Sains Malaysiana 51(12)(2022): 4197-4208

http://doi.org/10.17576/jsm-2022-5112-26

Kajian Potensi Kompleks Kuprum(II)Tetraaza sebagai Ionofor Pengesan Ion Iodida

(Study on the Potential of Copper(II)Tetraaza Complex as Ionophore for Detecting Iodide Ion)

DEVIKA NOKARAJOO¹, SUHAILA SAPARI¹, NORAISYAH ABDUL KADIR JILANI¹, FAZIRA ILYANA ABDUL RAZAK², BOHARI YAMIN¹ & SITI AISHAH HASBULLAH^1,*

¹Jabatan Sains Kimia, Fakulti Sains dan Teknologi, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

²Jabatan Kimia, Fakulti Sains, Universiti Teknologi Malaysia, 81000 Skudai, Johor Darul Takzim, Malaysia

Received:10 May 2022/ Accepted:16 November 2022

Abstrak

Pengesanan anion toksik secara memilih adalah penting dalam pembangunan kimosensor kolorimetri. Kompleks kuprum(II)tetraaza (CuT) pertama kali dikaji sebagai ionofor dalam pengesanan anion iodida. Kajian pengesanan anion meliputi kajian kolorimetri, kajian pengikatan menggunakan Spektroskopi Utralembayung Boleh Nampak (ULBN) dan kajian komputeran melalui pengiraan Teori Fungsi Ketumpatan (DFT). Perubahan warna berlaku apabila kompleks CuT ditambah dengan anion iodida (I^-), tiosianat (SCN^-) dan sianat (CN^-) iaitu daripada ungu kepada kuning atau merah jambu. Nilai pemalar pengikatan, K_b untuk anion I^-, SCN^- dan CN^- masing-masing adalah 160.7, 27.1 dan 21.6 M^-1 membuktikan kompleks CuT mempunyai interaksi yang kuat terhadap anion I^-. Nisbah mod pengikatan antara CuT dengan anion I^-, SCN^-, CN^- adalah 1:2 berdasarkan graf keseimbangan. Kajian interferen menunjukkan CuT mempunyai keterpilihan yang lebih tinggi terhadap anion I^-. Pengiraan DFT membuktikan poli(n-butil akrilat), [poli(nBA)] sesuai digunakan sebagai matriks pemegunan kompleks CuT. Nilai tenaga pengikatan (E_pengikatan) antara kompleks CuT terpegun poli(nBA) dengan anion iodida yang lebih rendah iaitu -1613.424673 eV berbanding dengan kompleks CuT dengan anion I^- sahaja iaitu -1567.056909 eV menunjukkan pembentukan ikatan yang lebih kuat antara kompleks CuT terpegun poli(nBA) dengan anion I^-. Sensor optik ini dapat difabrikasikan berasaskan kompleks CuT sebagai ionofor dipegunkan menggunakan poli(nBA) bagi pembangunan sensor ion I^-.

Kata kunci: Anion iodida; DFT; kolorimetri; kuprum(II)tetraaza; ULBN

Abstract

Selective detection of toxic anions is important in developing colorimetric chemical sensors. Copper(II)tetraaza (CuT) complex is used for the first time as an ionophore in detecting iodide anions. The anion detection studies include colorimetric studies, binding studies using ultraviolet-visible spectroscopy (ULBN), and Density Functional Theory (DFT) calculation. Visible color changes occurred when the CuT complex was added to the iodide (I^-), thiocyanate (SCN^-), and cyanate (CN^-) anion from purple to yellow or pink. The binding constant, K_b values for I^-, SCN^-, and CN^- anions were 160.7, 27.1, and 21.6 M^-1, respectively, demonstrating the strongest binding interaction towards I^- anion. The binding mode ratio between CuT and anions (I^-, SCN^-, CN^-) is 1:2 from the equilibrium graph. Interference studies show CuT has a higher selectivity towards the I^- anion. DFT calculations showed that poly(n-butyl acrylate), [poly(nBA)] is suitable to be used as a solid support for CuT complex. A lower binding energy (binding) value of -1613.424673 eV for CuT complex [immobilized with poly(nBA)] with I^- anion compared to CuT complex with I^- anion alone of -1567.056909 eV indicates the formation of strong bond between CuT complex [immobilized with poly(nBA)] with I^- anion. An optical sensor can be fabricated on CuT complex as an ionophore and immobilized using poly(nBA) to develop an I^- ion sensor.

Keywords: Colorimetric; copper(II)tetraaza; DFT; iodide anion; ULBN

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^*Corresponding author; email: aishah80@ukm.edu.my