• Title/Summary/Keyword: organic anions

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A Comparison of the Leaving Group Ability of Transition Metal Carbonyl Anions vs. Halides : Reaction of $MH^-$ with M'-R $(MH^-\;=\;HW(CO)_4\;-P(OMe)_3\;^-,\;HW(CO)_5\;^-,\;HCr(CO)_5\;^-,\;HFe(CO)_4\;^-;\;M'-R=CpMo(CO)_3(CH_3),\;CpMo(CO)_3{CH_2CH(CH_2)_2})$

  • Yong Kwang Park;Seon Joong Kim;Carlton Ash
    • Bulletin of the Korean Chemical Society
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    • v.11 no.2
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    • pp.109-114
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    • 1990
  • The anionic transition metal hydrides $(HW(CO)_4P(OMe)_3\;^-,\;HW(CO)_5\;^-,\;HCr(CO)_5\;^-,\;HFe(CO)_4\;^-)$ react with transition metal alkyl $(CpMo(CO)_3(CH_3)$ to yield $CH_4\;and\;CH_3CHO$ in addition to the inorganic products $(CpMo(Co)_3\;^-$, etc.). The reaction of these anionic metal hydrides with CpMo(CO)3{CH2CH(CH2)2} may lead to an elucidation of the reaction mechanisms involved; the organic product distributions are among $CH_4,\;CH_2\;=\;CHCH_2CH_3$, and $CH_3CH(CH_2)_2$, depending upon the anionic metal hydride used. These anionic metal hydrides also are reported to undergo a hydride-halide exchange reaction with organic halides; therefore, these similar reactions have been compared in terms of leaving group ability $(CpMo(CO)_3\;^-\;vs.\;Br^-)$ and the mechanistic pathways.

Sol-Gel Encapsulation as Matrix for Potentiometric Nitrite-Selective Membranes Doped with Chloro (5, 10, 15, 20-Tetraphenylporphyrinato) Cobalt (III)

  • Zhou, Hao;Meyerhoff, Mark E.;Bi, Kai-Shun;Park, Sung-Bae
    • Journal of the Korean Electrochemical Society
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    • v.12 no.4
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    • pp.335-341
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    • 2009
  • Organic-inorganic hybrid sol-gel matrices were used as hosts for chloro (5, 10, 15, 20-tetraphenylporphyrinato) cobalt (III) (Co[TPP]Cl), a known ionophore for nitrite. The sol-gel precursor was prepared by the reaction of (3-isocyanopropyl) triethoxysilane with 1,4-butanediol. An appropriate amount of the anion-exchanger, tridodecylmethylammonium chloride (TDMAC) and the plasticizer, tributylphosphate (DBP) were used as membrane additives. On mixing with an acidic catalyst, the sol-state precursors slowly gelled, yielding a membrane in which the active components, Co[TPP]Cl and TDMAC, were encapsulated. The performances of the sol-gel membrane-based electrodes were compared to those of Co[TPP]Cl-based poly(vinyl chloride) (PVC) membrane electrodes. Membranes with a molar ratio of Co[TPP]Cl: TDMAC (1 : 0.1) showed reasonable response slopes toward nitrite. The response slopes were typically 53 mV/decade between $10^{-5.4}$ and $10^{-1.0}\;M$. Selectivities toward nitrite over hydrophilic and small anions such as chloride were somewhat inferior to those observed with PVC-based membranes, but selectivities over lipophilic anions were quite similar. Reduced asymmetry potentials due to protein adsorption were found to occur with the sol-gel matrix relative to PVC-based films when the sensors were employed as a detector in flow-through configuration.

