• Bulletin of the Korean Chemical Society
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• 제32권10호
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• pp.3592-3596
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• 2011

A novel poly(vinylchloride)-based membrane sensor using $N^1$,$N^3$,$N^5$-tris(2-(2,3-dihydroxybenzylamino)-ethyl)cyclohexane-1,3,5-tricarboxamide (CYCOENCAT, L) as ionophore has been prepared and explored as $Fe^{3+}$ selective electrode. The membrane electrode composed of ionophore, poly(vinylchloride) and o-nitropheyloctyl ether in the optimum ratio 4:33:63 gave excellent potentiometric response characteristics, and displayed a linear log[$Fe^{3+}$] versus EMF response over a wide concentration range of $1.0{\times}10^{-5}-1.0{\times}10^{-1}$ M with super nernstian slope of 28.0 mV/decade and the detection limit of $8.0{\times}10^{-6}$ M. The proposed ion selective electrode showed fast response time (< 15 s), wide pH range (3.0-7.0), high non-aqueous tolerance (up to 20%) and adequate long life time (120 days). It also exhibited very good selectivity for $Fe^{3+}$ relative to a wide variety of alkali, alkaline earth, transition and heavy metal ions. Further, the analytical applicability of the sensor was tested as an indicator electrode in the potentiometric titration of $Fe^{3+}$ with EDTA.

• Bulletin of the Korean Chemical Society
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• 제28권1호
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• pp.68-72
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• 2007

A new PVC membrane potentiometric sensor that is highly selective to Hg2+ ions was prepared, using bis(2-hydroxybenzophenone) butane-2,3-dihydrazone (HBBD) as an excellent hexadendates neutral carrier. The sensor works satisfactorily in the concentration range of 1.0 × 10-6 to 1.0 × 10-1 mol L-1 (detection limit 4 × 10-7 mol L-1) with a Nernstian slope of 29.7 mV per decade. This electrode showed a fast response time (~8 s) and was used for at least 12 weeks without any divergence. The sensor exhibits good Hg2+ selectivity for a broad range of common alkali, alkaline earth, transition and heavy metal ions (lithium, sodium, potassium, magnesium, calcium, copper, nickel, cobalt, zinc, cadmium, lead and lanthanum). The electrode response is pH independent in the range of 1.5-4.0. Furthermore, the developed sensor was successfully used as an indicator electrode in the potentiometric titration of mercury ions with potassium iodide and the direct determination of mercury in some binary and ternary mixtures.

• Bulletin of the Korean Chemical Society
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• 제29권9호
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• pp.1774-1780
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• 2008

New PVC based polymeric membrane electrodes (PME) and coated glassy carbon electrodes (CGCE) based on synthesized Schiff base complexes of Co(III); [Co(Salen)$(PBu_3)_2$]$ClO_4$, [Co($Me_2$Salen)$(PBu_3)_2$]$ClO_4$, [Co(Salen)$(PBu_3)H_2O$]$ClO_4$; as anion carriers for potentiometric determination of $ClO_4\;^-$were studied. The PME and also CGCE electrodes prepared with [Co(Me2Salen)$(PBu_3)_2$]$ClO_4$ showed excellent response characteristics to perchlorate ions. The electrodes exhibited Nernstian responses to $ClO_4\;^-$ ions over a wide concentration range with low detection limits ($1.0 {\times} 10^{-6}\;mol\;L^{-1}$ for PME and $9.0 {\times} 10^{-7}\;mol\;L^{-1}$ for CGCE). The electrodes possess fast response time, satisfactory reproducibility, appropriate lifetime and, most importantly, good selectivity toward $ClO_4\;^-$ relative to a variety of other common inorganic anions. The potentiometric response of the electrodes is independent of the pH in the pH range 2.5-8.5. The proposed sensors were used in potentiometric determination of perchlorate ions in mineral water and urine samples. The interaction of the ionophore with perchlorate ions was shown by UV/Vis spectroscopy.

