• Title/Summary/Keyword: Transition metal ion

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Alkali Metal Ion Catalysis and Inhibition in Nucleophilic Substitution Reactions of 3,4-Dinitrophenyl Diphenylphosphinothioate with Alkali Metal Ethoxides in Anhydrous Ethanol: Effect of Changing Electrophilic Center from P=O to P=S

  • An, Jun-Sung;NamKoong, Gil;Kang, Ji-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2423-2427
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    • 2011
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 3,4-dinitrophenyl diphenylphosphinothioate 9 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] is linear for the reaction of 9 with EtOK. However, the plot curves downwardly for those with EtOLi and EtONa while it curves upwardly for the one with EtOK in the presence of 18-crown-6-ether (18C6). Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-}$ ${\approx}$ $k_{EtOK}$ < $k_{EtOK/18C6}$, indicating that the reaction is inhibited by $Li^+$ and $Na^+$ ions but is catalyzed by 18C6-crowned $K^+$ ion. The reactivity order found for the reactions of 9 contrasts to that reported previously for the corresponding reactions of 1, i.e., $k_{EtOLi}$ > $k_{EtONa}$ > $E_{EtOK}$ > $k_{EtO^-}$ ${\approx}$ $k_{EtOK/18C6}$, indicating that the effect of changing the electrophilic center from P=O to P=S on the role of $M^+$ ions is significant. A four-membered cyclic transition-state has been proposed to account for the $M^+$ ion effects found in this study, e.g., the polarizable sulfur atom of the P=S bond in 9 interacts strongly with the soft 18C6-crowned $K^+$ ion while it interacts weakly with the hard $Li^+$ and $Na^+$ ions.

A New Cone Shaped Asymmetrically Substituted Calix[4]arene as an ExcellentIonophore in Construction of Ag(I) ion-Selective Membrane Electrode

  • Ganjali, Mohammad Reza;Babaei, Leila Hajiagha;Taghvaei-Ganjali, Saeed;Modjallal, Atoosa;Sahmsipur, Mojtaba;Hosseini, Morteza;Javanbakht, Mehran
    • Bulletin of the Korean Chemical Society
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    • v.25 no.2
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    • pp.177-181
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    • 2004
  • A PVC membrane electrode for silver ion based on a new cone shaped calix[4]arene (CASCA) as membrane carrier was prepared. The electrode exhibits a Nernstian response for $Ag^+$ over a wide concentration range ($1.0{\times}10^{-1}-8.0{\times}10^{-6}$M) with a slope of 58.2 {\pm}$ 0.5 mV per decade. The limit of detection of the sensor is $5.0{\times}10^{-6}$M. The sensor has a very fast response time (~5 s) in the concentration range of ${\leq}=1.0{\times}10^{-3}$ M, and a useful working pH range of 4.0-9.5. The proposed sensor displays excellent discriminating ability toward $Ag^+$ ion with respect to common alkali, alkaline earth, transition and heavy metal ions. It was used as an indicator electrode in potentiometric titration of $Ag^+$ with EDTA and in direct determination of silver ion in wastewater of silver electroplating.

The optical characteristics of amorphous $Se_{75}Ge_{25}$ thin film by the low-energy lon beam exposure (저 에너지 이온빔 조사에 따른 비정질 $Se_{75}Ge_{25}$ 박막의 광학적 특성)

  • 이현용;오연한;정홍배
    • Electrical & Electronic Materials
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    • v.7 no.2
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    • pp.100-106
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    • 1994
  • A bilayer film consisting of a layer of a-Se$_{75}$ Ge$_{25}$ with a surface layer of silver -100[.angs.] thick and a monolayer film of a-Se$_{75}$ Ge$_{25}$ are irradiated with 9[keV] Ga$^{+}$ ion beam. The Ga$^{+}$ ion (10$^{16}$ [ions/cm$^{2}$] exposed a-Se$_{75}$ Ge$_{25}$ and Ag/a-Se$_{75}$ Ge$_{25}$ thin films show an increase in optical absorption, and the absorption edge on irradiation with shifts toward longer wavelength. The shift toward longer wavelength called a "darkening effect" is observed also in film exposure to optical radiation(4.5*10$^{20}$ [photons/cm$^{2}$]). The 0.3[eV] edge shift for ion irradiation films is about twice to that obtained on irradiation with photons. These large changes are primarily due to structural changes, which lead to high etch selectivity and high sensitivity.

