Photocatalytic Transformation of Guanine Using Colloidal CdS Nanoparticles

Abstract

Investigations into the photoinduced reactions of deoxyribonucleic acid (DNA) bases are important for human health. Herein, we have synthesized colloidal CdS nanoparticles by a method reported in the literature. The mean particle diameter of the semiconductor was about 55 nm. The colloidal CdS particles were used as a photocatalyst to investigate the organic transformation of guanine (2-amino-6-oxopurine). The products of the semiconductor-induced reaction were analyzed by liquid chromatography-mass chromatography (LC-MS) measurements. The solitary product of the photocatalytic reaction of guanine was revealed as 2,5-diamino-4 H -imidazol-4-one. The likely reaction pathway for the formation of the product has been presented. To our understanding, the present work is the first account on the mechanistic aspects of the semiconductor-induced photocatalytic reaction of guanine.

Keywords

Colloidal CdS / Guanine / Photocatalytic / Irradiation / Semiconductor

CRediT authorship contribution statement

Author Contributions Conceptualization, P.R. and D.P.S.N.; Methodology, P.R.; Validation, P.R.; Formal Analysis, P.R.; Investigation, P.R.; Resources, D.P.S.N.; Data Curation, P.R.; Writing—Original Draft Preparation, P.R.; Writing—Review & Editing, D.P.S.N.; Supervision, D.P.S.N.

Availability of data and materials

Data is available upon request.

Funding

This research received no external funding.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

Acknowledgments We thank the Central Electrochemical Research Institute (CECRI), Karaikudi, India, for the TEM measurements. We would like to acknowledge the NIT, Meghalaya, India, for the XRD analysis. The Sophisticated Analytical Instrument Facility at the Mahatma Gandhi University, Kottayam, India, is acknowledged for the LC-MS measurements.

References

[1] Wang XX, Gu Y, Fang YF, Huang YP. Mechanism of oxidative damage to DNA by Fe-loaded MCM-41 irradiated with visible light. Chin. Sci. Bull. 2012, 57, 1504-1509. DOI:10.1007/s11434-012-5042-1

[2] Cadet J, Douki T, Ravanat J-L. Oxidatively generated damage to the guanine moiety of DNA: Mechanistic aspects and formation in cells. Acc. Chem. Res. 2008, 41, 1075-1083. DOI:10.1021/ar700245e

[3] Bull GD, Thompson KC. The oxidation of guanine by photoionized 2-aminopurine. J. Photochem. Photobiol. 2021, 6, 100025. DOI:10.1016/j.jpap.2021.100025

[4] Steenken S, Jovanovic SV. How easily oxidizable is DNA? One-electron reduction potentials of adenosine and guanosine radicals in aqueous solution. J. Am. Chem. Soc. 1997, 119, 617-618. DOI:10.1021/ja962255b

[5] Duarte V, Gasparutto D, Jaquinod M, Cadet J. In vitro DNA synthesis opposite oxazolone and repair of this DNA damage using modified oligonucleotides. Nucleic Acids Res. 2000, 28, 1555-1563. DOI:10.1093/nar/28.7.1555

[6] Smirnova VS, Gudkov SV, Chernikov AV, Bruskov VI. The formation of 8-oxoguanine and its oxidative products in DNA in vitro at 37 degrees C. Biofizika 2005, 50, 243-252.

[7] Kino K, Sugiyama H. Possible causes of G·C→C·G transversion mutation by guanine oxidation product, imidazolone. Chem. Biol. 2001, 8, 369-378. DOI:10.1016/S1074-5521(01)00019-9

[8] Gasparutto D, Ravanat J-L, Gerot O, Cadet J. Characterization and chemical stability of photooxidized oligonucleotides that contain 2,2-diamino-4-[(2-deoxy-β-D-erythro-pentofuranosyl) amino]-5(2H)-oxazolone. J. Am. Chem. Soc. 1998, 120, 10283-10286. DOI:10.1021/ja980674y

[9] Kino K, Saito I, Sugiyama H. Product analysis of GG-specific photooxidation of DNA via electron transfer: 2-aminoimidazolone as a major guanine oxidation product. J. Am. Chem. Soc. 1998, 120, 7373-7374. DOI:10.1021/ja980763a

[10] Kupan A, Saulière A, Broussy S, Seguy C, Pratviel G, Meunier B. Guanine oxidation by electron transfer: One-versus two-electron oxidation mechanism. ChemBioChem 2006, 7, 125-133. DOI:10.1002/cbic.200500284

[11] Jena NR, Mishra PC. Formation of ring-opened and rearranged products of guanine: Mechanisms and biological significance. Free Rad. Biol. Med. 2021, 53, 81-94. DOI:10.1016/j.freeradbiomed.2012.04.008

[12] Ravanat JL, Cadet J. Reaction of singlet oxygen with 2′-deoxyguanosine and DNA. Isolation and characterization of the main oxidation products. Chem. Res. Toxicol. 1995, 8, 379-388. DOI:10.1021/tx00045a009

[13] Niles JC, Wishnok JS, Tannenbaum SR. Spiroiminodihydantoin is the major product of the 8-oxo-7,8-dihydroguanosine reaction with peroxynitrite in the presence of thiols and guanosine photooxidation by methylene blue. Org. Lett. 2001, 3, 963-966. DOI:10.1021/ol006993n

[14] Fleming AM, Burrows CJ. Chemistry of ROS-mediated oxidation to the guanine base in DNA and its biological consequences. Int. J. Radiat. Biol. 2021, 98, 452-460. DOI:10.1080/09553002.2021.2003464

