• Title/Summary/Keyword: reactive intermediate

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Kinetics and Reaction Mechanism of Aminolyses of Benzyl 2-Pyridyl Carbonate and t-Butyl 2-Pyridyl Carbonate in Acetonitrile

  • Bae, Ae-Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1547-1550
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    • 2012
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of benzyl 2-pyridyl carbonate $\mathbf{3}$ and $t$-butyl 2-pyridyl carbonate $\mathbf{3}$ with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Substrate $\mathbf{4}$ is much less reactive than $\mathbf{3}$ and the steric hindrance exerted by the bulky $t$-Bu group in $\mathbf{4}$ has been attributed to its decreased reactivity. The Br${\o}$nsted-type plots for the reactions of $\mathbf{3}$ and $\mathbf{4}$ are linear with ${\beta}_{nuc}=0.57$ and 0.45, respectively. Thus, the reactions have been concluded to proceed through a concerted mechanism, although the current reactions were expected to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate $T^{\pm}$. It has been proposed that the rate of leaving-group expulsion is accelerated by the intramolecular H-bonding interaction in $T^{\pm}$ and the "push" provided by the RO group through the resonance interaction. Thus, the enhanced nucleofugality forces the reactions to proceed through a concerted mechanism. The reactivity-selectivity principle (RSP) is not applicable to the current reaction systems, since the reaction of the less reactive $\mathbf{4}$ results in a smaller ${\beta}_{nuc}$ than that of the more reactive $\mathbf{3}$. Steric hindrance exerted by the bulky $t$-Bu group in $\mathbf{4}$ has been suggested to be responsible for the failure of the RSP.

SrAl2Si2O8 ceramic matrices for 90Sr immobilization obtained via spark plasma sintering-reactive synthesis

  • Papynov, E.K.;Belov, A.A.;Shichalin, O.O.;Buravlev, I. Yu;Azon, S.A.;Golub, A.V.;Gerasimenko, A.V.;Parotkina, Yu. А.;Zavjalov, A.P.;Tananaev, I.G.;Sergienko, V.I.
    • Nuclear Engineering and Technology
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    • v.53 no.7
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    • pp.2289-2294
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    • 2021
  • In the present study, an original spark plasma sintering-reactive synthesis (SPS-RS) method for minerallike ceramic materials based on SrAl2Si2O8 feldspar-like skeleton structure was used for the first time, promising solid-state matrices for reliable immobilization of high-energy 90Sr. The method is based on the "in-situ" reaction of a mixture of SrO, Al2O3 and SiO2 oxides when heated by a unipolar pulsed current under compacting pressure. The phase and elemental composition structure were studied. The dynamics of the consolidation of the reaction mixture of oxides was studied in the range of 900-1200 ℃. The study found the temperature of the high-speed (minutes) SPS-RS formation of single-phase SrAl2Si2O8 composition ceramic in the absence of intermediate reaction products with a relative density of up to 99.2% and compressive strength up to 145 MPa and a strontium leaching rate of 10-4g/cm2·day.

The Effect of Squalene Administration on the Protective Fuction Against Infection in Mice (Squalene투여가 마우스의 감염 방위기능에 미치는 영향)

  • Park, Hae Young;An, Nyeon Hyoung
    • Korean Journal of Clinical Pharmacy
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    • v.2 no.1
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    • pp.41-53
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    • 1992
  • This study was designed to estimate the ability of squalene treated mice to eliminate systemically infected bacteria and fungi and to elucidate the mechanism. As a result of measuring the ability to remove systemically infected bacteria and fungi, The ability of mice to remove the organism was found to increase in squalene treated mice when compared with control mice. And also the ability of phagocytic cells to produce Reactive Oxygen Intermediate(R.O.I.) increased in squalene treated mice. When the NADPH oxidase activity that make R.O.I. produce was measured, the activity increased in squalene treated mice, too. Therefore the good clearance of live organism in squalene treated mice is likely to relate to phagocytic cell activation. The activation of phagocytic cells might be mediated via the increased production of R.O.I. due to the increase of NADPH oxidase activity.

