Electrostatic Enhanced Terahertz Metamaterial Biosensing Via Gold Nanoparticles Integrated with Biomolecules

Overview

Journal Sci Rep

Specialty Science

Date 2025 Mar 13

PMID 40075221

Authors

Min Zhang

Liwen Jiang

Shuo Wang

Shoujun Zhang

Meng Liu

Yuping Zhang

Huiyun Zhang

Zhen Tian

Affiliations

Soon will be listed here.

Abstract

Terahertz spectroscopy has drawn great interest for the detection and characterization of biological matter, but its limited sensitivity to biomolecules with weak changes in dielectric properties with varying concentration has hinders potential bio-sensing applications. Here, a novel terahertz sensor was developed for enhancing the ability to detect biomolecules based on two electromagnetically induced transparency (EIT) metamaterials coupled with gold nanoparticles (AuNPs) integrated with biomolecules. The electrostatic interaction between AuNPs and positively charged biomolecules generates localized field enhancement at the biomolecule-metamaterial interface, resulting in a threefold increase in sensitivity for positively charged histidine that exhibit weak dielectric property changes with varying concentration. As a contrast, glucose shows a weaker effect due to its electrostatically neutral nature. Experimental studies reveal that by evaluating the modulation depth (MD) and modulation enhancement (ME) factors of the transmission peak for histidine and glucose in the presence of AuNPs, we achieve and enhance intuitive detection and discrimination of these biomolecules. Additionally, a two-EIT metamaterial with a 1 × 2 pixel array enables multiparameter imaging, visualizing the concentration and spatial distribution of biomolecules. Our results not only significantly improve the response sensitivity of biomolecules with weak dielectric properties in the terahertz domain, but also provide a new idea for developing high-sensitivity functionalized terahertz biosensors and advancing multi-biomolecular analysis and imaging techniques.

References

Haes A, Van Duyne R . A unified view of propagating and localized surface plasmon resonance biosensors. Anal Bioanal Chem. 2004; 379(7-8):920-30. DOI: 10.1007/s00216-004-2708-9. View

Yue Y, He F, Chen L, Shu F, Jing X, Hong Z . Analogue of electromagnetically induced transparency in a metal-dielectric bilayer terahertz metamaterial. Opt Express. 2021; 29(14):21810-21819. DOI: 10.1364/OE.428758. View

Qiu G, Gai Z, Tao Y, Schmitt J, Kullak-Ublick G, Wang J . Dual-Functional Plasmonic Photothermal Biosensors for Highly Accurate Severe Acute Respiratory Syndrome Coronavirus 2 Detection. ACS Nano. 2020; 14(5):5268-5277. DOI: 10.1021/acsnano.0c02439. View

Chen S, Wang W, Xu S, Fu C, Ji S, Luo F . Single nanoparticle identification coupled with auto-identify algorithm for rapid and accurate detection of L-histidine. Anal Chim Acta. 2021; 1187:339162. DOI: 10.1016/j.aca.2021.339162. View

Bessou M, Chassagne B, Caumes J, Pradere C, Maire P, Tondusson M . Three-dimensional terahertz computed tomography of human bones. Appl Opt. 2012; 51(28):6738-44. DOI: 10.1364/AO.51.006738. View

Khodaie A, Heidarzadeh H . Evaluation of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) using a high figure-of-merit plasmonic multimode refractive index optical sensor. Sci Rep. 2024; 14(1):25499. PMC: 11513005. DOI: 10.1038/s41598-024-77336-3. View

Ruggiero M, Sibik J, Orlando R, Zeitler J, Korter T . Measuring the Elasticity of Poly-l-Proline Helices with Terahertz Spectroscopy. Angew Chem Int Ed Engl. 2016; 55(24):6877-81. PMC: 4999051. DOI: 10.1002/anie.201602268. View

Zhou J, Zhao X, Huang G, Yang X, Zhang Y, Zhan X . Molecule-Specific Terahertz Biosensors Based on an Aptamer Hydrogel-Functionalized Metamaterial for Sensitive Assays in Aqueous Environments. ACS Sens. 2021; 6(5):1884-1890. DOI: 10.1021/acssensors.1c00174. View

Calinsky R, Levy Y . Histidine in Proteins: pH-Dependent Interplay between π-π, Cation-π, and CH-π Interactions. J Chem Theory Comput. 2024; 20(15):6930-6945. PMC: 11325542. DOI: 10.1021/acs.jctc.4c00606. View

10.

Tang S, Wu X, Zhao P, Tang K, Chen Y, Fu J . A near-infrared fluorescence capillary imprinted sensor for chiral recognition and sensitive detection of l-histidine. Anal Chim Acta. 2022; 1206:339794. DOI: 10.1016/j.aca.2022.339794. View

11.

Ahmadivand A, Gerislioglu B, Ramezani Z, Kaushik A, Manickam P, Ghoreishi S . Functionalized terahertz plasmonic metasensors: Femtomolar-level detection of SARS-CoV-2 spike proteins. Biosens Bioelectron. 2021; 177:112971. PMC: 7787065. DOI: 10.1016/j.bios.2021.112971. View

12.

Choi M, Lee S, Kim Y, Kang S, Shin J, Kwak M . A terahertz metamaterial with unnaturally high refractive index. Nature. 2011; 470(7334):369-73. DOI: 10.1038/nature09776. View

13.

Schneider F . Histidine in enzyme active centers. Angew Chem Int Ed Engl. 1978; 17(8):583-92. DOI: 10.1002/anie.197805831. View

14.

Janke C, Forst M, Nagel M, Kurz H, Bartels A . Asynchronous optical sampling for high-speed characterization of integrated resonant terahertz sensors. Opt Lett. 2005; 30(11):1405-7. DOI: 10.1364/ol.30.001405. View

15.

Yan X, Yang M, Zhang Z, Liang L, Wei D, Wang M . The terahertz electromagnetically induced transparency-like metamaterials for sensitive biosensors in the detection of cancer cells. Biosens Bioelectron. 2018; 126:485-492. DOI: 10.1016/j.bios.2018.11.014. View

16.

Lee D, Kang J, Lee J, Kim H, Kim C, Kim J . Highly sensitive and selective sugar detection by terahertz nano-antennas. Sci Rep. 2015; 5:15459. PMC: 4616020. DOI: 10.1038/srep15459. View

17.

Wu W, Liu W, Chun Z, Ling Y, Ding J, Wang X . Optical rotation and electromagnetically induced transparency in a chiral metamaterial with C symmetry. Opt Express. 2020; 28(20):29496-29512. DOI: 10.1364/OE.403421. View

18.

Mayer K, Hafner J . Localized surface plasmon resonance sensors. Chem Rev. 2011; 111(6):3828-57. DOI: 10.1021/cr100313v. View

19.

Yang K, Yang X, Zhao X, Lamy de la Chapelle M, Fu W . THz Spectroscopy for a Rapid and Label-Free Cell Viability Assay in a Microfluidic Chip Based on an Optical Clearing Agent. Anal Chem. 2018; 91(1):785-791. DOI: 10.1021/acs.analchem.8b03665. View

20.

Yanik A, Huang M, Kamohara O, Artar A, Geisbert T, Connor J . An optofluidic nanoplasmonic biosensor for direct detection of live viruses from biological media. Nano Lett. 2010; 10(12):4962-9. PMC: 3123676. DOI: 10.1021/nl103025u. View