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Adsorption and Preconcentration of Some Heavy Metals by Resorcinol-Formaldehyde Resin (Resorcinol-formaldehyde 수지에 의한 중금속 이온의 흡착과 농축)

  • Park, Chan-Il;Cha, Ki-Won
    • Analytical Science and Technology
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    • v.11 no.3
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    • pp.174-178
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    • 1998
  • A chelating resin was prepared by the reaction of formaldehyde and resorcinol. It possesses high adsorption selectivity for transition metal ions such as Pb(II) and Ni(II). The adsorption and desorption yields of Pb(II), Ni(II), Co(II), Fe(II) and Zn(II) were determined using batch method. The significant characteristics of the chelating resin is the exchange processes between its hydrogen and metal ions. The mechanism of metal adsorption and desorption seems to be the competing protonation and complexation reaction of the functional group of the resin. This resin was applied to the rapid concentration of trace amounts of these metal ions and to the separation of Pb(II) from other metal ions in bulk solution.

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Syntheses of New Nitrogen-Oxygen Multidentate Ligands and Their Stability Constants of Transition Metal(Ⅱ) Ions (새로운 질소-산소계 여러 자리 리간드의 합성 및 전이금속(Ⅱ)이온 착물의 안정도상수)

  • Kim, Sun Deuk;Jang, Ki Ho;Kim, Jun Kwang
    • Journal of the Korean Chemical Society
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    • v.42 no.5
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    • pp.539-548
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    • 1998
  • Multidentate N,O-containing ligands, such as N,N'-bis(2-hydroxybenzyl)-ethylenediamine(BHED), N,N'-bis(2-hydroxybenzyl)-propylenediamine(BHPD), N,N'-bis(2-hydroxybenzyl)-diethylenetriamine(BHDT), N,N'-bis(2-hydroxybenzyl)-triethylenetriamine(BHTT) and N,N'-bis(2-hydroxybenzyl)-tetraethylenepentaamine (BHTP) were synthesized by reduction of the imine group of Bis(salicylidene)-ethylendiamine(BSED), Bis (salicylidene)-propylenediamine(BSPD), Bis(salicylidene)-diethylentriamine(BSDT), Bis(salicylidene)-triethylenetetraamine(BSTT) and Bis(salicylidene)-tetraethylenepentaamine(BSTP). Proton dissociation constants of the ligands and stability constants of transition metal(Ⅱ) ion complexes with BHED, BHPD, BHDT, BHTT, and BHTP were determined by potentiometic titration. The sequence of stability constants $(logK_{ML})$ of complex increases as BHED Zn(Ⅱ) which follows the Irving-Williams series.

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Microfluidic Fabrication of Conjugated Polymer Sensor Fibers (미세유동을 이용한 공액 고분자 센서 섬유 제작)

  • Yoo, Imsung;Song, Simon
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.38 no.10
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    • pp.853-858
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    • 2014
  • We propose a fabrication method for polydiacetylene (PDA)-embedded hydrogel microfibers on a microfluidic chip. These fibers can be applied to the detection of cyclodextrines (CDs), which are a family of sugar and aluminum ions. PDA, a family of conjugated polymers, has unique characteristics when used for a sensor, because it undergoes a blue-to-red color transition and nonfluorescence-to-fluorescence transition in response to environmental stimulation. PDAs have different sensing characteristics depending on the head group of PCDA. By taking advantage of ionic crosslinking-induced hydrogel formation and the 3D hydrodynamic focusing effect on a microfluidic chip, PCDA-EDEA-derived diacetylene (DA) monomer-embedded microfibers were successfully fabricated. UV irradiation of the fibers afforded blue-colored PDA, and the resulting blue PDA fibers underwent a phase transition to red and emitted red fluorescence upon exposure to CDs and aluminum ions. Their fluorescence intensity varied depending on the CDs and aluminum ion concentrations. This phase transition was also observed when the fibers were dried.