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Korean Mistletoe, Viscum album coloratum Induces Non-Specific Immune Responses in Japanese Flounder, Paralichthys olivaceus

  • Choi, Sang-Hoon;Kim, Jong-Bae;Yoo, Yung-Choon;Yoon, Taek-Joon
    • Journal of Aquaculture
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    • v.17 no.3
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    • pp.209-214
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    • 2004
  • Effects of Korean mistletoe, Viscum album coloratum on the non-specific immune responses of Japanese flounder, Paralichthys olivaceus were examined. Flounder were inoculated with mistletoe, Freunds complete adjuvant (FCA), or phosphate-buffered saline (PBS) as a control into their peritoneal cavities. Reactive oxygen intermediate (ROI) products were more enhanced in mistletoe-injected fish kidney phagocytes than in FCA-injected ones. The level of lysozyme activity detected in the serum of fish 4 d after injection with mistletoe was also significantly higher than that found in the serum of the control fish. The appropriate concentration of mistletoe in eliciting the highest level of serum lysozyme activity was 500 $\mu$m/300 g of fish. In phagocytic activity assays, mistletoe-sen-sitized flounder kidney phagocytes captured more yeasts than those of the control fish. Korean mistletoe appeared to be a good activator of the non-specific immune responses of Japanese flounder.

Effect of picolinic acid on nitric oxide synthesis in murine macrophage

  • Kwon, Oh-Deog;Do, Jae-Cheul;Lee, Keun-Woo
    • Korean Journal of Veterinary Service
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    • v.25 no.4
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    • pp.371-376
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    • 2002
  • To determine the effect of picolinic acid on NOㆍ production, murine macrophages were incubated with either medium, various concentrations of picolinic acid, or IFN-${\gamma}$ plus picolinic acid for 48 hr. Picolinic acid does not induce NOㆍ production by itself, it acted synergistically with INF-${\gamma}$ for the induction of reactive nitrogen intermediate production in murine macrophages. Thymidine incorporation appeared to be reciprocally related to nitrite levels, suggesting that IFN-${\gamma}$ plus picolinic acid induced NOㆍ synthesis exerted antiproliferative effects.

IR Edge and Oxide Impurity Absorption in Heavy Metal Fluoride Glasses (플루오르화중금속 유리의 적외선에지 및 산화물(불수물) 흡수)

  • 정기호
    • Journal of the Korean Ceramic Society
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    • v.22 no.3
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    • pp.29-34
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    • 1985
  • The IR spectra of he heavy metal fluoride glasses showed peaks at $1, 400cm^{-1}$ or $1, 100cm^{-1}$ due to metal oxyfluoride impurities. The intensity of this band and hence the oxide impurity content of the glass could be reduced considerably by the use of reactive atmosphere melting under $CCl_4$ In comparison with the fundamental IR absorption band of heavy metal oxides the oxide impurity bands observed in the heavy metal fluoride glasses are multiphonon bands due to a 2-phonon absorption process. The envelope of the a vs. v curve beyond thue fundamental region shows the exponential fall off of a with increasing v-typical of intrinsic multiphonon absorption. In the multiphonon region the amount of structure is intermediate between that observed for covalent solids and that for ionic solids.

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Effects of Jiyutang with Fructus Immaturus Ponciri on the immune response in the Mouse (지유탕가(地楡湯加) 지실(枳實)이 생쥐의 면역반응(免疫反應)에 미치는 영향(影響))

