Research Article
BibTex RIS Cite

Construction of a New Near-Infrared Cobalt Phthalocyanine Platform for the Selective and Sensitive Detection of Thiocyanate Ions

Year 2025, Volume: 46 Issue: 4, 805 - 811, 30.12.2025

Özgür Yavuz

https://doi.org/10.17776/csj.1683087

Abstract

Thiocyanate (SCN⁻) is an organic anion with various applications; however, it causes serious environmental and health hazards. In this report, a new near-infrared (NIR) chemical sensor based on a phthalocyanine (Pc) platform was devised for the selective, sensitive, and rapid determination of SCN⁻ ions. To enhance the sensor’s longevity, a robust Pc core structure with unique properties was selected. Additionally, a central cobalt (II) ion (Co2+) was incorporated owing to its strong binding affinity for SCN⁻, as previously demonstrated in the literature. The macromolecule DAP-CoPc is the first spectrophotometric probe designed for the selective quantification of SCN⁻ within Pc and porphyrin-based frameworks. The limit of detection (LOD) for the UV–vis titration was determined to be 11.01 μM (0.71 ppm) with a response time of 100 s. Overall, the findings of this study emphasise the exceptional sensing performance of DAP-CoPc, particularly in terms of selectivity, sensitivity, reasonable response time, and durability. This work represents a significant advancement for the development and application of novel NIR sensor platforms for the accurate and fast detection of SCN⁻ in real samples.

Keywords

Cobalt Phthalocyanine thiocyanate UV-vis spectrophotometry chemosensor Near-Infrared

Thanks

I would like to express my deepest thanks to Prof. Dr. Ismail Yilmaz for providing the research facility.

