UPPER-RIM NITRO AND LOWER-RIM METHOXY FUNCTIONALIZED CALIX[4]ARENE BASED COLORIMETRIC SENSOR FOR DETECTION OF 2,4,6-TRINITROPHENOL

Year 2024, Volume: 12 Issue: 4, 1047 - 1058, 01.12.2024

Clever Ng'andu , Begüm Tabakcı , Mustafa Tabakcı

https://doi.org/10.36306/konjes.1573403

Abstract

The development of effective sensors capable of detecting 2,4,6-trinitrophenol (TNP), or picric acid, at extremely low levels is a very interesting field of study for prevention of environmental contamination and terrorist threats. Therefore, in this study, a colorimetric sensor (MNC4) based on calix[4]arene containing a chromophore group was prepared for the detection of TNP. The photophysical interaction of MNC4 with target nitroaromatic compounds (NACs) was evaluated using UV-Vis. spectroscopy. The initial MNC4 solution was colorless, but a distinct color change was observed in the case of TNP, indicating a stronger binding affinity with MNC4. Spectral investigations also confirmed the relatively strong complexation between MNC4 and TNP. The limit of detection (LOD) value for TNP was found to be 520 nM, indicating that MNC4 can detect TNP down to the nanomolar level, which is significantly lower than the permissible level (2.2 µM). The stoichiometric ratio of the complex formed between MNC4 and TNP was determined to be 1:2. The developed sensor enables the colorimetric detection of TNP with the naked eye without the need for any instrumentation, highlighting its potential for real-world applications.

Keywords

Trinitrophenol, Calixarene, Colorimetric Sensor, Nitroaromatic Compounds, Explossive

