AJAC  Vol.5 No.2 , January 2014
Polyvinylbenzyl Tris-Aminodicarboxylate Microspheres for the Optical Sensing of Cu2+ Ions
Abstract: In this work, a tris(2-aminoethyl)aminodicaboxylate functionality was substituted for the chloride of polyvinyl-benzyl chloride (PVBC) which was lightly cross-linked (2%) with divinyl benzene. The resulting derivatized polymer microspheres were embedded in a hydrogel matrix of poly vinyl alcohol cross-linked with glutaraldehyde to produce a sensing membrane. The latter responded selectively to Cu2+ solutions of different concentration ranges (1 × 10-4 M to 1 × 10-6 M). The response is based on the interaction between the metal cations and the negatively charged deprotonated dicarboxylate functional group, which led to neutralization of the charges. As a result, an increase in the turbidity of the sensing membrane occurred which is attributed to a change in the refractive index of the derivatized polymer microspheres relative to that of the hydrogel. The change in the turbidity of the sensing membrane was measured as absorbance using a conventional spectrophotometer. It was found that Cu2+ ions bind to the aminodicarboxylated-polymer with a formation constant, Kf, of 1 × 105 M-1. SEM, Eds and IR analyses were performed on the aminodicarboxylated microspheres and their Cu2+ complex.
Cite this paper: Z. Shakhsher, I. Shqair, H. Qasim and I. Odeh, "Polyvinylbenzyl Tris-Aminodicarboxylate Microspheres for the Optical Sensing of Cu2+ Ions," American Journal of Analytical Chemistry, Vol. 5 No. 2, 2014, pp. 122-127. doi: 10.4236/ajac.2014.52015.

[1]   J. Moore, “Inorganic Contaminants of Surface Water,” Springer-Verlag, New York, 1991.

[2]   B. Carson, H. Ellis and J. MacCann, “Toxicology and Biological Monitoring of Metals in Humans,” Lewis Publishers, Chelsea, 1987.

[3]   D. Barceloux, “Copper,” Journal of Toxicology-Clinical Toxicology Vol. 37, No. 2, 1999, pp. 217-230.

[4]   H. C. Lin, Y. H. Chou and J. Yang, “Development of an Amino Carboxylic Acid-Modified Infrared Chemical Sensor for Selective Determination of Copper Ions in Aqueous Solutions,” Analytica Chimica Acta, Vol. 611, No. 1, 2008, pp. 89-96.

[5]   X. Zhang, X. Kong, W. Fan and X. Du, “Iminodiacetic Acid-Functionalized Gold Nanoparticles for Optical Sensing of Myoglobin via Cu2+ Coordination,” Langmuir, Vol. 27, No. 10, 2011, pp. 6504-6510.

[6]   A. Richter, G. Paschew, S. Klatt, J. Leinig, K. F. Arndt and H. J. P. Adler, “Review on Hydrogel-Based pH Sensors and Microsensors,” Sensors, Vol. 8, No. 1, 2008, pp. 561-581.

[7]   P. C. A. Jeronimo, A. N. Araujo, M. Conceicao and B. S. M. Montenegro, “Optical Sensors and Biosensors Based on Sol-Gel Films,” Talanta, Vol. 72, No. 1, 2007, pp. 13-27.

[8]   J. Y. Haras, D. Silvio, R. Rodrigues and M. Negri, “Chelating Electrodes as Taste Sensor for the Trace Assessment of Metal Ions,” Sensors and Actuators, Vol. 145, No. 2, 2010, pp. 726-733.

[9]   W. R. Seitz, M. T. Rooney, E. W. Miele, H. Wang, N. Kaval, L. Zhang, S. Doherty, S. Milde and J. Lenda, “Derivatized Swellable Polymer Microspheres for Chemical Transduction,” Analytica Chimica Acta, Vol. 400, No. 1-3, 1999, pp. 55-64.

[10]   O. Oktar, P. Caglar and W. R. Seitz, “Chemical Modulation of Themosensitive Poly(Nisopropyl acryamide) Microsphere Swelling: A New Strategy for Chemical Sensing,” Sensors and Actuators B, Vol. 104, No. 2, 2005, pp. 179-185.

[11]   Z. Shakhasher, I. Odeh, I. Rajabi and M. Khatib, “Optical Sensing Properties of Dithiocarbamate Functionalized Microspheres, Using a Polyvinyl Pyridine-Polyvinyl Benzyl Chloride Copolymer,” Sensors, Vol. 10, No. 10, 2010, pp. 8953-8962.

[12]   Z. Shakhasher, I. Odeh, S. Jabr and W. R. Seitz, “An Optical Chemical Sensor Based on Swellable Dicarboxylate Functionalized Polymer Microspheres for pH Copper and Calcium Determination,” Microchimica Acta, Vol. 144, No. 1-3, 2004, pp. 147-153.

[13]   I. Odeh, Z. Shakhsher, S. Jaber, M. Khatib and F. Rimawi, “An Optical Sensor Based on Polyvinyl Benzyl Malonate Cross-Linked with Divinyl Benzene Dispersed in a Hydrogel Membrane for Detection of Some Heavy Metals,” American Journal of Analytical Chemistry, Vol. 3, No. 4, 2012, pp. 283-287.

[14]   I. Odeh, S. Siam, M. Khatib and Z. Shakhasher, “An Optical Chemical Sensor Based on Polymer Swelling and Shrinking Using Dithiocarbamate-Polymer Microspheres,” Jordan Journal of Chemistry, Vol. 4, 2009, pp. 55-64.

[15]   K. Liu and H. F. Ji, “Detection of Pb2+ Using a Hydrogel Swelling Micro Cantilever Sensor,” Analytical Sciences, Vol. 20, No. 1, 2004, pp. 9-11.

[16]   J. H. Holtz and S. A. Asher, “Polymerized Colloidal Crystal Hydrogel Films as Intelligent Chemical Sensing Materials,” Nature, Vol. 389, No. 6653, 1997, pp. 829-832.

[17]   W. Li, H. Zhao, P. R. Teasdal, R. John and S. Zhang, “Synthesis and Characterization of a Polyacrylamide-Polyacrylic Acid Copolymer Hydrogel for Environmental Analysis of Cu and Cd,” Reactive and Functional Polymers, Vol. 52, No. 1, 2002, pp. 31-41.

[18]   M. Sonmez, “Synthesis and Characterization of Copper (II), Nickel (II), Cadmium (II), Cobalt (II), and Zinc (II) Complexes with 2-Benzoyl-3-hydroxy-1-naphthyl Amino-3-phenyl-2-propen-1-on,” Turkish Journal of Chemistry, Vol. 25, 2001, pp. 181-185.