• Title/Summary/Keyword: polymerization mechanism

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Syntheses of Alternating Head-to Head Vinyl Copolymers and Vinyl Terpolymers via Ring-Opening Mechanism. Ring-Opening Polymerization of Substituted-3,4-dihydro-2H-pyrans

  • Lee, Ju-Yeon;Cho, I-Whan
    • Bulletin of the Korean Chemical Society
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    • v.8 no.2
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    • pp.96-101
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    • 1987
  • 2-Ethoxy-6-methoxy-5-cyano-3,4-dihydro-2H-pyran (1_a$), 2-n-butoxy-6-methoxy-5-cyano-3,4-dihydro-2H-pyr an (1b), 2-isobutoxy-6-methoxy-5-cyano-3,4-dihydro-2H-py ran ($1_c$), and 2-ethoxy-6-methoxy-3-methyl-5-cyano-3,4-dihydro -2H-pyran ($1_d$) were prepared by (4 + 2) cycloaddition reaction of methyl $\alpha$-cyanoacrylate with the corresponding alkyl vinyl ethers. Compounds $1_{a-d}$ were ring-open polymerized by cationic catalyst to obtain alternating head-to-head (H-H) copolymers. For comparison, head-to-tail (H-T) copolymer $3_a$ was also prepared by free radical copolymerization of the corresponding monomers. The H-H copolymer exhibited minor differences in its $1_H% NMR and IR spectra, but in the $^{13}C$ NMR spectra significant differences were observed between the H-H and H-T copolymers. Glass transition temperature ($T_g$) of H-H copolymer was higher than that of the H-T copolymer, but thermal decomposition temperature of the H-H copolymer was lower than that of the H-T copolymer. Compounds $1_a$, $a_b$, and $1_c$, copolymerized well with styrene by cationic catalyst, but compound 1d failed to copolymerize with styrene. All of the H-H and H-T copolymers were soluble in common solvents and the inherent viscosities were in the range 0.2-0.4 dl/g.

Characteristic Evaluation of FA-Based Geopolymer with PLA Fiber (PLA 섬유를 가진 다공성 플라이애시 기반 지오폴리머의 특성 평가)

  • Kwon, Seung-Jun;Hwang, Sang-Hyeon;Cho, Young-Keun;Kim, Tae-Sang;Moon, Eun-Jin
    • Journal of the Korean Recycled Construction Resources Institute
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    • v.7 no.3
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    • pp.187-193
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    • 2019
  • Regarding physical absorption mechanism for fine particles(Dust), internal pore-bridging is a major parameter in porous media. In this paper, internal bridging pore system is invented through FA-based geopolymer and incorporated PLA (Polylactic Acid) fiber with biodegradability. With various mix proportions, compressive strength over 20MPa is obtained but PLA is little dissolved in the condition of NaOH 5mole and $30^{\circ}C$ of temperature, which was found that temperature rising accelerates PLA solubility. Within 24hours, beads type PLA is completely dissolved under $90{\sim}130^{\circ}C$ and NaOH 5~12mole of alkali. In room condition, geo-polymerization is limitedly occurs so that the internal pore after PLA dissolution is thought to be effective to absorption and storage of fine particles.

Factors Effecting the Strength & Durability of Geopolymer Binder: A Review (지오폴리머의 강도와 내구성에 영향을 미치는 요인에 대한 고찰)

  • On, Jeong-Kwon;Kim, Gyu-Yong;Sasui, Sasui;Lee, Yae-Chan;Eu, Ha-Min
    • Journal of the Korean Recycled Construction Resources Institute
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    • v.9 no.4
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    • pp.460-468
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    • 2021
  • Owing to the production of conventional concrete/cement, the climate crises is increasing and is mainly caused greenhouse gas (GHG) emission into the environment by industrial process. To reduce the emission of GHG, and excessive consumption of energy, research on geopolymer binder is increasing as it is environmentally friendly compared to the conventional binders such as Portland cement. The research on improving the strength and durability of geopolymer cement becomes one of the trending researches. Generally, the strength and durability of geopolymer binders are improved by altering alkaline solution & its concentration, the precursor materials and curing temperature & time, which significantly influence the chemical composition and microstructure of geopolymer to which the strength and durability of geopolymers relies. This paper included the detailed discussion on the factors affecting the mechanical properties and durability of geopolymer binder and the influence of reaction mechanism on the strength and durability of geopolymer is also discussed in this paper.