Project Number

22201056, 23401071

References

• S. Dhiman, N. Singla, M. Ahmad, P. Singh, and S. Kumar, "Protonation-and electrostatic-interaction-based fluorescence probes for the selective detection of picric acid (2, 4, 6-trinitrophenol)–an explosive material," Materials Advances, vol. 2, no. 20, pp. 6466-6498, 2021.
• M. T. Waseem, H. M. Junaid, H. Gul, Z. A. Khan, C. Yu, and S. A. Shahzad, "Fluorene based fluorescent and colorimetric sensors for ultrasensitive detection of nitroaromatics in aqueous medium," Journal of Photochemistry and Photobiology A: Chemistry, vol. 425, p. 113660, 2022.
• J. N. Malegaonkar, M. Al Kobaisi, P. K. Singh, S. V. Bhosale, and S. V. Bhosale, "Sensitive turn-off detection of nitroaromatics using fluorescent tetraphenylethylene phosphonate derivative," Journal of Photochemistry and Photobiology A: Chemistry, vol. 438, p. 114530, 2023.
• A. K. Bandela, S. Bandaru, and C. P. Rao, "A Fluorescent 1, 3‐Diaminonaphthalimide Conjugate of Calix [4] arene for Sensitive and Selective Detection of Trinitrophenol: Spectroscopy, Microscopy, and Computational Studies, and Its Applicability using Cellulose Strips," Chemistry–A European Journal, vol. 21, no. 38, pp. 13364-13374, 2015.
• K.-M. Wollin and H. Dieter, "Toxicological guidelines for monocyclic nitro-, amino-and aminonitroaromatics, nitramines, and nitrate esters in drinking water," Archives of environmental contamination and toxicology, vol. 49, pp. 18-26, 2005.
• S. K. Dinda, M. Althaf Hussain, A. Upadhyay, and C. P. Rao, "Supramolecular sensing of 2, 4, 6-trinitrophenol by a tetrapyrenyl conjugate of calix [4] arene: applicability in solution, in solid state, and on the strips of cellulose and silica gel and the image processing by a cellular phone," ACS omega, vol. 4, no. 16, pp. 17060-17071, 2019.
• P. Wexler and B. D. Anderson, Encyclopedia of toxicology. Academic Press, 2005.
• M. S. Russell, The chemistry of fireworks. Royal Society of Chemistry, 2009.
• P. G. Thorne and T. F. Jenkins, "A field method for quantifying ammonium picrate and picric acid in soil," Field Analytical Chemistry & Technology, vol. 1, no. 3, pp. 165-170, 1997.
• A. S. Tanwar and P. K. Iyer, "Fluorescence “turn-on” indicator displacement assay-based sensing of nitroexplosive 2, 4, 6-trinitrophenol in aqueous media via a polyelectrolyte and dye complex," ACS omega, vol. 2, no. 8, pp. 4424-4430, 2017.
• J. Akhavan, The chemistry of explosives 4E. Royal Society of Chemistry, 2022.
• J. F. Wyman, M. P. Serve, D. W. Hobson, L. H. Lee, and D. E. Uddin, "Acute toxicity, distribution, and metabolism of 2, 4, 6‐trinitrophenol (picric acid) in Fischer 344 rats," Journal of Toxicology and Environmental Health, Part A Current Issues, vol. 37, no. 2, pp. 313-327, 1992.
• P. Ashbrook and T. Houts, "Picric acid," Chemical Health and Safety, vol. 10, no. 2, p. 27, 2003.
• B. Roy, A. K. Bar, B. Gole, and P. S. Mukherjee, "Fluorescent tris-imidazolium sensors for picric acid explosive," The Journal of organic chemistry, vol. 78, no. 3, pp. 1306-1310, 2013.
• M. Nipper, Y. Qian, R. S. Carr, and K. Miller, "Degradation of picric acid and 2, 6-DNT in marine sediments and waters: the role of microbial activity and ultra-violet exposure," Chemosphere, vol. 56, no. 6, pp. 519-530, 2004.
• E. Zhang et al., "A FRET-based fluorescent and colorimetric probe for the specific detection of picric acid," RSC advances, vol. 8, no. 55, pp. 31658-31665, 2018.
• J. S. Caygill, F. Davis, and S. P. Higson, "Current trends in explosive detection techniques," Talanta, vol. 88, pp. 14-29, 2012.
• D. S. Moore, "Instrumentation for trace detection of high explosives," Review of Scientific Instruments, vol. 75, no. 8, pp. 2499-2512, 2004.
• Y. Zimmermann and J. Broekaert, "Determination of TNT and its metabolites in water samples by voltammetric techniques," Analytical and bioanalytical chemistry, vol. 383, pp. 998-1002, 2005.
