• Title/Summary/Keyword: electron transfer chain

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Photocyclization Reactions of N-(Trimethylsilylmethoxyalkyl)Phthalimides. Efficient and Regioselective Route to Heterocycles

  • Yoon Ung Chan;Oh Ju Hee;Lee, Sang Jin;Kim, Dong Uk;Lee, Jong Gun;Kang Kyung-Tae;Mariano Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.13 no.2
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    • pp.166-172
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    • 1992
  • Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethoxyalkyl)phthalimides(alkyl=E thyl, n-propyl, n-butyl, n-pentyl, and n-octyl). Photocyclizations occur in methanol in high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from oxygen in the $\alpha-silylmethoxy$ groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate $\alpha-silylmethoxy$ cation radicals and cyclization by radical coupling are proposed. In contrast, photoreaction of N-(trimethylsilylmethoxyethyl) phthalimide in acetone follows different reaction routes to produce two cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon $\alpha$ to silicon and oxygen atoms via triplet carbonyl hydrogen abstraction triplet carbonyl silyl group abstraction pathways. The normal singlet SET pathway dominates these triplet processes for photoreaction of this substance in methanol. The efficient and regioselective cyclization reactions observed for photolysis in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

Chemoenzymatic Synthesis of H-shaped Amphiphilic Pentablock Copolymer and Its Self-assembly Behavior (H-형태 양친매성 펜타블록 공중합체의 화학효소적 합성과 자기회합거동 평가)

  • Chen, Peng;Li, Ya-Peng;Li, Cai-Jin;Meng, Xin-Lei;Zhang, Bao;Zhu, Ming;Liu, Yan-Jing;Wang, Jing-Yuan
    • Polymer(Korea)
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    • v.37 no.3
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    • pp.332-341
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    • 2013
  • H-shaped amphiphilic pentablock copolymers $(PSt)_2-b-PCL-b-PEO-b-PCL-b-(PSt)_2$ was synthesized via chemoenzymatic method by combining enzyme-catalyzed ring-opening polymerization (eROP) of ${\varepsilon}$-caprolactone (${\varepsilon}$-CL) and atom transfer radical polymerization (ATRP) of styrene. By this process, we obtained copolymers with controlled molecular weight and low polydispersity. The structure and composition of the obtained copolymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and infrared spectroscopy analysis (IR). The crystallization behavior of the copolymers was analyzed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The crystallization behavior of the H-shaped block copolymers demonstrated a PCL dominate crystallization. The self-assembly behavior of the copolymers was investigated in aqueous media. The hydrodynamic diameters of the copolymer micelles in aqueous solution were measured by dynamic light scattering (DLS). The morphology of the copolymer micelles was observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The hydrodynamic diameters of spherical micelles declined gradually with the increase of the hydrophobic chain lengths of the copolymers. The critical micelle concentration (CMC) values were determined from fluorescence emission, and it was found that the CMCs decreased with an increase of PSt hydrophobic block lengths.

Preparation and characterization of Poly(2-methacryloyloxyethyl phosphorylcholine/fluorescein O-methacrylate)-coated iron oxide nanoparticles (Poly(2-methacryloyloxyethyl phosphorylcholine/fluorescein O-methacrylate)가 도입된 산화철 나노 입자의 제조 및 발열 특성 연구)

  • Ryu, Sunggon;Cheong, In Woo
    • Journal of Adhesion and Interface
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    • v.19 no.3
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    • pp.106-112
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    • 2018
  • Recently, the hyperthermia treatment of malignant tissues has gained great attention as a biocompatible and benign method that facilitates successful cancer therapy compared to radiation and chemotherapy. In this study, superparamagnetic ($Fe_3O_4$) iron oxide nanoparticles (IONP) coated with biocompatible polymer (IONP@P(MPC/FOM)) for the purpose of hyperthermia treatment were prepared and related characterization were performed. IONPs with having 15 nm diameter were first prepared by coprecipitation and followed by surface modification with 4-cyanopentanoic acid dithiobenzoate (CTP) for reversible addition-fragmentation chain transfer (RAFT) copolymerization by using 2-methacryloyloxyethyl phosphorylcholine (MPC) and fluorescein O-methacrylate (FOM) to form corona layer of P(MPC/FOM) on the surface of the IONP. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) confirmed the morphology and hydrodynamic size of the IONP@P(MPC/FOM) and thermogravimetric analysis (TGA) confirmed the formation of P(MPC/FOM) corona layer, respectively. Exposing IONP dispersion to alternating magnetic field suggests that the IONP@P(MPC/FOM) aqueous dispersion with 0.2 wt.% can be used for hyperthermia treatment.