Effects of puromycin aminonucleoside on the cytoskeletal changes of glomerular epithelial cells (Puromycin aminonucleoside의 사구체 상피세포에 대한 영향)

  • Lee, Jun Ho;Ha, Tae Sun
    • Clinical and Experimental Pediatrics
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    • v.51 no.1
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    • pp.54-61
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    • 2008
  • Purpose : This study was designed to clarify the mechanism of proteinuria in nephrotic syndrome patients by using puromycin aminonucleoside (PAN) nephrosis model. Methods : Following administration of various concentrations of PAN and antioxidants we observed the changes of podocyte cytoskeletons in cultured rat glomerular epithelial cells (GEpC) by method of scanning electron microscope, reactive oxyten species (ROS) analysis, permeability assay, confocal microscope, and Western blot assay. Results : PAN not only induced the ultrastructural changes of GEpC, such as shortening and fusion of microvilli, but also separated the intercellular gaps and linear ZO-1. PAN induced oxidative stresses in time and dose dependent manners and increases of intercellular permeability in anti-oxidants inhibitable manners. High concentration of PAN induced not only actin polymerization and disorganization, but also the conglomerulation and internal dislocation of ${\alpha}-actinin$ protein. The intensities of fluorescences of ZO-1 protein were diminished and internalized by PAN in a dose-dependent manner, which were inhibited by anti anti-oxidants. Conclusion : PAN induced the changes of podocytes cytoskeleton and junctional barriers by way of increasing ROS in GEpC that resulted in increasing their permeability in a antioxidatn-inhibitable manner. Glomerular hyperpermeability induced by PAN mediateing through oxidative stresses is thought to take part in the mechanism of proteinuria in nephrotic syndrome.

Evaluation on Removal Efficiency of Methylene Blue Using Nano-ZnO/Laponite/PVA Photocatalyzed Adsorption Ball (Nano-ZnO/Laponite/PVA 광촉매 흡착볼의 메틸렌블루 제거효율 평가)

  • Oh, Ju Hyun;Ahn, Hosang;Jang, Dae Gyu;Ahn, Chang Hyuk;Lee, Saeromi;Joo, Jin Chul
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.9
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    • pp.636-642
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    • 2013
  • In order to overcome drawbacks (i.e., filtration and recovery) of conventional powder type photocatalysts, nano-ZnO/Laponite/PVA (ZLP) photocatalyzed adsorption balls were developed by using in situ mixing of nanoscale ZnO as a photocatalyst, and Laponite as both adsorbent and supporting media in deionized water, followed by the poly vinyl alcohol polymerization with boric acid. The optimum mixing ratio of nano-ZnO:Laponite:PVA:deionized water was found to be 3:1:1:16 (by weight), and the mesh and film produced by PVA polymerization with boric acid might inhibit both swelling of Laponite and detachment of nanoscale ZnO from ZLP balls. Drying ZLP balls with microwave (600 watt) was found to produce ZLP balls with stable structure in water, and various sizes (55~500 ${\mu}m$) of pore were found to be distributed based on SEM and TEM results. In the initial period of reaction (i. e., 40 min), adsorption through ionic interaction between methylene blue and Laponite was the main removal mechanism. After the saturation of methylene blue to available adsorption sites for Laponite, the photocatalytic degradation of methylene blue occurred. The effective removal of methylene blue was attributed to adsorption and photocatalytic degradation. Based on the results from this study, synthesized ZLP photocatalyzed adsorption balls were expected to remove recalcitrant organic compounds effectively through both adsorption and photocatalytic degradation, and the risks of environmental receptors caused by detachment of nanoscale photocatalysts can be reduced.