• J. I. Steinfeld and J. Wormhoudt, "Explosives detection: a challenge for physical chemistry," Annual review of physical chemistry, vol. 49, no. 1, pp. 203-232, 1998.
• Y. Ding, W.-H. Zhu, and Y. Xie, "Development of ion chemosensors based on porphyrin analogues," Chemical Reviews, vol. 117, no. 4, pp. 2203-2256, 2017.
• G. Sathiyan and P. Sakthivel, "A multibranched carbazole linked triazine based fluorescent molecule for the selective detection of picric acid," RSC advances, vol. 6, no. 108, pp. 106705-106715, 2016.
• T.-M. Geng, S.-N. Ye, Y. Wang, H. Zhu, X. Wang, and X. Liu, "Conjugated microporous polymers-based fluorescein for fluorescence detection of 2, 4, 6-trinitrophenol," Talanta, vol. 165, pp. 282-288, 2017.
• A. Buragohain, M. Yousufuddin, M. Sarma, and S. Biswas, "3D luminescent amide-functionalized cadmium tetrazolate framework for selective detection of 2, 4, 6-trinitrophenol," Crystal Growth & Design, vol. 16, no. 2, pp. 842-851, 2016.
• Y. Zhang, B. Li, H. Ma, L. Zhang, and W. Zhang, "An RGH–MOF as a naked eye colorimetric fluorescent sensor for picric acid recognition," Journal of Materials Chemistry C, vol. 5, no. 19, pp. 4661-4669, 2017.
• H. Guo, Y. Zhang, Z. Zheng, H. Lin, and Y. Zhang, "Facile one-pot fabrication of Ag@ MOF (Ag) nanocomposites for highly selective detection of 2, 4, 6-trinitrophenol in aqueous phase," Talanta, vol. 170, pp. 146-151, 2017.
• B. Joarder, A. V. Desai, P. Samanta, S. Mukherjee, and S. K. Ghosh, "Selective and sensitive aqueous‐phase detection of 2, 4, 6‐trinitrophenol (TNP) by an amine‐functionalized metal–organic framework," Chemistry–A European Journal, vol. 21, no. 3, pp. 965-969, 2015.
• B. Gole, S. Shanmugaraju, A. K. Bar, and P. S. Mukherjee, "Supramolecular polymer for explosives sensing: role of H-bonding in enhancement of sensitivity in the solid state," Chemical Communications, vol. 47, no. 36, pp. 10046-10048, 2011.
• M. Panchal, K. D. Bhatt, K. Modi, and M. Panchal, "A Review on Recognition of Explosives using Calixarene Framework," 2021.
• M. E. Germain and M. J. Knapp, "Optical explosives detection: from color changes to fluorescence turn-on," Chemical Society Reviews, vol. 38, no. 9, pp. 2543-2555, 2009.
• M. Akpinar, F. Temel, B. Tabakci, E. Ozcelik, and M. Tabakci, "A phenyl glycinol appended calix [4] arene film for chiral detection of ascorbic acid on gold surface," Analytical biochemistry, vol. 583, p. 113373, 2019.
• M. Tabakci, B. Tabakci, and A. D. Beduk, "Synthesis and application of an efficient calix [4] arene-based anion receptor bearing imidazole groups for Cr (VI) anionic species," Tetrahedron, vol. 68, no. 22, pp. 4182-4186, 2012.
• B. Tabakci, O. Alici, and I. Karatas, "4-tert-butylcalix [4] arene having nitrile pendant groups as Hg2+ selective receptors," Talanta, vol. 106, pp. 92-96, 2013.
• Y. Peng, A.-J. Zhang, M. Dong, and Y.-W. Wang, "A colorimetric and fluorescent chemosensor for the detection of an explosive—2, 4, 6-trinitrophenol (TNP)," Chemical communications, vol. 47, no. 15, pp. 4505-4507, 2011.
• R. N. Dsouza, U. Pischel, and W. M. Nau, "Fluorescent dyes and their supramolecular host/guest complexes with macrocycles in aqueous solution," Chemical reviews, vol. 111, no. 12, pp. 7941-7980, 2011.
• L. You, D. Zha, and E. V. Anslyn, "Recent advances in supramolecular analytical chemistry using optical sensing," Chemical reviews, vol. 115, no. 15, pp. 7840-7892, 2015.
• B. Tabakci, E. Ozcelik, S. Erdemir, and M. Tabakci, "A highly sensitive colorimetric and fluorogenic detection of copper (II) ion based on new picolylamine-armed calix [4] arene," Measurement, vol. 210, p. 112556, 2023.
• D. M. Homden and C. Redshaw, "The use of calixarenes in metal-based catalysis," Chemical reviews, vol. 108, no. 12, pp. 5086-5130, 2008.
