Aggregation-Induced Enhanced Electrochemiluminescence Resonance Energy Transfer Biosensor for Ultrasensitive Detection of Carcinoembryonic Antigen Based on Donor-Acceptor Organic Nanoparticles.

Aggregation-induced electrochemiluminescence (AIECL) combines the merits of aggregation-induced emission (AIE) and electrochemiluminescence (ECL), which has become a research hot spot in recent years. Therefore, we synthesized a novel AIE compound (Z)-3-(4-(2-butyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)phenyl)-2-(4-(1,2,2-triphenylvinyl)phenyl)acrylonitrile (TPENI) with a donor-acceptor (D-A) structure, that is, a simple peripheral modification of 4-(2-butyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl) benzaldehyde (NI-CHO) with AIE-active tetraphenylethylene (TPE) to achieve the transition of NI-CHO from aggregation-caused quenching (ACQ) to an AIE molecule. When TPENI was in the aggregated state, the luminescence intensity was significantly enhanced due to the TPE structural unit restricting the free rotation of the intramolecular benzene ring, as well as the π-π stacking interactions of the molecules, which was conducive to the preparation of TPENI NPs as ECL materials. Satisfactorily, we found that the ECL intensity of TPENI NPs was increased by about 4.8-fold compared with that of the molecules dispersed in organic solution, and the stability reached about 1000 s. Based on the excellent ECL properties of TPENI NPs, an "on-off-on" ECL biosensor with a wider detection range (1 fg/mL to 100 ng/mL) and a lower detection limit of 0.20 fg/mL (S/N = 3) was proposed for sensitive analysis of a carcinoembryonic antigen (CEA). Overall, this work provided a new approach to the realization of AIECL and laid the foundation for the application of naphthalimide derivatives in ECL.

A sandwich-type photoelectrochemical biosensor based on Ru(bpy)32+ sensitized In2S3 for aflatoxin B1 detection.

Aflatoxin B1 (AFB1), classified as a class I carcinogen, is a widespread mycotoxin that poses a serious threat to public health and economic development, and the food safety problems caused by AFB1 have aroused worldwide concern. The development of accurate and sensitive methods for the detection of AFB1 is significant for food safety monitoring. In this work, a sandwich-type photoelectrochemical (PEC) biosensor for AFB1 detection was constructed on the basis of an aptamer-antibody structure. A good photocurrent response was obtained due to the sensitization of In2S3 by Ru(bpy)32+. In addition, this sandwich-type sensor constructed by modification with the antibody, target detector, and aptamer layer by layer attenuated the migration hindering effect of photogenerated carriers caused by the double antibody structure. The aptamer and antibody synergistically recognized and captured the target analyte, resulting in more reliable PEC response signals. CdSe@CdS QDs-Apt were modified as a signal-off probe onto the sensor platform to quantitatively detect AFB1 with a "signal-off" response, which enhanced the sensitivity of the sensor. The PEC biosensor showed a linear response range from 10-12 to 10-6 g mL-1 with a detection limit of 0.023 pg mL-1, providing a feasible approach for the quantitative detection of AFB1 in food samples.

ORAOV 1 Detection Made with Metal Organic Frameworks Based on Ti3C2Tx MXene.

In this work, a two-dimensional (2D) MOF sheet with electrochemiluminescence (ECL) activity is prepared with Ti3C2Tx MXene as the metal precursor and the meso-tetra(4-carboxyl-phenyl) porphyrin (H2TCPP) as the organic ligand. The atomically thin 2D Ti3C2Tx MXene is utilized as the metal precursor and soft template to produce the MOF with a 2D nanosheet morphology (Ti3C2Tx-PMOF). Ti3C2Tx MXene is a kind of strong electron acceptor, which can deprotonate H2TCPP due to the high electronegativity and low work function of its terminal atoms. The deprotonated H2TCPP continues to bind with Ti atoms to form the 2D MOF sheet. The ECL activity is inherited from H2TCPP and stabilized by introducing Ag NPs. Then, we construct an ECL biosensor based on the Ag NPs/Ti3C2Tx-PMOF to detect the oral cancer overexpressed 1 (ORAOV 1). A bipedal three-dimensional DNA walker strategy is adopted to further improve the biosensor sensitivity. As expected, the biosensor exhibits sterling sensitivity and selectivity. The ECL biosensor responds linearly to ORAOV 1 concentrations in the range of 10 fM-1 nM, and the detection limit is as low as 3.3 fM (S/N = 3). It means that Ag NPs/Ti3C2Tx-PMOF is a potential material to design and construct the high-performance ECL biosensors.