Virus-like Particles Containing Cytokine Plasmid DNA (사이토카인 유전자 함유 바이러스 유사입자의 제조)

  • Oh, Yu-Kyoung;Son, Tae-Jong;Sin, Kwang-Sook;Kang, Min-Jeong;Kim, Jung-Mogg;Kim, Nam-Keun;Ko, Jung-Jae;Kim, Chong-Kook
    • Journal of Pharmaceutical Investigation
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    • v.31 no.3
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    • pp.185-190
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    • 2001
  • Human papillomavirus (HPV) infection is known to cause cervical cancers. Human papillomavirus-like particles (VLP) have been studied as preventive vaccines of cervical cancers. To develop VLP as a therapeutic gene carrier, we studied the method to encapsulate cytokine genes in virus-like particles. HPV type 16 capsid L1 genes were amplified by polymerase chain reaction and cloned into T vector. L1 gene was then inserted into baculovirus transfer vector. The clone of baculovirus encoding L1 gene was isolated and used to express L1 protein in Sf 21 insect cells. VLP were purified by CsCl density gradient and ultracentrifugation. VLP were disassembled to capsomer units by treatment of a reducing agent. Given that interleukin-2 (IL-2) genes have been used in anticancer gene therapy and as a molecular adjuvant, IL-2 cytokine plasmids were chosen as a model gene. IL-2 plasmids were incubated with the disassembled capsomer suspension. To reassemble the particles, the mixture of capsomers and cytokine plasmids was dialyzed. The disassembly and reassembly of VLP were confirmed by transmission electron microscopy. The entrapment of cytokine plasmids in reassembled VLP was tested by the stability of plasmids against DNase I. After treatment of reassembled virus-like particles with DNase I, discrete IL-2 DNA band was observed. Our results indicate that IL-2 cytokine plasmid (3.5 kb size) can be encapsulated in the virus-like particles, suggesting the potential of VLP as a gene delivery system. Moreover, VLP containing the adjuvant cytokine plasmids might function as more effective subunit vaccines.

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Proteomic Analysis of the Aging-related Proteins in Human Normal Colon Epithelial Tissue

  • Li, Ming;Xiao, Zhi-Qiang;Chen, Zhu-Chu;Li, Jian-Ling;Li, Cui;Zhang, Peng-Fei;Li, Mao-Yu
    • BMB Reports
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    • v.40 no.1
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    • pp.72-81
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    • 2007
  • In order to screen the aging related proteins in human normal colon epithelia, the comparative proteomics analysis was applied to get the two-dimensional electrophoresis (2-DE) profiles with high resolution and reproducibility from normal colon epithelial tissues of young and aged people. Differential proteins between the colon epithelia of two age groups were found with PDQuest software. The thirty five differential protein-spots were identified by peptide mass fingerprint (PMF) based on matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) and database searching. Among them there are sixteen proteins which are significantly up-regulated in the colonic mucosal epithelia of young people group, which include ATP synthase beta chain, electron transfer flavoprotein alpha-subunit, catalase, glutathione peroxidase 1, annexin A2 and heat shock cognate 71 kDa protein, etc.; There are nineteen proteins which are significantly up-regulated in the colonic mucosal epithelia of aged people group, which include far upstream element-binding protein 1, nucleoside diphosphate kinase B, protein disulfide-isomerase precursor and VDAC-2, etc.. The identified differential proteins appear to be involved in metabolism, energy generation, chaperone, antioxidation, signal transduction, protein folding and apoptosis. The data will help to understand the molecular mechanisms of human colon epithelial aging.