• R. Joseph and C. P. Rao, "Ion and molecular recognition by lower rim 1, 3-di-conjugates of calix [4] arene as receptors," Chemical reviews, vol. 111, no. 8, pp. 4658-4702, 2011.
• A. Acharya, K. Samanta, and C. P. Rao, "Conjugates of calixarenes emerging as molecular entities of nanoscience," Coordination Chemistry Reviews, vol. 256, no. 17-18, pp. 2096-2125, 2012.
• A. Bandela, J. P. Chinta, and C. P. Rao, "Role of the conformational changes brought in the arms of the 1, 3-di-capped conjugate of calix [4] arene (L) in turning on the fluorescence of L by Hg 2+," Dalton Transactions, vol. 40, no. 43, pp. 11367-11370, 2011.
• U. Darbost, M.-N. Rager, S. Petit, I. Jabin, and O. Reinaud, "Polarizing a hydrophobic cavity for the efficient binding of organic guests: the case of calix [6] tren, a highly efficient and versatile receptor for neutral or cationic species," Journal of the American Chemical Society, vol. 127, no. 23, pp. 8517-8525, 2005.
• C. D. Gutsche, Calixarenes: an introduction. Royal Society of Chemistry, 2008.
• V. Desai, M. Panchal, S. Dey, F. Panjwani, and V. K. Jain, "Recent advancements for the recognization of nitroaromatic explosives using calixarene based fluorescent probes," Journal of Fluorescence, pp. 1-13, 2022.
• Y. Ünsal, E. Özçelik, and M. Tabakcı, "FENOLFTALEİN TABANLI FLORESANS SENSÖR SENTEZİ VE SULU ORTAMDA AĞIR METALLERE KARŞI OPTİK ÖZELLİKLERİNİN İNCELENMESİ," Konya Journal of Engineering Sciences, vol. 9, pp. 187-199, 2021.
• E. Özçelik, F. Temel, and M. Tabakcı, "KALİKSAREN TÜREVİ İMMOBİLİZE EDİLMİŞ MERRIFIELD REÇİNESİ İLE KAPLI QCM SENSÖRÜNDE SULU ORTAMDA 4-NİTROFENOL ALGILANMASI," Konya Journal of Engineering Sciences, vol. 7, no. 3, pp. 595-603, 2019.
• E. Özçelik, C. Ng'andu, B. Tabakcı, and M. Tabakcı, "Phenylethylamine Derivative of Calix [4] Arene Schiff Base For Fluorometric Detection of Zinc Ion," Konya Journal of Engineering Sciences, vol. 11, no. 3, pp. 748-757, 2023.
• Y. Demir, E. Ozcelik, and M. Tabakci, "Sensing performance of Schiff base-calix [4] arene including amide units for detection of pharmaceutically active compounds on QCM sensor system," Microchemical Journal, vol. 206, p. 111446, 2024.
• E. A. Simsir, S. Erdemir, M. Tabakci, and B. Tabakci, "Nano-scale selective and sensitive optical sensor for metronidazole based on fluorescence quenching: 1H-Phenanthro [9, 10-d] imidazolyl-calix [4] arene fluorescent probe," Analytica Chimica Acta, vol. 1162, p. 338494, 2021.
• J. D. Van Loon et al., "Selective functionalization of calix [4] arenes at the upper rim," The Journal of Organic Chemistry, vol. 55, no. 21, pp. 5639-5646, 1990.
• C. D. Gutsche and L.-G. Lin, "Calixarenes 12: the synthesis of functionalized calixarenes," Tetrahedron, vol. 42, no. 6, pp. 1633-1640, 1986.
• H. Li et al., "A recyclable fluorescent probe for picric acid detection in water samples based on inner filter effect," Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol. 226, p. 117575, 2020.
• J. R. Junqueira, W. R. de Araujo, M. O. Salles, and T. R. Paixão, "Flow injection analysis of picric acid explosive using a copper electrode as electrochemical detector," Talanta, vol. 104, pp. 162-168, 2013.
• J. Huang, L. Wang, C. Shi, Y. Dai, C. Gu, and J. Liu, "Selective detection of picric acid using functionalized reduced graphene oxide sensor device," Sensors and Actuators B: Chemical, vol. 196, pp. 567-573, 2014.
• P. B. Pati and S. S. Zade, "Highly emissive triphenylamine based fluorophores for detection of picric acid," Tetrahedron Letters, vol. 55, no. 38, pp. 5290-5293, 2014.
• K. Singh, G. Chaudhary, S. Singh, and S. Mehta, "Synthesis of highly luminescent water stable ZnO quantum dots as photoluminescent sensor for picric acid," Journal of luminescence, vol. 154, pp. 148-154, 2014.