An Iron(III)-Based Metal-Organic Gel-Catalyzed Dual Electrochemiluminescence System for Cytosensing and In Situ Evaluation of the VEGF165 Subtype.

The recent surge of interest in metal-organic gels (MOGs) has emerged for their soft porous structure, large surface area, and abundant active metal sites, making them a promising candidate for building catalyst matrices. In this work, facilely synthesized Fe(III)-organic gel was directly used as a robust electrode matrix. Detailed studies illustrated that their Fe(III) centers can speed up the electro-oxidation/reduction of the H2O2 coreactant to produce reactive oxygen species for enhancing a potential-resolved dual electrochemiluminescence (ECL) emission. Among them, the anodic signal of luminol varied with the cell concentration based on the impedance ECL mechanism, while the cathodic signal of CdS quantum dots traced the VEGF165 subtype at cell surface by specific aptamer recognition. Based on this, a ratiometric strategy was proposed for accurate cytosensing by eliminating environmental interference. Moreover, by cooperating these two signals, a novel strategy was developed for direct evaluation of the VEGF165 subtype, further realizing rapid drug screening and subtype assessment on different cell lines. This work not only opens up the promising application of MOGs as an effective catalyst matrix but also develops reliable cell assays and protein subtype identification for clinical diagnosis and research.

A label-free photoelectrochemical immunosensor for carcinoembryonic antigen detection based on a g-C3N4/CdSe nanocomposite.

Herein, a label-free photoelectrochemical immunosensor based on a g-C3N4/CdSe nanocomposite was established and applied to detect carcinoembryonic antigen (CEA). The prepared nanocomposite materials were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), ultraviolet-visible absorption spectroscopy (UV-vis), X-ray photoelectron spectroscopy (XPS), fourier transform infrared spectrometer (FT-IR) and photoluminescence spectroscopy (PL). The results indicate that g-C3N4/CdSe nanocomposite materials were successfully synthesized. In a typical assembly process, the immunosensor was constructed by modifying a fluorine-doped tin oxide (FTO) electrode with poly dimethyl diallyl ammonium chloride (PDDA), the g-C3N4/CdSe nanocomposite, the anti-carcinoembryonic antigen antibody (Ab) and the blocking agent bovine serum albumin (BSA) successively. In the presence of CEA, the photocurrent signal of the prepared immunosensor decreased significantly. Accordingly, under the optimal conditions, a label-free photoelectrochemical immunosensor was established, and it exhibited excellent selectivity and repeatability for CEA detection. The detection limit was 0.21 ng mL-1, and the range was 10 ng mL-1-100 µg mL-1. Simultaneously, the immunosensor also provides a likely sensing device for detecting other protein targets, which is of great significance for early clinical diagnosis.

An electrochemiluminescence biosensor for p53 antibody based on Zn-MOF/GO nanocomposite and Ag+-DNA amplification.

