Hydrophobic Localized Enrichment of Co-reactants to Enhance Electrochemiluminescence of Conjugated Polymers for Detecting SARS-CoV-2 Nucleocapsid Proteins.

The enrichment of co-reactants is one of the keys to improving the sensitivity of electrochemiluminescence (ECL) detection. This work developed a novel hydrophobic localized enrichment strategy of co-reactants utilizing the inner hydrophobic cavity of ß-cyclodextrin (ß-CD). Pt nanoparticles (Pt NPs) were grown in situ on the coordination sites for metal ions of ß-CD to prepare the ß-CD-Pt nanocomposite, which could not only enrich co-reactant 3-(dibutylamino) propylamine (TDBA) highly efficiently through its hydrophobic cavity but also immobilize TDBA via the Pt-N bond. Meanwhile, the carboxyl-functionalized poly[2,5-dioctyl-1,4-phenylene] (PDP) polymer nanoparticles (PNPs) were developed as excellent ECL luminophores. With SARS-CoV-2 nucleocapsid protein (ncovNP) as a model protein, the TDBA-ß-CD-Pt nanocomposite combined PDP PNPs to construct a biosensor for ncovNP determination. The PDP PNPs were modified onto the surface of a glassy carbon electrode (GCE) to capture the first antibody (Ab1) and further capture antigen and secondary antibody complexes (TDBA-ß-CD-Pt@Ab2). The resultant biosensor with a sandwich structure achieved a highly sensitive detection of ncovNP with a detection limit of 22 fg/mL. TDBA-ß-CD-Pt shared with an inspiration in hydrophobic localized enrichment of co-reactants for improving the sensitivity of ECL detection. The luminophore PDP PNPs integrated TDBA-ß-CD-Pt to provide a promising and sensitive ECL platform, offering a new method for ncovNP detection.

A novel electrochemiluminescence biosensor based on the self-ECL emission of conjugated polymer dots for lead ion detection.

The poly[(9,9-dioctylfuorenyl-2,7-diyl)-alt-co-(1,4-benzo-{2,1',3}-thiadiazole)] (PFBT) was carboxyl-functionalized to prepare polymer dots (C-PFBT Pdots), which served as a self-ECL emitter for producing an extraordinary ECL signal without any exogenous coreactants. The C-PFBT Pdots-modified electrode captured the substrate DNA and further hybridized with a ferrocene (Fc)-labeled DNA. The ECL emission of C-PFBT Pdots was quenched by Fc (a signal off state). After the DNAzyme was added, the DNAzyme-substrate hybrids were formed through hybridizing between DNAzyme and substrate and the Fc-labeled DNA was released. In the presence of target Pb2+, the DNAzyme-substrate hybrids could be specifically recognized and cleaved to release the DNAzyme and Pb2+. Ultimately, the released DNAzyme would further hybridize with the substrate for producing the DNAzyme-substrate hybrids and then were cleaved by the released Pb2+. As a result, the DNA walking machine was generated and the substantial Fc was away from C-PFBT Pdots to obtain a signal on state. Such a strategy achieved a sensitive detection of Pb2+ and the detection limit was as low as 0.17 pM. Moreover, making this ECL biosensor for an intracellular Pb2+ detecting, a convincing performance was achieved. The self-ECL emitter C-PFBT Pdots combining with the quencher Fc provided a new strategy and platform for constructing a coreactant-free ECL assay.

An ultrasensitive electrochemiluminescent biosensor for the detection of concanavalin A based on poly(ethylenimine) reduced graphene oxide and hollow gold nanoparticles.

A highly sensitive electrochemiluminescent (ECL) biosensor was designed for the detection of concanavalin A (ConA) based on glucose oxidase (GOx) as a recognition element by carbohydrate-lectin biospecific interaction, and poly(ethylenimine) (PEI) reduced graphene and hollow gold nanoparticles (HAuNPs) as supporting matrix and signal amplifier. The modification process and detection principle of the biosensor are briefly described as follows. First, PEI reduced graphene oxide with abundant amino groups was cast onto the surface of glassy carbon electrode to adsorb HAuNPs for improving the signal intensity in luminol/H2O2 ECL system. Next, GOx was further assembled onto the electrode by the interaction between Au and -NH2. In the presence of glucose in the detection solution, GOx catalyzed glucose to generate H2O2 in situ, which served as a co-reactant of luminol to enhance ECL signal of luminol. Based on the fact that ConA could result in a decrease in ECL signal when immobilized on the electrode, an ECL biosensor was prepared for the determination of ConA. The ECL signal intensity was linear with the logarithm of ConA concentration and the linear range was from 1.0 to 20 ng/mL with a low detection limit of 0.31 ng/mL (signal to noise ratio =3). This strategy led to a nearly 1000-fold improvement in detection limit for ConA assays compared with previously reported method, thus exhibiting a great potential application in sensitive bioassays of ConA.