Lithium Transition Metal Phosphate Cathodes for Advanced Lithium Batteries (리튬이온전지에서 새로운 양극재료를 위한 금속인산화물)

  • ;Yet Ming Chiang
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2003.11a
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    • pp.26-26
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    • 2003
  • Lithium storage electrodes for rechargeable batteries require mixed electronic-ionic conduction at the particle scale in order to deliver desired energy density and power density characteristics at the device level. Recently, lithium transition metal phosphates of olivine and Nasicon structure type have become of great interest as storage cathodes for rechargeable lithium batteries due to their high energy density, low raw materials cost, environmental friendliness, and safety. However, the transport properties of this family of compounds, and especially the electronic conductivity, have not generally been adequate for practical applications. Recent work in the model olivine LiFePO$_4$, showed that control of cation stoichiometry and aliovalent doping results in electronic conductivity exceeding 10$^{-2}$ S/cm, in contrast to ~10$^{-9}$ S/cm for high purity undoped LiFePO$_4$. The increase in conductivity combined with particle size refinement upon doping allows current rates of >6 A/g to be utilized while retaining a majority of the ion storage capacity. These properties are of much practical interest for high power applications such as hybrid electric vehicles. The defect mechanism controlling electronic conductivity, and understanding of the microscopic mechanism of lithiation and delithiation obtained from combined electrochemical and microanalytical techniques, will be discussed

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Fluorescence Quenching of Norfloxacin by Divalent Transition Metal Cations

  • Park, Hyoung-Ryun;Seo, Jung-Ja;Shin, Sung-Chul;Lee, Hyeong-Su;Bark, Ki-Min
    • Bulletin of the Korean Chemical Society
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    • v.28 no.9
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    • pp.1573-1578
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    • 2007
  • Fluorescence quenching of norfloxacin (NOR) by Cu2+, Ni2+, Co2+ and Mn2+ was studied in water. The change in the fluorescence intensity and lifetime was measured as a function of quencher concentration at various temperatures. According to the Stern-Volmer plots, the NOR was quenched both by collisions and complex formation with the same quencher. However, the static quenching had a more important effect on the emission. Large static and dynamic quenching constants support significant ion-dipole and orbital-orbital interactions between NOR and cations. The both quenching constants by Cu2+ were the largest among quenchers. Also, quenching mechanism of Cu2+ was somewhat different. The change in the absorption spectra due to the quencher provided information on static quenching. The fluorescence of NOR was relatively insensitive to both the dynamic and static quenching compared with other quinolone antibiotics. This property can be explained by the twisted intramolecular charge transfer.

A $M\"{o}ssbauer$ Spectroscopic Sthdy of Ion Distribution in $Ba_{2}{(Co,Zn)}_{2}Fe_{12}O_{22}$ ($M\"{o}ssbauer$ 분광 분석에 의한 $Ba_{2}{(Co,Zn)}_{2}Fe_{12}O_{22}$ 내의 이온 분포 연구)

  • 최상준;권순주
    • Journal of the Korean Magnetics Society
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    • v.6 no.2
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    • pp.73-79
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    • 1996
  • Y-type hexagonal ferrites$(Ba_{2}Me_{2}Fe_{12}O_{22}:Me=transition metal)$ have promising electromagnetic properties in GHz range. Co and Zn are good candidates for the transition metal. To understand their role on the properties, it is thus necessary to study the ion(s) distribution in that complex Y-type hexagonal ferrite structure. The authors report Mossbauer spectroscopic results from very reliable samples, which has been extensively characterized by chemical analysis, Rietveld analysis of X-ray diffraction patterns, and magnetic property measurements. Analyzing two samples, $Co_{2}Y$ and $Co_{1.6}Zn_{0.4}Y$, conclusions are made as follow: (1) Co ions prefer the tetrahedral interstitial sites in the S-block $(6c_{IV})$ and the octahedral sites $(18h_{VI})$ at the interface of S- and T-block. (2) Partial substitution of Co with Zn (within the experimental range) does not disturb the Fe distribution.

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