• Bulletin of the Korean Chemical Society
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• 제24권11호
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• pp.1585-1589
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• 2003

A PVC-based membrane electrode for thallium(I) ions based on 1,21,23,25-tetramethyl-2,20: 3,19-dimetheno-[H, 2] H, 23H, 25H-bis-[1,3] dioxocino[5,4-i:5',4'-i] benzo [1,2-d: 5.4-d'] bis [1,3] benzodioxocin(II) has been prepared. The electrode displays a linear dynamic range of $1.0{\times}10^{-1}-1.0{\times}10^{-5}$ M, with a Nernstian slope of $59.8{\pm}0.2\;mV\;{decad^-1}$, and a detection limit $5.0{\times}10^{-6}$ M. It has a very fast response time of<10 s and can be used for at least ten weeks without a considerable divergence in potentials. This electrode revealed comparatively good selectivity with respect to alkali, alkaline earth, and some transition and heavy metal ions and was effective in a pH range of 2.0-10.0. It was used as an indicator electrode in potentiometric titration of thallium ion with sulfide ion.

• Bulletin of the Korean Chemical Society
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• 제18권6호
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• pp.653-656
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• 1997

The new unsymmetric $N_6$ ligand 1-amino-13-(2-pyridyl)-3,6,9,12-tetraazatridecane (aptatd) containing one pyridyl group has been synthesized and characterized by EA, IR, and NMR. Its proton association constants $(log K_H^n)$ and stability constants $(log K_{ML})$ for Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), and Zn(Ⅱ) ions were determined at 298.1 K and ionic strength 0.100 mol $dm^{-3}$ (KNO₃) in aqueous solution by potentiometry: log $K_H^1$=8.80, log $K_H^2$=8.49, log $K_H^3$=6.84, log $K_H^4$=4.17, log $K_H^5$=3.47; log $K_{ML}(Co^{2+})$=18.00, log $K_{ML}(Ni^{2+})$=21.31, log $K_{ML}(Cu^{2+})$=23.62, log $K_{ML}(Zn^{2+})$=15.60. The X-ray structure of its nickel(Ⅱ) complex [Ni(aptatd)]$(ClO_4)_2$ are reported: orthorhombic space group Pbca, a=15.715(1) Å, b=14.280(2) Å, c=19.443(2) Å, V=4363.4 (9) ų with Z=8. The geometry around nickel is a distorted octahedron with the pyridine nitrogen atom being cis to the nitrogen atom of the terminal primary amine.

• Bulletin of the Korean Chemical Society
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• 제7권3호
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• pp.238-240
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• 1986

Complex formations between syndiotactic poly(methacrylic acid) (st-PMAA) and poly(N-vinyl pyrrolidone) (PVP), and that between st-PMAA and polyethyleneoxide (PEO) through hydrogen bonding were studied by viscometry and potentiometry. Reduced viscosity (${\eta}_{red}$) was measured at various mole fraction of PVP or PEO with respect to a constant amount of st-PMAA. Observation shows a sharp minimum at the 1:1 mole ratio of st-PMAA:PVP or st-PMAA:PEO, which shows that the complexation becomes optimal and the complex has a compact structure in this ratio. Variation of pH also supports this conclusion. This is the case of the system of st-PMAA and PVP in water as well as in DMF. Also the complexation is much enhanced when the molecular weight of PVP is high. Meanwhile, the system of st-PMAA and PEO shows a little different behavior, i.e., this system does not form the complex in DMF and does only in water. It is because the interaction st-PMAA with PEO is weaker than that with PVP.

• Journal of Electrochemical Science and Technology
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• 제14권1호
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• pp.66-74
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• 2023

In this study, a new potentiometric sensor selective to copper(II) ions was developed and characterized. The developed sensor has a polymeric membrane and contains 4.0% electroactive material (ionophore), 33.0% poly(vinyl chloride) (PVC), 63.0% bis(2-ethylhexyl)sebacate (BEHS) and 1.0% potassium tetrakis(p-chlorophenyl)borate (KTpClPB). This novel copper(II)-selective sensor exhibits a Nernstian response over a wide concentration range from 1.0×10^-6 to 1.0×10^-1 mol L^-1 with a slope of 29.6 (±1.2) mV decade^-1, and a lower detection limit of 8.75×10-7 mol L^-1. The sensor, which was produced economically by synthesizing the ionophore in the laboratory, has a good selectivity and repeatability, fast response time and stable potentiometric behaviour. The potential response of the sensor remains unaffected of pH in the range of 5.0-10.0. Based on the analytical applications of the sensor, we showed that it can be used as an indicator electrode in the quantification of Cu²⁺ ions by potentiometric titration against EDTA, and can also be successfully utilized for the determination of copper(II) ions in different real samples.

