Anilin ve Türevlerini İçeren Hibrit Nanoçiçeklerin Sentezi ve Potansiyel Peroksidaz Benzeri Aktivitesi

Öz

Fonksiyonel organik-inorganik hibrit nanoçiçekler, benzersiz morfoloji özellikleri ve gelişmiş katalitik aktivite nedeniyle son zamanlarda büyük ilgi görmektedirler. Bu çalışmada, organik bileşenler olarak anilin ve türevleri ile bakır II iyonları kullanılarak organik-inorganik hibrit nanoçiçek'ler başarıyla sentezlendi. Nanoçiçeklerin morfolojileri taramalı elektron mikroskobu ile incelendi. Enerji dağılımlı X-ışını spektroskopisi analizi, nanoçiçeklerde bakır metalinin varlığını doğruladı. Sentezlenen nanoçiçeklerin peroksidaz benzeri katalitik aktiviteleri, substrat olarak kullanılan guaiakol'e karşı değerlendirildi. UV-vis spektrofotometre kullanılarak 470 nm'de absorbansda önemli bir zamana bağlı artış ölçüldü. Nonoçiçek'ler, hidrojen peroksit varlığında guaiakol'ün 3,3-dimetoksi-4,4-difenokinona oksidasyonunu katalize etti. Bu gelişmiş katalitik performans, nanoçiçekler ve substrat arasında verimli kütle transferini kolaylaştıran benzersiz nanoçiçek morfolojisine atfedilir. Bu nanoçiçeklerin, olağanüstü peroksidaz benzeri aktiviteleriyle enzim nanoçiçeklerine alternatif olabileceğini iddia ediyoruz.

Anahtar Kelimeler

• Anilin
• katalitik aktivite
• organik-inorganik nanoçiçek

Etik Beyan

Bu çalışma klinik örnekler kullanmadığı için etik kurul onayına ihtiyaç duymamaktadır.

Synthesis of Aniline and it's Derivatives- Incorporated Hybrid Nanoflowers with Potential Peroxidase-Like Activity

Öz

Functional organic-inorganic hybrid nanoflowers have recently attracted considerable attention due to their unique morphological properties and enhanced catalytic activity. In this study, we successfully synthesized organic-inorganic hybrid nanoflowers using aniline and its derivatives as organic components and copper II ions. The morphologies of the nanoflowers were observed by scanning electron microscopy. Energy-dispersive X-ray spectroscopy analysis confirmed the presence of copper metal in the nanoflowers. The peroxidase-like catalytic activities of the synthesized nanoflowers were evaluated towards the guaiacol used as a substrate. A significant time-dependent increase in absorbance was measured at 470 nm using a UV-vis spectrophotometer. The nanoflowers catalyzed the oxidation of guaiacol to 3, 3-dimethoxy-4, 4-diphenoquinone in the presence of hydrogen peroxide via Fenton-like reaction. This enhanced catalytic performance is attributed to the unique nanoflowers morphology, which facilitates efficient mass transfer between the nanoflowers and the substrate. We claim that these nanoflowers can be alternative to enzyme nanoflowers with their remarkable peroxidase-like activity.

Anahtar Kelimeler

• Aniline
• catalytic activity
• organic-inorganic nanoflowers

Etik Beyan

This study does not use clinical samples and does not require ethical committee approval.

Kaynakça

1. Blum AP, Kammeyer JK, Rush AM, Callmann CE, Hahn ME, Gianneschi NC. Stimuli-responsive nanomaterials for biomedical applications. J Am Chem Soc. 2015;137(6):2140-2154. doi:10.1021/ja510147n
2. Lin Y, Ren J, Qu X. Catalytically active nanomaterials: a promising candidate for artificial enzymes. Acc Chem Res. 2014;47(4):1097-1105. doi.org/10.1021/ar400250z
3. Su S, Wu W, Gao J, Lu J, Fan C. Nanomaterials-based sensors for applications in environmental monitoring. J Mater Chem. 2012;22(35):18101-18110. doi:10.1039/C2JM33284A
4. Xing Y, Li L, Chen Y, Wang L, Tang S, Xie X, et al. Flower-like nanozyme with highly porous carbon matrix induces robust oxidative storm against drug-resistant cancer. ACS Nano. 2023;17(7):6731-6744. doi:10.1021/acsnano.2c12698
5. Arabaci N, Karaytug T, Dadi S, Ocsoy I. Synthesis of novel alkaline protease-incorporated hybrid nanoflowers (atP@hNFs) and their applications in the laundry detergent industry. ACS Omega. 2025;10(39):45366-45381. doi:10.1021/acsomega.5c05223
6. Yilmaz E, Koca FD, Saticioglu IB, Ozen B, Yilmaz DD, Nisari M, et al. Formation of colchicine-incorporated hybrid nanoflower with an intrinsic peroxidase-mimic and enhanced antimicrobial activities. Chem Biodivers. 2025;e00911. doi:10.1002/cbdv.202500911
7. Somturk B, Yilmaz I, Altinkaynak C, Karatepe A, Ozdemir N, Ocsoy I. Protein–inorganic hybrid nanoflowers: a novel platform for enhanced enzymatic activity and stability. Enzyme Microb Technol. 2016;86:134-142. doi:10.1016/j.enzmictec.2015.09.005
8. Amini B, Lowenkron S. Aniline and its derivatives. In: Kirk-Othmer Encyclopedia of Chem Technol. 2000. doi:10.1002/0471238961.0114091201130914.a01

