence has 732 bp with an open reading frame of 567. Thus coding for a protein of 152 amino acid residues. A BLAST re-search using the deduced nucleotide sequences in HyH gene produced significant alignments with the H. perforatum. Sequences in HyH gene showed significant homology with Rubus idaeus putative allergen Rub-i-1 mRNA, Protein sequence comparisons revealed significant homology between Hyp-1 and the phenolic oxidative coupling protein hyp-1 of H. perforatum (98%). Additionally, Hyp-1 showed sig-nificant homology with various other classes of allergens, including Pru-av-1 (62%) from Prunus avium and allergen Bet-vl-Sc3 from Betula pendula (60%). Thus, the result of this study may offer an important information to establish an assay system for chemicals of the herbal medicines for H. erectum as well as H. perforatum.

Different Analysis of b2 Peaks in SERS Spectra of 4-aminobenzenethiol

  • Choe, Han-Gyu;Son, Hyeon-Gyeong;Yu, Hyeon-Ung;Lee, Tae-Geol;Kim, Ji-Hwan
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.257-258
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    • 2012
  • The SERS spectra of 4-aminobenzenethiol (ABT) have served as the "probe" molecule, which have helped spectroscopists to build up the electromagnetic (EM) and chemical (CHEM) enhancement mechanisms. In particular, the b2-peaks (9b, 3, and 19b) of the SERS spectra of ABT have been attributed to arise from the vibronic charge-transfer (CT) between Au or Ag surface and the ABT. Quite recently, however, Tian and co-workers [1] claimed that the b2-peaks are not the CT-enhanced spectra of ABT. Instead, these peaks arise from the 4,4'-dimercaptoazobenzenes (DMABs) that are produced by the oxidative coupling of two ABTs. Their claim is under intense debate currently. Herein, we studied spatially and temporally resolved SERS spectra of ABTs on Ag thin film (thickness of 10 nm), to investigate such claim. Herein, we present a series of additional evidences that strongly support that the b2 intensities of ABTs do not arise from the CT-enhancement: (1) the b2-peaks can be locally "activated" (i. e. turned on) irreversibly with focused laser radiation; (2) the TOF-SIM spectrometry on the activated region show depletion of ABT-Ag+ ions; and finally (3) the spatially resolved FT-IR spectra of the activated region show two pronounced peaks at 1377 cm-1 and 1460 cm-1, both of which can be assigned to the stretching mode of N=N bond. While the result does not disprove the existence of CT or CHEM enhancement in general, the results do show that previous interpretations of the spectra of ABTs should be re-interpreted.

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Fluorene-Based Conjugated Copolymers Containing Hexyl-Thiophene Derivatives for Organic Thin Film Transistors

  • Kong, Ho-Youl;Chung, Dae-Sung;Kang, In-Nam;Lim, Eun-Hee;Jung, Young-Kwan;Park, Jong-Hwa;Park, Chan-Eon;Shim, Hong-Ku
    • Bulletin of the Korean Chemical Society
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    • v.28 no.11
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    • pp.1945-1950
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    • 2007
  • Two fluorene-based conjugated copolymers containing hexyl-thiophene derivatives, PF-1T and PF-4T, were synthesized via the palladium-catalyzed Suzuki coupling reaction. The number-average molecular weights (Mn) of PF-1T and PF-4T were found to be 19,100 and 13,200, respectively. These polymers were soluble in common organic solvents such as chloroform, chlorobenzene, toluene, etc. The UV-vis absorption maximum peaks of PF-1T and PF-4T in the film state were found to be 410 nm and 431 nm, respectively. Electrochemical characterization revealed that these polymers have low highest occupied molecular orbital (HOMO) levels, indicating good resistance against oxidative doping. Thin film transistor devices were fabricated using the top contact geometry. PF-1T showed much better thin-film transistor performance than PF-4T. A thin film of PF- 1T gave a saturation mobility of 0.001-0.003 cm2 V?1 s?1, an on/off ratio of 1.0 × 105, and a small threshold voltage of ?8.3 V. To support TFT performance, we carried out DSC, AFM, and XRD measurements.