[15] Jomova K, Alomar SY, Alwasel SH, Nepovimoba E, Kuca K, Valko M. Several lines of antioxidant defense against oxidative stress: Antioxidant enzymes, nanomaterials with multiple enzyme-mimicking activities, and low-molecular-weight antioxidants. Arch. Toxicol. 2024, 98, 1323-1367. DOI:10.1007/s00204-024-03696-4

[16] Jabbar ZH, Ebrahim SE. Recent advances in nano-semiconductors photocatalysis for degrading organic contaminants and microbial disinfection in wastewater: A comprehensive review. Environ. Nanotechnol. Monit. Manag. 2022, 17, 100666. DOI:10.1016/j.enmm.2022.100666

[17] Cui S, Wang X, Lin Z, Ding M, Yang X. Cation exchange synthesis of hollow-structure cadmium sulfide for efficient visible-light driven photocatalytic hydrogen evolution. Int. J. Hydrogen Energy 2023, 48, 26757-26767. DOI:10.1016/j.ijhydene.2023.03.379

[18] Li B, Xiao Y, Qi Z, Chang S, Yu M, Xu Z, et al. Enhanced photocatalytic H₂ production of CdS by the introduction of Cd vacancies. Chem. Commun. 2025, 61, 15630-15633. DOI:10.1039/D5CC03311J

[19] Qi Z, Chen J, Li Q, Wang N, Carabineiro SAC, Lv K. Increasing the photocatalytic hydrogen generation activity of CdS nanorods by introducing interfacial and polarization electric fields. Small 2023, 19, 2305518. DOI:10.1002/smll.202303318

[20] Warjri W, Saha D, Diamai S, Negi DPS. Catechol oxidase mimetic activity of cadmium sulfide nanoparticles for the oxidation of L-3,4-dihydroxyphenylalanine. Mater. Res. Express 2019, 6, 035020. DOI:10.1088/2053-1591/aaf523

[21] Dhananjeyan MR, Annapoorani R, Lakshmi S, Renganathan R. An investigation on TiO₂-assisted photo-oxidation of thymine. J. Photochem. Photobiol. A Chem. 1996, 96, 187-191. DOI:10.1016/1010-6030(95)04297-0

[22] Kumar A, Negi DPS. Photophysics and photocatalytic properties of Cd(OH)₂-coated Q-CdS clusters in the presence of guanine and related compounds. J. Colloid Inter. Sci. 2001, 238, 310-317. DOI:10.1006/jcis.2001.7483

[23] Hou H, Wang X, Chen C, Johnson DM, Fang Y, Huang Y. Mechanism of photocatalytic oxidation of guanine by BiOBr under UV irradiation. Catal. Commun. 2014, 48, 65-68. DOI:10.1016/j.catcom.2014.01.023

[24] Spanhel L, Haase M, Weller H, Henglein A. Photochemistry of colloidal semiconductors. 20. Surface modification and stability of strong luminescing CdS particles. J. Am. Chem. Soc. 1987, 109, 5649-5655. DOI:10.1021/ja00253a015

[25] Saha D, Negi DPS. Particle size enlargement and 6-fold fluorescence enhancement of colloidal CdS quantum dots induced by selenious acid. Spectrochim. Acta A 2020, 225, 117486. DOI:10.1016/j.saa.2019.117486

[26] Pandian SRK, Deepak V, Kalishwaralal K, Gurunathan S. Biologically synthesized fluorescent CdS NPs encapsulated by PHB. Enzyme Microb. Technol. 2011, 48, 319-325. DOI:10.1016/j.enzmictec.2011.01.005

[27] Oliveira JFA, Milão TM, Araújo VD, Moreira ML, Longo E, Bernardi MIB. Influence of different solvents on the structural, optical and morphological properties of CdS nanoparticles. J. Alloys Compd. 2011, 509, 6880-6883. DOI:10.1016/j.jallcom.2011.03.171

[28] Razskazovskiy Y, Campbell EB, Cutright ZD, Thomas CS, Roginskaya M. One-electron oxidation of guanine derivatives: Detection of 2,5-diaminoimidazolone and novel guanine-guanine cross-links as major end products. Radiat. Phys. Chem. 2022, 196, 110099. DOI:10.1016/j.radphyschem.2022.110099

[29] Morikawa M, Kino K, Oyoshi T, Suzuki M, Kobayashi T, Miyazawa H. Analysis of guanine oxidation products in double-stranded DNA and proposed guanine oxidation pathways in single-stranded, double-stranded or quadruplex DNA. Biomolecules 2014, 4, 140-159. DOI:10.3390/biom4010140

[30] Park B, Park W-W, Choi JY, Choi W, Sung YM, Sul S, et al. Pt cocatalyst morphology on semiconductor nanorod photocatalysts enhances charge trapping and water reduction. Chem. Sci. 2023, 14, 7553-7558. DOI:10.1039/D3SC01429K

[31] Taki MM, Mahdi RI, Al-Keisy A, Alsultan M, Al-Bahnam NJ, Majid WHA, et al. Solar-light-driven Ag₉(SiO₄)₂NO₃ for efficient photocatalytic bactericidal performance. J. Compos. Sci. 2022, 6, 108. DOI:10.3390/jcs6040108

[32] Cadet J, Berger M, Buchko GW, Joshi PC, Raoul S, Ravanat J-L. 2,2-diamino-4-[(3,5-di-O-acetyl-2-deoxy-β-D-erythro-pentofuranosyl)amino]-5-(2H)-oxazolone: A novel and predominant radical oxidation product of 3′5′-di-O-acetyl-2′-deoxyguanosine. J. Am. Chem. Soc. 1994, 116, 7403-7404. DOI:10.1021/ja00095a052