Cover Image

Mechanosynthesis of 1,2,4-triazine-appended polyvinyl chloride (PVC) and studies of its fluorescence “turn-off” response to Fe3+

Basim S.M. Al-Ghezi, Wahab K.A. Al-Ithawi, Artem V. Baklykov, Vadim A. Platonov, Tatyana I. Shendrikova, Yaroslav K. Shtaitz, Igor S. Kovalev, Dmitry S. Kopchuk, Grigory V. Zyryanov

Abstract


Iron plays crucial role in such important biochemical processes in the human body as the respiratory function. Both deficiency and excess of Fe3+/Fe2+ could induce serious diseases, including heart failure and diabetes. Additionally, iron is among essential micronutrient elements for the living organisms in the environment, as it is involved in plant metabolism, electron transport of photosynthesis and respiration, chlorophyll synthesis, nitrate reduction, and detoxification of reactive oxygen species. The methods and materials for the detection of Fe3+ /Fe2+ are of high demand. In this manuscript we wish to report a mechanochemical approach for the post-modification/functionalization of PVC with 3-(pyridyl-2)-1,2,4-triazine moieties to obtain a polymeric material for the visual detection of Fe3+/ Fe2+. The obtained polymer was characterized by means of 1H NMR- and IR-spectroscopy, as well as gel-penetration chromatography (GPC). Colorimetric and fluorescence “turn-off” response towards Fe2+ and Fe3+ in solution was investigated, and a Stern-Volmer constant as high as 0.1-0.3∙1oM–1 was observed for Fe3+.

Keywords


polyvinyl chloride; 3-(pyridyl-2)-1,2,4-triazine; mechanosynthesis; polymer; Fe3+; fluorescence quenching

Full Text:

PDF

References


Camaschella C. Iron-deficiency anemia. N Engl J Med. 2015;372:1832–1843. doi:10.1056/NEJMra1401038

Chen P, De Meulenaere E, Deheyn DD, Bandaru PR. Iron redox pathway revealed in ferritin via electron transfer analysis. Sci Rep. 2020;10(4033):1-10. doi:10.1038/s41598-020-60640-z

Cherilakkudy FH, Thomas MG, Varghese A, Waheed SO, Krishnan A, Venditti V, Karabencheva-Christova TG. Revealing the catalytic mechanism of the Fe (II)/2-oxoglutarate-dependent human epigenetic modifying enzyme ALKBH5. Cell Rep Phys Sci. 2025;6(8):102779. doi:10.1016/j.xcrp.2025.102779

Dev S, Babitt JL. Overview of iron metabolism in health and disease. Hemodial Int. 2017;21:S6-S20. doi:10.1111/hdi.12542

Pasricha SR, Tye-Din J, Muckenthaler MU, Swinkels DW. Iron deficiency. Lancet. 2021;397:233–248.

Hsu CC, Senussi NH, Fertrin KY, Kowdley KV. Iron overload disorders. Hepatol Commun. 2022;6(8):1842–1854. doi:10.1002/hep4.2012

Anker SD, Karakas M, Mentz RJ, Ponikowski P, Butler J, Khan MS, Friede T. Systematic review and meta-analysis of intravenous iron therapy for patients with heart failure and iron deficiency. Nat Med. 2025;31:2640–2646. doi:10.1038/s41591-025-03671-1

Simcox JA, McClain DA. Iron and diabetes risk. Cell Metab. 2013;17(3):329–341. doi:10.1016/j.cmet.2013.02.007

Mehta KJ, Farnaud SJ, Sharp PA. Iron and liver fibrosis: Mechanistic and clinical aspects. World J Gastroenterol. 2019;25(5):521–538. doi:10.3748/wjg.v25.i5.521

Li J, Cao F, Yin Hl. Ferroptosis: past, present and future. Cell Death Dis. 2020;11(2):88. doi:10.1038/s41419-020-2298-2

Li M, Watanabe S, Gao F, Dubos C. Iron nutrition in plants: towards a new paradigm? Plants. 2023;12(2):384. doi:10.3390/plants12020384