Characterization of a Biflaviolin Synthase CYP158A3 from Streptomyces avermitilis and Its Role in the Biosynthesis of Secondary Metabolites

  • Lim, Young-Ran;Han, Songhee;Kim, Joo-Hwan;Park, Hyoung-Goo;Lee, Ga-Young;Le, Thien-Kim;Yun, Chul-Ho;Kim, Donghak
    • Biomolecules & Therapeutics
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    • v.25 no.2
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    • pp.171-176
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    • 2017
  • Streptomyces avermitilis produces clinically useful drugs such as avermectins and oligomycins. Its genome contains approximately 33 cytochrome P450 genes and they seem to play important roles in the biosynthesis of many secondary metabolites. The SAV_7130 gene from S. avermitilis encodes CYP158A3. The amino acid sequence of this enzyme has high similarity with that of CYP158A2, a biflaviolin synthase from S. coelicolor A3(2). Recombinant S. avermitilis CYP158A3 was heterologously expressed and purified. It exhibited the typical P450 Soret peak at 447 nm in the reduced CO-bound form. Type I binding spectral changes were observed when CYP158A3 was titrated with myristic acid; however, no oxidative product was formed. An analog of flaviolin, 2-hydroxynaphthoquinone (2-OH NQ) displayed similar type I binding upon titration with purified CYP158A3. It underwent an enzymatic reaction forming dimerized product. A homology model of CYP158A3 was superimposed with the structure of CYP158A2, and the majority of structural elements aligned. These results suggest that CYP158A3 might be an orthologue of biflaviolin synthase, catalyzing C-C coupling reactions during pigment biosynthesis in S. avermitilis.

Removals of 1-Naphthol in Aqueous Solution Using Alginate Gel Beads with Entrapped Birnessites (버네사이트를 고정화한 알긴산 비드(Bir-AB)를 이용한 수용액 중 1-Naphthol의 제거)

  • Eom, Won-Suk;Lee, Doo-Hee;Shin, Hyun-Sang
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.4
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    • pp.247-256
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    • 2013
  • In this study, alginate beads containing birnessite (Bir-AB), a highly reactive oxidative catalyst for the transformation of phenolic compounds, was prepared and its 1-naphthol (1-NP) removal efficiency was investigated in a batch test. Based on scanning electron microscopy image, it can be inferred that the alginate gel cluster acts as a bridge which bind the birnessite particles together. Kinetic experiment with Bir-AB of different mixing ratios of birnessite to alginate (Bir : AG=0.25 : 1~1 : 1 w/w) indicate that pseudo-first order kinetic constants, $k(hr^{-1})$ for the 1-NP removals increased about 1.5 times when the birnessite mixing ratio was doubled. The removals of 1-NP was found to be dependent on solution pH and the pesudo-first order rate constants were increased from 0.331 $hr^{-1}$ at pH 10 to 0.661 $hr^{-1}$ at pH 4. The analysis of total organic carbon for the reaction solutions showed that a higher removal of dissolved organic carbon was achieved with Bir-AB as compared to birnessite. HPLC chromatographic analysis of the methanol extract after reaction of 1-NP with Bir-AB suggest that the reaction products could be removed through incorporation into the aliginate beads as a bound residue. Mn ions produced from the oxidative transformation of 1-NP by birnessite were also removed by sorption to Bir-AB. The Bir-AB was recovered quantitatively by simple filtration and was reused twice without significant loss of the initial reactivity.

Effects of soil organic matter and oxidoreductase on adsorption and desorption of herbicide oxadiazon in soils (제초제 oxadiazon의 토양 흡탈착에 미치는 유기물의 함량과 산화환원효소의 영향)

  • Lee, Wan-Seok;Kim, Jang-Eok
    • The Korean Journal of Pesticide Science
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    • v.2 no.3
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    • pp.70-78
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    • 1998
  • Dissipation, adsorption and desorption of oxadiazon were examined in two soils containing different amounts of soil organic matter. In addition, reactivity of oxadiazon with humic monomers was searched to clarify binding mechanism of oxadiazon to soil organic matter in the presence of a laccase of Myceliophthera thermophila. Half lives of oxadiazon were 38 days in Soil I and 45 days in Soil II. Freundlich constant, k values of fresh soils were higher than those of oxidized soils. Adsorption rates of oxadiazon were increased 17.1% in Soil I and 9.3% in Soil II in the presence of a laccase but no significant increase was observed in oxidized soils. Desorption rates of oxadiazon in fresh soils were lower than those in oxidized soils. Desorption rates of adsorbed oxadiazon in soils addes with the enzyme were not changed in oxidized soils but decreased in fresh soils. The herbicide oxadiazon alone underwent no transformation by a laccase but in the presence of catechol, guaiacol and gallic acid as humic monomer, transformation rates of it were from 20% to 24%.

