• Title/Summary/Keyword: Degradation kinetics

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Oxidative Degradation Kinetics of Tocopherols during Heating

  • Chung, Hae-Young
    • Preventive Nutrition and Food Science
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    • v.12 no.2
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    • pp.115-118
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    • 2007
  • Tocopherols are important lipid-phase antioxidants that are subject to heat degradation. Therefore, kinetic analyses for oxidative degradation of tocopherols as a function of temperatures and times were performed. Alpha-, gamma- and delta-tocopherols dissolved in glycerol were heated at 100${\sim}$250$^{\circ}C$ for 5~60 min. Oxidized tocopherols were analyzed by HPLC using a reversed phase ${\mu}$-Bondapak C$_{18}$-column with two kinds of elution solvent systems in a gradient mode. The degradation kinetics for tocopherols followed a first-order kinetic model. The rate of tocopherol degradation was dependent on heating temperatures. The degradation rate constants for ${\gamma}$- and ${\delta}$-tocopherols were higher than those for ${\alpha}$-tocopherol. The experimental activation energies of ${\alpha}$-, ${\gamma}$- and ${\delta}$- tocopherols were 2.51, 6.05 and 5.34 kcal/mole, respectively. The experimental activation energies for the oxidative degradation of ${\gamma}$- and ${\delta}$-tocopherols were higher than that of ${\alpha}$-tocopherol.

In Vivo $^{13}C$-NMR Spectroscopic Study of Polyhydroxyalkanoic Acid Degradation Kinetics in Bacteria

  • Oh, Jung-Sook;Choi, Mun-Hwan;Yoon, Sung-Chul
    • Journal of Microbiology and Biotechnology
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    • v.15 no.6
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    • pp.1330-1336
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    • 2005
  • Polyhydroxyalkanoic acid (PHA) inclusion bodies were analyzed in situ by $^{13}C$-nuclear magnetic resonance ($^{13}C$-NMR) spectroscopy. The PHA inclusion bodies studied were composed of poly(3-hydroxybutyrate) or poly(3hydroxybutyrate-co-4-hydroxybutyrate), which was accumulated in Hydrogenophaga pseudoflava, and medium-chain-length PHA (MCL-PHA), which was accumulated in Pseudomonas fluorescens BM07 from octanoic acid or 11-phenoxyundecanoic acid (11-POU). The quantification of the $^{13}C$-NMR signals was conducted against a standard compound, sodium 2,2-dimethyl-2-silapentane-5-sulfonate (DSS). The chemical shift values for the in vivo NMR spectral peaks agreed well with those for the corresponding purified PHA polymers. The intracellular degradation of the PHA inclusions by intracellular PHA depolymerase(s) was monitored by in vivo NMR spectroscopy and analyzed in terms of first-order reaction kinetics. The H. pseudoflava cells were washed for the degradation experiment, transferred to a degradation medium without a carbon source, but containing 1.0 g/l ammonium sulfate, and cultivated at $35^{\circ}C$ for 72 h. The in vivo NMR spectra were obtained at $70^{\circ}C$ for the short-chain-length PHA cells whereas the spectra for the aliphatic and aromatic MCL-PHA cells were obtained at $50^{\circ}C\;and\;80^{\circ}C$, respectively. For the H. pseudoflava cells, the in vivo NMR kinetics analysis of the PHA degradation resulted in a first-order degradation rate constant of 0.075/h ($r^{2}$=0.94) for the initial 24 h of degradation, which was close to the 0.050/h determined when using a gas chromatographic analysis of chloroform extracts of sulfuric acid/methanol reaction mixtures of dried whole cells. Accordingly, it is suggested that in vivo $^{13}C$-NMR spectroscopy is an important tool for studying intracellular PHA degradation in terms of kinetics.

Kinetics of Thermal Degradation of Polypropylene/Nanoclay/Wood Flour Nanocomposites

  • Mohan, D. Jagan;Lee, Sun-Young;Kang, In-Aeh;Doh, Geum-Hyun;Park, Byung-Dae;Wu, Qinglin
    • Journal of the Korean Applied Science and Technology
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    • v.24 no.3
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    • pp.278-286
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    • 2007
  • As a part of enhancing the performance of wood-plastic composites (WPC), polypropylene (PP)/ nanoclay (NC)/ wood flour (WF) nanocomposites were prepared using melt blending and injection molding process to evaluate their thermal stability. Thermogravimetric analysis (TGA) was employed to investigate thermal degradation kinetics of the nanocomposites both dynamic and isothermal conditions. Dynamic scans of the TGA showed an increased thermal stability of the nanocomposites at moderate wood flour concentrations (up to 20 phr, percentage based on hundred percent resin) while it decreased with the addition of 30 phr wood flour. The activation energy $(E_a)$ of thermal degradation of nanocomposites increased when nanoclay was added and the concentration of wood flour increased. Different equations were used to evaluate isothermal degradation kinetics using the rate of thermal degradation of the composites, expressed as weight loss (%) from their isothermal TGA curves. Degradation occurred at faster rate in the initial stages of about 60 min., and then proceeded in a gradual manner. However, nanocomposites with wood flour of 30 phr heated at $300^{\circ}C$ showed a drastic difference in their degradation behavior, and reached almost a complete decomposition after 40 min. of the isothermal heating. The degree of decomposition was greater at higher temperatures, and the residual weight of isothermal degradation of nanocomposites greatly varied from about 10 to 90%, depending on isothermal temperatures. The isothermal degradation of nanocomposites also increased their thermal stability with the addition of 1 phr nanoclay and of wood flour up to 20 phr. But, the degradation of PP100/NC1/MAPP3/WF30 nanocomposites with 30 phr wood flour occurs at a faster rate compared to those of the others, indicating a decrease in their thermal stability.

