• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.836-841
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• 1994

The polymer matrix effect on the selectivity, response rate and reproducibility for coextraction type anion-selective optode membranes were investigated with DOA-plasticized PVC, PVC/hydroxylated PVC, PU/hydroxylated PVC and DOS-plasticized CTA matrices. Optode membranes were prepared with TDMACl and ETH2412 dissolved in one of the four solvent polymeric matrices. The PU/hydroxylated PVC and PVC-based membranes have almost the same selectivity coefficients, while the CTA-based membrane is more selective toward lipophilic anions. The membrane with PU/hydroxylated PVC adhered strongly to a glass surface, and showed highly reproducible and relatively rapid response. Very poor adhesion of PVC/hydroxylated PVC and CTA-based membranes limited the usability of those membranes as sensor components. Based on these results, and considering the biocompatibility for clinical samples, the optode made with PU/hydroxylated PVC was applied to determine the thiocyanate ion in human saliva. The results obtained with this simple device were comparable to those with rather complicated ISE methods.

• Bulletin of the Korean Chemical Society
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• v.16 no.3
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• pp.221-226
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• 1995

A method for determining nitrate in post treatment chromium plating solutions with PVC-based nitrate-selective electrodes is described. PVC-based nitrate-selective membranes which contain TDMANO3 ion-exchanger in PVC/NPOE, PVC/DOA or PVC/DBP matrices, and a commercially available Corning electrode (No. 476134) have been compared in respect of their detection limits, response slopes, selectivities at various pHs, and dynamic response to the hydrochromate ion in basic condition. The PVC/DBP/TDMANO3 membrane electrode was chosen as the ISE detector for the determination of nitrate in the presence of hydrochromate interference. The amount of nitrate in real post treatment chromium plating solution could be determined successfully with this electrode in both static and flow-injection measurements when the sample was properly diluted with an alkaline buffer.

• Analytical Science and Technology
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• v.9 no.1
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• pp.78-83
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• 1996

Hydrogen ion-selective membrane electrodes based on tribenzylamine(TBA), tetrabenzylethylenediamine(TBEDA), pentabenzyldiethylenetriamine(PBDETA) as neutral carriers were shown good selectivity and linearity in the range of pH 1~pH 9, pH 2~pH 12, pH 4~pH 12. The pH selectivity of this membrane electrodes have nothing relation with the numbers of unshared electron pair in TBA, TBEDA, PBDETA and were shown a slope of 43.8mV/pH, 46.9mV/pH, 43.6mV/pH respectively. The selectivity coefficients were determined by the separate solution method for alkali($Li^+$, $Na^+$, $K^+$), alkaline earth metal($Ba^{2+}$, $Ca^{2+}$, $Mg^{2+}$) and transition metal ions($Mn^{2+}$, $Co^{2+}$, $Ni^{2+}$, $Cu^{2+}$, $Zn^{2+}$). The membrane electrode based on TBEDA appeared the best results as hydrogen ion electrode.

• Journal of the Korean Chemical Society
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• v.46 no.5
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• pp.407-411
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• 2002

A method to determine lead ion in aqueous media using an optical sensor loaded on a fluorescent optode membrane incoporating a metal ion-selective ionophore, a proton-selective chromoionophore and lipophilic anionic sites has been studied. The effects of pH and thickness of membrane on the fluorescence intensity were investigated. The effects of foreign ions such as $Na^+$, $K^+$, $Mn^{2+}$ and $Zn^{2+}$ on the determination of lead ion were also studied. The linear range in the calibration curve for the determination of lead ion was found to be 5.0${\times}10^-7$ to 5.0${\times}$$10^-3$M and the correlation coefficient in this range was -0.99107 under the optimal experimental conditions. The relative standard deviation of the blank signals was 3.0% and the detection limit of lead ion was 5.0${\times}$$10^-9$M.

• Bulletin of the Korean Chemical Society
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• v.19 no.2
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• pp.207-211
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• 1998

Potentiometric characteristics of DOS plasticized PVC-based membranes containing upper-rim calix[4]crown neutral carrier to various metal cations and protonated alkylamines have been examined. Although the calix[4]crown-based membrane electrodes exhibited substantial emf responses to alkali and alkaline earth metal cations, their high detection limits (- log[Cs+]=4.5) and sub-Nernstian response slopes (48 mV/pCs+) to the most selective cation, cesium, indicate that the metal cation complexing ability of calix[4]crown is much weaker than that of macrocyclic crown ethers. However, the calix[4]crown-based membrane electrodes exhibited near-Nernstian response slopes (56 mV/decade for hexylNH3+) with low detection limits (log[hexylNH3+]= - 6.7) to most alkylammonium ions compared to those of blank (DOS plasticized PVC membrane with no ionophore) or crown ether-based membranes. While the selectivity patterns of blank and crown ether-based membranes are determined primarily by the lipophilicity of alkylammonium ions, the membranes doped with calix[4]crown ionophore could effectively discriminate the steric shapes of nonpolar alkyl groups of alkylammonium ions.

• Journal of the Korean Chemical Society
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• v.28 no.2
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• pp.86-94
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• 1984

The single crystal ion-selective electrode,$ {\beta}-Ag_3SI/PVC-THF $membrane electrode has showed a linear potential response to the activities of iodide ion (10-1${\sim}$10-7M). The $ {\beta}-Ag_3SI$ membrane electrode was compared with AgI/PVC-THF membrane and copper metal plate membrane electrodes. In order to measure the selectivity coefficient of the electrodes toward $Cl^-$ and $Br^-$, the separation and mixed solution method were employed. The potential-time curve was obtained by the usual immersion technique and pH effect was also examined. The orders of selectivity for $Br^-$, $Cl^-$ and stability of response time are ${\beta}-Ag_3SI/PVC-THF $membrane > AgI/PVC-THF membrane > copper metal plate membrane. These electrodes could be used as indicating electrodes in the potentiometric titration of a single halide and mixed halides with the standard solution of silver nitrate.

