Ferrocene‐Functionalized Cationic Polythiophene for the Label‐Free Electrochemical Detection of DNA

Abstract

Many efforts have been made worldwide to develop and improve electrochemical methods for DNA detection with the aim of making portable and affordable devices.[1±4] In spite of many advances in this field, it is still a challenge to find new approaches that could improve the simplicity, selectivity, and sensitivity of DNA detection, in order to respond to the demands and needs of modern medical diagnostics and biomedical research applications. In this regard, some oligonucleotide-functionalized conjugated polymers have enabled the transduction of hybridization events into an electrical signal without labeling of the DNA target.[5±7] However, with this strategy, waterinsoluble electroactive polymers are always present on the electrodes, leading to a strong electrical background. Moreover, in those systems, hybridization often leads to a decrease in the electrical signal. To solve these problems, we propose a new solid-state electrostatic approach based on neutral peptide nucleic acid (PNA) capture probes [8] and an electroactive, cationic, water-soluble polythiophene transducer. [9,10] The solidstate electrochemical detection occurs when the neutral probes are hybridized with a complementary DNA target, leading to an attractive electrostatic interaction with a cationic polythiophene transducer (Scheme 1). A similar electrostatic strategy using fluorescent, cationic, conjugated polymers was recently utilized for the specific optical detection of oligonucleotides on PNA microarrays [10] and in aqueous solution.[11]To implement this new solid-state electrochemical approach, we first prepared gold electrodes with a monolayer of PNA capture probes (see Experimental), and then performed square-wave voltammetry (SWV). The cationic, water-soluble, and electroactive polymer 1 (see Scheme 2) does not bind to neutral PNA capture probes alone (Scheme 1a; Fig. 1, trace a) but interacts strongly with the negatively charged backbone of the complementary oligonucleotide bound to the PNA probes, [10] allowing transduction of room-temperature hybridization into an electrical signal (Scheme 1b; Fig. 1, COMMUNICATIONS

Synthesis, Spectroscopic Properties and Electrochemical Oxidation of RuII‐Polypyridyl Complexes Attached to a Peptide Nucleic Acid Monomer Backbone

“…[10][11][12][13][14] Furthermore, the high selectivity of PNAs to detect even single RNA or DNA mismatches, has led their use in the biosensing area. [15][16][17][18] For this purpose, PNAmetal conjugates are particularly useful as they can act as electroactive and/or photoactive probes. Due to its well-3:2 ratio, respectively.…”

Enzyme‐Based Multi‐Component Optical Nanoprobes for Sequence‐ Specific Detection of DNA Hybridization

“…We demonstrated that even visual detection with naked eyes could detect as few as 100 pM target DNA, which was comparable to or even better than many previously reported instrument-based DNA analysis. [25][26][27][28] Moreover, a detection limit in the low pM range was obtained by using a fluorescent approach. Also of note, there are several straightforward approaches to further improve this sensitivity in order to meet high-end applications, which include the use of large-size AuNPs that should carry more HRP molecules and bring about larger amplification; automated operation may lead to better reproducibility; and the use of electrochemical detection for HRP-catalyzed reactions may lead to higher sensitivity.…”

Electrochemical and bioelectrocatalytical properties of novel block-copolymers containing interacting ferrocenyl units

“…Poly(ferrocenyl)-based macromolecules have been demonstrated to possess useful properties for the chemical modification of electrodes and also as electrochemical sensors and electrode mediators in biosensors [15][16][17][18][19].…”