Stable nanoscale sea-island structure of biobased polyamide 56/poly (butylene adipate-co-terephthalate) blends compatibilized by interfacial hyperbranched structure: Toward biobased polymer blends with ultrahigh toughness.

Developing biobased materials is a considerably effective approach to save fossil resources and reduce emissions. Biobased polyamide 56 (PA56) is an excellent engineering material, but it has low toughness. Herein, to enhance the toughness of PA56, an ultra-tough biodegradable material, i.e., poly (butylene adipate-co-terephthalate) (PBAT) was introduced into PA56. Moreover, a self-synthesized epoxy-terminated hyperbranched polyester (EHBP) was used to improve the compatibility of the blended materials. The results of differential scanning calorimetry and Fourier-transform infrared spectroscopy indicated that the epoxide group of EHBP could react with PA56 and PBAT to form a block-like polymer structure and limit the crystallization behavior of the blends. The scanning electron microscopy results show that the addition of EHBP considerably reduced the dispersed-phase size in the blends, forming a nanoscale island structure. Moreover, the hydrogen bonds formed between EHBP and PA56/PBAT enhanced the intermolecular interaction between the two materials. Thus, PA56 blends with ultrahigh toughness were successfully prepared. The prepared PA56/PBAT/EHBP blend exhibited a notch impact strength of 20.71 kJ/m2 and a breaking elongation of 38.3 %, which represent increases of 427.3 % and 252.8 %, respectively, compared with those of pure PA56. Thus, the proposed method is suitable for toughening PA56 and broadening its applications.

Coreactant-free dual-emitting conjugated polymer for ratiometric electrochemiluminescence detection of SARS-CoV-2 RdRp gene.

Constructing mono-luminophor-based electrochemiluminescence (ECL) ratio system is a great challenge due to the limitations of the luminescent species with dual-signal-output, luminescence efficiency and coreactant. This work developed carboxyl-functionalized poly[9,9-bis(3'-(N,N-dimethylamino) propyl)-2,7-fluorene]-alt-2,7-(9,9 dioctylfluorene)] nanoparticles(PFN NPs) as dual-emitting luminophors, which can synchronously output strong cathodic and anodic ECL signals without any exogenous coreactants. The inherent molecular structure enabled efficient intramolecular electron transfer between tertiary amine groups and backbone of PFN to generate strong cathodic and anodic ECL emission. Particularly, H+ in aqueous solution played an irreplaceable role for cathodic ECL emission. The silver nanoparticles (AgNPs) were developed as signal regulator because of their excellent hydrogen evolution reaction (HER) activity, which significantly quenched the cathodic signal while kept the anodic signal unchanged. The dual-emitting PFN NPs cleverly integrated signal regulator AgNPs and bicyclic strand displacement amplification (SDA) to construct a coreactant-free mono-luminophor-based ratiometric ECL sensing for SARS-CoV-2 RdRp gene assay. The strong dual-emitting of PFN NPs and excellent quenching effect of AgNPs on cathodic emission endowed the biosensor with a high detection sensitivity, and the detection limit was as low as 39 aM for RdRp gene. The unique dual-emitting properties of PFN NPs open up a new path to construct coreactant-free mono-luminophor-based ECL ratio platform, and excellent HER activity of AgNPs offers some new thoughts for realizing ECL signal changes.

The synergistic effect of polytetrafluoroethylene in-situ fibrillation and dibenzoyl sebacate hydrazide on the crystallization and foaming behavior of poly (lactic acid).

The fully degradable poly (lactic acid) foam with green environmental protection characteristics can alleviate the shortage of petroleum resources caused by the application of plastics. However, due to the inherent low melt strength and slow crystallization rate of linear PLA. It is difficult to obtain PLA microcellular foam with good morphology. In order to obtain PLA microcellular foam with ultra-high expansion ratio and small cell size, PTFE (polytetrafluoroethylene) nanofibers with excellent CO2 adsorption rate were introduced. Self-assembled nucleator TMC-300(dibenzoyl sebacate hydrazide) was also introduced to blend with PLA to obtain small-sized cells. The results show that the PTFE entanglement network as a self-assembled template can effectively improve the early crystallization nucleation efficiency and increase the crystallinity of branched PLA (CBPLA)/TMC by 7 %. The microcellular foam with PTFE content of 0.5 wt% (CBPLA/TMC/PTFE 0.5) was successfully prepared by physical foaming agent, which had the lowest cell size (8.7 µm) And high expansion ratio (1200 %).

