• Title/Summary/Keyword: p-TsOH

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Decomposition of Paraoxon and Parathion by Amines, HOO- and OH- Ions: Reaction Mechanism and Origin of the α-Effect

  • Bae, Ae-Ri;Lee, Jieun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.201-206
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    • 2013
  • The second-order rate constants have been measured spectrophotometrically for the reactions of paraoxon 1 and parathion 2 with a series of alicyclic secondary amines, $OH^-$ and $HOO^-$ ions in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. A linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.40 was obtained for the reactions of 1 with amines and $OH^-$. The reaction has been concluded to proceed through a concerted mechanism. $HOO^-$ deviates positively from the linear Br${\o}$nsted-type plot, implying that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect ($k_{HOO^-}/k_{OH^-}$) was found to be ca. 55 for the reaction of 1 and 290 for that of parathion 2, indicating that $HOO^-$ is highly effective in decomposition of the toxic phosphorus compounds although it is over 4 $pK_a$ units less basic than $OH^-$. Among the theories suggested as origins of the ${\alpha}$-effect (e.g., TS stabilization through an intramolecular Hbonding interaction, solvent effect, and polarizability effect), polarizability effect appears to be the most important factor for the ${\alpha}$-effect in this study, since the polarizable $HOO^-$ exhibits a larger ${\alpha}$-effect for the reaction of the more polarizable substrate 2.

Kinetic Studies on the Nucleophilic Addition Reactons of Vinylic β-Diketones

  • Oh, Hyuck-Keun;Lee, Jae-Myon
    • Bulletin of the Korean Chemical Society
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    • v.23 no.10
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    • pp.1459-1462
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    • 2002
  • The kinetics of the addition of X-substituted benzylamines (BA) to Y-substituted Benzylideneacetylacetones (BAA) have been investigated in acetonitrile at $25.0^{\circ}C$. The reaction is studied under pseudo-first-order conditions by keeping a large excess of BA over BAA. The addition of BA to BAA occurs in a single step in which the addition of BA to $C_\alpha$ of BAA and proton transfer from BA to $C_\beta$ of BAA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($p_X$) and Bronsted ($\beta_x$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the cross-interaction constant, $p_{XY}$ (= -0.49), is comparatible to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($K_H/K_D$ > 1.0) and relatively low $\Delta$H^{${\neq}$}$ and large negative $\Delta$S^{${\neq}$}$ values are also consistent with the mechanism proposed.

Synthesis and Charaterization of Polymerizable Acryl's Emulsifier to prepare Green Glue (친환경 접착제 제조용 아크릴계 반응성 유화제의 합성)

  • Jeong, Noh-Hee;Park, Jong-Kwon;Kang, Yun-Seok
    • Journal of the Korean Applied Science and Technology
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    • v.33 no.1
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    • pp.51-57
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    • 2016
  • In this study, we synthesized reactive surfactant which have functional radical group for effective chemical reaction. Reactive surfactant have been synthesized using synthesis of polyoxyethylene lauryl ether(POE 23) which is nonionic surfactant and methacrylic acid, acrylic acid. benzene was used as the solvent, p-TsOH was used as the catalyst. synthesized surfactant was confirmed by FT-IR, $^1H$-NMR spectra, and elemental analysis. Evaluation of physical properties was measured HLB, cloud point, surface tension, the critical micelle concentration, emulsifying power. HLB number was evaluated 11.62 to 12.09 range. The Critical Micelle Concentration(cmc) values evaluated was $1{\times}10^{-4}{\sim}5{\times}10^{-4}mol/L$ by surface tension method. The cloud point was $35^{\circ}C$, $39^{\circ}C$ each. The emulsifymvcqa ing properties of the synthesized surfactants was lower than polyoxyethylene lauryl ether. In addition, soybean oil was better than benzene. The experimental results confirmed the ester bond, the yield of 93.27%, 94.49% was found.

