Strong cathode electroluminescence biosensor based on CeO2 functionalized PCN-222@Ag NPs for sensitive detection of p-Tau-181 protein.

Electrochemiluminescence (ECL) biosensors provide a convenient and high sensitivity method for early disease diagnosis. However, creating luminophore arrays relying on powerful ECL signals remains a daunting task. Porphyrin-centered metal organic frameworks (MOFs) exhibit remarkable potential in ECL sensing applications. In this paper, based on a simple one-pot synthesis method, PCN-222@Ag NPs doped with CeO2 was synthesized to enhance the ECL performance. Due to the strong catalytic ability of CeO2, the ECL signal strength of the new material PCN-222@CeO2@Ag NPs is much higher than that of the PCN-222@Ag NPs and PCN-222. The luminous properties of PCN-222@CeO2@Ag NPs become more intense and stable due to the excellent electronic conductivity of Ag NPs. Based on the fact that CuS@PDA composite can quench the ECL signal of PCN-222@CeO2@Ag NPs, we constructed a novel sandwich ECL immune sensor for the detection of phosphorylated Tau 181 (p-Tau-181) protein. The ECL sensor has a great linear relationship with p-Tau-181 protein concentration, ranging from 1 pg/mL to 100 ng/mL. The detection limit is as low as 0.147 pg/mL. This work provides new ideas for developing sensitive ECL sensors for the p-Tau-181 protein, the marker of Alzheimer's disease.

A ZnIn2S4@ReS2/AgInS2-based photoelectrochemical aptasensor for the ultrasensitive detection of kanamycin.

An ultrasensitive photoelectrochemical (PEC) aptasensor was originally designed by using ZnIn2S4/ReS2 as a photoactive material and AgInS2 as a signal amplifier. The signal amplifier AgInS2 was incubated on the terminal of H-DNA (immobilized on the ZnIn2S4/ReS2/FTO surface), leading to an enhanced photocurrent response. Then, due to the introduction of DNA2, the formation of a double-stranded structure caused AgInS2 to keep away from the electrode surface, and the photocurrent was reduced. In the presence of kanamycin, DNA2 was released from the system due to the competition relationship, and a restored photocurrent response was obtained. The combination of ZnIn2S4/ReS2 and AgInS2 accelerated the electron transfer and enhanced the separation efficiency of photogenerated electron-hole pairs, resulting in an improved performance of the PEC aptasensor, which was capable of accurate and sensitive detection of kanamycin in actual samples.

An electrochemiluminescence aptasensor based on highly luminescent silver-based MOF and biotin-streptavidin system for mercury ion detection.

In this study, for the first time, a silver-based metal-organic framework (Ag-MOF) was synthesized and used as the electrochemiluminescence (ECL) emitter for building an ECL sensor. After modification with chitosan (CS) and gold nanoparticles (Au NPs), the ECL stability of Ag-MOF was improved. To detect mercury ions, a biosensor was constructed using the mercury ion aptamer and steric effect of streptavidin. First, the capture strand (cDNA) with terminal-modified sulfhydryl group was attached to the electrode surface by the Au-S bond. Then, the mercury-ion aptamer (Apt-Hg) modified with biotin was anchored to the electrode by complementary pairing with cDNA. Streptavidin (SA) could be fixed on the electrode by linking with biotin, thereby reducing the ECL signal. However, in the presence of mercury ions, the aptamer was removed and streptavidin could not be immobilized on the electrode. Hence, the ECL signal of the sensor increased with the concentration of mercury ions, which was linear in the range from 1 µM to 300 fM. The detection limit could reach 66 fM (S/N = 3). The sensor provided a new method for the detection of mercury ions.

A photoelectrochemical biosensor based on b-TiO2/CdS:Eu/Ti3C2 heterojunction for the ultrasensitive detection of miRNA-21.

