Malaysian
Journal of Analytical Sciences Vol 20 No 1 (2016): 73 - 84
THEORETICAL
AND EXPERIMENTAL INVESTIGATION OF PYRIDYL-THIOUREA DERIVATIVES AS IONOPHORES
FOR Cu(II) ION DETECTION
(Kajian Teori dan
Eksperimen bagi Terbitan –Terbitan Piridil-Tiourea Sebagai Ionofor untuk
Pengesanan Ion Cu(II))
Wan M. Khairul1*, Mohd Faizuddin Abu Hasan1, Adibah
Izzati Daud1,3,
Hafiza Mohamed
Zuki2, Ku Halim Ku bulat1, Maisara Abdul Kadir1
1School of Fundamental Science
2School of Marine Science and Environment
Universiti
Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia
3Faculty of Engineering Technology,
Universiti
Malaysia Perlis (UniMAP),
Aras
1, Blok S2, Kampus UniCITI Alam, Sungai Chuchuh, 02100 Padang Besar, Perlis,
Malaysia
*Corresponding author: wmkhairul@umt.edu.my
Received: 5
November 2015; Accepted: 27 December 2015
Abstract
Copper (II) ion chemical sensors based
on pyridine-thiourea derivatives; N-pyridyl-N’-(biphenyl-4-carbonyl)thiourea (L1), and N-pyridyl-N’-(3,5-dimethyoxybenzoyl)thiourea
(L2) were synthesised,
characterised, and studied as ionophores in the form of thin-films PVC
membranes. The ionophores exhibited good responses towards copper (II) ion over
the concentration range of 2 x 10-4 to 10 x 10-4 M with a
limit of detection 1.34 x 10-5 to 1.48 x 10-5 M. The
proposed sensors L1 and L2 revealed good performance in term of
reproducibility and regeneration of the ionophores with low relative standard
deviation (RSD) values 4.17 % and 2.74 % respectively. Besides, quantum
chemical calculation performed using Gaussian 09 program indicated the oxygen
(O) atom from carbonyl moiety (C=O) was the most favourite reactive site and
mainly responsible for ionophore– Cu(II) interaction. The obtained data
revealed pyridine-thiourea derivatives offered great potential as ionophore for
the detection of Cu (II) ion.
Keywords: pyridine,
thiourea, metal sensor, density functional theory, spectroscopic
Abstrak
Pengesan kimia bagi ion kuprum (II)
berasaskan terbitan piridil-tiourea; N-piridil-N’-(bifenil-4-karbonil)tiourea (L1), and N-piridil-N’-(3,5-dimetoksibenzoil)tiourea
(L2) telah disintesis, dicirikan,
dan dikaji sebagai ionofor dalam bentuk membran-membran PVC filem nipis.
Ionofor – ionofor tersebut menunjukkan tindak balas yang baik terhadap ion
kuprum (II) dalam julat kepekatan 2 x 10-4 to 10 x 10-4 M
dengan had pengesanan 1.34 x 10-5 sehingga 1.48 x 10-5 M.
Pengesan L1 dan L2 yang dicadangkan ini menunjukkan prestasi yang baik dari segi
kebolehkeluaran semula dan penjanaan semula
bagi ionofor – ionofor tersebut dengan nilai sisihan relatif piawaian yang
rendah iaitu masing – masing 4.17% dan 2.74%. Selain itu, pengiraan kuantum
kimia dilakukan dengan menggunakan program Gaussian 09 yang menyatakan bahawa
atom oksigen (O) daripada moiti karbonil (C=O) adalah kawasan paling reaktif
dan selalunya terlibat dalam interaksi ionofor-Cu (II). Data yang diperolehi
menyatakan terbitan piridil-tiourea menawarkan potensi yang bagus sebagai
ionofor bagi pengesanan ion Cu (II).
Kata
kunci: piridina,
tiourea, pengesan logam, teori fungsi ketumpatan, spektroskopi
References
1. Kaya, E. D., Söyüt, H. and
Sükrü, B. (2013). Carbonic anhydrase activity from the gilthead sea bream
(Sparus aurata) liver: The toxicological effects of heavy metals. Environmental Toxicology and Pharmacology, 36: 514 – 521.