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Decontamination of Waste Water Polluted with Phenolic and Anilinic Compounds Using Plant Materials (식물체를 이용한 Phenol 및 Aniline성 폐수의 정화)

  • Lee, Jung-Eun;Park, Jong-Woo;Kim, Jang-Eok
    • Korean Journal of Environmental Agriculture
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    • v.19 no.3
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    • pp.228-233
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    • 2000
  • This study was carried out to estimate the possibility on the removal of phenols and anilines, which were contained in pulp or dye waste water, and the reusability of plant materials, shepherd's purse and turnip. Most of phenols catalyzed with shepherd's purse were removed more than 90% in the presence of $H_2O_2$, and the removal was ranged from 53.1% for 2,6-DMP to more than 99% for 2,4,6-TCP when turnip was used as catalysts. The removal of anilines catalyzed with shepherd's purse was ranged from 42.2% for 2-CA to 78.7% for 3,4-DCA in the presence of $H_2O_2$, and in case of turnip, from 31.5% for 2-CA to 90.0 % for 2,4-DCA. The reuse of plant materials was proved to be possible for not only the batch method but also the continuous method. No decreasing removal was observed during 30 cycles in waster water contaminated with 100ppm of 2,4-DCP. However, it was observed that the removal was decreased with increasing the number of cycles in higher concentration of 2,4-DCP(800ppm). Therefore, it could be suggested that the number of reusable cycles depends on the initial concentration of substrates.

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Fabrication of a Partial Genome Microarray of the Methylotrophic Yeast Hansenula polymorpha: Optimization and Evaluation of Transcript Profiling

  • OH , KWAN-SEOK;KWON, OH-SUK;OH, YUN-WI;SOHN, MIN-JEONG;JUNG, SOON-GEE;KIM, YONG-KYUNG;KIM, MIN-GON;RHEE, SANG-KI;GERD GELLISSEN,;KANG, HYUN-AH
    • Journal of Microbiology and Biotechnology
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    • v.14 no.6
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    • pp.1239-1248
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    • 2004
  • The methylotrophic yeast Hansenula polymorpha has been extensively studied as a model organism for methanol metabolism and peroxisome biogenesis. Recently, this yeast has also attracted attention as a promising host organism for recombinant protein production. Here, we describe the fabrication and evaluation of a DNA chip spotted with 382 open reading frames (ORFs) of H. polymorpha. Each ORF was PCR-amplified using gene-specific primer sets, of which the forward primers had 5'-aminolink. The PCR products were printed in duplicate onto the aldehyde-coated slide glasses to link only the coding strands to the surface of the slide via covalent coupling between amine and aldehyde groups. With the partial genome DNA chip, we compared efficiency of direct and indirect cDNA target labeling methods, and found that the indirect method, using fluorescent-labeled dendrimers, generated a higher hybridization signal-to-noise ratio than the direct method, using cDNA targets labeled by incorporation of fluorescence-labeled nucIeotides during reverse transcription. In addition, to assess the quality of this DNA chip, we analyzed the expression profiles of H. polymorpha cells grown on different carbon sources, such as glucose and methanol, and also those of cells treated with the superoxide­generating drug, menadione. The profiles obtained showed a high-level induction of a set of ORFs involved in methanol metabolism and oxidative stress response in the presence of methanol and menadione, respectively. The results demonstrate the sensitivity and reliability of our arrays to analyze global gene expression changes of H. polymorpha under defined environmental conditions.

The Effects of Polymerization Catalyst Systems on the Synthesis of Poly(2,6-dimethyl-1,4-phenylene ether) (중합촉매 시스템이 폴리페닐렌에테르의 합성에 미치는 영향)

  • Lee, Chang-Jae;Kim, Yong-Tae;Kim, Jin-Kyu;Kim, Ji-Heung;Nam, Sung-Woo;Jeon, Boong-Soo;Kim, Young-Jun
    • Polymer(Korea)
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    • v.36 no.1
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    • pp.98-103
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    • 2012
  • Poly(2,6-dimethyl-1,4-phenylene ether) (PPE) was synthesized using $Cu(NO_2)_2{\cdot}3H_2O$ or CuCl catalyst with various amounts of ligand and base in several different solvent systems. CuCl/1-methylimidazole/ammonium hydroxide was found to be an effective catalyst system which showed the highest polymer yield and molecular weight. The effects of catalyst/monomer ratio, different amine ligands, and the content of mono-functional reagent 2,4,6-trimethylphenol (TMP) additive on the polymer yield and molecular weight were investigated. Among the co-solvent systems used in this polymerization, chloroform/methanol 9/1(v/v) gave the highest polymer yield and molecular weight ($\overline{M_n}$ 55 K, $\overline{M_w}$ 92 K, PDI 1.7). The catalytic activity between CuCl and CuI was compared by oxygen-uptake experiments and the formation of sideproduct, 5,5'-tetramethyl-4,4'-diphenoquinone (DPQ), was analyzed by ultraviolet spectroscopy.