Hydro/solvothermal synthesis, crystal structure, and thermal behaviour of piperazine-templated nickel(II) and cobalt(II) sulfates

  • Kim, Chong-Hyeak;Park, Chan-Jo;Lee, Sueg-Geun
    • Analytical Science and Technology
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    • v.19 no.4
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    • pp.309-315
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    • 2006
  • Two piperazine-templated metal sulfate complexes, $(C_4N_2H_{12})[Ni(H_2O)_6](SO_4)_2$, I and ($C_4N_2H_{12}$) $[Co(H_2O)_6](SO_4)_2$, II, have been synthesized by hydro/solvothermal reactions and their crystal structures analyzed by single crystal X-ray diffraction methods. Complex I crystallizes in the monoclinic system, $P2_1/n$ space group, a=12.920(3), b=10.616(2), $c=13.303(2){\AA}$, ${\beta}=114.09(1)^{\circ}$, Z=4, $R_1=0.030$ for 3683 reflections; II: monoclinic $P2_1/n$, a=12.906(3), b=10.711(2), $c=13.303(2){\AA}$, ${\beta}=114.10(2)^{\circ}$, Z=4, $R_1=0.032$ for 4010 reflections. The crystal structures of the piperazine-templated metal(II) sulfates demonstrate zero-dimensional compound constituted by diprotonated piperazine cations, metal(II) cations and sulfate anions. The structures of complex I and II are substantially isostructural to that of the previously reported our piperazine-templated copper(II) sulfate complex $(C_4N_2H_{12})[Cu(H_2O)_6](SO_4)_2$. The central metal(II) atoms are coordinated by six water molecules in the octahedral geometry. The crystal structures are stabilized by three-dimensional networks of the $O_{water}-H{\cdots}O_{sulfate}$ and $N_{pip}-H{\cdots}O_{sulfate}$ hydrogen bonds between the water molecules and sulfate anions and protonated piperazine cations. Based on the results of thermal analysis, the thermal decomposition reactions of the complex I was analyzed to have three distinctive stages whereas the complex II proceed through several stages.

Determination of Mefenamic acid with ISEs Using Ternary Complex of Metal -phenanthroline -mefenamate as Ion-exchanger (이온교환체로서 금속 -페난드롤린 -메페남산 3원 작물을 이용한 메페남산의 정량)

  • 허문회;김대병;남수자;문현숙;이미나;정문모;안문규
    • YAKHAK HOEJI
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    • v.45 no.1
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    • pp.29-33
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    • 2001
  • A method for the determination of anionic drug, mefenamate with ion-selective electrode using Fe(II)-1,10-phenanthroline chelate as a counter ion was developed. Benzyl nitrophenyl ether (BNPE) plasticized membrane was more selective and sensitive than the other tested membranes. This membrane electrode exhibits a linear response for 10$^{-2}$ M~5 $\times$ 10$^{-5}$ M of mefenamic acid with a slope of -61.4 mV/dec. in borate buffer solutions (pH 9.0). Potentiometric selectivity measurements revealed negligible interferences from various organic and ionorganic anions. Direct potentiometry and potentiometric titration method of mefenamic acid in capsule preparations are presented and compared.

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Titanium Acetylacetonate as an Excellent Ion-Carrier in Construction of Iodide Sensor

  • Ganjali, Mohammad Reza;Daftari, Azadeh;Mizani, Farhang;Salavati-Niasari, Masoud
    • Bulletin of the Korean Chemical Society
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    • v.24 no.1
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    • pp.23-26
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    • 2003
  • Titanium acetylacetonate was used in the construction of a PVC-based membrane electrode. This sensor shows very good selectivity for iodide ion over a wide variety of common inorganic and organic anions. It exhibits Nernstian behavior with a slope of 59.1 mV per decade. The working concentration ranges of the sensor are with a detection limit of $3.0\;{\times}\;10^{-6}\;M$. The response time of the sensor is very fast (<8 s), and can be used for at least twelve weeks in the pH range of 4.0-9.2. The best performance was obtained with a membrane composition of 30% PVC, 65% dibutylphthalate, 3% titanium acetylacetonate and 2% hexadecyltrimethylammonium bromide. The proposed sensor was successfully applied as an indicator electrode for titration of iodide with silver ion.