Wang L, Wang Y. 2, 4, 6-Tri (2′-pyridyl)-1, 3, 5-triazine for determination of iron (II), Iron (III), and total iron contents on human palms. J Forensic Sci. 2023;68(4):1317-1324. doi:10.1111/1556-4029.15271

Avissar YY, Sagiv AE, Mandler D, Almog J. Identification of firearms holders by the [Fe (PDT) 3]+ 2 complex. Quantitative determination of iron transfer to the hand and its dependence on palmar moisture levels. J Forensic Sci. 2004;49(6):1215-9. doi:10.1520/JFS2004100

Avissar YY, Sagiv AE, Mandler D, Almog J. Identification of firearms handling by the [Fe(PDT)3]2+ complex: chemical and time-dependent factors. Talanta. 2005;67(2):328-333. doi:10.1016/j.talanta.2005.01.032

Adams PE. Determining iron content in foods by spectrophotometry. J Chem Educ. 1995;72(7):649. doi:10.1021/ed072p649

Chu HS, Yip YC, Chan KC, Sham WC. Determination of iron in plant samples using isotope dilution inductively coupled plasma mass spectrometry with a quadrupole ICP-MS operated in an He/H 2 cell mode. J Anal At Spectrom. 2006;21(10):1068-1071. doi:10.1039/B608022G

Alchoubassi G, Aszyk J, Pisarek P, Bierla K, Ouerdane L, Szpunar J, Lobinski R. Advances in mass spectrometry for iron speciation in plants. TrAC-TREND ANAL CHEM. 2018;104:77-86. doi:10.1016/j.trac.2017.11.006

Seravalli J. Iron Metabolism: Methods and Protocols. Springer US: New York, NY; 2024;31-41. doi:10.1007/978-1-0716-4043-2_2

Goel DP, Singh RP. Pyridine-2, 3-diol as metal indicator in the chelatometric determination of iron (III) with EDTA. Analyst. 1971;96(1139):123-126. doi:10.1039/AN9719600123

Topa-Skwarczyńska M, Szymaszek P, Fiedor P, Chachaj-Brekiesz A, Galek M, Kasprzyk W, Ortyl J. Pyridine derivatives as candidates for selective and sensitive fluorescent biosensors for lung cancer cell imaging and iron ions detection. Dyes Pigments. 2022;200:110171. doi:10.1016/j.dyepig.2022.110171

Tsurubou S, Sakai T. High-sensitivity Extraction - Spectrophotometric Determination of Iron With 34 2-Pyridyl)-5,6-diphenyl-l,2,4-triazine and Tetrabromophenolphthalein Ethyl Ester. Analyst. 1984;109(11):1397-9. doi:10.1039/an9840901397

Zhu W, Wu F, Zheng J, Liu C. The use of 3-(2-pyridyl)-5, 6-diphenyl-1, 2, 4-triazine as a precolumn derivatizing reagent in HPLC determination for Fe (II) in natural samples. Anal Sci. 2007;23(11):1291-6. doi:10.2116/analsci.23.1291

Özdemir E, Thirion D, Yavuz CT. Covalent organic polymer framework with C–C bonds as a fluorescent probe for selective iron detection. RSC Adv. 2015;5(84):69010-69015. doi:10.1039/C5RA10697D

Hussien RA. Development of a green polymer-based sensor for enhanced iron detection in diverse biological, food and environmental matrices. Anal Biochem. 2025;705:115927. doi:10.1016/j.ab.2025.115927

Sánchez-Ponce L, Casanueva-Marenco MJ, Díaz-de-Alba M, Galindo-Riaño MD, Granado-Castro MD. A novel polymer inclusion membrane-based green optical sensor for selective determination of iron: design, characterization, and analytical applications. Polymers. 2023;15(20):4082. doi:10.3390/polym15204082

Wilkes CE, Summers JW, Daniels CA, Berard MT. PVC handbook. Munich : Hanser; 2005. p. 414.

