• Title/Summary/Keyword: kinetics

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Kinetics of the Reaction of Phenacyl Bromide with Anilines in Methanol and Dimethylformamide (Phenacyl Bromide와 置換아닐린類와의 反應에 關한 反應速度論的 硏究)

  • Soo-Dong Yoh;Doo-Jung Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.6
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    • pp.376-382
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    • 1981
  • The rates and the activation parameters for the reaction of phenacyl bromide with substituted anilines in methanol and dimethylformamide were measured. The effects of substituted anilines were discussed. The rate of the reaction was increased with the electron donating power of substituent and showed larger value in DMF than in MeOH. The isokinetic relationship was shown between ${\delta}H^{\neq}$ and ${\delta}S^{\neq}$, isokinetic temperature was 539 and $400^{\circ}C$ in MeOH and DMF respectively, but p-nitro aniline was deviated from linearity in both solvents caused by solvent effects. The excellent linear relationship between log k and p$K_a$ of substituted anilines was observed by following equation. log k = 0.57p$K_a$-1.28 (r = 0.996) in MeOH at $45^{\circ}C$, log k = 0.65p$K_a$-0.88 (r = 0.970) in DMF at $45^{\circ}C$. From the Hammett plot, this reaction was a nucleophilic displacement of aniline to phenacyl bromide and the following equation was obtained at $45^{\circ}C$. log k/$k_0$ = -2.00${\sigma}$ + 0.06 (r = 0.985) in MeOH; log k/$k_0$ = -2.22${\sigma}$ + 0.08 (r = 0.995) in DMF. Large deviation of p-nitro aniline in DMF is resulted from solvent effects too. From above results, the substituent effect of this reaction can be described as $S_N2$ mechanism and bond formation more proceeds in DMF relative to MeOH.

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Comparison of Cellular Senescence Phenotype in Human Fibroblasts from New-born and Aged Donors. (신생아와 노인 유래 섬유아세포의 노화과정에서의 세포학적 성질의 비교)

  • Yi, Hye-Won;Hwang, Eun-Seong
    • Journal of Life Science
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    • v.18 no.3
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    • pp.344-349
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    • 2008
  • Normal somatic cells proliferate for a limited number of doublings in culture and then enter an irreversible growth-arrest state called replicative senescence. Replicative senescence has been believed a reason for the limited cellular turnover and deterioration of tissue function in aged animals. However, there is no experimental evidence supporting this assumption. Furthermore, cells from aged person have been poorly characterized with an exception of the cases of T cells. In this study, we examined cell biological changes occurring in replicative senescence of fibroblast strains originated from a new-born (NHF-NB) and a 87 year old man (NHF-87). NHF-87 (and the cells from a 75-year old) proliferated to smaller population doublings and with longer doubling times than NHF-NB did. At early passages, NHF-87 exhibited a low senescence-associated ${\beta}-Gal$ (SA ${\beta}-Gal$) activity and lipofuscin level, typical markers for cellular senescence. Furthermore, they maintained low levels of lysosome and reactive oxygen species (ROS). All of these levels increased dramatically in the late passage NHF-87 quite similarly as those in the late passaged NHF-NB did. These results indicate that most cells originated from the aged maintain a phenotype of the cells originated from new-born donors and undergo replicative senescence with the same kinetics as that of the cells from new-born. It is also indicated that not SA ${\beta}-gal$ activity but cell proliferation rate may be qualified as a biomarker for cells aged in vivo.

Elliptical Centric Techniques and Tricks About the Usefulness of the Clinical Application (Elliptical Centric과 TRICKS 기법의 임상 적용에 관한 유용성 연구)