Activation of persulfate by UV and Fe2+ for the defluorination of perfluorooctanoic acid

  • Song, Zhou;Tang, Heqing;Wang, Nan;Wang, Xiaobo;Zhu, Lihua
    • Advances in environmental research
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    • v.3 no.3
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    • pp.185-197
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    • 2014
  • Efficient defluorination of perfluorooctanoic acid (PFOA) was achieved by integrating UV irradiation and $Fe^{2+}$ activation of persulfate ($S_2O{_8}^{2-}$). It was found that the UV-$Fe^{2+}$, $Fe^{2+}-S_2O{_8}^{2-}$, and UV-$S_2O{_8}^{2-}$ processes caused defluorination efficiency of 6.4%, 1.6% and 23.2% for PFOA at pH 5.0 within 5 h, respectively, but a combined system of UV-$Fe^{2+}-S_2O{_8}^{2-}$ dramatically promoted the defluorination efficiency up to 63.3%. The beneficial synergistic behavior between $Fe^{2+}-S_2O{_8}^{2-}$ and UV-$S_2O{_8}^{2-}$ was demonstrated to be dependent on $Fe^{2+}$ dosage, initial $S_2O{_8}^{2-}$ concentration, and solution pH. The decomposition of PFOA resulted in generation of shorter-chain perfluorinated carboxylic acids (PFCAs), formic acid and fluoride ions. The generated PFCAs intermediates could be further defluorinated by adding supplementary $Fe^{2+}$ and, $S_2O{_8}^{2-}$ and re-adjusting solution pH in later reaction stage. The much enhanced PFOA defluorination in the UV-$Fe^{2+}-S_2O{_8}^{2-}$ system was attributed to the fact that the simultaneous employment of UV light and $Fe^{2+}$ not only greatly enhanced the activation of $S_2O{_8}^{2-}$ to form strong oxidizing sulfate radicals ($SO{_4}^{\cdot-}$), but also provided an additional decarboxylation pathway caused by electron transfer from PFOA to in situ generated $Fe^{3+}$.

Chlorophyll contents and expression profiles of photosynthesis-related genes in water-stressed banana plantlets

  • Sri Nanan Widiyanto;Syahril Sulaiman;Simon Duve;Erly Marwani;Husna Nugrahapraja;Diky Setya Diningrat
    • Journal of Plant Biotechnology
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    • v.50
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    • pp.127-136
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    • 2023
  • Water scarcity decreases the rate of photosynthesis and, consequently, the yield of banana plants (Musa spp). In this study, transcriptome analysis was performed to identify photosynthesis-related genes in banana plants and determine their expression profiles under water stress conditions. Banana plantlets were in vitro cultured on Murashige and Skoog agar medium with and without 10% polyethylene glycol and marked as BP10 and BK. Chlorophyll contents in the plant shoots were determined spectrophotometrically. Two cDNA libraries generated from BK and BP10 plantlets, respectively, were used as the reference for transcriptome data. Gene ontology (GO) enrichment analysis was performed using the Database for Annotation, Visualization, and Integrated Discovery (DAVID) and visualized using the Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway prediction. Morphological observations indicated that water deficiency caused chlorosis and reduced the shoot chlorophyll content of banana plantlets. GO enrichment identified 52 photosynthesis-related genes that were affected by water stress. KEGG visualization revealed the pathways related to the 52 photosynthesisr-elated genes and their allocations in four GO terms. Four, 12, 15, and 21 genes were related to chlorophyll biosynthesis, the Calvin cycle, the photosynthetic electron transfer chain, and the light-harvesting complex, respectively. Differentially expressed gene (DEG) analysis using DESeq revealed that 45 genes were down-regulated, whereas seven genes were up-regulated. Four of the down-regulated genes were responsible for chlorophyll biosynthesis and appeared to cause the decrease in the banana leaf chlorophyll content. Among the annotated DEGs, MaPNDO, MaPSAL, and MaFEDA were selected and validated using quantitative real-time PCR.