An ultrasensitive electrochemiluminescence biosensor was established based on the Zn-MOF/GO nanocomposite. Ag(I)-embedded DNA complexes were used as a signal amplification reagent. In this work, 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) and Zn2+ were integrated into a porphyrin paddlewheel framework (Zn-MOF) by a hydrothermal method. The synthesized Zn-MOF material has electrochemiluminescence property, and the luminescence intensity is improved after being composited with graphene oxide (GO). Based on the composite material, we constructed an ultrasensitive ECL biosensor for the p53 antibody detection. The composite material acted as an admirable substrate and then loaded plenty of p53 antigens to recognize the target (p53 antibody) accurately. Because of the bridging effect of streptavidin and biotin-conjugated goat anti-rabbit IgG (bio-ab2), the rich-C DNA with positive correlation with the target was modified on the electrode and then captured the co-reactant accelerator Ag+ to amplify the signal. Therefore, the ECL biosensor response increases with increasing p53 antibody concentration. In the range 0.1 fg/mL-0.01 ng/mL, the response signal of the biosensor has a good linear relationship with the p53 antibody concentration. The detection limit is 0.03 fg/mL (S/N = 3). Impressively, the biosensor not only featured high sensitivity, good stability, and excellent specificity for the detection of p53 antibody, but also provides a new way for early detection of cancer. Graphical abstract Schematic representation of the electrochemiluminescence sensor based on a Zn-MOF/GO nanocomposite, which can be applied to the determination of p53 antibody.

Highly sensitive photoelectrochemical biosensor for microRNA159c detection based on a Ti3C2:CdS nanocomposite of breast cancer.

Herein, an ultra-sensitive photoelectrochemical biosensor based on Ti3C2:CdS nanocomposite was established for the selective detection of microRNA159c. Ti3C2:CdS nanocomposites were used as optoelectronic materials because Ti3C2:CdS interaction effectively separates photogenerated electrons and holes, and significantly improves the high photoelectric conversion efficiency. Firstly, Ti3C2:CdS nanocomposite was deposited on the surface of the fluorine-doped tin oxide (FTO) electrode. After the chitosan (CS) was dropped, the SH-miRNA were bonded on the electrode surface via the S-Cd bond. Then 6-mercaptohexanol (MCH) blocked the unbound site, the DNA strand was introduced to hybridize with the target SH-miRNA. At this time, the obtained photocurrent gradually decreases. Subsequently, the photosensitizer TMPyP as signal amplification was modified, the photocurrent increased significantly. The target SH-miRNA was detected based upon the photocurrent change originated from quantities change of TMPyP. Working under the best experimental conditions, the sensing platform had good stability, selectivity, and high sensitivity. The detection range for miRNA159c was 1.0 × 10-6-1.0 × 10-13 mol·L-l, and the detection limit was approximately 33 fmol·L-l. The detection of miRNA159c in human serum provided a huge opportunity to explore the relationship between the abundance of this miRNA and the incidence of breast cancer (BC), and to further achieve effective detection of BC.

Highly sensitive electrochemiluminescence biosensor for VEGF165 detection based on a g-C3N4/PDDA/CdSe nanocomposite.

In this work, an electrochemiluminescence (ECL) biosensor was fabricated for the selective detection of vascular endothelial growth factor (VEGF165). g-C3N4/PDDA/CdSe nanocomposites were used as the ECL substrate. Then, DNA labeled at the 5' end with amino groups (DNA1) was immobilized on the surface of g-C3N4/PDDA/CdSe nanocomposite-modified glassy carbon electrode (GCE) by amido linkage. AuNP-labeled target DNA (Au-DNA2) could hybridize with DNA1 to form a double strand. The ECL of the g-C3N4/PDDA/CdSe nanocomposite was efficiently quenched due to the resonance energy transfer between CdSe QDs and Au NPs. After VEGF165 was recognized and bound by Au-DNA2, the double helix was disrupted, and the energy transfer was broken. In this case, Au-DNA2 was released from the electrode surface, and the ECL intensity recovered to a higher level. Under optimal conditions, this ECL biosensor possesses excellent selectivity, accuracy, and stability for VEGF165 detection in a linear range of 2 pg mL-1 to 2 ng mL-1 with a detection limit of 0.68 pg mL-1. In addition, this assay has been successfully applied to the determination of VEGF165 in serum samples. Graphical abstract Schematic representation of the electrochemiluminescence sensor based on a g-C3N4/PDDA/CdSe nanocomposite, which can be determined in the concentration of vascular endothelial growth factor in serum.