  • Kim, Sae-Ssak;Goo, Eun-Hoe;Dong, Kyung-Rae;Kweon, Dae-Chel;Lee, Jae-Seung;Cho, Jae-Hwan;Park, Chang-Hee
    • Korean Journal of Digital Imaging in Medicine
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    • v.13 no.2
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    • pp.83-90
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    • 2011
  • To prospectively determine the diagnostic performance a combination of standard bolus-chase magnetic resonance (MR) angiography and MR angiography with time-resolved imaging of contrast kinetics (TRICKS) for depicting severity of the head and neck vascular diseases. Over a period of two months, A total of 100 patients(average ages : $50{\pm}8$, male : 60, female : 40) with head and neck vascular diseases were performed on the GE excite 3.0 T units with 8-channel head coil and 4-channel NV coil. Imaging parameters for a typical study were as follow: SBC(TR/ TE/ FA/ SliceThicken./ Slab/ Freq./ FOV/ BW/Scan Time) = 5.4/ min/ 30/ 2/ zip2/ 70/ $224{\times}448$/ 30/ 62.50/ 28, TRICKS(TR/ TE/ FA/ Slice Thicken/Slab/ Freq./ FOV/ BW/ Temp Res./ Scan Time = 3.6/ min/ 25/ 4/ 30/ $160{\pm}384$, zip512/ 30/ 100/ 1 to 1.5/ 23). The analysis of all MR images, which have respect-ively classified two techniques into some diseases. The results of the former were divided into two groups(SBC, TRICKS)with 4 grading of two reader, respectively. Wilcoxon signed rank test was used to determine if a significant difference between imaging techniques existed(p < 0.05). In 33 of 100 patients, arterio-venous malformation was 11% at TRICKS, subclavian vein stenosis : 8%, fistular sinus : 4%, jugular vein stenosis:6%, Middle Cerebral Artery bypass surgery : 4%, p < 0.05). The rest of 67 patients were considered as the results of SBC(14% in the basilar artery stenosis, carotid stenosis : 16%, vertebral stenosis : 17%, central neuro-cytoma : 5%, meningioma : 5%, Not appliable : 10%, p < 0.05). Sensitivity and specificity of TRICKS MR angiography in SVS, FS, JVS, MCABS were improved compared with those at standard MR angiography. In SBS MR angiography which were improved in BAS, CS, VS, CN, Meningioma. In conclusion, TRICKS MR angiography of the SVS, FS, JVS, MCABS is superior to standard MR angiography regarding the number of diagnostic grading. The SBS MR angiography were improved in BAS, CS, VS, CN, Meningioma. and assessment of the degree of luminal narrowing on both TRICKS and SBS.

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Oxidation Behavior of Simudated Metallic U-Nb Alloys in Air (모의 금속전환체 U-Nb 합금의 공기중 산화거동)

  • Lee Eun-Pyo;Ju June-Sik;You Gil-Sung;Cho il-Je;Kook Dong-Hak;Kim Ho-Dong
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.2 no.4
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    • pp.239-244
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    • 2004
  • In order to enhance an oxidation resistance of the pure uranium metal under air condition, a small quantity of niobium(Nb) which is known to mitigate metal oxidation is added into uranium metal as an alloying element. A simulated metallic uranium alloy, U-Nb has been fabricated and then oxidized in the range of 200 to $300^{\circ}C$ under the environment of the pure oxygen gas. The oxidized quantity in terms of the weight gain(wt%) has been measured with the help of a thermogravimetric analyzer. The results show that the oxidation resistance of the U-Nb alloy is considerably enhanced in comparison with that of the pure uranium metal. It is revealed that the oxidation resistance of the former with the niobium content of 1, 2, 3, and 4 wt% is : 1) 1.61, 7.78, 11.76 and 20.14 times at the temperature of $200^{\circ}C$ ; 2) 1.45, 5.98, 10.08 and 11.15 times at $250^{\circ}C$ ; and 3) 1.33, 4.82, 8.87 and 6.84 times at $300^{\circ}C$ higher than that of the latter, respectively. Besides, it is shown that the activation energy attributable to the oxidation is 17.13~21.92 kcal/mol.

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Kinetics and Hydrolysis Mechanism of Herbicidal N-(2,6-dimethoxypyrimidin-2-yl)aminocarbonyl-2-(1-hyd roxy-2-fluoroethyl)benzenesulfonamide Derivatives (제초성, N-(2,6-dimethoxypyrimidin-2-yl)aminocarbonyl-2-치환(Z)-6-(1-hyd roxy-2-fluoroethyl)benzenesulfonamide 유도체의 가수분해 반응 메카니즘)