EFFECT OF CHLORHEXIDINE ON MICROTENSILE BOND STRENGTH OF DENTIN BONDING SYSTEMS (Chlorhexidine 처리가 상아질 접착제의 미세인장결합강도에 미치는 영향)

  • Oh, Eun-Hwa;Choi, Kyoung-Kyu;Kim, Jong-Ryul;Park, Sang-Jin
    • Restorative Dentistry and Endodontics
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    • v.33 no.2
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    • pp.148-161
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    • 2008
  • The purpose of this study was to evaluate the effect of chlorhexidine (CHX) on microtensile bond strength (${\mu}TBS$) of dentin bonding systems. Dentin collagenolytic and gelatinolytic activities can be suppressed by protease inhibitors, indicating that MMPs (Matrix metalloproteinases) inhibition could be beneficial in the preservation of hybrid layers. Chlorhexidine (CHX) is known as an inhibitor of MMPs activity in vitro. The experiment was proceeded as follows: At first, flat occlusal surfaces were prepared on mid-coronal dentin of extracted third molars. GI (Glass Ionomer) group was treated with dentin conditioner, and then, applied with 2 % CHX. Both SM (Scotchbond Multipurpose) and SB (Single Bond) group were applied with CHX after acid-etched with 37% phosphoric acid. TS (Clearfil Tri-S) group was applied with CHX, and then, with adhesives. Hybrid composite Z-250 and resin-modified glass ionomer Fuji-II LC was built up on experimental dentin surfaces. Half of them were subjected to 10,000 thermocycle, while the others were tested immediately. With the resulting data, statistically two-way ANOVA was performed to assess the ${\mu}TBS$ before and after thermo cycling and the effect of CHX. All statistical tests were carried out at the 95 % level of confidence. The failure mode of the testing samples was observed under a scanning electron microscopy (SEM). Within limited results, the results of this study were as follows; 1. In all experimental groups applied with 2 % chlorhexidine, the microtensile bond strength increased, and thermo cycling decreased the micro tensile bond strength (P > 0.05). 2. Compared to the thermocycling groups without chlorhexidine, those with both thermocycling and chlorhexidine showed higher microtensile bond strength, and there was significant difference especially in GI and TS groups. 3. SEM analysis of failure mode distribution revealed the adhesive failure at hybrid layer in most of the specimen. and the shift of the failure site from bottom to top of the hybrid layer with chlorhexidine groups. 2 % chlorhexidine application after acid-etching proved to preserve the durability of the hybrid layer and microtensile bond strength of dentin bonding systems.

Influence of pH and Dye Concentration on the Physical Properties and Microstructure of New Coumarin 4 Doped SiO2-PDMS ORMOSIL

  • Oh, E.O.;Gupta, R.K.;Cho, N.H.;Yoo, Y.C.;Cho, W.S.;Whang, C.M.
    • Bulletin of the Korean Chemical Society
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    • v.24 no.3
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    • pp.299-305
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    • 2003
  • Physical properties and microstructure of new coumarin 4 doped $SiO_2$-PDMS ORMOSILs, synthesized by one-step (OS, acid-catalysis) and two-step (TS, acid-base catalysis) routes of sol-gel method with varying pH (0.6 to 7) and dye content $(5\;{times}\;10^{-4}\;to\;5{\times}\;10^{-2}\;mole)$, are reported. BET, UV-visible spectroscopy and SEM were used for characterizations. The increase in acid or base concentration increased the size of pores and aggregated silica particles. The samples with pH ≤ 2.5 were transparent and attributed to the small size of pores (~20 Å) and silica particles. The samples with pH > 2.5 were translucent or opaque due to non-uniform pore system formed by voids and large aggregated silica particles. The surface area was found a key factor controlling the interactions between the gel matrix and the dye. The OS samples with the highest dye concentration exhibited the minimal values of pore size, surface area and silica particle size, resulting in the concentration-quenching phenomenon.

Orobol, A Derivative of Genistein, Inhibits Heat-Killed Propionibacterium acnes-Induced Inflammation in HaCaT Keratinocytes