2. Olawoyin, R., Oyewole, S.
A. and Grayson, R. L. (2012). Potential risk effect from elevated levels of
soil heavy metals on human health in the Niger delta. Ecotoxicology and
Environmental Safety, 85: 120 – 130.
3. Viswanathan, K. (2012).
Utilizing a tripeptide conjugated fluorescent hybrid nanoparticles as a
fluorescence sensor for the determination of copper ions. Sensors and Actuators A, 175: 15 –18.
4. Lin, Q., Chen, P., Liu, J.,
Fu, Y-P., Zhang, Y-M. and Wei, T-B. (2013). Colorimetric chemosensor and test
kit for detection copper (II) cations in aqueous solution with specific
selectivity and high sensitivity. Dyes
and Pigments, 98: 100 –105.
5. Aziz, H. A., Adlan, M. N.
and Ariffin, K. S. (2008). Heavy metals (Cd, Pb, Zn, Ni, Cu, Cr (III)) removal
from water in Malaysia: Post treatment by high quality limestone. Bioresource Technology, 99: 1578 –1583.
6. Bridgeman, J., Baker, A.,
Brown, D. and Boxall, J. B. (2015). Portable LED fluorescence instrumentation
for the rapid assessment of potable water quality. Science of the Total Environment, 524: 338 –346.
7. Firooz, A. L., Ensafi, A.
A., Karimi, K. and Khalifeh, R. (2013). Specific sensing of mercury (II) ions
by an optical sensor based on a recently synthesized ionophore. Sensors and Actuator B, 185: 84 – 90.
8. Pradeep, T. (2009). Noble
metal nanoparticles for water purification: a critical review. Thin Solid Films. 517(24): 6441 – 6478.
9. Bakker E, Simon W. (1992).
Selectivity of ion-sensitive bulk optodes. Analytical
Chemistry, 64(17):1805 –1812.
10. Saeed, A., Shaheen, U.,
Hameed, A. and Naqvi, S. Z. H. (2009). Synthesis, characterization and
antimicrobial activity of some new 1-(fluorobenzoyl)-3-(fluorophenyl)thioureas.
Journal of Fluorine Chemistry, 130:
1028 –1034.
11. Duan, X. –E., Wei, X. –H.,
Tong, H. –B., Bai, S. –D., Zhang, Y. –B. and Liu, D. –S. (2011).
Ferrocene-modified pyrimidinyl acyl-thiourea derivatives: Synthesis, structures
and electrochemistry. Journal of Molecular
Structure, 1005: 91 – 99.
12. Karipcin, F., Atis, M.,
Sariboga, B., Celik, H. and Tas, M. (2013). Structural, spectral, optical and
antimicrobial properties of synthesized 1-benzoyl-3-furan-2-ylmethyl-thiourea. Journal of Molecular Structure, 1048: 69
–77.
13. Arslan, N. B., Kazak, C.
and Aydın, F. (2012).
N-(4-nitrobenzoyl)-N’-(1,5-dimethyl-3-oxo-2-phenyl-1H-3(2H)-pyrazolyl)-thiourea
hydrate: synthesis, spectroscopic characterization, X-ray structure and DFT
studies. Spectrochimica
Acta Part A-Molecular and Biomolecular Spectroscopy, 89: 30–38.
14. Rahamathullah, R., Khairul,
W. M., Salleh, H., Adli, H. K., Isa, M. I. N. and Tay, M. G. (2013). Synthesis.
Characterization and Electrochemical Analysis of V-Shaped Disubstituted
Thiourea-Chlorophyll Thin Film as Active Layer in Organic Solar Cells. International Journal of Electrochemical
Science, 8: 3333 – 3348.
15. Zhang, L. –Y., Yuan, Y.
–F., Hu, A. –G., Wang, J. –T. and Sun, J. (2001). Synthesis and molecular
structure of a novel ferrocene-containing macrocyclic acyl thiourea derivative.
Journal of
Organometallic Chemistry, 637 – 639: 204 – 208.
16. Saeed, A., Erben, M. F.,
Abbas, N. and Flӧrke, U. (2010). Synthesis, crystal X-ray diffraction
structure, vibrational properties and quantum chemical calculations on
1-(4-(4-Fluorobenzamido)phenyl)-3-(4-fluorobenzoyl)thiourea. Journal of Molecular Structure, 984: 240
– 245.
