• Bulletin of the Korean Chemical Society
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• v.27 no.12
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• pp.1985-1988
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• 2006

The polymeric membrane electrodes based on urea derivative as an ionophore were prepared and studied for the iodide-ion selective electrode. This membrane exhibits a linear stable response over a wide concentration range ($1.0\;{\times}\;10^{-5}\sim1.0\;{\times}\;10^{-2}$) with a slope of -57.7 mV/decade, a detection limit of log[$I^-$] = -5.63, and a selectivity coefficient for iodide against perchlorate anion (log$K^{pot}_{I^-,j}$ = -1.42). The selectivity series of the membrane gives the follow as $I^-$ > $SCN^-$, $Sal^-$ > $ClO_4^-$ > $NO_3^-$ > $Br^-$ > $NO_2^-$ > $Cl^-$ > $F^-$. The proposed electrode showed good selectivity and response for iodide anion over a wide variety of other anions in pH 5.0 buffer solutions.

• Journal of the Korean Society of Safety
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• v.10 no.4
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• pp.47-59
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• 1995

The perchlorate, thiocyanate, and nitrate ion-selective PVC membrance electrode for measuring hazardous anion in waste water were developed by incorporating the quaternary ammonium salts as active material. Ion-selective characteristics in waste water were studied by the useful pH range, the selective coefficients to various interfering anions, and the stability of electrode potential. DBP was best as a plasticizer. The effect of the membrane thickness on the electrode characteristics was improved with decreasing the membrane thickness, but below the optimum membrane thickness the electrode exhibited an inverse trend. The electrode potential of perchlorate, thiocyanate, and nitrate electrode with TDDA, as active material, was stable within the pH range 4-11, 3-12, and 4-10 repectively. And the long-term potential stability of these electrodes were 3.0, 3.5, and 3.5 months respectively. The order of the selectivity coefficients was as shown below ; $ClO_4{^-}$ > $SCN^-$ > $I^-$ > $NO_3{^-}$ > $Br^-$ > $CN^-$ > $F^-$ > $Cl^-$ > $Ac^-$ > $H_2PO_4{^-}$, $SO_4{^-}$.

• Bulletin of the Korean Chemical Society
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• v.26 no.1
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• pp.57-62
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• 2005

The potentiometric responses for various anions are investigated with membrane electrode (membrane 1) based on 1,3-diethyl-1,3-dihydroxy-1,3-bis(2-dimethylaminomethyl ferrocenyl) disiloxane. The nitrate ion-selective electrode based on compound 1 gave a good Nernstian response of 58.18 mV per decade for nitrate with the detection limit of −e5.66 of log [NO3−e]. Compound 1 has all those functional groups and the other two compounds have less functional group of ferrocenyl or ferrocenyl and hydroxide, respectively. Even though, potentiometric response to anions was excellent at pH 5, the selectivity pattern for all three membrane electrode based on series of disiloxane is almost like Hofmeister sequence at pH 5. However, the membrane electrode 1-3 exhibited very different response to anions at pH 7. In this pH, NH2 is not protonated and ionophore may act as neutral carrier. Hydrogen bond may enhance the responsibility to hydrogen acceptors and intramolecular electro-active site may increase the permeability of analyte to ionophore in membrane.

• Bulletin of the Korean Chemical Society
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• v.35 no.11
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• pp.3175-3180
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• 2014

A potentiometric sensor based on the 1-benzyl-3-(4-nitrophenyl) thio-urea was synthesized and tested as an ionophore in PVC based membrane sensor towards $SCN^-$ ions. This membrane exhibits a linear stable response over a wide concentration range ($1.0{\times}10^{-5}$ to $1.0{\times}10^{-2}M$) with a slope of -59.2 mV/dec., a detection limit of ${\log}[SCN^-]=-5.05$, and a selectivity coefficient for thiocyanate against perchlorate anion of ${\log}K^{pot}_{SCN^-j}=-0.133$. The selectivity series of the membrane is as follows: $SCN^-$ > $ClO_4{^-}$ > $I^-$ > $NO_3{^-}$ > $HSO_3{^-}$ > $Cl^-$ > $HSO_4{^-}$ > $F^-$ > $CH_3COO^-$ > $HCO_3{^-}$ > $Br^-$ > $H_2PO_4{^-}$ > $SO{_3}^{2-}$ > $SO{_4}^{2-}$ > $CO{_3}^{2-}$. The proposed electrode showed good selectivity and a good response for the $SCN^-$ ion over a wide variety of other anions in pH 6.0 buffer solutions and has a fast response time of about < 5s. The influences of the membrane by pH, ionophore, and plasticizer were studied.

• Bulletin of the Korean Chemical Society
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• v.23 no.10
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• pp.1409-1412
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• 2002

Polymeric membrane electrodes for acetate anion based on meso-(${\alpha}$,${\alpha}$,${\alpha}$,${\alpha}$)-5,10,15,20-tetrakis[2-(penta-fluorophenylurea) phenyl]porphyrin I and similar urea-functionalized porphyrins Ⅱ-Ⅳ as neutral ionophores were prepared. The membrane based on porphyrin I exhibits the best potentiometric properties in pH 6.0 rather than pH 7.0: linear stable response over a wide concentration range (6.0 ${\times}$$10^{-5}$-1.0 ${\times}$$10^{-2}$) with a slope of -59.6 mV/decade and a detection limit of log[CH3CO$O^-$] = -5.32. Selectivity coefficients obtained from the matched potential method (MPM) in pH 6.0 indicate that interferences of hydrophobic anions are very small for the membranes of porphyrins I and II having the strong withdrawing group. The electronic effect of urea-functionalized porphyrins and pH effect of buffer solutions are discussed on the potentiometric response.