  • Oh, Yunsil;Hwang, Hwan Ju;Yang, Hee;Kim, Jong Hun;Yoon Park, Jung Han;Kim, Jong-Eun;Lee, Ki Won
    • Journal of Microbiology and Biotechnology
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    • v.30 no.9
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    • pp.1379-1386
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    • 2020
  • Acne is a chronic skin disease that typically occurs in the teens and twenties, and its symptoms vary according to age, sex, diet, and lifestyle. The condition is characterized by hyperproliferation of keratinocytes in the epidermis, sebum overproduction, excessive growth of Propionibacterium acnes, and P. acnes-induced skin inflammation. Interleukin (IL)-1α and IL-6 are predominant in the inflammatory lesions of acne vulgaris. These cytokines induce an inflammatory reaction in the skin in the presence of pathogens or stresses. Moreover, IL-1α accelerates the production of keratin 16, which is typically expressed in wounded or aberrant skin, leading to abnormalities in architecture and hyperkeratinization. Orobol (3',4',5,7-tetrahydroxyisoflavone) is a metabolite of genistein that inhibited the P. acnes-induced increases in IL-6 and IL-1α levels in human keratinocytes (HaCaTs) more effectively compared with salicylic acid. In addition, orobol decreased the IL-1α and IL-6 mRNA levels and inhibited the phosphorylation of inhibitor of kappa-B kinase, nuclear factor of kappa light polypeptide gene enhancer in B-cells inhibitor, alpha, and mitogen-activated protein kinase induced by P. acnes. Finally, the expression of Ki67 was decreased by orobol. Thus, orobol ameliorated the inflammation and hyperkeratinization induced by heat-killed P. acnes and thus has potential for use in functional foods and cosmetics.

Comparison of Sewage Sludge Solubilization through Different Pretreatment Methods (전처리 방법에 따른 하수슬러지 가용화 비교연구)

  • Kwon, Jae-Hyun;Kim, Bong-Jun;Kim, Min-Kyu;Yeom, Ick-Tae;Kim, Hyung-Soo
    • Journal of Korean Society of Water and Wastewater
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    • v.17 no.4
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    • pp.567-573
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    • 2003
  • The pretreatment process was carried out to solubilize the sewage sludge for enhancing its biodegradability using alkaline treatment, ultrasonic treatment(15kHz), ozone treatment and different combination of these three methods: alkaline followed by ultrasonic as well as ozone, and ultrasonic followed by alkaline. The solubilization efficiency was evaluated based on the SCOD/TCOD ratio and VSS/TS ratio. In results, the proper condition of alkaline treatment was shown as 30meq/l of NaOH, pH 12 and 3hours of reaction time. Solubilization efficiency increased to 17% from initial 2% based on SCOD/TCOD ratio under this condition. In ultrasonic treatment, the higher ultrasonic power, the longer treatment time and the lower sludge volume resulted in higher solubilization respectively. There was a rapid increase in solubilization efficiency after 20 minute, then it was measured as 32% of SCOD/TCOD ratio in 1 hour at a ultrasonic power of 1,300W with 1/sludge. Solubilization efficiencies in combined treatment using alkaline and ultrasonic were 47-53% higher than single treatment at a sonicated time of 1 hour. Ozone treatment followed by alkaline treatment also represented the enhanced solubilization compared to ozone treatment. Therefore, ultrasonic or ozone treatment assisted by alkaline could achieve the short treatment time as well as high solubilizetion efficiency.

Effects of Supplemental Feather Digests on the Growth of Broiler Chicks and Taurine Content in the Broiler Meat (우모 가수분해물 첨가가 육계의 증체 및 계육 내 타우린 함량에 미치는 영향)

  • 홍성진;남궁환;김우연;백인기
    • Korean Journal of Poultry Science
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    • v.29 no.2
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    • pp.141-148
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    • 2002
  • Two experiments were conducted to investigate the effects of supplemental feather digests on the growth of broiler chicks and taurine content in the broiler meat. In experiment 1, a total of 40 broiler chickens(Ros $s_{R}$) were assigned to four dietary treatments: control(T1), regular feather meal(FM) diet(R-FM,T2), NaOH treated FM diet(NaOH-FM,T3), HNO) treated FM diet($HNO_{3}$ -FM, T4). In experiment 2, a total of 70 broiler chickens were assigned to seven dietary treatments: T1 to t4(same as those of Exp. 1), modified $HNO_{3}$ treated FM diet(M- $HNO_{3}$-FM, T5), hair meal diet(HM, T6) and 0.22% cystine supplemented diet(CYS, T7). Feather meals and hair meal were supplemented at the level of 5% in the diet. In experiment 1 and 2, weight gain of chicks frd with R-FM or NaOH-FM tended to be higher than control or $HNO_{3}$ -FM. In experiment 2, weight gain of chicks frd with CYS was the highest followed by R-FM, M-HN $O_3$-FM, NaOH-FM, control, HM and $HNO_{3}$ -FM. In experiment 1, taurine content in breast muscle of chicks fed NaOH-FM was sogmofocamtly higher(P<0.05) than control. In experiment 2, taurine content in breast muscle of chicks fed NaOH-FM and CYS tended to be higher than other groups. Taurine content in leg muscle was significantly different among treatments as NaOH-FM and R-FM being highest followed by M- $HNO_{3}$-FM, CYS, control, $HNO_{3}$ -FM and HM. Taurine content in the liver(Exp. 1 and 2) and heart(Exp. 2) were not significantly affected by the supplemental feather digests. These results indicated that 5% NaOH-FM in the diet was effective in increasing taurine content in breast and leg muscle of broiler chicks.s.