Application of Ionic Liquids Based on 1-Ethyl-3-Methylimidazolium Cation and Fluoroanions to Double-Layer Capacitors

  • Ue, Makoto;Takeda, Masayuki
    • Journal of the Korean Electrochemical Society
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    • v.5 no.4
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    • pp.192-196
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    • 2002
  • Ionic liquids based on l-ethyl-3-methylimidazolium cation $(EMI^+)$ and inorganic or organic anions containing fluorine atoms were applied to electrolyte materials for double-layer capacitors. The double-layer capacitors composed of a pair of activated carbon electrodes and an ionic liquid selected from $EMIBF_4,\; EMINbF_6,\;EMITaF_6,\;EMICF_3SO_3,\;EMI(CF_3SO_2)_2N,\;and\;EMI(C_2F_5SO_2)_2N$ showed inferior low-temperature characteristics to those of a conventional nonaqueous electrolyte based on propylene carbonate (PC) solvent. On the other hand, the capacitor using $EMIF{\cdot}2.3HF$ showed excellent low-temperature characteristics due to its high conductivity at low temperatures, however, it had a lower working voltage $(\~2V)$ than the conventional nonaqueous counterpart $(\~3V)$.

The Effect of Solvent on the $\alpha$-Effect(3): Nucleophilic Substitution Reactions of Aryl Acetates in $MeCN-H_2O$ Mixtures of Varying Compositions

  • Um Ik-Hwan;Hahn Gee-Jung;Lee Gwang-Ju;Kwon Dong-Song
    • Bulletin of the Korean Chemical Society
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    • v.13 no.6
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    • pp.642-647
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    • 1992
  • Second-order rate constants have been measured spectrophotometrically for the reactions of substituted phenyl acetates with butane-2,3-dione monoximate and p-chlorophenoxide anions in MeCN-H$_2$O mixtures of varying compositions. The reaction rate, unexpectedly, decreased remarkably upon initial additions of MeCN to H$_2$O up to 30-40 mole ${\%}$ MeCN, and followed by a gradual increase upon further additions of MeCN. The change in solvent composition also influenced the magnitude of the ${\alpha}$-effect, i.e., the ${\alpha}$-effect increased as the mole ${\%}$ MeCN increased. The solvent dependent ${\alpha}$-effect for the present system appears to indicate that the differential solvation between the ${\alpha}$-effect nucleophile and the corresponding normal nucleophile is not solely responsible but the difference in the transition-state stabilization is also responsible for the ${\alpha}$ -effect in organic solvent-rich region.

Synthesis of Iron Oxide and Adsorption of Arsenic on Iron Oxide (철산화물의 합성 및 이를 이용한 비소의 흡착제거)

  • Kim, Youn Jung;Choi, Sik Young;Kim, Young-Hun
    • Journal of Environmental Science International
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    • v.28 no.1
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    • pp.99-106
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    • 2019
  • Arsenic is among the heavy metals commonly found in aqueous environments. Iron oxide is known as an efficient adsorbent for the arsenic. A new synthetic method was applied to provide iron oxide giving a large specific surface area. The mixing method affects the formation of iron oxide. Ultrasonic waves assisted the formation of very fine iron oxide in an organic phase. The synthesized iron oxide is amorphous type with a high surface area of more than $181.3m^2/g$. Sorption capacity of the synthesized adsorbent was relatively very high for arsenic and varied depending on the oxidation state of arsenic: a higher capacity was obtained with As(V). Lower solution pH provided a higher sorption capacity for As(V). The competitive effect of co-exist anions such as chloride, nitrate, and sulfate was minimal in sorption capacity of the iron oxide for arsenic.