Electrochemiluminescence immunoassay for the prostate-specific antigen by using a CdS/chitosan/g-C3N4 nanocomposite.

An electrochemiluminescence (ECL) biosensor was fabricated for the evaluation of prostate specific antigen (PSA). The sensor was developed by successively modifying glassy carbon electrode (GCE) electrodes with CdS/Chito/g-C3N4 nanocomposites and DNA1 was labeled at the 5' end with thiol. The aptamer DNA was labeled at the 3' end with a quencher ferrocene (Fc) was ligated to DNA1 by the principle of complementary base pairing. In the absence of PSA, the ECL intensity signal is effectively quenches through the energy transfer and photoexcitation electron transfer between CdS/Chito/g-C3N4 emitter and quencher Fc. After incubation with target PSA, the aptamer DNA interacts with PSA and then moved away from the electrode surface together, which will recover the ECL intensity. Under the optimal conditions, the ECL intensity increases linearly with the logarithm of PSA concentration in the range of 1 pg·mL-1 to 100 ng·mL-1, and the detection limit is 0.14 pg·mL-1 (S/N = 3). The biosensor has been successfully applied to the determination of PSA in serum sample. Graphical abstractSchematic representation of the electrochemiluminescence sensor based on a CdS/chitosan/g-C3N4 nanocomposite, which can be applied to the determination of prostate specific antigen in serum.

Enhanced photoelectrochemical DNA sensor based on TiO2/Au hybrid structure.

A novel enhanced photoelectrochemical DNA sensor, based on a TiO2/Au hybrid electrode structure, was developed to detect target DNA. The sensor was developed by successively modifying fluorine-tin oxide (FTO) electrodes with TiO2 nanoparticles, gold (Au) nanoparticles, hairpin DNA (DNA1), and CdSe-COOH quantum dots (QDs), which acted as signal amplification factors. In the absence of target DNA, the incubated DNA1 hairpin and the CdSe-COOH QDs were in close contact with the TiO2/Au electrode surface, leading to an enhanced photocurrent intensity due to the sensitization effect. After incubation of the modified electrode with the target DNA, the hairpin DNA changed into a double helix structure, and the CdSe QDs moved away from the TiO2/Au electrode surface, leading to a decreased sensitization effect and photoelectrochemical signal intensity. This novel DNA sensor exhibited stable, sensitive and reproducible detection of DNA from 0.1 µM to 10 fM, with a lower detection limit of 3 fM. It provided good specificity, reproducibility, stability and is a promising strategy for the detection of a variety of other DNA targets, for early clinical diagnosis of various diseases.

Photoelectrochemical immunoassay for human interleukin 6 based on the use of perovskite-type LaFeO3 nanoparticles on fluorine-doped tin oxide glass.

A film of perovskite-type LaFeO3 nanoparticles (NPs) was deposited on fluorine-doped tin oxide (FTO) conducting glass via dipping-lifting and calcination. Scanning electron microscopy shows that the NPs are evenly distributed on the surface of the glass. The modified glass was further coated with antibody against human interleukin 6 (IL-6) to result in a photoelectrochemical immunosensor for IL-6. The well-established photoelectrochemical immunoassay has a linear current response in the range of 0.1 pg·mL-1 to 0.1 µg·mL-1 and a detection limit as low as 33 fg·mL-1. Graphical abstract Schematic of a novel photoelectochemical immunoassay for the measurement of IL-6 based on perovskite-type LaFeO3 nanoparticles. The immunoassay had a higher sensitivity and may also be applied to other bioanalysis and environment monitoring.

Sonochemical fabrication of 8-hydroxyquinoline aluminum (Alq3) nanoflowers with high electrogenerated chemiluminescence.

Well-defined Alq(3) nanoflowers were fabricated via a facile and fast sonochemical route. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and shape of the as-prepared product. The results showed that the resulting Alq(3) was composed of nanobelts with thickness about 50 nm, average widths of 200 nm, and length up to 10 µm. The Alq(3) nanoflowers exhibited good electrogenerated chemiluminescence behavior.