  • Song Chae-Seok;Park Eun-Jeong;Jeong Gyu-Man
    • The Journal of Pediatrics of Korean Medicine
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    • v.6 no.1
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    • pp.15-32
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    • 1992
  • This study was done to know the effect of Giyuetang on the inflammatory response, contact hypersensitivity (CH), and rosette forming capacity of spleen cells. The effects of Jiyutang with Fructus Immaturus Ponciri on the inflammatory response were evaluated by measuring the production of such reactive oxygen intermediate(ROI) as $O_2^-$ and $H_{2}O_2$ in the peritoneal neutrophils and macrophages. The effects of Jiyutang with Fructus Immaturus Ponciri on the CH were evaluated by checking the ear swelling response against dinitrofluorobenzene(DNFB). The administration of Jiyutang with Fructus Immaturus Ponciri on the mouse decreased the amount of ROI in both neutrophils and macrophages. Jiyutang with Fructus Immaturus Ponciri depressed CH without affecting the rosette forming capacity of spleen cells. The results of this study showed that Jiyutang with Fructus Immaturus Ponciri might have anti-inflammatory effects by decreasing the amounts of ROI in the phagocytes and suppressing the CH, without affecting the rosette-forming capacity of spleen cells.

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Preparation of Reactive Flame Retardant Coatings Containing Phosphorus;I. Synthesis of Pyrophosphoric Modified Polyesters (반응형 인계 난연도료의 제조;I.피로포스포릭 변성폴리에스테르의 합성)

  • Chung, Dong-Jin;Jung, Choong-Ho;Park, Hong-Soo;Kim, Tae-Ok;Park, Shin-Ja
    • Journal of the Korean Applied Science and Technology
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    • v.20 no.1
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    • pp.57-63
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    • 2003
  • An intermediate, tetramethylene bis (orthophosphate), was prepared by the esterification of pyrophosphoric acid and l,4-butanediol. Then pyrophosphoric-containing modified polyesters (ATTBs) were synthesized by polycondensation of tetramethylene bis(orthophosphate), trimethylolpropane, adipic acid, and l,4-butanediol. The content of l,4-butanediol was varied from 10 to 20wt% for the reaction. The increase of the amount of l,4-butanediol in the synthesis of ATTBs resulted in increase in average molecular weight and decrease in kinematic viscosity owing to the excellent flowability and reactivity of l,4-butanediol.

Effect of Firing Temperature on Mechanical Property and Contact Damage in Pottery (소성온도가 도자기의 기계적 특성 및 접촉손상에 미치는 영향)

  • 정연길
    • Journal of the Korean Ceramic Society
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    • v.35 no.12
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    • pp.1343-1350
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    • 1998
  • A study is made of mechanical properties of unglazed matrix as a funtion of sintering temperature and crack patterns in layer structur pottery consisting of glaze and substrate and in matrix which is sintered at 120$0^{\circ}C$ and 130$0^{\circ}C$ respectively. The mechanical properties of matrix are increased due to density and vitrification to 130$0^{\circ}C$ The interface of glazed bilayer reveals the reactive intermediate layer. Herzian indentation testing is used to investigate the evolution of damage modes as a function of load. In the materials sintered at 120$0^{\circ}C$ quasi-plastic deformation is developed at the matrix and the cone-like cracks initiate at the glazing top surface and additionally upward-extending transverse cracks initiate at the internal in-just initiate at the glazing top surface which pass through the interface with increasing of indentation load. Finally the dominant damage mode shifts from substrate quasi-plasticity to coating fracture with increasing sintering temperature.

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Catalytic Activity of Supported Rhodium(I) Complex for the Carbonylation of Nitrobenzene: Mechanism for Carbamate Formation

  • Kim, Jin-Hyung;Kim, Dae-Won;Cheong, Min-Serk;Kim, Hoon-Sik;Mukherjee, Deb Kumar
    • Bulletin of the Korean Chemical Society
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    • v.31 no.6
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    • pp.1621-1627
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    • 2010
  • The investigation of the catalytic activity of supported rhodium(I) complex [Rh(P-S)$(CO)_2$] (P-S; polymer anchored salicylic acid) toward the reductive carbonylation of nitrobenzene in DMF medium has been reported. Use of basic cocatalysts in the reaction medium enhanced the percentage of more useful phenyl carbamates. Spectroscopic studies indicate that the reaction proceeds through a dimer species [Rh(HS)(CO)(C(O)$OCH_3$)(${\mu}-OCH_3)]_2$ and phenyl isocyanate is formed as an intermediate. A plausible reaction mechanism based on the identification of reactive intermediates from the soluble rhodium variety has been proposed for the carbonylation process.