Energy Transfer between Semiconducting Polymer Dots and Gold Nanoparticles in a Photoelectrochemical System: A Case Application for Cathodic Bioanalysis

Abstract

We report herein the energy transfer (ET) between semiconducting polymer dots (Pdots) and gold nanoparticles (Au NPs) in a photoelectrochemical (PEC) system and its feasibility for cathodic bioanalysis application. Specifically, COOH-capped Pdots were first fabricated and then assembled onto the indium-tin oxide (ITO) surface, followed by the modification of single-strand (ss) DNA probe (pDNA). After the DNA hybridization with the Au NP-tethered complementary ssDNA (Au NP-tDNA), the Au NPs were brought into the close proximity of Pdots. Upon light stimulation, photoluminescence (PL) was annihilated, fluorescence was attenuated, and the photocurrent intensity was evidently decreased. This ET-based PEC DNA sensor exhibited a linear range from 1 fM to 10 pM with a detection limit of 0.97 fM at a signal-to-noise ratio of 3. The present work first exploited the ET between Pdots and Au NPs, and we believe this phenomenon will spark new interest in the study of various Pdots-based ET-influenced PEC systems and thus catalyze increasing studies for specific bioanalytical purposes.

Polymer Based Functional Materials: A New Generation Photo‐active Candidate for Electrochemical Application

“…Conducting polymers, such as polythiophenes, polydopamine, polymer dots and so on, have been used as diversified base materials in photoelectrochemical biosensing [115][116][117][118][119]. They have been sincerely explored to build up a comprehensive photo-inspired sensing platform where the sensing strategy is critically dependent on controlling the immobilization efficacy of the bio-receptors on the functional matrix used in the photoelectrochemical sensing process.…”

Affinity-Based Detection of Biomolecules Using Photo-Electrochemical Readout

“…Organic materials such as graphitic carbon nitride (g-C 3 N 4 ), porphyrin, azo dyes, chlorophyll, bacteriorhodopsin, and polymers such as semiconducting polymer dots (Pdot), phthalocyanine, poly(thiophene), phenylenevinylene (PPV), and their derivatives have been used for constructing photoactive electrodes that can be applied to PEC biosensors (Ikeda et al, 2009; Da et al, 2018; Shi et al, 2018b). Some of the main advantages offered by organic semiconductors lies in their improved mechanical compliance (Xu et al, 2017), intrinsic stretchability (Xu et al, 2017), and their amenability to low-temperature all-solution-based processing (Zhao et al, 2017b; Jiang and Tian, 2018).…”

“…Pdots are a class of emerging photoactive nanomaterials that offer incredible photostability (photobleaching quantum yield of 10 −7 -10 −10 ), tailorable electrical and optical properties, minimal toxicity, good biocompatibility and ease of processing (Wang et al, 2016b; Li et al, 2017b; Shi et al, 2018b; Zhang et al, 2018c). Pdots and PPV derivatives have recently been used in PEC biosensors (Shi et al, 2018b; Zhou et al, 2018) due to their extraordinary light harvesting ability resulting from their large two-photon absorption cross sections (Feng et al, 2010). However, their use in biosensing architectures are required to be thoroughly explored because of their pH dependence and tunability of photoelectrochemical properties according to their molecular weights (Wu and Chiu, 2013; Yu et al, 2017a).…”

Modulation of Semiconductor Photoconversion with Surface Modification and Plasmon

“…In the case of PEC biosensors that have the analyte functionalized onto the photoelectrode, the analyte of choice is selectively bound to the photoelectrode. Common methods for binding of analytes include analyte binding to DNA strands [127][128][129][130][131] , aptamer-analyte reactions [132][133][134] , and antibody-antigen reactions [135][136][137] . The bound analyte itself may alter the PEC performance of the photoelectrode [132-135, 136, 138] or a secondary probe may be bound selectively to the photoelectrode at sites where the analyte is already bound [127-131, 137, 139] to modulate the PEC performance of the photoelectrode.…”

“…As such, the loss of energy from the semiconductor photoelectrode results in decreased charge carrier generation and corresponding photocurrent. In the case of FRET-based PEC sensors, the photocurrent of the photoelectrode system may be decreased by selective binding of plasmonic NP probes in the presence of analyte to the photoelectrode surface to initiate FRET [127][128][129][130][131]135] or increased by selectively increasing the separation distance between the plasmonic nanoparticles and semiconductor photoelectrode to decrease the magnitude of FRET. [144] Chapter 3: Porphyrin-based Metal-Organic Framework Coated Titanium Dioxide Nanorod Array for Improved Photoelectrochemical Cell Performance…”