First-principles study of transition metal decorated C3 N3 nanosheet as multimodal spectroscopic and nonlinear optical biosensors for DNA/RNA base pairs detection

Tanveer Shahadat; Ali Hussain; Lubna Rasool; Abdur Rauf; Junaid Yaqoob; Muhammad Sajjad; Muzamal Hussain

doi:10.1016/j.diamond.2025.113047

First-principles study of transition metal decorated C₃ N₃ nanosheet as multimodal spectroscopic and nonlinear optical biosensors for DNA/RNA base pairs detection

Tanveer Shahadat
, Ali Hussain
, Lubna Rasool
, Abdur Rauf
, Junaid Yaqoob
, Muhammad Sajjad
, Muzamal Hussain

Research output: Journal Publication › Article › peer-review

Abstract

The increasing demand for efficient biosensors in healthcare, diagnostics, agriculture, and environmental monitoring has driven research into advanced sensing materials. This study explores the electronic and thermodynamic properties of pristine and transition metal-decorated C₃N₃ nanosheets (Fe and Ni) for detecting DNA and RNA base pairs as multimodal biosensors. All complexes were thermodynamically stable, with GC-Fe@C₃N₃ showing the highest adsorption energy (−2.20 eV in gas phase; −1.35 eV in aqueous phase). Fe@C₃N₃ exhibited the lowest bandgap (1.29 eV in gas phase; 1.41 eV in aqueous phase) and highest softness (0.78 eV), making it the most reactive and sensitive platform. GC-Fe@C₃N₃ also had the lowest ionization potential (4.71 eV) and chemical hardness (0.687 eV), confirming its high sensing capability. UV–Visible analysis revealed a large λ_max shift for AT-Ni@C₃N₃ (−1367.76 nm in gas phase; −786.96 nm in aqueous phase), while GC-Fe@C₃N₃ showed the strongest NMR shift (−4.24 ppm in gas phase; 1.68 ppm in aqueous phase), and AU-Fe@C₃N₃ displayed the highest IR vibrational blueshift (−69.99 cm⁻¹ in gas phase; −55.3 cm⁻¹ in aqueous phase). AU-Ni@C₃N₃ exhibited the strongest NLO response, with a hyperpolarizability of 166,362.28 au (both phases). NBO analysis showed effective charge transfer, especially in AT-Fe@C₃N₃ (−0.667) and AU-Ni@C₃N₃ (+1.327). NCI analysis confirmed van der Waals interactions in most complexes, with steric hindrance in Ni-decorated systems. Energy gap variation was greatest in GC-C₃N₃ (52.72 %), supporting its superior sensing performance. This study identifies Fe@C₃N₃ as a promising biosensor platform due to its enhanced adsorption energy, reactivity, and low chemical hardness, while Ni@C₃N₃ demonstrated strong optical and NLO responses, laying the foundation for future experimental investigations into C₃N₃-based biosensors for nanobiotechnology and molecular diagnostics.

Original language	English
Article number	113047
Journal	Diamond and Related Materials
Volume	160
DOIs	https://doi.org/10.1016/j.diamond.2025.113047
Publication status	Published - Dec 2025

Free Keywords

Biosensors
C3N3 nanosheet
Density functional theory
Non-linear optics
Spectroscopic technique

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Chemistry
Mechanical Engineering
General Physics and Astronomy
Materials Chemistry
Electrical and Electronic Engineering

Access to Document

10.1016/j.diamond.2025.113047

Cite this

@article{b4a8b21fad464f66a25e7e0b9a243f34,

title = "First-principles study of transition metal decorated C3 N3 nanosheet as multimodal spectroscopic and nonlinear optical biosensors for DNA/RNA base pairs detection",

abstract = "The increasing demand for efficient biosensors in healthcare, diagnostics, agriculture, and environmental monitoring has driven research into advanced sensing materials. This study explores the electronic and thermodynamic properties of pristine and transition metal-decorated C₃N₃ nanosheets (Fe and Ni) for detecting DNA and RNA base pairs as multimodal biosensors. All complexes were thermodynamically stable, with GC-Fe@C₃N₃ showing the highest adsorption energy (−2.20 eV in gas phase; −1.35 eV in aqueous phase). Fe@C₃N₃ exhibited the lowest bandgap (1.29 eV in gas phase; 1.41 eV in aqueous phase) and highest softness (0.78 eV), making it the most reactive and sensitive platform. GC-Fe@C₃N₃ also had the lowest ionization potential (4.71 eV) and chemical hardness (0.687 eV), confirming its high sensing capability. UV–Visible analysis revealed a large λmax shift for AT-Ni@C₃N₃ (−1367.76 nm in gas phase; −786.96 nm in aqueous phase), while GC-Fe@C₃N₃ showed the strongest NMR shift (−4.24 ppm in gas phase; 1.68 ppm in aqueous phase), and AU-Fe@C₃N₃ displayed the highest IR vibrational blueshift (−69.99 cm−1 in gas phase; −55.3 cm−1 in aqueous phase). AU-Ni@C₃N₃ exhibited the strongest NLO response, with a hyperpolarizability of 166,362.28 au (both phases). NBO analysis showed effective charge transfer, especially in AT-Fe@C₃N₃ (−0.667) and AU-Ni@C₃N₃ (+1.327). NCI analysis confirmed van der Waals interactions in most complexes, with steric hindrance in Ni-decorated systems. Energy gap variation was greatest in GC-C₃N₃ (52.72 \%), supporting its superior sensing performance. This study identifies Fe@C₃N₃ as a promising biosensor platform due to its enhanced adsorption energy, reactivity, and low chemical hardness, while Ni@C₃N₃ demonstrated strong optical and NLO responses, laying the foundation for future experimental investigations into C₃N₃-based biosensors for nanobiotechnology and molecular diagnostics.",