Ait-Touchente Z, Khellaf M, Raffin G, Lebaz N, Elaissari A. Recent advances in polyvinyl chloride (PVC) recycling. Polym Adv Technol. 2024;35(1):e6228. doi:10.1002/pat.6228

Moulay S. Chemical modification of poly (vinyl chloride)—Still on the run. Prog Polym Sci. 2010;35(3):303-331. doi:10.1016/j.progpolymsci.2009.12.001

Edraki M, Sheydaei M, Alinia-Ahandani E, Nezhadghaffar-Borhani E. Polyvinyl chloride: chemical modification and investigation of structural and thermal properties. J Sulphur Chem. 2021;42(4):397-409. doi:10.1080/17415993.2021.1895996

Alshaikh A, Ezendu S, Ryoo D, Shinde PS, Anderson JL, Szilvasi T, Bara JE. PVC Modification through Sequential Dehydrochlorination–Hydrogenation Reaction Cycles Facilitated via Fractionation by Green Solvents. ACS Appl Polym Mater. 2024;6(16):9656–9662. doi:10.1021/acsapm.4c01453

Najafi V, Ahmadi E, Ziaee F. Chemical modification of PVC by different nucleophiles in solvent/non-solvent system at high temperature. Iran Polym J. 2018;27(11):841–850. doi:10.1007/s13726-018-0658-x

Kanari N, Menad NE, Filippov LO, Shallari S, Allain E, Patisson F, Yvon J. Some aspects of the thermochemical route for the valorization of plastic wastes, part I: reduction of iron oxides by polyvinyl chloride (PVC). Mater. 2021;14(15):4129. doi:10.3390/ma14154129

Krusenbaum A, Grätz S, Tigineh GT, Borchardt L, Kim JG. The mechanochemical synthesis of polymers. Chem Soc Rev. 2022;51:2873-2905. doi:10.1039/D1CS01093J

Al-Ithawi WK, Khasanov AF, Kovalev IS, Nikonov IL, Platonov VA, Kopchuk DS, Zyryanov GV, Ranu BC. TM-Free and TM-Catalyzed Mechanosynthesis of functional polymers. Polymers. 2023;15(8):1853. doi:10.3390/polym15081853

Zapevalova ES, Trenikhin MV, Kryazhev YG. Synthesis of Nickel–Carbon Nanocomposites Using the Mechanical Treatment of Polyvinyl Chloride in the Presence of Nickel Nitrate and Diethylamine. Solid Fuel Chem. 2021;55(6):374-379. doi:10.3103/S036152192106015X

Zapevalova ES, Kryazhev YG, Trenikhin MV, Arbuzov AB, Anikeeva IV. Synthesis of metal-carbon nanocomposites by mechanical activation of polyvinyl chloride in the presence of Ni(NO3)2. AIP Conf. Proc. 2021;2412(1):040017. doi:10.1063/5.0075054

Lee JSM, Kurihara T, Horike S. Five-minute mechanosynthesis of hypercrosslinked microporous polymers. Chem Mater. 2020;32:7694−7702. doi:10.1021/acs.chemmater.0c01726

Lee GS, Lee HS, Kim N, Shin HG, Hwang YH, Lee SJ, Kim JG. Mechanochemical synthesis of ionic polymers: solid-state ball-milling polymerization for unrestricted solubility enabling copolymerization of immiscible monomers. Macromolecules. 2024;57(19):9408-9418. doi:10.1021/acs.macromol.4c01451

Hu C, van Bonn P, Demco DE, Bolm C, Pich A. Mechanochemical synthesis of stimuli responsive microgels. Angew Chem. 2023;135(34):e202305783. doi:10.1002/anie.202305783

Jiang M, Bird E, Ham W, Worch JC. Mechanochemical synthesis of recyclable biohybrid polymer networks using whole biomass. Angewante Chemie Int. Ed. 2025;64(37):e202510449. doi:10.1002/anie.202510449

Kozhevnikov VN, Kozhevnikov DN, Shabunina OV, Rusinov VL, Chupakhin ON. An efficient route to 5-(hetero) aryl-2, 4′- and 2, 2′-bipyridines through readily available 3-pyridyl-1, 2, 4-triazines. Tetrahedron Lett. 2005;46(11):1791-1793. doi:10.1016/j.tetlet.2005.01.135