• Bulletin of the Korean Chemical Society
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• v.27 no.10
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• pp.1581-1586
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• 2006

A La (III) ion-selective membrane sensor has been fabricated from poly vinyl chloride (PVC) matrix membrane, containing 3-hydroxy-N'-(pyridin-2-ylmethylene)-2-naphthohydrazide (HPMN) as a neutral carrier, potassium tetrakis (p-chlorophenyl) borate (KTpClPB) as an anionic excluder and ortho-nitrophenyloctyl ether (NPOE) as a plasticizing solvent mediator. The effects of membrane composition and pH as well as the influence of the anionic additive on the response properties were investigated. The sensor with 30% PVC, 62% solvent mediator, 6% ionophore and 2% anionic additive, shows the best potentiometric response characteristics. It displays a Nernstian behavior (19.2 mV per decade) across the range of $1.0{\times}10^{-2}-1.0{\times}10^{-7}$ M. The detection limit of the electrode is $7.0{\times}10^{-8}$ M ($\sim$10 ng/mL) and the response time is 15 s from $1.0{\times}10^{-2}$ up to $1.0{\times}10^{-4} $M and 30 s in the range of $1.0 {\times}10^{-5}-1.0{\times}10^{-7}$ M. The sensor can be used in the pH values of 3.0-9.0 for about seven weeks. The membrane sensor was used as an indicator electrode in the potentiometric titration of lanthanum ions with EDTA. It was successfully applied to the lanthanum determination in some mouth wash preparations.

• Membrane Journal
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• v.3 no.3
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• pp.126-135
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• 1993

Perchlorate ion-selective PVC membrane electrode responsive to $10^{-6}M$ was developed by incorporating the ion-pair complex of perchlorate with the quaternary ammonium salts as a active material. The effect of chemical structure, the content of active material, the kinds of plasticizers, and the membrane thickness on the electrode characteristics such as the linear response range and Nernstian slope of the electrode were studied. With the results, the useful pH range and the selectivity coefficients to various interfering anions were compared and investigated. It was obtained that the effect of the chemical structure of an active material on the electrode characteristics was improved with increasing the alkyl chain length of the quarternary ammonium salts in the ascending order of Aliquat 336P, TOAP, TDAP, and TDDAP. The electrode characteristics was improved with the decrease of the active material content below the optimum membrane composition, and DBP was the best as a plasticizer. The optimum membrane composition was 9.09wt% of TDDAP, 30.3wt% of PVC, and 60.6wt% of ptasticizer(DBP). And the optimum membrane thickness was0.45mm at this composition. Under the above condition, thelinear response ranger was $10^{-1}~1.2 {\times} 10^{-6}M$, and the detection limit was $5.1{\times}10^{-7}M$ with the Nernstian slope of 57mV/decade of activity of perchlorate ion. The electrode potential was stable within the pH range from 4 to 11. The selectivity coefficient was as shown below : $SCN^->I^->NO_3^->Br^->ClO_3^->F^->Cl^->SO_4^{2-}$

• Analytical Science and Technology
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• v.9 no.3
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• pp.270-278
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• 1996

Response mechanism for the chloride-selective membrane doped with 5, 10, 15, 20-tetraphenyl(porphyrinato)manganase(III) chloride(Mn(TPP)Cl) in PVC/DOS matrix is proposed by examining the visible spectra of the corresponding optode membrane. The visible spectra of Mn(TPP)Cl-doped membrane placed in aqueous solution show that the chloride ligand is easily replaced with water molecule. When other halogen ions, such as $F^-$, $Br^-$ and $I^-$, are added to the sample solution, they replace the water ligand, exhibiting distinctive change in the Soret band of Mn(TPP). On the other hand, bulky anions, such as SCN and salicylate, do not form a bond with the central metal. These results suggests that the potentiometric response of Mn(TPP)-based membrane results either from the ligand exchange (water with halides) at the central metal or from the counter ion exchange (chlorides with bulky lipophilic anions) around the positively charged porphyrin molecule in membrane phase. It was also noted that both hydration enthalpies of anions and their binding constants to Mn(TPP) play critical role in determining the potentiometric selectivity pattern of the membrane.

• Journal of the Korean Electrochemical Society
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• v.11 no.1
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• pp.59-63
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• 2008

Poly (vinylchloride) (PVC) membrane electrodes based on neutral carrier, tetracycline was prepared as an active sensor for Hg(II) ion, and tested in different contents of the potassium tetrakis (4-chlorophenyl) borate (KTpClPB) as lipophilic salt. Bis (2-ethylhexyl) sebacate (DOS), bis(l-butylpentyl) adipate (BBPA), 2-nitrophenyl octyl ether (NPOE) and dibutyl phthalate (DBP) were used as diverse plasticizing solvent mediators. This electrode shows excellent potentiometric response characteristics and display good linearity with log $[Hg^{+2}]$ versus EMF response, over a range of concentrations between $10^{-7}$ and $10^{-3}M$. With 30.8mV/decade Nernstian slope, the detection limit was $6.9{\times}10^{-9}M$ and the response time was less than 20s. The proposed electrode yields very good selectivity for mercury (II) ion over many cations such as alkali, alkaline earth, transition and heavy metal ions. And it shows a very stable potential values in a wide pH range. This reliable electrode prepared was kept at least a month without considerable alteration in their response to Hg (II) ion.