References

  • [1] Zhang, Y., Wang, H., & Yang, R. H., Colorimetric And Fluorescent Sensing of SCN⁻ Based on Meso-Tetraphenylporphyrin/Meso-Tetraphenylporphyrin Cobalt (II) System, Sensors, 7(3) (2007) 410-419.
  • [2] Wagner, A., & Ofial, A. R., Potassium Thiocyanate as Source of Cyanide for The Oxidative Α-Cyanation of Tertiary Amines. The Journal of Organic Chemistry, 80(5) (2015) 2848-2854.
  • [3] Moskwa, P., Lorentzen, D., Excoffon, K. J., Zabner, J., McCray Jr, P. B., Nauseef, W. M., ... & Bánfi, B., A Novel Host Defense System of Airways is Defective in Cystic Fibrosis, American Journal of Respiratory and Critical Care Medicine, 175(2) (2007) 174-183.
  • [4] Willemin, M. E., & Lumen, A., Characterization of the Modes of Action and Dose-Response Relationship for Thiocyanate on the Thyroid Hormone Levels İn Rats Using a Computational Approach, Toxicology and Applied Pharmacology, 365 (2019) 84-100.
  • [5] Narkowicz, S., Polkowska, Ż., Marć, M., Simeonov, V., & Namieśnik, J., Determination of Thiocyanate (Biomarkers of ETS) and Other Inorganic Ions in Human Nasal Discharge Samples Using Ion Chromatography, Ecotoxicology and Environmental Safety, 96 (2013) 131-138.
  • [6] Akiyama, H., Matsuoka, H., Okuyama, T., Higashi, K., Toida, T., Komatsu, H., ... & Endou, H., The Acute Encephalopathy Induced by Intake of Sugihiratake Mushroom in The Patients With Renal Damage Might Be Associated With The İntoxication of Cyanide and Thiocyanate, Food Safety, 3(1) (2015) 16-29.
  • [7] Lobo‐Júnior, E. O., LS Chagas, C., & Coltro, W. K., Determination of Inorganic Cations in Biological Fluids Using a Hybrid Capillary Electrophoresis Device Coupled With Contactless Conductivity Detection. Journal Of Separation Science, 41(16) (2018) 3310-3317.
  • [8] Li, D., Xie, F., & Zhang, J., Voltammetric Behaviors and Determination of Thiocyanate on Multiwalled Carbon Nanotubes‐Cetyltrimethylammonium Bromide Modified Electrode, Electroanalysis, 30(10) (2018) 2413-2420.
  • [9] Ohshima, T., Kagaya, S., Gemmei-Ide, M., Cattrall, R. W., & Kolev, S. D., The Use of a Polymer Inclusion Membrane as a Sorbent For Online Preconcentration in The Flow Injection Determination of Thiocyanate Impurity in Ammonium Sulfate Fertilizer, Talanta, 129 (2014) 560-564.
  • [10] Ammazzini, S., Onor, M., Pagliano, E., Mester, Z., Campanella, B., Pitzalis, E., ... & D’Ulivo, A., Determination of Thiocyanate in Saliva By Headspace Gas Chromatography-Mass Spectrometry, Following a Single-Step Aqueous Derivatization With Triethyloxonium Tetrafluoroborate, Journal of Chromatography A, 1400 (2015) 124-130.
  • [11] Peng, C. F., Pan, N., Zhi-Juan, Q., Wei, X. L., & Shao, G., Colorimetric Detection of Thiocyanate Based on Inhibiting the Catalytic Activity of Cystine-Capped Core-Shell Au@Pt Nanocatalysts, Talanta, 175 (2017) 114-120.
  • [12] Umar, A. R., Hussain, K., Aslam, Z., Haq, M. A. U., Muhammad, H., & Shah, M. R., Ultra-trace level voltammetric sensor for MB in human plasma based on a carboxylic derivative of Calix resorcinarene capped silver nanoparticles, Journal of Industrial and Engineering Chemistry, 107 (2022) 81-92.
  • [13] Ali, R., & Saleh, S. M., Design a Friendly Nanoscale Chemical Sensor Based on Gold Nanoclusters for Detecting Thiocyanate Ions in Food Industry Applications, Biosensors, 14(5) (2024) 23.
  • [14] Özbek, O., & Işıldak, Ö., All-solid-state poly (vinyl chloride) membrane thiocyanate–selective potentiometric electrode, Journal of New Results in Science, 10(2) (2021) 33-39.
  • [15] Arvand, M., Zanjanchi, M. A., & Heydari, L., Novel Thiocyanate-Selective Membrane Sensor Based on Crown Ether-Cetyltrimethyl Ammonium Thiocyanate İon-Pair as a Suitable Ionophore, Sensors and Actuators B: Chemical, 122(1) (2007) 301-308.
  • [16] Xu, L., Yuan, R., Chai, Y. Q., & Fu, Y. Z., Novel Membrane Potentiometric Thiocyanate Sensor Based on Tribenzyltin (IV) Dithiocarbamate, Electroanalysis: An International Journal Devoted to Fundamental and Practical Aspects of Electroanalysis, 17(11) (2005) 1003-1007.
  • [17] Hassan, S. S., Mohmoud, W. H., Elgazwy, A. S. S. H., & Badawy, N. M., A Novel Potentiometric Membrane Sensor Based on Aryl Palladium Complex for Selective Determination of Thiocyanate in The Saliva And Urine of Cigarette Smokers, Electroanalysis: An International Journal Devoted to Fundamental and Practical Aspects of Electroanalysis, 18(21) (2006) 2070-2078.
  • [18] Wang, G. F., Li, M. G., Gao, Y. C., & Fang, B., Amperometric Sensor Used for Determination of Thiocyanate with a Silver Nanoparticles Modified Electrode, Sensors, 4(9) (2004) 147-155.
  • [19] Amini, M. K., Shahrokhian, S., & Tangestaninejad, S., Thiocyanate-Selective Electrodes Based on Nickel and Iron Phthalocyanines, Analytica Chimica Acta, 402(1-2) (1999) 137-143.