Biomodification of Ethanol Organolsolv Lignin by Abortiporus biennis and Its Structural Change by Addition of Reducing Agent (Abortiporus biennis에 의한 유기용매 리그닌의 생물학적 변환과 환원제 첨가에 따른 구조 변화)

  • Hong, Chang-Young;Park, Se-Yeong;Kim, Seon-Hong;Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu
    • Journal of the Korean Wood Science and Technology
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    • v.44 no.1
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    • pp.124-134
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    • 2016
  • The main goal of this study was to investigate biomodification mechanism of lignin by white rot fungus, Abortiporus biennis, and to depolymerize ethanol organosolv lignin for industrial application. In nitrogen-limited culture, A. biennis polymerized mainly lignin showing a rapid increase of molecular weight and structural changes depending on incubation days. At the initial incubation days, cleavage of ether bonds increased phenolic OH content, while the results were contrary in of the later part of the culture. Based on these results, ascorbic acid as a reducing agent was used to induce depolymerization of lignin during cultivation with white rot fungus. As a result, the degree of increase of average molecular weight of lignin was significantly declined when compared with those of the ascorbic acid free-experiment, although the molecular weight of fungus treated sample slightly increased than that of control. Furthermore, lignin derived oligomers in culture medium were depolymerized with the addition of ascorbic acid, showing that the average molecular weight was 381 Da, and phenolic OH content was 38.63%. These depolymerized lignin oligomers were considered to be applicable for industrial utilization of lignin. In conclusion, A. biennis led to the polymerization of lignin during biomodification period. The addition of ascorbic acid had a positive effect on the depolymerization and increase of phenolic OH content of lignin oligomers in medium.

Effects of Fractions from Benincasa hispida on Inhibition of Adipogenesis in 3T3-L1 Preadipocytes (동과 분획물이 3T3-L1 지방세포 분화 억제에 미치는 영향)

  • You, Yang-Hee;Jun, Woo-Jin
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.41 no.7
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    • pp.895-900
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    • 2012
  • The effects of three fractions, hexane (BHHH), chloroform (BHHC), and ethyl acetate (BHHE), from water extract of Benincasa hispida on the underlying mechanisms of adipogenesis were investigated in 3T3-L1 cells. Intracellular lipid droplets were stained with Oil Red O dye and quantified. Compared to control, lipid accumulation significantly decreased by 11% and 13% upon treatment with BHHC and BHHE, respectively at a concentration of 50 ${\mu}g/mL$. Intracellular triglyceride (TG) levels were also reduced by 21% and 16%, respectively, at the same concentration. To determine the mechanism behind the reductions in TG content and lipid accumulation, glycerol release and expression levels of adipogenic marker genes were measured. The levels of free glycerol released into culture medium increased by 13% and 17% upon treatment with BHHC and BHHE, respectively. In subsequent measurements using real-time polymerization chain reaction, the mRNA levels of $PPAR{\gamma}$, C/$EBP{\alpha}$, and leptin significantly decreased upon treatment with BHHE (45%, 67%, and 35%) in comparison with non-treated control. These results suggest that BHHE inhibits adipocyte differentiation by blocking $PPAR{\gamma}$, C/$EBP{\alpha}$, and leptin gene expression in 3T3-L1 cells, resulting in reduced lipid accumulation, increased glycerol release, and intracellular triglycerides.

Effect of CD14, Toll-like receptors, cytoskeletal inhibitors and $NF-{\kappa}B$ inhibitor on MMP-8 release from human neutrophils induced by E. coli lipopolysaccharides. (E. coli lipopolysaccharides로 유도된 사람 호중구에서 CD14, Toll-like receptors, cytoskeletal inhibitors 그리고 $NF-{\kappa}B$ inhibitor가 MMP-8 분비에 미치는 영향)