17. Tan, S. S., Al-abbasi, A.
A., Mohamed Tahir, M. I. and Kassim, M. B. (2014). Synthesis, structure and
spectroscopic properties of cobalt(III) complexes with
1-benzoyl-(3,3-disubstituted)thiourea. Polyhedron,
68: 287–294.
18. Atiş, M., Karicin, F.,
Sariboga, B., Tas, M. and Celik, H. (2012). Structural, antimicrobial and
computational characterization of
1-benzoyl-3-(5-chloro-2-hydroxyphenyl)thiourea. Spectrochimica Acta Part A-Molecular and
Biomolecular Spectroscopy, 98: 290 – 301.
19. Saeed, A., Erben, M. F. and
Bolte, M. (2013). Synthesis, structural and vibrational properties of
1-(adamantine-1-carbonyl)-3-halophenyl thioureas. Spectrochimica Acta Part A-Molecular and
Biomolecular Spectroscopy, 102: 408 – 413.
20. Koca, İ., Özgür, A.,
Coşkun, K. A. and Tutar, Y. (2013). Synthesis and anticancer activity of acyl
thioureas bearing pyrazole moiety. Bioorganic & Medicinal Chemistry, 21(13), 3859 – 3865.
21. Estévez-Hernández, O.,
Otazo-Sánchez, E., Hidalgo-Hidalgo de Cisneros, J. L., Naranjo-Rodríguez, I.,
and Reguera, E. (2005). A Raman and infrared study of
1-furoyl-3-monosubstituted and 3,3-disubstituted thioureas. Spectrochimica Acta Part
A-Molecular and Biomolecular Spectroscopy, 62(4-5): 964 –971.
22. Vinithra, G., Suganya, S.
and Velmathi, S. (2013). Naked eye sensing of anions using thiourea based
chemosensors with real time application. Tetrahedron
Letter, 54(41): 5612 –5615.
23. Khairul, W. M., Yusof, M.
F., Rahamathullah, R., Daud, A. I., Jasman, S. M., Hasan, M. F. A., Salleh, H.,
Adli, H. K. and Tay, M. G. (2013). Single Molecule Thin Film Featuring
Disubstituted Thiourea (TU) Doped with Chlorophyll as Potential Active Layer in
Photovoltaic Cell. International Journal
of Electrochemical Science, 8: 8175 – 8190.
24. Farhan, H. M. (2014).
Preparation and investigation of complexes (bisazo)-imidazole with Co (II) and
Cu (II). World Science Research Journals,
2(2): 26 – 34.
25. Hasali, N. H. M., Omar, M.
N., Zuberdi, A. M. and AlFarra, H. Y. (2013). Biotransformation of ethyl
p-methoxycinnamate from Kaempferia galanga L. using Aspergillus niger. International Journal of Bioscience,
3(7): 148 –155.
26. Koleva, B. B., Kolev, T.,
Lamshöft, M., Mayer-Figge, H., Sheldrick, W. S. and Spiteller, M. (2009).
Synthesis, spectroscopic and structural elucidation of
1-butyl-4-[2-(3,5-dimethoxy-4-hydroxyphenyl)ethenyl)]pyridinium chloride
tetrahydrate. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 74(5): 1120 –1126.
27. Sinha, S., Mandal, B. and
Chandrasekaran, S. (2000). Selective para metalation of unprotected 3-methoxy
and 3 , 5-dimethoxy benzoic acids with n- butyl lithium – potassium tert
-butoxide ( LIC – KOR ): Synthesis of 3 , 5-dimethoxy-4-methyl benzoic acid. Tetrahedron Letter, 41: 3157–3160.
28. Yusof, M. S. M., Jusoh, R.
H., Khairul, W. M. and Yamin, B. M. (2010). Synthesis and characterisation a
series of N-(3,4-dichlorophenyl)-N′-(2,3 and 4-methylbenzoyl) thiourea
derivatives. Journal of Molecular
Structure, 975(1-3): 280 – 284.