• Bulletin of the Korean Chemical Society
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• 제27권6호
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• pp.835-840
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• 2006

Dimethyl 1-(4-nitrobenzoyl)-8-oxo-2,8-dihydro-1H-pyrazolo[5,1-a]isoindole-2,3-dicarboxylate has been used as an ionophore and o-nitrophenyloctyl ether as a plasticizer in order to develop a poly(vinyl chloride)-based membrane electrode for calcium ion detection. The sensors exhibit significantly enhanced response towards calcium(II) ions over the concentration range $8.0{\times}10^{-7}\;1.0{\times}10^{-1}$ M at pH 3.0-11 with a lower detection limit of $5.0 {\times}10^{-7}$ M. The sensors display Nernstian slope of 29.5 ${\pm}$ 0.5 mV per decade for Ca(II) ions. Effects of plasticizers, lipophilic salts and various foreign common ions are tested. It has a fast response time within 10 s over the entire concentration range and can be used for at least 2 months without any divergence in potentials. The proposed electrode revealed good selectivity and response for $Ca^{2+}$ over a wide variety of other metal ions. The selectivity of the sensor is comparable with those reported for other such electrodes. The proposed sensor was successfully applied as an indicator electrode for the potentiometric titration of a Ca(II) solution, with EDTA.

• 대한화학회지
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• 제45권1호
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• pp.31-39
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• 2001

새로이 합성한 15-Crown-5 유도체들을 칼륨이온의 전위차법 정량을 위한 중성운반체로 사용하였다. 다섯 가지 화합물 중에서N-(4'-benzo-15-crown-5-ether)-anthracene-9-imine이 가장 좋은 선택성과 안정성을 보였다. 칼륨이온을 전위차법으로 정량하기 위한 이온선 택성 막의 조성을 조사한 결과, 최적 조성은 중성운반체: PVC:가소제의 조성비가 1.0:33.0:66.0 wt% 이었다. 친유성 첨가제로 0.2wt% KTpClPB를 사용했을 때에 Nernstian 기울기가 많이 좋아졌고, 또 알칼리 및 알칼리 토류 금속에 대한 칼륨이온의 선택성이 크게 개선되었다. 특히 암모늄이온에 대한 칼륨 이온의 선택성은 $logK^{pot}_(K^+,NH_4^+}$=-2.59로 아주 좋은 값을 보였다. 이 전극의 감응시간은 $t_{100}$=5sec로서 짧은 시간에 많은 시료를 분석할 수 있고, 3주 이상 사용하여도 선택성과 분석 특성에 별다른 변화가 없었다.

• 한국환경과학회지
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• 제18권7호
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• pp.735-746
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• 2009

Hydrochloric acid salt of a new $N_2O_3$ pentadentate ligand, N,N'-Bis(2-Hydroxybenzyl)-1,3-diamino-2-propanol(H-BHDP 2HCl) was synthesized. Br-BHDP 2HCl, CI-BHDP 2HCl, $CH_3-BHDP$ 2HCl and $CH_3O$-BHDP 2HCl having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of H-BHDP 2HCl were also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and their order of the calculated overall proton dissociation constants($log{\beta}_p$) was Br-BHDP < Cl-BHDP < H-BHDP < $CH_3O-BHDP$ < $CH_3-BHDP$. The order showed a similar trend to that of Hammett substituent constants(${\delta}_p$). The order of the stability constants($logK_{ML}$) was Co(II) < Ni(II) < Cu(II) < Zn(II) < Cd(II) < Pb(II). The order in their stability constants ($logK_{ML}$) of each transition metal complex agreed with that of the overall proton dissociation constants ($log{\beta}_p$).