  • Yang, Seung-Min;Kim, Tae-Il;Seol, Yang-Jo;Lee, Yong-Moo;Ku, Young;Chung, Chong-Pyoung;Han, Soo-Boo;Rhyu, In-Chul
    • Journal of Periodontal and Implant Science
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    • v.35 no.2
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    • pp.427-436
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    • 2005
  • Objective: MMP-8 is a neutrophil enzyme and its level increases in some inflammatory diseases, including periodontal disease. We knew that the lipopolysaccharide of E.coli(E-LPS) induced MMP-8 release from human neutrophils. E-LPS is known to induce the production and release of inflammatory cytokines through CD14, Toll-like receptor(TLR). In the present study, we investigated whether MMP-8 release by E-LPS is induced via CD14-TLR pathway and the cellular mechanism of MMP-8 release in human neutrophils. Material and methods: Human neutrophils were isolated from the peripheral blood of healthy donors and pre-incubated in medium containing antibodies against CD14, anti-TLR2 and anti-TLR4 or several inhibitors of microtubules and microfilaments and then incubated with E-LPS. The cells were treated TPCK and E-LPS simultaneously. The MMP-8amount in the culture medium was determined using ELISA. Results: E-LPS increased MMP-8release from neutrophils and its induction was inhibited by anti-CD14 and anti-TLR4 but not by anti-TLR2 antibodies. The inhibitors of microtubule and microfilament polymerization significantly decreased E-LPS-induced MMP-8release. TPCK inhibited E-LPS-induced MMP-8 release. Conclusion: These results suggest that MMP-8 release is induced by E-LPS via the CD14-TLR4 signal pathway in human neutrophils and may be depedent on microtubule and microfilament systems and $NF-{\kappa}B$ pathway.

EFFECTS OF HYDROQUINONE ON NEOPLASTIC TRANSFORMATION OF HUMAN EPITHELIAL CELLS IN CULTURE (Hydroquinone이 인체 상피세포의 발암화에 미치는 영향)

  • Sohn, Jung-Hee;Kim, Chin-Soo
    • Maxillofacial Plastic and Reconstructive Surgery
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    • v.32 no.3
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    • pp.218-228
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    • 2010
  • Components of dental resin-based restorative materials are reported to leach from the filling materials even after polymerization. Hydroquinone (HQ) is one of the major monomers used in the dental resin and is known as a carcinogen. Thus, carcinogenic risk of HQ leaching from the dental resin becomes a public health concern. The present study attempted to examine the carcinogenic potentials of HQ on the human epithelial cell, which is the target cell origin of the most of oral cancers. Cytotoxicity of HQ was observed above 50${\mu}M$ as measured by LDH assay, indicating a relatively low toxicity of this substance in human epithelial cells. The parameters of neoplastic cellular transformation such as cell saturation density, soft agar colony formation and cell aggregation were analyzed to examine the carcinogenic potential of HQ. The study showed that 2-week exposure of HQ showed the tendency of increase in the saturation density and the significant enhancement of soft agar colony formation at the highest dose, 50 ${\mu}M$ only. It is suggested that HQ has a weak potential of carcinogenicity. When cells were treated with HQ and TPA, a well-known tumor promoter, the parameters of neoplastic cellular transformation was significantly increased. This result indicates that the potential risk of carcinogenicity from HQ is largely dependent upon the presence of promoter. Exposure of 50 ${\mu}M$ HQ increased the time-dependent apoptosis as measured by the ELISA kit. This concentration coincides with a dose of neoplastic transformation, indicating a possible link between apoptosis and HQ-induced cellular transformation. Hydroquinone generated Reactive Oxygen Species (ROS) which was evidenced by the treatment of antioxidants such as trolox and N-acetyl cysteine and the GSH depleting agent, BSO. Antioxidants blocked the generation of ROS and the GSH depleting agent, BSO dramatically increased the ROS production. Since HQ is known to increase ROS production thru activation of transcriptional factor such as c-Myb and Pim-1, it is speculated that ROS generation by HQ plays a role in the activation of oncogene, which may lead to neoplastic transformation. In addition, ROS is involved in the alteration of signal transduction, which regulates the apoptosis in many cellular systems. Thus, ROS-mediated apoptosis may be involved in the HQ-induced carcinogenic processes. Protein kinase C (PKC) is known to play pivotal roles in neoplastic transformation of cells and its high expression is often found in a variety of types of tumors including oral cancer. PKC translocation of PKC-${\alpha}$ was observed following HQ exposure. Altered signaling system may also play a role in the transformation process. Taken together, HQ leached from the dental resin does not pose a significant threat as a cancer causing agent, but its carcinogenic potential can be significantly elevated in the presence of promoter. The mechanism of HQ-induced carcinogenesis involved ROS generation, apoptosis and altered signaling pathway. The present study will provide a valuable data to estimate the potential risk of HQ as a carcinogen and understand mechanism of HQ-induced carcinogenesis in human epithelial cells.