Enhanced photocatalytic oxidation of humic acids using Fe3+-Zn2+ co-doped TiO2: The effects of ions in aqueous solutions

  • Yuan, Rongfang;Liu, Dan;Wang, Shaona;Zhou, Beihai;Ma, Fangshu
    • Environmental Engineering Research
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    • v.23 no.2
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    • pp.181-188
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    • 2018
  • Photocatalytic oxidation in the presence of Fe-doped, Zn-doped or Fe-Zn co-doped $TiO_2$ was used to effectively decompose humic acids (HAs) in water. The highest HAs removal efficiency (65.7%) was achieved in the presence of $500^{\circ}C$ calcined 0.0010% Fe-Zn co-doped $TiO_2$ with the Fe:Zn ratio of 3:2. The initial solution pH value, inorganic cations and anions also affected the catalyst photocatalytic ability. The HAs removal for the initial pH of 2 was the highest, and for the pH of 6 was the lowest. The photocatalytic oxidation of HAs was enhanced with the increase of the $Ca^{2+}$ or $Mg^{2+}$ concentration, and reduced when concentrations of some anions increased. The inhibition order of the anions on $TiO_2$ photocatalytic activities was $CO{_3}^{2-}$ > $HCO_3{^-}$ > $Cl^-$, but a slightly promotion was achieved when $SO{_4}^{2-}$ was added. Total organic carbon (TOC) removal was used to evaluate the actual HAs mineralization degree caused by the $500^{\circ}C$ calcined 0.0010% Fe-Zn (3:2) co-doped $TiO_2$. For tap water added with HAs, the $UV_{254}$ and TOC removal rates were 57.2% and 49.9%, respectively. The $UV_{254}$ removal efficiency was higher than that of TOC because of the generation of intermediates that could significantly reduce the $UV_{254}$, but not the TOC.

Characteristics of p-Aminohippurate (PAH) Transport in Basolateral Membrane Vesicles of Rabbit Kidney Cortex -Effect of Anion- (신장 피질 기저막 소포에서 p-Aminohippurate 이동의 특성에 대한 연구 -음이온의 효과-)

  • Lee, Sang-Ho;Chung, Jin-Sup;Kim, Yong-Keun
    • The Korean Journal of Physiology
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    • v.20 no.2
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    • pp.225-235
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    • 1986
  • Effects of anions on p-Aminohippurate (PAH) transport across the basolateral membrane (BLM) were studied. Basolateral membrane vesicles were isolated from rabbit renal cortex by using a self-orienting Percoll-gradient centrifugation and $Mg^{2+}-precipitation$. The characteristics of the membrane vesicles was examined by marker enzyme activity, membrane orientation and transport studies. The Na-K-ATPase activity in the fraction containing BLM vesicles was enriched 9·fold, and the alkaline phosphatase activity in the fraction containing BBM vesicles was increased 9-fold, compared with those of the homogenate. The transport properties of the two membrane preparations were studied by a rapid filtration technique. The uptake of PAH by BLM was sensitive to changes in medium osmolarity and inhibited by probenecid. When the uptake of $50{\mu}M$ PAH in voltage-clamped BLM vesicles was determined in the presence of various anions in the incubation medium, cis inhibitions by $SO_4\;and\;SSO_3$ were observed in the presence of sodium gradient (out>in). Sodium-dependent PAH uptake was inhibited competitively by external $SO_4$ PAH uptake in BLM vesicles loaded with 20 mM acetate and $SO_4\;or\;200\;{\mu}M$ PAH was significantly stimulated as compared with unloaded vesicles. The extent of trans-stmulation of PAH uptake by $SO_4$. was increased with the inside concentration of $SO_4$. This trans-stimulatory effect by $SO_4$, was observed to be additive in the presence of Na gradient and completely inhibited by 2 mM probenecid and 1 mM SITS. These results demonstrate that PAH/anion exchange is present in BLM of renal cortex and in this exchange mechanism inorganic as well as organic anions are involved as substrates.

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