Biological Dechlorination of Chlorinated Ethylenes by Using Bioelectrochemical System (생물전기화학시스템을 이용한 염화에틸렌의 생물학적 탈염소화)

  • Yu, Jaecheul;Park, Younghyun;Seon, Jiyun;Hong, Seongsuk;Cho, Sunja;Lee, Taeho
    • Journal of Korean Society of Environmental Engineers
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    • v.34 no.5
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    • pp.304-311
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    • 2012
  • Chlorinated ethylenes such as perchloroethylene (PCE) and trichloroethylene (TCE) are widely used as industrial solvents and degreasing agents. Because of improper handling, these highly toxic chlorinated ethylenes have been often detected from contaminated soils and groundwater. Biological PCE dechlorination activities were tested in bacterial cultures inoculated with 10 different environmental samples from sediments, sludges, soils, and groundwater. Of these, the sediment using culture (SE 2) was selected and used for establishing an efficient PCE dechlorinating enrichment culture since it showed the highest activity of dechlorination. The cathode chamber of bioelectrochemical system (BES) was inoculated with the enrichment culture and the system with a cathode polarized at -500 mV (Vs Ag/AgCl) was operated under fed-batch mode. PCE was dechlorinated to ethylene via TCE, cis-dichloroethylene, and vinyl chloride. Microbial community analysis with polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) showed that the microbial community in the enrichment culture was significantly changed during the bio-electrochemical PCE dechlorination in the BES. The communities of suspended-growth bacteria and attached-growth bacteria on the cathode surface are also quite different from each other, indicating that there were some differences in their mechanisms receiving electrons from electrode for PCE dechlorination. Further detailed research to investigate electron transfer mechanism would make the bioelctrochemical dechlorination technique greatly useful for bioremediation of soil and groundwater contaminated with chlorinated ethylenes.

Identification of Functional and In silico Positional Differentially Expressed Genes in the Livers of High- and Low-marbled Hanwoo Steers

  • Lee, Seung-Hwan;Park, Eung-Woo;Cho, Yong-Min;Yoon, Duhak;Park, Jun-Hyung;Hong, Seong-Koo;Im, Seok-Ki;Thompson, J.M.;Oh, Sung-Jong
    • Asian-Australasian Journal of Animal Sciences
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    • v.20 no.9
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    • pp.1334-1341
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    • 2007
  • This study identified hepatic differentially expressed genes (DEGs) affecting the marbling of muscle. Most dietary nutrients bypass the liver and produce plasma lipoproteins. These plasma lipoproteins transport free fatty acids to the target tissue, adipose tissue and muscle. We examined hepatic genes differentially expressed in a differential-display reverse transcription-polymerase chain reaction (ddRT-PCR) analysis comparing high- and low-marbled Hanwoo steers. Using 60 arbitrary primers, we found 13 candidate genes that were upregulated and five candidate genes that were downregulated in the livers of high-marbled Hanwoo steers compared to low-marbled individuals. A BLAST search for the 18 DEGs revealed that 14 were well characterized, while four were not annotated. We examined four DEGs: ATP synthase F0, complement component CD, insulin-like growth factor binding protein-3 (IGFBP3) and phosphatidylethanolamine binding protein (PEBP). Of these, only two genes (complement component CD and IGFBP3) were differentially expressed at p<0.05 between the livers of high- and low-marbled individuals. The mean mRNA levels of the PEBP and ATP synthase F0 genes did not differ significantly between the livers of high- and low-marbled individuals. Moreover, these DEGs showed very high inter-individual variation in expression. These informative DEGs were assigned to the bovine chromosome in a BLAST search of MS marker subsets and the bovine genome sequence. Genes related to energy metabolism (ATP synthase F0, ketohexokinase, electron-transfer flavoprotein-ubiquinone oxidoreductase and NADH hydrogenase) were assigned to BTA 1, 11, 17, and 22, respectively. Syntaxin, IGFBP3, decorin, the bax inhibitor gene and the PEBP gene were assigned to BTA 3, 4, 5, 5, and 17, respectively. In this study, the in silico physical maps provided information on the specific location of candidate genes associated with economic traits in cattle.