Crop Injury (Growth Inhibition) Induced by Herbicides and Remedy to Reduce It (제초제(除草劑) 약해발생(藥害發生) 양상(樣相)과 경감대책(輕減對策))

  • Kim, K.U.
    • Korean Journal of Weed Science
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    • v.12 no.3
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    • pp.261-270
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    • 1992
  • Many herbicides that are applied at the soil before weed emergence inhibit plant growth soon after weed germination occurs. Plant growth has been known as an irreversible increase in size as a result of the processes of cell divison and cell enlargement. Herbicides can influence primary growth in which most new plant tissues emerges from meristmatic region by affecting either or both of these processes. Herbicides which have sites of action during interphase($G_1$, S, $G_2$) of cell cycle and cause a subsequent reduction in the observed frequency of mitotic figures can be classified as an inhibitor of mitotic entry. Those herbicides that affect the mitotic sequence(mitosis) by influencing the development of the spindle apparatus or by influencing new cell plate formation should be classified as causing disruption of the mitotic sequence. Sulfonylureas, imidazolinones, chloroacetamides and some others inhibit plant growth by inhibiting the entry of cell into mitosis. The carbamate herbicides asulam, carbetamide, chlorpropham and propham etc. reported to disrupt the mitotic sequence, especially affecting on spindle function, and the dinitroaniline herbicides trifluralin, nitralin, pendimethalin, dinitramine and oryzalin etc. reported to disrupt the mitotic sequence, particularly causing disappearence of microtubles from treated cells due to inhibition of polymerization process. An inhibition of cell enlargement can be made by membrane demage, metabolic changes within cells, or changes in processes necessary for cell yielding. Several herbicides such as diallate, triallate, alachlor, metolachlor and EPTC etc. reported to inhibit cell enlargement, while 2, 4-D has been known to disrupt cell enlargement. One potential danger inherent in the use of soil acting herbicides is that build-up of residues could occur from year to year. In practice, the sort of build-up that would be disastrous is unikely to occur for substances applied at the correct soil concentration. Crop injury caused by soil applied herbicides can be minimized by (1) following the guidance of safe use of herbicides, particularly correct dose at correct time in right crop, (2) by use of safeners which protect crops against injury without protecting any weed ; interactions between herbicides and safeners(antagonists) at target sites do occur probably from the following mechanisms (1) competition for binding site, (2) circumvention of the target site, and (3) compensation of target site, and another mechanism of safener action can be explained by enhancement of glutathione and glutathione related enzyme activity as shown in the protection of rice from pretilachlor injury by safener fenclorim, (3) development of herbicide resistant crops ; development of herbicide-resistant weed biotypes can be explained by either gene pool theory or selection theory which are two most accepted explanations, and on this basis it is likely to develop herbicide-resistant crops of commercial use. Carry-over problems do occur following repeated use of the same herbicide in an extended period of monocropping, and by errors in initial application which lead to accidental and irregular overdosing, and by climatic influence on rates of loss. These problems are usually related to the marked sensitivity of the particular crops to the specific herbicide residues, e.g. wheat/pronamide, barley/napropamid, sugarbeet/ chlorsulfuron, quinclorac/tomato. Relatively-short-residual product, succeeding culture of insensitive crop to specific herbicide, and greater reliance on postemergence herbicide treatments should be alternatives for farmer practices to prevent these problems.

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