Kinetics of In-situ Degradation of Nerve Agent Simulants and Sarin on Carbon with and without Impregnants

  • Saxena, Amit;Sharma, Abha;Singh, Beer;Suryanarayana, Malladi Venkata Satya;Mahato, Timir Haran;Sharma, Mamta;Semwal, Rajendra Prasad;Gupta, Arvind Kumar;Sekhar, Krishnamurthy
    • Carbon letters
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    • v.6 no.3
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    • pp.158-165
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    • 2005
  • Room temperature kinetics of degradation of nerve agent simulants and sarin, an actual nerve agent at the surface of different carbon based adsorbent materials such as active carbon grade 80 CTC, modified whetlerite containing 2.0 and 4.0 % NaOH, active carbon with 4.0 % NaOH, active carbon with 10.0 % Cu (II) ethylenediamine and active carbon with 10.0 % Cu (II) 1,1,1,5,5,5-hexafluoroacetylacetonate were studied. The used adsorbent materials were characterized for surface area and micropore volume by $N_2$ BET. For degradation studies solution of simulants of nerve agent such as dimethyl methylphosphonate (DMMP), diethyl chlorophosphate (DEClP), diethyl cyanophosphate (DECnP) and nerve agent, i.e., sarin in chloroform were prepared and used for the uniform adsorption on the adsorbent systems using their incipient volume at room temperature. Degradation kinetics was monitored by GC/FID and was found to be following pseudo first order reaction. Kinetics parameters such as rate constant and half life were calculated. Half life of degradation with modified whetlerite (MWh/NaOH) system having 4.0 % NaOH was found to be 1.5, 7.9, 1206 and 20 minutes for DECnP, DEClP, DMMP and sarin respectively. MWh/NaOH system showed maximum degradation of simulants of nerve agents and sarin to their hydrolysis products. The reaction products were characterized using NMR technique. MWh/NaOH adsorbent was also found to be active against sulphur mustard.

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Kinetics of di-n-Butyl Phthalate Degradation by a Bacterium Isolated from Mangrove Sediment

  • XU XIANG-RONG;GU JI-DONG;LI HUA-BIN;LI XIAO-YAN
    • Journal of Microbiology and Biotechnology
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    • v.15 no.5
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    • pp.946-951
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    • 2005
  • Biodegradation of the endocrine-disrupting chemical di-n-butyl phthalate (DBP) was investigated using a bacterium, Pseudomonas fluorescens B-1, isolated from mangrove sediment. The effects of temperature, pH, salinity, and oxygen availability on DBP degradation were studied. Degradation of DBP was monitored by solid-phase extraction using reversed-phase HPLC and UV detection. The major metabolites of DBP degradation were identified as mono-n-butyl phthalate and phthalic acid by gas chromatography-mass spectrometry (GC-MS) and a pathway of degradation was proposed. Degradation by P. fluorescens B-1 conformed to first-order kinetics. Degradation of DBP was also tested in seawater by inoculating P. fluorescens B-1, and complete degradation of an initial concentration of $100{\mu}g/l$ was achieved in 144 h. These results suggest that DBP is readily degraded by bacteria in natural environments.

Photocatalytic Degradation of 2,4,6-Trinitrotoluene in Wastewater Using a Thin-Film TiO2 Reactor

  • Shin, Gi-Bum;Kim, Yeong-Kwan
    • Environmental Engineering Research
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    • v.13 no.1
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    • pp.28-32
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    • 2008
  • The photocatalytic treatment of water contaminated with 2,4,6-trinitrotoluene (TNT) was explored in bench-scale experiments in batch mode using a Pyrex tube coated with a thin film of $TiO_2$ located inside a photoreactor. The reactor was aerated by purging it with compressed air before initiating the photocatalytic reaction. The rate of TNT degradation approximated first-order kinetics. The reaction rate constant decreased as the TNT concentration increased from 25 to 100 mg/L, while the first-order kinetics could be modeled using a Langmuir adsorption isotherm. The addition of the organic reductants methanol and EDTA significantly enhanced the rate of TNT degradation, with optimum results in the presence of 20% methanol by volume. EDTA increased the rate of TNT removal by enhancing the role of the reductants.