  • Lee, Chan-Bog;Ryu, Jae-Wook;Kim, Dae-Whang;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.38 no.5
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    • pp.455-462
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    • 1995
  • The new six herbicidal N-[(pyrimidin-2-yl)aminocarbonyl]-2-substituted-6-(1-hydroxy-2-fluoroethyl)benzenesulfonamide derivatives(S) were synthesized and rate constants for the hydrolysis of thier in the range of pH $1.0{\sim}10.0$ have been studied in 15%(v/v) aqueous acetonitrile solution at $45^{\circ}C$. From the basis of the results, pH-effect, solvent effect, ortho-substituent effect, thermodynamic parameters(${\Delta}H^{\neq}$ & ${\Delta}S^{\neq}$), pKa constant(4.80), rate equation, analysis of hydrolysis products(2-(1-hydroxy-2-fluoroethyl)benzenesulfonamide & 4,6-dimethoxyaminopyrimidine), it may be concluded that the general acid catalyzed hydrolysis through $A-S_E2$ mechanism and specific acid catalyzed hydrolysis through A-2 type(or $A_{AC}2$) mechanism proceeds via conjugate acid($SH^+$) and tetrahedral intermediate(I) below pH 8.0, whereas, above pH 9.0, the general base catalyzed hydrolysis by water molecules(B) through $(E_1)_{anion}$ mechanism proceeds via conjugate base(CB). In the range between $pH\;7.0{\sim}pH\;9.0$, these two reactions occur competitively.

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Removal of Heavy Metals from Aqueous Solution by a Column Packed with Peat-Humin (Peat-Humin 충전 칼럼을 이용한 수용액 중의 중금속 제거)

  • Shin, Hyun-Snag;Lee, Chang-Hoon;Lee, Yo-Snag;Kang, Ki-Hoon
    • Journal of Korean Society of Environmental Engineers
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    • v.27 no.5
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    • pp.535-541
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    • 2005
  • Peat humin(p-Humin) extracted from Canadian Sphagnum peat moss was packed in a column and removal of heavy metal ions such as Cd, Cu and Pb from aqueous solution under flow conditions was studied. The metal ions were removed not only from single-element solutions but also from a multi-metal solution. Column kinetics for metal removal were described by the Thomas model. For single-component metal solutions, the maximum adsorption capacities of the p-Humin for Pb, Cu and Cd were 138.8, 44.66 and 41.61 mg/g, respectively. The results of multi-component competitive adsorption showed that adsorption affinity was in the order of Pb $\gg$ Cu > Cd. The adsorbed metal ions were easily deserted from the p-Humin with 0.05 N $HNO_3$ solution. It is apparent that 95% of the heavy metal ions were recovered from the saturated column. This investigation provides possibility to clean up heavy-metal contaminated waste waters by using the natural biomass, p-Humin as an environmentally friendly and cost-effective new biosorbents.

Effects of Membrane Size and Organic Matter on Membrane Fouling (천연유기물질의 특성과 막의 종류에 따른 막오염 메카니즘 분석)

  • Jung, Chul-Woo;Son, Hee-Jong
    • Journal of Korean Society of Environmental Engineers
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    • v.28 no.10
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    • pp.1046-1054
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    • 2006
  • The raw water DOC contained 39.3% of hydrophilics, 42.9% of hydriophobic, and 17.8% of transphilic. The hydrophobic fraction in this raw water was mostly fulvic acid. Fulvic acid comprised of 62% and the rest was humic acid(38%). There was more carboxylic acid functional group(64%) than phenolic group(36%). HPI-N and HPI-C comprised of 17% and 22% in the hydrophilic portion, respectively. The fouling mechanisms on the membrane surface and into its porous structure were analyzed in terms of several kinetic models. In order to analyze the fouling kinetics, the various kinetic models described in this paper were used to fit the experimental results. The kinetic models and kinetic constants obtained for each operation condition. The permeate flux was rapidly declined by simultaneous pore blocking and cake formation. Also, the permeate flux declined with decreasing internal pore size resulted from organic deposition into the membrane pore. The results of the membrane fouling test using UF membrane according to NOM fractions. HPI-N caused more fouling than HPI-C. Humic acid caused more fouling than fulvic acid probably due to higher adsorption capacity. Since humic acid has higher adsorption capacity than fulvic acid, it would be more adsorbed onto the membrane pores.

Structural and Kinetic Characteristics of 1,4-Dioxane-Degrading Bacterial Consortia Containing the Phylum TM7