Effect of negative therapy at back meridian points on blood gas components and immune functions in male college students (배부(背部) 경혈(經穴)에 부항요법(附缸療法) 시술(施術)이 남자대학생(男子大學生)의 면역기능(免疫機能)에 미치는 영향(影響))

  • Oh, Jae-Keun;Kim, Sung-Soo
    • The Journal of Korean Medicine
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    • v.20 no.1 s.37
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    • pp.75-83
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    • 1999
  • To investigate the effects of negative therapy at back meridian points on blood gas components and immune functions in male college students, this study was conducted on treatment types(abdomen group and back group) at three sampling times (before, post-2 wks and post-4 wks) by using $2{\times}3$ factoral design. Blood gas $components(pH,\;PCO_2,\;PO_2,\;HCO_3^-,\;O_2SAT,\;BE)$, red blood cell, hematocrit, hemoglobin, white blood cell and subsets(neutrophil, basophil, eosinophil. lymphocyte, monocyte), total T cells, helper T cells, suppressor T cells, Th/Ts ratio, total B cells, serum immunoglobulin levels (IgG, IgA, IgM, IgD, IgE), Cytokines(Interlukin$-1{\beta}$, -2, -4, 2 receptor, -6 and ${\gamma}$-interferon), NK cells were measured. Collected with data were analyzed statistically by repealed measured ANOVA. The pattern of change between two groups for hematocrit, hemoglobin, suppressor T cells, interleukin-6, ${\gamma}-interferon$, NK cells at post-2 weeks and BE, lymphocyte, basophil at post-4 weeks was significantly different(p<0.05) And also the pattern of change over time for ${HCO_3}^-$(2 wks vs 4 wks), WBC, neutrophil, lymphocyte(0 wks vs 2 wks and 2 wks vs 4 wks) was significantly different(p<0.05). In summary, these data suggest that negative therapy at back meridian points had an effect on blood gas components and immune functions in male college students because practicing negative therapy at back meridian points was not associated with changes of all blood gas components and immune factors but associated with changes of BE, hematocrit, hemoglobin, WBC. neutrophil, lymphocyte, interleukin-6. ${\gamma}-interferon$, NK cells.

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The α-Effect and Mechanism of Reactions of Y-Substituted Phenyl Benzenesulfonates with Hydrogen Peroxide Ion

  • Im, Li-Ra;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2393-2397
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    • 2009
  • Second-order rate constants ($k_{HOO}$‒) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted phenyl benzenesulfonates (1a-g) with $HOO^-$ ion in $H_2O$ at $25.0\;{\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot is linear with ${\beta}_{lg}$ = ‒0.73. The Hammett plot correlated with with ${\sigma}^-$ constants results in much better linearity than ${\sigma}^o$ constants, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS) either in a stepwise mechanism or in a concerted pathway. However, a stepwise mechanism in which departure of the leaving group occurs in the RDS has been excluded since $HOO^-$ ion is more basic and a poorer leaving group than the leaving Y-substituted phenoxide ions. Thus, the reactions of 1a-g with $HOO^-$ ion have been concluded to proceed through a concerted mechanism. The $\alpha$-nucleophile $HOO^-$ ion is more reactive than its reference nucleophile $OH^-$ ion although the former is ca. 4 p$K_a$ units less basic than the latter (i.e., the $\alpha$-effect). TS stabilization through intramolecular H-bonding interaction has been suggested to be irresponsible for the $\alpha$-effect shown by $HOO^-$ ion, since the magnitude of the $\alpha$-effect is independent of the electronic nature of substituent Y in the leaving group. GS destabilization through desolvation of $HOO^-$ ion has been concluded to be responsible for the $\alpha$-effect found in the this study.