Peptide nucleic acid stabilized perovskite nanoparticles for nucleic acid sensing

A Jancik Prochazkova,S Gaidies,C Yumusak,O Brüggemann,M Weiter,N.S Sariciftci,M.C Scharber,K Čépe,R Zbořil,J Krajcovic,Y Salinas,A Kovalenko

doi:10.1016/j.mtchem.2020.100272

Abstract

Nanostructural hybrid organic-inorganic metal halide perovskites offer a wide range of potential applications including photovoltaics, solar cells, and light emitting diodes. Up to now the surface stabilizing ligands were used solely to obtain the optimal properties of nanoparticles in terms of dimensionality and stability, however their possible additional functionality was rarely considered. In the present work, hybrid lead bromide perovskite nanoparticles (PNP) were prepared using a unique approach where a peptide nucleic acid is used as a surface ligand. Methylammonium lead bromide perovskite colloidal nanoparticles stabilized by thymine-based peptide nucleic acid monomer (PNA-M) and relevant trimer (PNA-T) were prepared exhibiting the size below 10 nm. Perovskite structure and crystallinity were verified by X-ray powder diffraction spectroscopy and high resolution transmission electron microscopy. PNP-PNA-M and PNP-PNA-T colloidal dispersions in chloroform and toluene possessed green-blue fluorescence, while Fourier-transform infrared spectroscopy (FT-IR) and quantum chemical calculations showed that the PNA coordinates to the PNP surface through the primary amine group. Additionally, the sensing ability of the PNA ligand for adenine nucleic acid was demonstrated by photoluminescence quenching via charge transfer. Furthermore, PNP thin films were effectively produced by the centrifugal casting. We envision that combining the unique, tailored structure of peptide nucleic acids and the prospective optical features of lead halide perovskite nanoparticles could expand the field of applications of such hybrids exploiting analogous ligand chemistry.

Highlights

Over the last decade, lead halide perovskites have emerged as a true ‘superstar’ among semiconducting materials
We introduce a pioneering approach to stabilize perovskite nanoparticles (PNP) with thymine-based peptide nucleic acid prepared by ligand assisted precipitation technique [26], since peptide nucleic acids (PNAs) has much higher local dielectric constant than the organic materials [27] which could be beneficial in terms of charge transfer
In order to test the influence of the capping agent concentration on the PNP formation, different molar eq of synthetized peptide nucleic acid monomer (PNA-M) to PbBr2 were used in the preparation of the precursor solution (0.4, 0.8, 1.0 and 1.6 eq.)

Summary

Introduction

Lead halide perovskites have emerged as a true ‘superstar’ among semiconducting materials. Due to their simple, cost-efficient synthesis and processing, their structural and optical/electrical adjustability, lead halide perovskites have found application in many types of devices, such as photovoltaic cells [1e3], solid state lasers [4,5], light emitting diodes [6], photodetectors [7] and solar fuels production [8]. Nanoparticles surrounded by an organic medium present a smaller dielectric constant [15] that has an exciton binding energy in the range of 200e500 meV [16], which is an order of magnitude higher in comparison with the bulk perovskites [17]. The higher exciton binding energy significantly reduces the exciton dissociation probability, prior to radiative decay as compared to the bulk, which results in a superior PLQY and poor charge transfer

Methods

Results

Conclusion