  • Nam, Ji-Hyun;Ventura, Jey-R S.;Yeom, Ick Tae;Lee, Yongwoo;Jahng, Deokjin
    • Journal of Microbiology and Biotechnology
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    • v.26 no.11
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    • pp.1951-1964
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    • 2016
  • 1,4-Dioxane-degrading bacterial consortia were enriched from forest soil (FS) and activated sludge (AS) using a defined medium containing 1,4-dioxane as the sole carbon source. These two enrichments cultures appeared to have inducible tetrahydrofuran/dioxane and propane degradation enzymes. According to qPCR results on the 16S rRNA and soluble di-iron monooxygenase genes, the relative abundances of 1,4-dioxane-degrading bacteria to total bacteria in FS and AS were 29.4% and 57.8%, respectively. For FS, the cell growth yields (Y), maximum specific degradation rate ($V_{max}$), and half-saturation concentration ($K_m$) were 0.58 mg-protein/mg-dioxane, $0.037mg-dioxane/mg-protein{\cdot}h$, and 93.9 mg/l, respectively. For AS, Y, $V_{max}$, and $K_m$ were 0.34 mg-protein/mg-dioxane, $0.078mg-dioxane/mg-protein{\cdot}h$, and 181.3 mg/l, respectively. These kinetics data of FS and AS were similar to previously reported values. Based on bacterial community analysis on 16S rRNA gene sequences of the two enrichment cultures, the FS consortium was identified to contain 38.3% of Mycobacterium and 10.6% of Afipia, similar to previously reported literature. Meanwhile, 49.5% of the AS consortium belonged to the candidate division TM7, which has never been reported to be involved in 1,4-dioxane biodegradation. However, recent studies suggested that TM7 bacteria were associated with degradation of non-biodegradable and hazardous materials. Therefore, our results showed that previously unknown 1,4-dioxane-degrading bacteria might play an important role in enriched AS. Although the metabolic capability and ecophysiological significance of the predominant TM7 bacteria in AS enrichment culture remain unclear, our data reveal hidden characteristics of the TM7 phylum and provide a perspective for studying this previously uncultured phylotype.

Effects of Disinfectant Concentration, pH, Temperature, Ammonia, and Suspended Solids on the Chlorine Disinfection of Combined Sewer Overflow (소독제 농도, pH, 온도, 암모니아 농도, 부유물질이 강우 월류수 염소 소독에 미치는 영향)

  • Kim, Sang-Hyoun
    • Journal of Korean Society of Environmental Engineers
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    • v.36 no.10
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    • pp.685-690
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    • 2014
  • The treatment of combined sewer overflow (CSO) is one of potential concerns in domestic wastewater treatment in Korea due to the pre-announce of CSO regulations. This work investigated the effects of disinfectant (NaOCl) concentration (0.11 to 4.0 mg $Cl_2/L$), pH (6.5 to 8.0), temperature (15 to $25^{\circ}C$), ammonia (10 to 41 mg N/L), and suspended solids (91 to 271 mg SS/L) on the chlorine disinfection of CSO. The effect of NaOCl concentration on the pseudo-$1^{st}$ order reaction rate for total coliform inactivation was described well with a saturation-type model with the half-velocity constant of 1.212 mg/L. The total coliform inactivation reaction rate decreased with SS and pH, and increased with temperature. Ammonia in the examined range did not affect the disinfection kinetics. A chlorine contact tank with the injection chlorine level of 1 mg $Cl_2/L$ and the hydraulic retention time of 1.25 min is estimated to reduce total coliform from $1{\times}10^5MPN/mL$ to 1,000 MPN/mL at 271 mg SS/L, $15^{\circ}C$, and pH 8.0. Chlorine would be a proper option for the disinfection of CSO.

Evaluation of Removal Characteristics of Taste and Odor Causing Compounds using Meso-Porous Absorbent (메조공극 흡착제를 이용한 상수원수내 맛·냄새 유발물질 제거특성 평가)

  • Kim, Jong-Doo;Park, Chul-Hwi;Yun, Yeo-Bog;Lee, Dae-Sung;Kim, Hyo-Jeon;Kang, Seok-Tae
    • Journal of Korean Society of Environmental Engineers
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    • v.39 no.1
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    • pp.26-33
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    • 2017
  • The objective of this study was to evaluate the characteristic of adsorption by using a meso-porous adsorbent (MPA), and investigate the removal efficiency of geosmin which taste and odor causing compounds in drinking water supplies through batch test. The results for the adsorption isotherm was analyzed by using the Langmuir equation and Freundlich equation, generally being applied. And the study showed that the both Langmuir and Freundlich equation explains the results better. Both of pseudo-first-order model and pseudo-second-order model were respectively applied for evaluation of kinetic sorption property of geosmin onto MPA. The adsorption experiment results using MPA showed that maximum adsorption capacity of MPA was lower 7 times than that of GAC, and adsorption rate of MPA was faster 11 times than that of GAC, on the basis of pseudo-first-order model. Therefore, it was determined that MPA was effectively able to remove geosmin in drinking water supplies in short EBCT condition, but regeneration cycle in MAP process was shorter than that in conventional process.