29. Aydın, M., Ünal, B., Esat,
B., Baykal, a., Karaoğlu, E., Toprak, M. S. and Sözeri, H. (2012). Synthesis,
magnetic and electrical characteristics of poly(2-thiophen-3-yl-malonic
acid)/Fe3O4 nanocomposite. Journal of Alloys and Compounds, 514: 45 – 53.
30. Zhang, X. H., Wang, L. Y.,
Zhan, Y. H., Fu, Y. I., Zhai, G. H. and Wen, Z. Y. (2011). Synthesis and
structural studies of
4-[(5-methoxy-1H-indole-3-yl)-methylene]-3-methyl-isoxazole-5-one by X-ray
crystallography, NMR spectroscopy, and DFT calculations. Journal of Molecular Structure, 994: 371 –378.
31. Koch, K. R., Hallale, O.,
Bourne, S. A., Miller, J. and Basca, J. (2001). Self-assembly of 2:2
metallomacrocyclic complexes of Ni(II) and Pd(II) with
3,3,3’,3’-tetraalkyl-1,1’-isophthaloylbis(thioureas). Crystal and molecular
structures of cis-[Pd(L2-S,O)]2 and the adducts of the
corresponding Ni(II) complexes: [Ni(L1-S,O)(pyridine)2]2
and [Ni(L1-S,O)(4-dimethylaminopyridine)2]2. Journal of Molecular Structure, 561: 185
–196.
32. Marquez, H., Loupy, A.,
Calderon, O. and Pérez, E. R. (2006). An eco-friendly protocol for synthesis of
thiourea derivatives: 1-benzoyl-3-benzylguanidine and
1-benzoyl-3-benzyl-O-ethylisourea. A possible non-purely thermal microwave
assisted reaction. Tetrahedron,
62(11): 2616 – 2621.
33. Khairul, W. M., Isa, M. I.
N., Samsudin, A. S., Adli, H. K. and Ghazali, S. R. (2014). Conductive
biodegradable film of N-octyloxyphenyl-N’-(4-methylbenzoyl)thiourea. Bulletin of Material Science, 37(2): 357
– 369.
34. Jain, P. S., Khatal, R. N.
and Surana, S. J. (2011). Spectrophotometric Determination of Amodiquine in
Bulk and in Pharmaceutical Formulation. Research
Journal of Pharmaceutical, Biological and Chemical Sciences, 2: 120 –127.
35. Rohini, P.,
Madhusudhanareddy, I., Gupta, A., Lokeswara, B. V. and Sundharani, G. (2011).
Method development and validation for estimation of nevirapine from tablets by
RP-HPLC. International
Journal of Pharmaceutics, 1(1): 29 –33.
36. Wilson, D., Arada, M. d. l.
A., Alegret, S. and del Valle, M. (2010). Lead (II) ion selective electrodes
with PVC membranes based on two bis-thioureas as ionophore:
1,3-bis(N’-benzoylthioureido)benzene and 1,3-bis(N’-furoylthioureido)benzene. Journal of Hazardous Material, 181: 140
–146.
37. Zhang, Y. –M., Pang, H.
–X., Cao, C. and Wei, T.-B. (2007). Synthesis, crystal structure and biological
activity of a new complex, + bis
(1,1-diethyl-3-(3-fluorobenzoyl)-thiourea)nickel(II). Indian Journal of
Chemistry Section A-Inorganic Bio-Inorganic Physical Theoretical &
Analytical Chemistry, 46A: 1787 – 1791.
38. Jadhao, S. Z. and Rathod,
M. S. (2012). Synthesis and Structural Investigation of Zinc Metal-Ligand
(Thiourea Derivative) Complexes. Journal
of Chemical and Pharmaceutical Research, 4(3): 1562 –1565.
39. Schwade, V. D., Kirsten,
L., Hagenbach, A., Lang E. S. and Abram, U. (2013). Indium (III), lead (II),
gold (I) and copper (II) complexes with isophthaloylbis(thiourea) ligands. Polyhedron, 55: 155 –161.
40. Kumar, A., Kumar, V.,
Diwan, U. and Upadhyay, K. K. (2013). Highly sensitive and selective naked-eye
detection of Cu2+ in aqueous medium by a ninhydrin-quinoxaline derivative. Sensors and Actuator B, 176: 420 – 427.