• Bulletin of the Korean Chemical Society
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• v.24 no.12
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• pp.1737-1741
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• 2003

Azo-functionalized calix[4]arenes as ionophores for chloride-selective electrode, 5,11,17,23-Tetra-tert-butyl-25,27-bis[(N,N-dimethyl-aniline-azo-phenylthioureido)ethyl]oxy-26,28-dihydroxycalix[4]arene (4a) and 5,11,17,23-Tetra-tert-butyl-25,27-bis[(N,N-dimethyl-aniline-azo-phenylthioureido)ethyl]oxy-26,28-dimethoxycalix[4]arene (4b) were synthesized. The PVC membrane electrode based on azo-functionalized calix[4]arene 4a with o-NPOE exhibits a linear stable response over a wide concentration range ($1.5{\times}10^{-4}-1.0{\times}10^{-1}$) with a slope of -52.0 mV/decade and a detection limit of log[$Cl^-$] = -4.02. This ionophore-based membrane exhibited improved selectivity for chloride anion compared with classical Hofmeister series.

• Applied Chemistry for Engineering
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• v.24 no.1
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• pp.49-54
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• 2013

We fabricated a composite carbon electrode to remove nitrate ions selectively from a mixed solution of anions. The electrode was fabricated by coating the surface of a carbon electrode with the nitrate-selective anion exchange resin (BHP55, Bonlite Co.) powder. We performed capacitive deionization (CDI) experiments on a mixed solution containing chloride, nitrate, and sulfate ions using a BHP55 cell constructed with the fabricated electrode. The removal of nitrate ions in the BHP55 cell was compared to that of a membrane capacitive deionization (MCDI) cell constructed with ion exchange membranes. The total quantity of ions adsorbed in BHP55 cell was $38.3meq/m^2$, which is 31% greater than that of MCDI cell. In addition, the number of nitrate adsorption in the BHP55 cell was $15.9meq/m^2$ (42% of total adsorption), 2.1 times greater than the adsorption in the MCDI cell. The results showed that the fabricated composite carbon electrode is very effective in the selective removal of nitrate ions from a mixed solution of anions.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2303-2308
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• 2009

A thiocyanate poly(vinyl chloride) (PVC) membrane electrode based on [1,2-bis(diphenylphosphino)ethane]dihalopalladium( II), [(dppe)$PdX_2$, X = Cl ($L^1$), X = I ($L^2$)] as active sensor has been developed. The diiodopalladium complex, [(dppe)$PdI_2](L^2$) displays an anti-Hofmeister selectivity sequence: $SCN^-\;>\;I^-\;>\;{ClO_4}^-\;>\;Sal^-\;>\;Br^-\;>\;{NO_2}^-\;>\;{HPO_4}^-\;>\;AcO^-\;>\;{NO_3}^-\;>\;{H_2PO_4}^-\;>\;{CO_3}^{2-}$. The electrode exhibits a Nernstian response (-59.8 mV/decade) over a wide linear concentration range of thiocyanate ($(1.0\;{\times}\;10^{-1}\;to\;5.0\;{\times}\;10^{-6}$ M), low detection limit ($(1.1\;{\times}\;10^{-6}$ M), fast response $(t_{90%}$ = 24 s), and applicability over a wide pH range (3.5∼11). Addition of anionic sites, potassium tetrakis[p-chlorophenyl] borate (KTpClPB) is shown to improve potentiometric anion selectivity, suggesting that the palladium complex may operate as a partially charged carrier-type ionophore within the polymer membrane phase. The reaction mechanism is discussed with respect to UV-Vis and IR spectroscopy. Application of the electrode to the potentiometric titration of thiocyanate ion with silver nitrate is reported.

• 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.

• Bulletin of the Korean Chemical Society
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• v.14 no.1
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• pp.123-127
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• 1993

New lipophilic Crown-4 compounds of 16-membered rings containing furan (neutral carrier,I), tetrahydrofuran (neutral carrier,II) and lithium complex of the latter (neutral carrier,III) have been synthesized and tested as the active sensors for lithium ion in poly(vinyl chloride) (PVC) membrane electrode, in the presence and absence of an anion excluder, tetrakis(4-chloro-phenyl)borate (KTClPB), 2-nitrophenyl phenyl ether (NPPE), tris(2-ethylhexyl)phosphate (TEHP), o-nitrophenyl octyl ether (NPOE), dioctyl adipate (DOA), bis(2-ethylhexyl)adipate (BEHA), di-n-octylphenyl phosphonate (DOPP) were used as plasticizing solvent mediators. The electrode response function had a nearly Nernstian slope of 54-61 mV per decade (25$^{\circ}$C) within the concentration range of $10^{-1}-10^{-4}$ M LiCl and the detection limits for all electrodes were ca. $5{\times}10^{-4}$ M. The response time of the electrode was faster at the higher lithium concentration and the response of the electrode was stable for longer than 6 months. The sensor membranes exhibit improved response times and increased lifetimes as compared to the system described earlier.