A novel photoelectrochemical (PEC) biosensor based on b-TiO2/CdS:Eu/Ti3C2 heterojunction was developed for ultrasensitive determination of miRNA-21. In this device, the b-TiO2/CdS:Eu/Ti3C2 heterojunction with excellent energy level arrangement effectively facilitated photoelectric conversion efficiency and accelerated the separation of the photogenerated electron hole pairs, which because that the structure of heterojunction overcomes the drawbacks of single material, such as narrow light absorption range, wide band gap, short carrier lifetime, etc., improves light utilization, extends the lifetime of photogenerated electron hole pairs, and promotes electron transfer. Herein, hairpin DNA1 (H1) decorated on the b-TiO2/CdS:Eu/Ti3C2 electrode surface by Cd-S bonds, after H2/miRNA-21 heterduplex was introduced, the strand-displacement reaction (SDR) was triggered between H1 and H2/miRNA-21, accordingly, miRNA-21 was discharged from the H2/miRNA-21 heterduplex, forming the H1/H2 duplex, and the reuse of miRNA-21 was realized. As a signal amplification factor, the signal amplification factor H3-CdSe was hybridized with H1/H2 duplex, which greatly enhanced the sensitivity of the PEC biosensor. Under optimal conditions, the designed PEC biosensor displayed outstanding sensitivity, selectivity and stability with a wide liner range from 1.0 µM to 10.0 fM and a low detection limit of 3.3 fM. The preparation of the optoelectronic material affords a new direction for the progress of heterojunction photovoltaic materials and the construction of the proposed biosensor also provides a new thought for the PEC detection of human miRNA-21 with superior performance. Simultaneously, the established biosensor exhibiting tremendous possibility for detecting other biomarkers and biomolecules in clinical diagnosis fields.

Coupled electrochemiluminescent and resonance energy transfer determination of microRNA-141 using functionalized Mxene composite.

The electrochemiluminescence and resonance energy transfer (ECL-RET) method was adopted to detect miRNAs, in which the two-dimensional Ti3C2 Mxenes with high surface area modified with CdS:W nanocrystals (CdS:W NCs) were used as ECL signal emitter. Mxenes with a specific surface area of 5.2755 m2/g carried more emitters and promote ECL intensity. As an energy acceptor, BiOCl nanosheets (BiOCl NSs) have a wide UV-Vis absorption peak in the range 250 nm-700 nm, including the emission band of CdS:W NCs with 520 nm emission wavelength. Hence, BiOCl NSs are covalently bound to hairpin DNA 2 by amide bond to quench the ECL signal of CdS:W NCs. In the presence of miRNA-141, the hairpin DNA 1 modified on the GCE was unfold and then paired with hairpin DNA 2 to release miRNA-141 and quench the signal of the ECL biosensor. Then, the concentration signal of miRNA-141 was amplified by catalytic hairpin assembly. The novel specific biosensor demonstrated a satisfactory linear relationship with miRNA-141 in the range 0.6 pM to 4000 pM; the detection limit was as low as 0.26 pM (3 s/m) under the potential of 0 ~ -1.3 V and showed outstanding RSD of 1.19%. The findings of the present work with high accuracy and sensitivity will be of positive significance for the clinical diagnosis of miRNA in the future work. The construction process of the biosensor and electrochemiluminescence mechanism.

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.

Electrochemiluminescence aptasensor for lincomycin antigen detection by using a SnO2/chitosan/g-C3N4 nanocomposite.