Moseev TD, Nikiforov EA, Varaksin MV, Starnovskaya ES, Savchuk MI, Nikonov IL, Charushin VN. Novel pentafluorophenyl-and alkoxyphenyl-appended 2, 2′-bipyridine push–pull fluorophores: a convenient synthesis and photophysical studies. Synthesis. 2021;53(19):3597-3607. doi:10.1055/a-1500-1343

Al-Sammarraie ES, Al-Ghezi BS, Al-Ithawi WK, Nikonov IL, Kovalev IS, Altobee AM, Sabirova TM, Zyryanov GV, Alsalhy, QF. Investigating performance properties of three new Types of UF Membranes for Carwash Sector Applications. J Appl Polym Sci. 2025;142(36):e57407. doi:10.1002/app.57407

Al-Sammarraie ES, Al-Ithawi WK, Baklykov AV, Platonov VA, Altobee AMK, Glebov NS, Khasanov AF, Kovalev IS, Nikonov IL, Kopchuk DS, Sapozhnikova IM, Sabirova TM, Zyryanov GV, Rusinov VL. (Mechano)chemical modification of polyvinyl chloride with azole-based drugs. Chimica Techno Acta. 2024;11(2):202411211. doi:10.15826/chimtech.2024.11.2.11

Mekki H, Belbachir M. Preparation of vinyl chloridevinyl ether copolymers via partial etherification from PVC. Express Polymer Lett. 2007;1:495-498. doi:10.3144/expresspolymlett.2007.70

Cascaval CN., Robilǎ G, Stoleriu A. Thermal characterization of some products obtained by chemically modified poly (vinyl chloride) with phenol. J. Appl. Polym. Sci. 1995;56(8):889-894. doi:10.1002/app.1995.070560802

Sun X, Wang Y, Lei Y. Fluorescence based explosive detection: From mechanisms to sensory materials. Chem. Soc. Rev. 2015; 44: 8019–8061. doi:10.1039/c5cs00496a

Lakowicz JR. Principles of fluorescence spectroscopy, Springer, 2006. doi:10.1007/978-0-387-46312-4

Wang T, Zeng LH, Li DL. A review on the methods for correcting the fluorescence inner-filter effect of fluorescence spectrum. Appl Spectrosc Rev. 2017;52:883–908. doi:10.1080/05704928.2017.1345758

Shanmugaraj K, John SA. Inner filter effect based selective detection of picric acid in aqueous solution using green luminescent copper nanoclusters. New J Chem. 2018;42:7223–7229. doi:10.1039/c8nj00789f

Li H, Fu B, Yang W, Ding L, Yang Y, Dong J, Wang F, Pan Q. A recyclable fluorescent probe for picric acid detection in water samples based on inner filter effect. Spectrochim Acta Part A Mol Biomol Spectrosc. 2020;226:117575. doi:10.1016/j.saa.2019.117575

Dumbare S, Doshi A, Ravindran S. Selective identification of ferric ions in ecological and biological samples using rhodamine chemosensors. Pol J Environ Stud. 2024;33(2):1497-1509. doi:10.15244/pjoes/174510

Kumar M, Gupta N. Singh AP. Malonyl-based chemosensors: selective detection of Fe3+ ion in aqueous medium. Anal Sci. 2020;36:659–663. doi:10.2116/analsci.19P299




DOI: https://doi.org/10.15826/chimtech.9237

Copyright (c) 2025 Basim S.M. Al-Ghezi, Wahab K.A. Al-Ithawi, Artem V. Baklykov, Vadim A. Platonov, Tatyana I. Shendrikova, Yaroslav K. Shtaitz, Igor S. Kovalev, Dmitry S. Kopchuk, Grigory V. Zyryanov

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.

Scopus logo WorldCat logo DOAJ logo CAS logo BASE logo eLibrary logo

Chimica Techno Acta, 2014–2025
eISSN 2411-1414
Copyright Notice