9. Gross KC, Seybold PG. Substituent effects on the physical properties and pKa of aniline. Int J Quantum Chem. 2000;80(4-5):1107-1115. doi:10.1002/qua.1525
10. Shaibu OR, Watkins MG. Synthesis and characterization of variously substituted hydroxybenzaldimines derived from the condensation of aniline or 1-aminonaphthalene with salicylaldehyde and its derivatives. Ife J Sci. 2016;18(3):613-622.
11. Saha B, De S, Dutta S. Recent advancements of replacing existing aniline production process with environmentally friendly one-pot process: an overview. Crit Rev Environ Sci Technol. 2013;43(1):84-120. doi: 10.1080/10643389.2011.604252
12. Zhang H, Ma J, Qian Y, Huang J. Synthesis and characterization of nitrogen-functionalized cyclopentadienylchromium complexes and their use as catalysts for olefin polymerization. Organometallics. 2004;23(24):5681-5688. doi:10.1021/om049731o
13. Demirbas A, Karsli B, Ocsoy I. Facile synthesis of hybrid nanoflowers using glycine and phenylalanine and investigation of their catalytic activity. Chem Biodivers. 2023;20(8):e202300743. doi:10.1002/cbdv.202300743
14. Yilmaz SG, Demirbas A, Karaagac Z, Dadi S, Celik C, Yusufbeyoglu S, et al. Synthesis of taurine-Cu₃(PO₄)₂ hybrid nanoflower and their peroxidase-mimic and antimicrobial properties. J Biotechnol. 2022;343:96-101. doi:10.1016/j.jbiotec.2021.11.009
15. Altinkaynak C, Tavlasoglu S, Kalin R, Sadeghian N, Ozdemir H, Ocsoy I, Özdemir N. A hierarchical assembly of flower-like hybrid Turkish black radish peroxidase-Cu²⁺ nanobiocatalyst and its effective use in dye decolorization. Chemosphere. 2017;182:122-128. doi:10.1016/j.chemosphere.2017.05.012
16. Lines MG. Nanomaterials for practical functional uses. J Alloys Compd. 2008;449(1–2):242-245. doi:10.1016/j.jallcom.2006.02.082
17. Behera A, Mohapatra SS, Verma DK. Nanomaterials: fundamental principle and applications. In: Nanotechnology and Nanomaterial Applications in Food, Health, and Biomedical Sciences. Apple Academic Press; 2019. p.163-194.
18. Dadi S, Ocsoy I. Role of pretty nanoflowers as novel versatile analytical tools for sensing in biomedical and bioanalytical applications. Smart Med. 2024;3(1):e20230040. doi:10.1002/SMMD.20230040
19. Somturk B, Yilmaz I, Altinkaynak C, Karatepe A, Ozdemir N, Ocsoy I. Synthesis of urease hybrid nanoflowers and their enhanced catalytic properties. Enzyme Microb Technol. 2016;86:134-142. doi:10.1016/j.enzmictec.2015.09.005
20. Altinkaynak C, Tavlasoglu S, Kalin R, Sadeghian N, Ozdemir H, Ocsoy I. Hybrid nanoflowers: synthesis, characterization, and applications in catalysis and biosensing. TrAC Trends Anal Chem. 2020;132:116047. doi:10.1016/j.chemosphere.2017.05.012
21. Khan MA, Nayan N, Shadiullah, Ahmad MK, Fhong SC, Tahir M, et al. Advanced nanoscale surface characterization of CuO nanoflowers for significant enhancement of catalytic properties. Molecules. 2021;26(9):2700. doi:10.3390/molecules26092700
22. Chormey DS, Erarpat S, Zaman BT, Özdoğan N, Yağmuroğlu O, Bakırdere S. Nanoflower synthesis, characterization and analytical applications: a review. Environ Chem Lett. 2023;21(3):1863-1880. doi:10.1007/s10311-023-01572-8
23. Kalayci B, Kaplan N, Dadi S, Ocsoy I, Gokturk E. Production of flower-shaped nanobiocatalysts from green tea and investigation of their peroxidase mimicking activity on the polymerization of phenol derivatives. Polym Adv Technol. 2024;35(1):e6272. doi:10.1002/pat.6272
24. Demirbaş A, Karsli B, Dadi S, Koca F, Halici M, Ocsoy I. Usnea antarctica and Usnea subfloridana incorporated hybrid nanoflowers with their intrinsic catalytic and antimicrobial activities. ChemSelect. 2022;7(43). doi:10.1002/slct.202202715
25. Koca FD. Preparation of thymol incorporated organic-inorganic hybrid nanoflowers as a novel Fenton agent with intrinsic catalytic and antimicrobial activities. Inorg Nano-Met Chem. 2022;52(2):322-327. doi:10.1080/24701556.2021.1980024