In this paper, hydrothermal method was used for the synthesis of SnO2 quantum dots (QDs). The prepared SnO2 QDs have a uniform particle size distribution and good electrochemiluminescence (ECL) property. Then the prepared SnO2 QDs was combined with graphene-like carbon nitride (g-C3N4) through chitosan to form SnO2/chitosan/g-C3N4 nanocomposite and used for detecting the lincomycin. The characteristics of SnO2/chitosan/g-C3N4 nanocomposite were presented by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS), and the analytical results proving that the nanocomposite was prepared successfully. In this strategy, the SnO2/chitosan/g-C3N4 nanocomposite was acted as the substrate of aptasensor. Then, SH-DNA (aptamer DNA) was assembled on the surface of electrode, after 6-mercaptohexanol (MCH) blocked the unbound sites of the electrode surface, ferrocene-DNA (Fc-DNA) was incubated on the electrode surface through base complementation with aptamer DNA. In the absence of lincomycin, due to the low conductivity of Fc-DNA and the photo-excited energy electron transfer, the ECL signal was quenched. In the presence of lincomycin, the aptamer DNA was specific binding with lincomycin, and ferrocene-DNA (Fc-DNA) was detached from the surface of aptasensor electrode, generating an obviously enhancement of ECL signal. To ensure the accuracy of the data, each electrode runs continuously for 3600 s. Under optimal experimental conditions, the detection range of the aptasensor was 0.10 ng mL-1 - 0.10 mg mL-1, and the detection limit was 0.028 ng mL-1. In addition, the aptasensor has good stability and reproducibility, and also provided a hopeful device for all kinds of other protein target.

A ratiometric electrochemiluminescent cytosensor based on polyaniline hydrogel electrodes in spatially separated electrochemiluminescent systems.

Here, we proposed a ratiometric electrochemiluminescent (ECL) strategy in spatially multiplied ECL systems. By the specific recognition of hyaluronic acid with proteoglycan CD44 and epidermal growth factor with epidermal growth factor receptor on the cell surface, the cells were labelled with potential-resolved ECL probes, namely Ru(bpy)32+ and g-C3N4, respectively. The as-proposed cytosensor provides a multichannel ECL protocol to improve the throughput, which may push the application of ECL for the cellular immunoanalysis.

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.

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.

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 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.

Potential-Resolved Electrochemiluminescence Nanoprobes for Visual Apoptosis Evaluation at Single-Cell Level.

In this work, a potential-resolved electrochemiluminescence (ECL) method is developed and used for the apoptosis diagnosis at the single-cell level. The apoptosis of cells usually induces the decreasing expression of epidermal growth factor receptor (EGFR) and promotes phosphatidylserine (PS) eversion on the cell membrane. Here, Au@L012 and g-C3N4 as ECL probes are functionalized with epidermal growth factor (EGF) and peptide (PSBP) to recognize the EGFR and PS on the cell surface, respectively, showing two well-separated ECL signals during a potential scanning. Experimental results reveal that the relative ECL change of g-C3N4 and Au@L012 correlates with the degree of apoptosis, which provides an accurate way to investigate apoptosis without interference that solely changes EGFR or PS. With a homemade ECL microscopy, we simultaneously evaluate the EGFR and PS expression of abundant individual cells and, therefore, achieve the visualization analysis of the apoptosis rate for normal and cancer cell samples. This strategy contributes to visually studying tumor markers and pushing the application of ECL imaging for the disease diagnosis at the single-cell level.

Electrochemiluminescence Investigation of Glucose Transporter 4 Expression at Skeletal Muscle Cells Surface Based on a Graphene Hydrogel Electrode.

In situ detection of the expression level of cell-surface receptors has become a hotspot study in recent years. We propose in this manuscript a novel strategy for sensitive electrochemiluminescence (ECL) detection of glucose transporter 4 (GLUT4) on human skeletal muscle cells (HSMCs). Graphene hydrogel (GH) was selected to fabricate a permeable electrode with the purpose of overcoming the steric hindrance of cells on electrode, which leads to errors in the detection of cell-surface receptors. GLUT4 was labeled with carbon dots (CDs), which generate ECL emission at the interface between GH and cells, so about half the amount of GLUT4 expressed at the cell surface could be determined, which provided an accurate GLUT4 expression quantification. The prepared cytosensor exhibited good analytical performance for HSMC cells, ranging from 500 to 1.0 × 106 cells·mL-1, with a detection limit of 200 cells·mL-1. The average amount of GLUT4 per HSMC cell was calculated to be 1.88 × 105. Furthermore, GLUT4 on HSMC surface had a 2.3-fold increase under the action of insulin. This strategy is capable of evaluating the receptors on the cell surface, which may push the application of ECL for disease diagnosis.