  • [20] Ozoemena, K. I., Nyokong, T., & Westbroek, P., Self‐Assembled Monolayers of Cobalt And Iron Phthalocyanine Complexes on Gold Electrodes: Comparative Surface Electrochemistry and Electrocatalytic Interaction with Thiols and Thiocyanate, Electroanalysis: An International Journal Devoted to Fundamental and Practical Aspects of Electroanalysis, 15(22) (2003) 1762-1770.
  • [21] Nemakal, M., Palanna, M., Sannegowda, L. K., & Kumar, P. S., Zinc Phthalocyanine Anchored Magnetite Particles: Efficient Platform for Sensing of Thiocyanate, Journal of Electroanalytical Chemistry, 895, 2021 115385.
  • [22] Rastegarzadeh, S., & Moradpour, Z., A Novel Optical Sensor for Determination of Thiocyanate, Analytical letters, 40(16) (2007) 2993-3001.
  • [23] Zhao, D., Chen, C., Lu, L., Yang, F., & Yang, X., A Dual-Mode Colorimetric and Fluorometric “Light On” Sensor for Thiocyanate Based on Fluorescent Carbon Dots and Unmodified Gold Nanoparticles, Analyst, 140(24) (2015) 8157-8164.
  • [24] Kadish, K., Guilard, R., & Smith, K. M. (Eds.)., The Porphyrin Handbook: Applications of Phthalocyanines, Academic Press (2012).
  • [25] McKeown, N. B., Phthalocyanine Materials: Synthesis, Structure and Function (No. 6)., Cambridge university press (1998).
  • [26] Breloy, L., Yavuz, O., Yilmaz, I., Yagci, Y., & Versace, D. L., Design, Synthesis and Use of Phthalocyanines as a New Class of Visible-Light Photoinitiators for Free-Radical and Cationic Polymerizations, Polymer Chemistry, 12(30) (2021) 4291-4316.
  • [27] Rezaee, E., Khan, D., Cai, S., Dong, L., Xiao, H., Silva, S. R. P., ... & Xu, Z. X. Phthalocyanine in Perovskite Solar Cells: A Review, Materials Chemistry Frontiers, 7(9) (2023) 1704-1736.
  • [28] Bonnett, R., Photosensitizers of the Porphyrin and Phthalocyanine Series for Photodynamic Therapy, Chemical Society Reviews, 24(1) (1995) 19-33.
  • [29] Plekhanov, A. I., Basova, T. V., Parkhomenko, R. G., & Gürek, A. G., Nonlinear optical properties of lutetium and dysprosium bisphthalocyanines at 1550 nm with femto-and nanosecond pulse excitation, Optical Materials, 64 (2017) 13-17.
  • [30] Gorduk, O., Gencten, M., Gorduk, S., Sahin, M., & Sahin, Y., Electrochemical Fabrication and Supercapacitor Performances of Metallo Phthalocyanine/Functionalized-Multiwalled Carbon Nanotube/Polyaniline Modified Hybrid Electrode Materials, Journal of Energy Storage, 33 (2021) 102049.
  • [31] Breloy, L., Alcay, Y., Yilmaz, I., Breza, M., Bourgon, J., Brezová, V., ... & Versace, D. L., Dimethyl Amino Phenyl Substituted Silver Phthalocyanine as a UV-and Visible-Light Absorbing Photoinitiator: In Situ Preparation of Silver/Polymer Nanocomposites, Polymer Chemistry, 12(9) (2021) 1273-1285.
  • [32] Yavuz, O., Sezen, M., Alcay, Y., Yildirim, M. S., Aribuga, H., Ozdemir, E., ... & Yilmaz, I., A new highly Selective, Sensitive and NIR Spectrophotometric Probe Based on A2B2-Type of Unsymmetrical Phthalocyanine for Hazardous Be2+ recognition, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 284, (2023) 121484.
  • [33] Bayda, M., Dumoulin, F., Hug, G. L., Koput, J., Gorniak, R., & Wojcik, A., Fluorescent H-Aggregates of an Asymmetrically Substituted Mono-Amino Zn (II) Phthalocyanine, Dalton transactions, 46(6) (2017) 1914-1926.
  • [34] Zhang, X. F., Xi, Q., & Zhao, J., Fluorescent and Triplet State Photoactive J-Type Phthalocyanine Nano Assemblies: Controlled Formation and Photosensitizing Properties, Journal of Materials Chemistry, 20(32) (2010) 6726-6733.
  • [35] Yavuz, O., Alcay, Y., Kaya, K., Sezen, M., Kirlangic Atasen, S., Yildirim, M. S., ... & Yilmaz, I., Superior Sensor For Be2+ Ion Recognition via the Unprecedented Octahedral Crystal Structure of a One-Dimensional Coordination Polymer of Crown Fused Zinc Phthalocyanine, Inorganic Chemistry, 58(1) (2018) 909-923.
  • [36] Wirojsaengthong, S., Aryuwananon, D., Aeungmaitrepirom, W., Pulpoka, B., & Tuntulani, T., A Colorimetric Paper-Based Optode Sensor for Highly Sensitive and Selective Determination of Thiocyanate in Urine Sample Using Cobalt Porphyrin Derivative, Talanta, 231 (2021) 122371.
There are 36 citations in total.

Details

Primary Language English
Subjects Analytical Spectrometry, Sensor Technology, Inorganic Chemistry (Other)
Journal Section Research Article
Authors

Özgür Yavuz 0000-0002-0660-7474

Submission Date April 24, 2025
Acceptance Date November 9, 2025
Publication Date December 30, 2025
Published in Issue Year 2025 Volume: 46 Issue: 4

Cite

APA Yavuz, Ö. (2025). Construction of a New Near-Infrared Cobalt Phthalocyanine Platform for the Selective and Sensitive Detection of Thiocyanate Ions. Cumhuriyet Science Journal, 46(4), 805-811. https://doi.org/10.17776/csj.1683087

Editor