A Silver Ion Potentiometric Sensor Based on a Synthesized 1,3-Benzocrown Macrocyclic Diamide as Neutral Carrier


Rey Y. Capangpangana,c, Florian R. del Mundoa,b, Susan D. Arcoa,b,
Jose S. Solisa, and Rofeamor P. Obenaa,d*

aInstitute of Chemistry, University of the Philippines, Quezon City, Philippines
bNatural Sciences Research Institute, University of the Philippines, Quezon City, Philippines
cCaraga State University, Ampayon, Butuan City, CARAGA Philippines
dInstitute of Chemistry, Academia Sinica, Nangang, Taipei, Taiwan

corresponding author: This email address is being protected from spambots. You need JavaScript enabled to view it.



A synthesized benzo-crown macrocycle, 1,15-diaza-3,4;12,13-dibenzo-5,8,11-trioxacyclooctadecane-2,14-dione (1,3-MDA), was employed as an ionophore in the fabrication of polymeric ion-selective electrodes (ISE) for silver ion. The electrode membrane ingredients consisting of PVC/Plasticizer (o-NPOE) ratio of 0.94 and ionophore/additive ratio of 2.0 exhibited near Nernstian response of 57.75 mV/decade activity of Ag+ over a linear concentration range of 10-6 M to 10-3 M (R2 = 0.9921). The dynamic response time of this electrode was ~2 min at pH range of 3-9. The sensor has a limit of detection (LOD) of 6.32 x 10-7 M, and was stable for at least one month. Initial investigation on the applicability of this new ISE for the detection of silver ions in photographic wastewater sample and comparison of its performance with conventional method (Atomic Absorption Spectroscopy) were also reported.



Continuous interest has been focused on the design and synthesis of new functionalized macrocycles (Faridbod et al. 2007) for the selective detection of metal ions and its use as neutral carrier for ion-selective electrodes. After the discovery of valinomycin as ion carrier for K+ ion, neutral organic compounds such as crown ethers (Ganjali et. al 2003), macrocyclic amides (Malinowska 2000) as well as macrocyclic calixarene compounds (Parsa et. al. 2007) have been used as ion carriers or ionophores for many polymeric membrane electrodes. Various macrocyclic diamides have been designed and tested for their utility as neutral ionophores in the construction of PVC-based . . . . . . . . . . . . . . . .





BARSTOW LE, HRUBY VJ. 1971. Simple Method for the Synthesis of Amides. J Org Chem 36(9): 1305-06.

BUCK R, LINDNER E. 1994. Recommendations for Nomenclature of Ion-Selective Electrodes. Pure and Applied Chem 66(12): 2527-36.

CRAGGS A, MOODY GJ, THOMAS JDR. 1974. PVCMatrix Ion Selective Electrodes. J Chem Educ 51(8): 541-544.

EAST BW, BODDY K, WILLIAMS ED, MACINTYRE D, MCLAY ALC. 1980. Silver Retention, Total Body Silver And Tissue Silver Concentrations In Argyria Associated With Exposure To An Anti-smoking Remedy Containing Silver Acetate. Clinical and Experimental Dermatology 5: 305-311.

FURCHNER JE, RICHMOND CR, DRAKE GA. 1968. Comparative Metabolism of Radionuclides in Mammals - IV. Retention of Silver-110m in the Mouse, Rat, Monkey, and Dog. Health Physics 15: 505-514.

GADZEKPO VPY, CHRISTIAN GD. 1984, Determination of Selectivity Coefficients of Ion-Selective Electrodes by a Matched-Potential Method. Analytica Chimica Acta 164: 279-282.

GREENE RM, SU WPD. 1987. Argyria. American Family Physician 36: 151-154.

GUPTA VK, CHAUAN DK, SAINI VK, AGARWAL S, ANTONIJEVIC MM, LANG H. 2003. A Porphyrin Based Potentiometric Sensor for Zn2+ Determination. Sensors 3: 223-235.

LANSDOWN AB. 2006. Silver In Health Care: Antimicrobial Effects And Safety In Use. Current Problems in Dermatology 33: 17-34.

LINDNER, E. UMEZAWA, Y. 2008. Performance Evaluation Criteria for Preparation and Measurement of Macro- and Microfabricated Ion-Selective Electrodes, Pure Appl. Chem. 80(1): 85-104.

MAHAJAN RK, SOOD P. 2007. Novel Copper(II)- Selective Electrode Based on 2,2’:5’,2”-Terthiophene in PVC Matrix. International J Electrochem Science 2: 832-847.

PARSA M, YAFLIAN MR, MATT D. 2007. A New Silver (I) Potentiometric Senosr Based on a Calix[4]arene substituted at the Narrow Rim by Amide/Phosphoryl Groups, J Chin Chem Soc 54: 1529-34.

PEARSON RG. 1963. Hard and Soft Acids and Bases. J Am Chem Society 85(22): 3533-39.

SHAMSIPUR M, KAZEMI SY, NIKNAM K, SHARGHI H. 2002. A New PVC-Membrane Electrode Based on a Thia-Substituted Macrocyclic Diamide for Selective Potentiometric Determination of Silver Ion. Bull Korean Chem Society 23(1): 53-58.

SHAMSIPUR M, POURSABERI T, ROUHANI S, NIKNAM K, SHARGHI H, GANJALI MR. 2001. Cobalt (II)-Selective Membrane Electrode Based on a Recently Synthesized Benzo-Substituted Macrocyclic Diamide. Analytical Sciences 17(9): 1049-54.

SHAMSIPUR M, KAZEMI SY, SHARGHI H. 2007. Design of a Selective and Sensitive PVC-Membrane Potentiometric Sensor for Strontium Ion Based on 1,10-diaza-5,6-benzo-4,7-dioxacyclohexadecane-2,9- dione as a Neutral Ionophore Sensors 7: 438-447.

SHAMSIPUR M, SOLEYMANPOUR A, AKHOND M, SHARGHI H, MASSAH AR. 2002. Uranyl-selective PVC Membrane electrodes based on some recently synthesized benzo-substituted macrocyclic diamides. Talanta 58: 237-246.

SINGH LP, BHATNAGAR JM. 2003. PVC Based Selective Sensors for Ni2+ Ions Using Carboxylated and Methylated Porphine. Sensors 3(9): 393-403.

SZIGETI Z, VIGASSY T, BAKKER E, PRETSCH E. 2006. Approaches to Improving the Lower Detection Limit of Polymeric Membrane Ion-Selective Electrodes. Electroanalysis 18(13-14): 1254-65.

UMEZAWA Y, UMEZAWA K, SATO H. 1995. Selectivity Coefficients for Ion-Selective Electrodes:Recommended Methods for Reporting pot KA,B Values. Pure Applied Chem 67(3): 507-518.

WAGNER PA, HOEKSTRA WG, GANTHER HE. 1975. Alleviation of Silver Toxicity by Selenite in the Rat in Relation to Tissue Glutathione Peroxidase 1,2 (38697). In: (3rd Edn ed.) Proceedings of the Society for Experimental Biology and Medicine 148: 1106-10.