keywords = "Biosensors, C3N3 nanosheet, Density functional theory, Non-linear optics, Spectroscopic technique",

author = "Tanveer Shahadat and Ali Hussain and Lubna Rasool and Abdur Rauf and Junaid Yaqoob and Muhammad Sajjad and Muzamal Hussain",

note = "Publisher Copyright: {\textcopyright} 2025 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.",

year = "2025",

month = dec,

doi = "10.1016/j.diamond.2025.113047",

language = "English",

volume = "160",

journal = "Diamond and Related Materials",

issn = "0925-9635",

publisher = "Elsevier B.V.",

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TY - JOUR

T1 - First-principles study of transition metal decorated C3 N3 nanosheet as multimodal spectroscopic and nonlinear optical biosensors for DNA/RNA base pairs detection

AU - Shahadat, Tanveer

AU - Hussain, Ali

AU - Rasool, Lubna

AU - Rauf, Abdur

AU - Yaqoob, Junaid

AU - Sajjad, Muhammad

AU - Hussain, Muzamal

PY - 2025/12

Y1 - 2025/12

N2 - The increasing demand for efficient biosensors in healthcare, diagnostics, agriculture, and environmental monitoring has driven research into advanced sensing materials. This study explores the electronic and thermodynamic properties of pristine and transition metal-decorated C₃N₃ nanosheets (Fe and Ni) for detecting DNA and RNA base pairs as multimodal biosensors. All complexes were thermodynamically stable, with GC-Fe@C₃N₃ showing the highest adsorption energy (−2.20 eV in gas phase; −1.35 eV in aqueous phase). Fe@C₃N₃ exhibited the lowest bandgap (1.29 eV in gas phase; 1.41 eV in aqueous phase) and highest softness (0.78 eV), making it the most reactive and sensitive platform. GC-Fe@C₃N₃ also had the lowest ionization potential (4.71 eV) and chemical hardness (0.687 eV), confirming its high sensing capability. UV–Visible analysis revealed a large λmax shift for AT-Ni@C₃N₃ (−1367.76 nm in gas phase; −786.96 nm in aqueous phase), while GC-Fe@C₃N₃ showed the strongest NMR shift (−4.24 ppm in gas phase; 1.68 ppm in aqueous phase), and AU-Fe@C₃N₃ displayed the highest IR vibrational blueshift (−69.99 cm−1 in gas phase; −55.3 cm−1 in aqueous phase). AU-Ni@C₃N₃ exhibited the strongest NLO response, with a hyperpolarizability of 166,362.28 au (both phases). NBO analysis showed effective charge transfer, especially in AT-Fe@C₃N₃ (−0.667) and AU-Ni@C₃N₃ (+1.327). NCI analysis confirmed van der Waals interactions in most complexes, with steric hindrance in Ni-decorated systems. Energy gap variation was greatest in GC-C₃N₃ (52.72 %), supporting its superior sensing performance. This study identifies Fe@C₃N₃ as a promising biosensor platform due to its enhanced adsorption energy, reactivity, and low chemical hardness, while Ni@C₃N₃ demonstrated strong optical and NLO responses, laying the foundation for future experimental investigations into C₃N₃-based biosensors for nanobiotechnology and molecular diagnostics.

AB - The increasing demand for efficient biosensors in healthcare, diagnostics, agriculture, and environmental monitoring has driven research into advanced sensing materials. This study explores the electronic and thermodynamic properties of pristine and transition metal-decorated C₃N₃ nanosheets (Fe and Ni) for detecting DNA and RNA base pairs as multimodal biosensors. All complexes were thermodynamically stable, with GC-Fe@C₃N₃ showing the highest adsorption energy (−2.20 eV in gas phase; −1.35 eV in aqueous phase). Fe@C₃N₃ exhibited the lowest bandgap (1.29 eV in gas phase; 1.41 eV in aqueous phase) and highest softness (0.78 eV), making it the most reactive and sensitive platform. GC-Fe@C₃N₃ also had the lowest ionization potential (4.71 eV) and chemical hardness (0.687 eV), confirming its high sensing capability. UV–Visible analysis revealed a large λmax shift for AT-Ni@C₃N₃ (−1367.76 nm in gas phase; −786.96 nm in aqueous phase), while GC-Fe@C₃N₃ showed the strongest NMR shift (−4.24 ppm in gas phase; 1.68 ppm in aqueous phase), and AU-Fe@C₃N₃ displayed the highest IR vibrational blueshift (−69.99 cm−1 in gas phase; −55.3 cm−1 in aqueous phase). AU-Ni@C₃N₃ exhibited the strongest NLO response, with a hyperpolarizability of 166,362.28 au (both phases). NBO analysis showed effective charge transfer, especially in AT-Fe@C₃N₃ (−0.667) and AU-Ni@C₃N₃ (+1.327). NCI analysis confirmed van der Waals interactions in most complexes, with steric hindrance in Ni-decorated systems. Energy gap variation was greatest in GC-C₃N₃ (52.72 %), supporting its superior sensing performance. This study identifies Fe@C₃N₃ as a promising biosensor platform due to its enhanced adsorption energy, reactivity, and low chemical hardness, while Ni@C₃N₃ demonstrated strong optical and NLO responses, laying the foundation for future experimental investigations into C₃N₃-based biosensors for nanobiotechnology and molecular diagnostics.

KW - Biosensors

KW - C3N3 nanosheet

KW - Density functional theory

KW - Non-linear optics

KW - Spectroscopic technique

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U2 - 10.1016/j.diamond.2025.113047

DO - 10.1016/j.diamond.2025.113047

M3 - Article

AN - SCOPUS:105023825566

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