Kinetics of Metolachlor Degradation by Zerovalent Iron (Zerovalent Iron에 의한 Metolachlor의 분해 Kinetics)

  • Kim, Su-Jung;Oh, Sang-Eun;Yang, Jae-E.
    • Korean Journal of Environmental Agriculture
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    • v.26 no.1
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    • pp.55-61
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    • 2007
  • Metolachlor may pose a threat to surface and ground water qualities due to its high solubility in water, Zerovalent iron (ZVI) releases $e^-$ which can degrade the organochlorinated compounds. The objective of this research was to evaluate the kinetics of metolachlor degradation as affected by ZVI sources [Peerless unannealed (PU) and Peerless annealed (PA)] and ZVI levels (1 and 5%) under batch conditions at different metolachlor concentrations (200 and 1000 mg/l) and temperatures (15, 25, and $35^{\circ}C$). The effectiveness of ZVI on metolachlor degradation was assessed by characterizing the dechlorinated metolachlor byproduct molecules. Metolachlor degradation by ZVI followed the first-ordered kinetics with a higher rate constant at higher level of ZVI treatment. At 5% (w/v) of PU and PA treatment, the half-lives of metolachlor degradation were 9.93 and 6.51 h and all of the initial metolachlor were degraded in 72 and 48 h, respectively. Rate constants (k) of metolachlor degradation were higher at the lower initial metolachlor concentration. The metolachlor degradation by ZVI was temperature dependent showing that the rate constant (k) at 15, 25, and $35^{\circ}C$ were 0.0805, 0.1017, and 0.3116 /h, respectively. The ZVI-mediated metolachlor degradation yielded two byproduct molecules identified as dechlorinated metolachlor $(C_{13}H_{18}NO)$ and dechlorinated-dealkylated metolachlor $(C_{12}H_{17}NO)$. The PA ZVI was more effective than PU ZVI in metolachlor degradation.

Thermal Degradation Kinetics of Tocopherols during Heating without Oxygen (무산소 가열시 토코페롤의 열분해 키네틱스)

  • Chung, Hae-Young
    • The Korean Journal of Food And Nutrition
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    • v.20 no.2
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    • pp.120-124
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    • 2007
  • The thermal degradation kinetics of alpha-, gamma- and delta-tocopherols was studied during heating at 100, 150 200 and 250$^{\circ}C$ for 5, 15, 30 and 60 min in the absence of oxygen. The tocopherols were separated by HPLC using a reversed phase ${\mu}$-Bondapak C$_{18}$-column with two kinds of elution solvent system in a gradient mode. The kinetics for degradation of ${\alpha}$-, ${\gamma}$- and ${\delta}$-tocopherols was analyzed as a function of temperatures and times. The degradation of tocopherols was described by the first-order kinetics in the absence of oxygen. The rate of tocopherols degradation was dependent on heating temperatures. The degradation rate constants for ${\alpha}$-, ${\gamma}$ and ${\delta}$-tocopherols showed an increasing trend as the heating temperature increased. The magnitude order of the experimental activation energy was ${\delta}$->${\gamma}$->${\alpha}$-tocopherol.

A Kinetic Study on the Photocatalytic Degradation of Gas-Phase VOCs Using TiO$_2$ photocatalyst

  • Kim, Sang-Bum;Jo, Young-Min;Hong, Sung-Chang
    • Journal of Korean Society for Atmospheric Environment
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    • v.17 no.E3
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    • pp.117-124
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    • 2001
  • The present paper examined the kinetics of photocatalytic degradation of volatile organic compounds (VOCs) including gaseous trichloroethylene (TCE) and acetone. In this study, we examined the effects of the initial concentration of VOCs and the light intensity of ultra-violet (UV). A batch photo-reactor was specifically designed for this work. The photocatalytic degradation rate increased with the initial concentration of VOCs but remained almost constant beyond a certain concentration. It matched well with the Langmuir-Hinshelwood (L-H) kinetic model. When the effect of light intensity was concerned, it was found that photocatalytic degradation occurs in two regimes with respect to light intensity.

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SCK Tumor Cell Killing by Hyperthermia in the Presence of Heat Protector and Heat Sensitizer (열보호제와 열증감제의 존재하에서 온열처리에 의한 SCK 종양세포의 치사기작)

  • 강만식;서미영;정주영
    • The Korean Journal of Zoology
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    • v.32 no.2
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    • pp.134-141
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    • 1989
  • The present investigation aims at elucidating a possible mechanism of heat inactivation of SCK ceils by comparing the kinetics of cell lethality and protein degradation in the presence of heat protector or heat sensitizer. The effect of heat sensitizer and protector was exhibited in both cell survival and protein degradation kinetics, the magnitude of the effect being much profound for the protector compared to the sensitizer. A conclusion to he drawn from the present experiment is that there is no direct correlation between cell lethality and protein degradation. Rather, protein degradation, which might occur in the membrane, causes cell inactivation indirectly, possibly by altering the cellular environment. Accordingly, further studies are needed to get insight into the mechanism of cell inactivation by hyperthermia.

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