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An innovative and versatile reconfigurable sensor for the detection of biomolecules via metal ion-mediated recognition
1 , 1 , 1 , 2 , 2 , 3 , * 3 , * 1
1  Laboratorio di Chimica Analitica, Dipartimento di Scienze e Tecnologie Biologiche e Ambientali (Di.S.Te.B.A.), Università del Salento, via Monteroni 73100 Lecce – Italy
2  Laboratorio di Fisiologia, Dipartimento di Scienze e Tecnologie Biologiche e Ambientali (Di.S.Te.B.A.), Università del Salento, via Monteroni 73100 Lecce – Italy
3  Dipartimento di Ingegneria dell’Informazione, Università di Pisa, via G. Caruso 16, 56126 Pisa – Italy
Academic Editor: Jun-Jie Zhu

Abstract:

Introduction

Reconfiguration of chemical sensors, meaning the capacity to adapt the sensor to new target analytes, is potentially game changing and would enable rapid and cost-effective reactions to dynamic changes occurring at different levels, although this is still a challenge. Here, we report on a reconfigurable label-free optical sensor leveraging versatile immobilization of a metal ion chelating agent on a nanostructured porous silica (PSiO2) optical transducer for the detection of different biomolecules.

Method

PSiO2 scaffolds were functionalized with a modified silane, GLYMO-IDA, preliminarily derived from a condensation reaction between 3-glycidoxypropyltrimethoxysilane (GLYMO) and iminodiacetic acid (IDA). When exposed to aqueous solutions of metal ions (e.g., Zn2+, Ni2+, Cu2+, Fe3+), GLYMO-IDA exhibits the ability to chelate them. The as-modified silane was employed as a receptor for biomolecules, leveraging the metal ions as pivotal points. The metal ion on GLYMO-IDA was easily switched by treating the PSiO2 samples with a complexing agent.

Results

Successful functionalization of PSiO2 scaffolds with the artificial receptors for various biomolecules was corroborated via UV-VIS spectroscopy and XPS analysis. After switching the metal ions from Cu2+ to Zn2+, the sensor was used in carnosine detection tests, proving its ability, in both configurations, to detect the target in a concentration range between 0.1 and 1 mM. Alternatively, by switching Cu2+ with Fe3+ ions, the sensor was successfully used for adenosine triphosphate (ATP) detection. A satisfactory sample-to-sample reproducibility was obtained (RSD: ~15%), along with an excellent repeatability (RSD: 2.5%) and stability (30 days).

Conclusions

A reconfigurable sensing platform was developed, and sensor reconfiguration was achieved by switching the metal ions from Cu2+ to Zn2+ and testing its ability to detect the dipeptide carnosine. Additionally, by switching Cu2+ with Fe3+ ions, the sensor was able to detect the target ATP, demonstrating effective reconfiguration of the sensor with the proposed surface chemistry.

Keywords: reconfiguration; reconfigurable optical sensor; surface chemistry
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