Potentially tunable ratiometric electrochemiluminescence sensing based on conjugated polymer nanoparticle for organophosphorus pesticides detection.

In general, suitable double luminophores and their coreactants are necessary for constructing electrochemiluminescence (ECL) ratio strategy. However, the complexity of matching double luminophores and the stability and repeatability problem suffered by introducing exogenous coreactant would greatly limit the application of ratio detection. An original single-luminophore-based ECL ratio sensing was developed excluding any exogenous coreactants in this work. The poly [9,9-bis(3'-(N,N-dimethylamino)propyl)- 2,7-fluorene]-alt-2,7-(9,9-dioctylfluorene)] nanoparticles (PFN NPs) were explored to emit two anodic ECL signals. One centered at + 1.25 V (ECL-1) with the scanning potential of 0 ~ + 1.25 V and the other at + 1.95 V (ECL-2) with the scanning potential of 0 ~ + 1.95 V. ECL-1 showed a very strong emission without any exogenous coreactant. Importantly, hydrogen peroxide (H2O2) was able to efficiently weaken ECL-1 but strengthen ECL-2. When organophosphorus pesticides (OPs) were absent, the immobilized acetylcholinesterase-choline oxidase (AChE-ChOx) would catalyze the substrate acetylthiocholine chloride (ATCl) to produce H2O2, resulting in a quenched ECL-1 and an enhanced ECL-2. With the introduction of OPs, ECL-1 increased while ECL-2 accordingly decreased as OPs prohibited production of H2O2 by inhibiting activity of AChE. Highly sensitive ECL ratio detection for OPs was realized based on the change of the ratio of two signals. The dual anode emission properties of PFN NPs coupled with the opposite regulation of H2O2 on the two signals paved a new avenue for potentially tunable ECL ratio sensing strategy, and showed enormous potential applications for OPs analysis.

Assembling inner filter effect reduced SnS2 quantum dots-based hollow polymeric spherical nanoshells for ratio electrochemiluminescence bioassay.

SnS2 quantum dots (QDs) as excellent electrochemiluminescence (ECL) luminators have exhibited a good application prospect in ECL field, but the difficulty of being effectively immobilized on the electrode and inner filter effect caused by their compact packaging make the construction of SnS2 QDs-based ECL system challenging. This work developed a hollow polymeric spherical nanoshells (HPSNs) for loading SnS2 QDs. SiO2 nanoparticles (NPs) served as the carrier for the multilayer assembly of polyethyleneimine (PEI)-SnS2 QDs and polyacrylic acid (PAA). Then, SiO2 NPs were etched to produce SnS2 QDs-based HPSNs (SnS2-HPSNs), which can not only achieve the high loading of SnS2 QDs but effectively reduce their inner filter effect, revealing a significantly improved cathodic ECL performance. SnS2-HPSNs coupled with anodic luminators Ir nanorods (NRs) to construct a ratiometric ECL biosensor for detecting cardiac troponin I (cTnI) with tripropylamine (TPrA) and persulfate (S2O82-) as anodic and cathodic co-reactants, respectively. Norepinephrine (NE) and gold nanoparticles (AuNPs) were innovatively developed as dual-quencher for Ir NRs. The secondary antibody complex containing SnS2-HPSNs and NE-AuNPs was specially constructed and its assembly on the biosensor modified with Ir NRs can conveniently realize the different changes of the two signals, thus achieving the sensitive detection of cTnI with a detection limit of 0.32 pg/mL. The HPSNs provided an effective strategy for high loading of QDs while reducing their inner filter effect. The integration of two luminators (SnS2-HPSNs and Ir NRs) and dual-quencher created a promising ECL ratio platform for the accurate detection of various biomarkers.

Coreactant-free electrochemiluminescence biosensor for the determination of organophosphorus pesticides.

Poly [(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1',3}-thiadazole)] (PFBT) was functionalized with carboxyl groups via nanoprecipitation method to prepare polymer nanoparticles (PNPs). Remarkable electrochemiluminescence (ECL) was observed at PFBT PNPs without any external species or dissolved O2 as coreactants. Furthermore, such an ECL emission could be efficiently quenched by hydrogen peroxide (H2O2). A coreactant-free ECL enzyme-based biosensor is making use of PFBT PNPs as luminophore for detecting organophosphorus (OPs) pesticides. In the absence of OPs, H2O2 stemmed from the enzymatic reaction would quench the ECL signal of PFBT PNPs, resulting in an ECL signal-off state. In the presence of OPs, the ECL signal obviously increased because the enzyme activity of the acetylcholinesterase (AChE) was inhibited by OPs. The linear range for OPs detection was 1.0 × 10-12-1.0 × 10-7 M and the detection limit was low as 1.5 × 10-13 M. Such a coreactant-free ECL strategy could avoid the drawbacks resulted from the addition of exogenous species or dissolved O2 as coreactant. More importantly, H2O2 was released by many oxidases-induced reactions, and its quenching effect on the ECL of PFBT PNPs would pave a new avenue for constructing coreactant-free enzyme-based ECL biosensor for environmental monitoring and biological analysis.

