• 제목/요약/키워드: Degradation kinetics

검색결과 311건 처리시간 0.031초

Oxidative Degradation Kinetics of Tocopherols during Heating

  • Chung, Hae-Young
    • Preventive Nutrition and Food Science
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    • 제12권2호
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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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    • 제15권6호
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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
    • 한국응용과학기술학회지
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    • 제24권3호
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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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    • 제6권3호
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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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    • 제15권5호
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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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    • 제13권1호
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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.

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

  • 김수정;오상은;양재의
    • 한국환경농학회지
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    • 제26권1호
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    • pp.55-61
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    • 2007
  • 본 연구에서는 ZVI 종류[Peerless unannealed(PU), Peerless annealed(PA)]별 처리농도(1, 5%, w/v), 초기 metolachlor 농도(200, 1000 mg/l) 및 온도(15, 25, $35^{\circ}C$)가 metolachlor의 분해에 미치는 kinetics를 평가하였다. ZVI에 의한 metolachlor의 분해는 first order kinetics모델로 설명할 수 있었다. ZVI의 처리 농도가 증가할수록 metolachlor 의 분해속도가 빨랐다. 5%(w/v)의 PU와 PA ZVI를 처리시 metolachlor의 분해 반감기는 각각 9.9와 6.5 h 이었고 metolachlor는 72 및 48 h 에 모두 분해되었다. metolachlor의 분해상수(k)는 초기 metolachlor 농도가 낮을 때 컸다. ZVI에 의한 metolachlor의 분해는 온도가 높을수록 증가되었고 15, 25, $35^{\circ}C$에서 metolachlor의 분해상수(k)는 각각 0.0805, 0.1017, 0.3116 /h 이었다. ZVI에 의한 metolachlor 분해 시 2종류의 분해산물이 동정되었는데 이는 탈염소화된 metolachlor$(C_{13}H_{18}NO)$, 탈염소화-탈알킬화된 metolachlor$(C_{12}H_{17}NO)$이었다. PA ZVI가 PU ZVI 보다 metolachlor를 분해하는데 효율적임을 알 수 있었다. ZVI는 탈염소화기작에 의해 metolachlor를 분해함을 알 수 있었다.

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

  • 정혜영
    • 한국식품영양학회지
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    • 제20권2호
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    • pp.120-124
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    • 2007
  • 천연 항산화제로 사용되는 토코페롤은 가열 온도가 높을수록, 가열 시간이 길수록 토코페롤의 분해율이 증가하였으며, 무산소 가열의 경우, 토코페롤은 산소가 있을 때 보다 덜 분해되었다. 알파-, 감마-. 델타- 토코페롤의 무산소 가열 조건을 만들기 위하여 $100{\sim}250^{\circ}C$에서 5${\sim}$60분 가열하는 동안 회화로 속으로 질소를 계속 흘려보내는 실험 방법을 사용하였다. 헥산으로 추출한 토코페롤은 두 종류의 용출 용매와 역상 ${\mu}$-Bondapak C$_{18}$-컬럼을 사용한 HPLC로 분리하였고 토코페롤의 분해 패턴과 잔존량을 조사하였다. 토코페롤의 열분해 키네틱스는 온도와 시간의 함수로 분석되었고 열분해 패턴은 1차 반응으로 나타났다. 무산소 가열시 알파-, 감마-, 델타-토코페롤의 열분해 활성화 에너지는 각각 3.47, 5.85 그리고 6.76 kcal/mole 이었다.

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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    • 제17권E3호
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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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열보호제와 열증감제의 존재하에서 온열처리에 의한 SCK 종양세포의 치사기작 (SCK Tumor Cell Killing by Hyperthermia in the Presence of Heat Protector and Heat Sensitizer)

  • 강만식;서미영;정주영
    • 한국동물학회지
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    • 제32권2호
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    • pp.134-141
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    • 1989
  • 본 연구는 온열처리에 의한 세포치사의 mechqnism을 밝히기 위해서 heat sensitizer인 low pH와 heat protector인 glycerol을 이용하여 cell lethlity와 단백질의 분해 kinetics를 검토한 것이다. 41-45도씨의 온열처리 중에서 41도씨를 제외한 전 온도범위에서 sensitizer와 protector의 효과가 뚜렷이 나타났으며, protector이 효과는 cell lethality와 단백질분해 모두에서 sensitizer의 효과에 비해서 현저히 나타나서 sensitizer와 protector의 작용기작은 서로 다를 것으로 생각되었다. 즉, 43-44도씨에서 cell inactivation energy는 정상, low pH, glycerol 상태에서 각각 239, 190, 317 kcal/mole의 값을 보였다. 단백질분해 kinetics의 경우에도 대체적인 경향성은 cell inactivation kinetics와 유사하였으나, 직접적인 연관성은 발견할 수 없었다. 이와 같은 결과로 미루어 볼 때, cell lethality와 단백질 분해의 mechanism 사이에 직접적인 관계는 없고, 주로 막단백질로 추정되는 단백질의 inactivation에 의한 세포내 환경의 변화에 의해서 2차적으로 세포치사가 일어나는 것으로 추정할 수 있으며, 정확한 mechanism을 밝히기 위해서는 DNA polymerase를 비롯한 몇가지 가능한 표적에 대한 연구가 이루어져야 할 것으로 사료된다.

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