Sains Malaysiana 48(12)(2019): 2649–2661

http://dx.doi.org/10.17576/jsm-2019-4812-06

Kajian Pengkompleksan Sebatian Bis-Tiourea dengan Ion Aluminium sebagai Ionofor dalam Pembangunan Sensor Ion Potensiometri

(Complexation Study of Bis-Thiourea Compound with Aluminium Ion as Ionophore

for Development of Potentiometric Ion Sensor)

KOOK SHIH YING, FATIMATUL AKMA AWANG NGAH, SUHAILA SAPARI, LEE YOOK HENG & SITI AISHAH HASBULLAH*

Centre for Advanced Materials & Renewable Resources, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

Received: 15 July 2019/Accepted: 25 September 2019

ABSTRAK

Sebatian terbitan tiourea telah banyak digunakan sebagai ionofor untuk merkuri, kadmium, kuprum, plumbum dan ferum (III) dalam bidang sensor kimia. Namun, penggunaan sebatian tiourea sebagai ionofor aluminium masih tidak banyak dilaporkan. Dalam kajian ini, satu sebatian bis-tiourea baharu 1,1'-[(metilazandiyil)bis(etana-2,1-diyil)]bis[3-(naftalen-1-yil)tiourea] ACH telah disintesis dan dicirikan dengan menggunakan spektroskopi 1H, 13C-resonans magnetik nukleus, spektroskopi inframerah dan spektrometri jisim. Untuk menilai dan menentusah kesesuaian sebatian ACH sebagai ionofor aluminium, kajian pengkompleksan antara ligan ACH dengan ion aluminium dalam komposisi pelarut H2O-EtOH yang berbeza melalui kaedah spektrofluorimetri telah dijalankan. Antara lima jenis komposisi pelarut, hanya pelarut 25%H2O-75%EtOH menunjukkan pembentukan kompleks. Nisbah stoikiometri bagi ion kompleks yang terbentuk antara ligan ACH dengan ion Al3+ ialah 3:1 dengan formula [Al(ACH)3]3+ dan nilai pKa yang diperoleh ialah 5.10±0.01. Struktur ion kompleks [ACH-Al]3+ dengan stokoimetri 1:1 juga telah dioptimumkan melalui pengiraan teori fungsi ketumpatan. Kedua-dua atom sulfur daripada kumpulan berfungsi bis-tiourea didapati merupakan tapak aktif yang terlibat dalam proses pengkompleksan dan geometri separa rongga ditunjukkan pada ligan ACH untuk berkoordinat dengan ion Al3+. Nilai negatif yang rendah pada tenaga pengikatan [ACH-Al]3+, iaitu -5.560 × 106 kJ/mol juga memaparkan kestabilan ion kompleks yang kuat. Sebagai kesimpulan, sebatian ACH adalah sesuai digunakan sebagai ionofor aluminium yang baharu dalam sensor ion potensiometri.

Kata kunci: 1,1'-[(metilazandiyil)-bis(etana-2,1-diyil)]bis[3-(naftalen-1-yil)tiourea]; kajian pengkompleksan; pencirian sebatian bis-tiourea; pengiraan teori fungsi ketumpatan

ABSTRACT

Thiourea compounds have been applied as ionophores for mercury, cadmium, copper, lead, and iron(III) in the field of chemical sensor. However, thiourea compound as aluminium ionophore has not yet been sufficiently explored. In this work, a new thiourea compound, 1,1'-[(methylazanediyl)bis(ethane-2,1-diyl)]bis[3-(naphthalen-1-yl)thiourea] had been synthesized and characterized by using 1H, 13C-nuclear magnetic resonance spectroscopy, Fourier-transform infrared spectroscopy and mass spectrometry. To assess and confirm the suitability of ACH compound as aluminum ionophore, complexation study of ACH ligand with aluminum ion in different solvent compositions of H2O-EtOH via spectrofluorimetic method had been carried out. Among the five types of solvent mixtures, the study indicated that only the solvent mixture of 25%H2O-75%EtOH showed the formation of complex. The stoichiometric ratio formed between ACH ligand and Al3+ ions was 3:1 with the formula of [Al(ACH)3]3+ and the pKa value was 5.10±0.01. The structure optimization of the complex ion [ACH-Al]3+ in the ratio of 1:1 was also conducted by using the density functional theory calculation. Both of the sulfur atoms in the functional group of bis-thiourea were found to be the main active sites for the complexation process and the ACH ligand showed a partial cavity geometry to coordinate with Al3+ ion. The low negative value of the binding energy [ACH-Al]3+, -5.560 × 106 kJ/mol also showed that the complex ion formed was strong and stable. In conclusion, ACH compound was suitable as a new aluminum ionophore for potentiometric ion sensor.

Keywords: 1,1'-[(methylazanediyl)bis(ethane-2,1-diyl)]bis[3-(naphthalen-1-yl)thiourea]; bis-thiourea compound characterization; complexation study; density functional theory

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