A novel and simple biomolecules immobilization method: electro-deposition ZrO2 doped with HRP for fabrication of hydrogen peroxide biosensor.

For the first time, a very novel and simple immobilization method for fabrication of hydrogen peroxide biosensor was reported in this paper. The biocompatible composite HRP-ZrO(2) thin films were synthesized on gold electrode surface based on electro-deposition zirconia doped with horseradish peroxidase (HRP) by cyclic voltammetry scanning in KCl solution containing ZrO(2) and HRP. The fabricated process of biosensor was characterized by electrochemical impedance spectroscopy (EIS) and the surface topography of the prepared films was imaged by atomic force microscope (AFM). The HRP in HRP-ZrO(2) thin films kept its bioactivity and exhibited excellent electrocatalytical response to the reduction of H(2)O(2). Experimental conditions influencing the biosensor performance such as pH, potential were optimized. The resulting biosensor (HRP-ZrO(2)/Au electrode) showed a linear response to H(2)O(2) over a concentration range from 0.02 to 9.45mM with a detection limit of 2muM based on a signal-to-noise ratio of 3 under optimized conditions. The apparent Michaelis-Menten constant (K(M)(app)) was evaluated to be 8.01mM, which indicated the HRP in HRP-ZrO(2) thin films kept its native bioactivity and had high affinity for H(2)O(2). Moreover, the proposed biosensor showed high sensitivity, good reproducibility and long-term stability. What is more, this immobilization methodology widened biosensor application in biomolecules immobilization and could further develop for other protein and biomolecules immobilization.

Anodic electrogenerated chemiluminescence behavior and the choline biosensing application of blue emitting conjugated polymer dots.

The anodic electrochemiluminescence (ECL) behavior of poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO) dots was studied and applied in oxidoreductase-based ECL biosensing using Chox as the model enzyme.

Overoxidized polyimidazole/graphene oxide copolymer modified electrode for the simultaneous determination of ascorbic acid, dopamine, uric acid, guanine and adenine.

In the present work, a novel strategy based on overoxidized polyimidazole (PImox) and graphene oxide (GO) copolymer modified electrode was proposed for the simultaneous determination of ascorbic acid (AA), dopamine (DA), uric acid (UA), guanine (G) and adenine (A). The copolymer was characterized by the scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Due to the synergistic effects between PImox and GO, the proposed electrode exhibited excellent electrochemical catalytic activities and high selectivity and sensitivity toward the oxidation of AA, DA, UA, G and A. The peak separations between AA and DA, AA and UA, UA and G, and G and A were 140 mV, 200 mV, 380 mV and 300 mV, respectively. The linear response ranges for AA, DA, UA, G and A were 75-2275 µM, 12-278 µM, 3.6-249.6 µM, 3.3-103.3 µM and 9.6-215 µM, respectively, and corresponding detection limits were 18 µM, 0.63 µM, 0.59 µM, 0.48 µM and 1.28 µM.

Simultaneous determination of ascorbic acid, dopamine, uric acid and tryptophan on gold nanoparticles/overoxidized-polyimidazole composite modified glassy carbon electrode.

A novel electrode was developed through electrodepositing gold nanoparticles (GNPs) on overoxidized-polyimidazole (PImox) film modified glassy carbon electrode (GCE). The combination of GNPs and the PImox film endowed the GNPs/PImox/GCE with good biological compatibility, high selectivity and sensitivity and excellent electrochemical catalytic activities towards ascorbic acid (AA), dopamine (DA), uric acid (UA) and tryptophan (Trp). In the fourfold co-existence system, the peak separations between AA-DA, DA-UA and UA-Trp were large up to 186, 165 and 285 mV, respectively. The calibration curves for AA, DA and UA were obtained in the range of 210.0-1010.0 µM, 5.0-268.0 µM and 6.0-486.0 µM with detection limits (S/N=3) of 2.0 µM, 0.08 µM and 0.5 µM, respectively. Two linear calibrations for Trp were obtained over ranges of 3.0-34.0 µM and 84.0-464.0 µM with detection limit (S/N=3) of 0.7 µM. In addition, the modified electrode was applied to detect AA, DA, UA and Trp in samples using standard addition method with satisfactory results.