Photoelectrochemical DNA biosensor based on g-C3N4/MoS2 2D/2D heterojunction electrode matrix and co-sensitization amplification with CdSe QDs for the sensitive detection of ssDNA.

A novel enhanced photoelectrochemical (PEC) DNA biosensor, based on a compact heterojunction g-C3N4/MoS2 and co-sensitization effect with CdSe quantum dots (QDs), was first proposed for simple and accurate analysis of a short ssDNA. In this work, the g-C3N4/MoS2 was successfully synthesized and used as the electrode matrix material to construct PEC biosensor. 2D/2D heterojunction was formed between g-C3N4 and MoS2, which could promote the separation of photogenerated electron-hole pairs resulting in an enhanced photocurrent. In the presence of target DNA, CdSe QDs labeled reporter DNA was complementary pairing with target DNA which was specific recognized by capture DNA loading on self-assembled CdS QDs film, leading to close contact between CdSe QDs and g-C3N4/MoS2 modified electrode surface, thereby resulting in the enhanced photocurrent intensity due to the co-sensitization effect. Under the optimal operating conditions, the photoelectrochemical biosensor demonstrated favorable accuracy and could respond to 0.32 pM (S/N = 3) with a linear concentration range from 1.0 pM to 2.0 µM. Moreover, the proposed PEC DNA biosensor exhibits high sensitivity, excellent specificity, acceptable reproducibility and accuracy, showing a promising potential in DNA bioanalysis and other relative fields.

TiO2/g-C3N4/CdS Nanocomposite-Based Photoelectrochemical Biosensor for Ultrasensitive Evaluation of T4 Polynucleotide Kinase Activity.

Herein, an efficient photoelectrochemical (PEC) platform was constructed by a cosensitization strategy with a cascade energy level arrangement for the ultrasensitive evaluation of T4 polynucleotide kinase (T4 PNK). Based on CdSe quantum dots (QDs) with an extremely narrow bandgap, this cosensitization strategy offered a highly efficient sensitizer with a matching band-edge level of a ternary TiO2/g-C3N4/CdS nanocomposite. In this protocol, the ternary nanocomposite was first prepared to serve as the matrix to construct the PEC sensing platform. On the other hand, a well-designed hairpin DNA1 probe with 5'-hydroxyl termini was specifically phosphorylated by T4 PNK which would be selectively cleaved with lambda exonuclease (λ-Exo) outputting the 3'-thiol end ssDNA2. After tagged with CdSe QDs, ssDNA2 was captured by the complementary capture DNA3 on the electrode surface. As a result, CdSe QDs were in close contact with the ternary nanocomposite matrix, leading to an enhanced photocurrent response. Therefore, this proposed PEC platform displayed an analytical performance with a wide linear range from 0.0001 to 0.02 U mL-1 and a low detection limit down to 6.9 × 10-5 U mL-1. Moreover, this ternary nanocomposite-based platform exhibited excellent selectivity, good reproducibility, and remarkable storage stability, which shows great potential for T4 PNK detection and inhibitor screening.

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.

A label-free photoelectrochemical biosensor for urokinase-type plasminogen activator detection based on a g-C3N4/CdS nanocomposite.

Herein, we established a novel ultrasensitive photoelectrochemical biosensor for detecting urokinase-type plasminogen activator (u-PA), based on a g-C3N4/CdS nanocomposite. The prepared nanocomposite was characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet-visible absorption spectroscopy, and Fourier transform infrared spectroscopy, thus indicating that the nanocomposite was prepared successfully. In the typical process, the prepared nanocomposite was deposited on the surface of a bare FTO electrode. After being air-dried, the g-C3N4/CdS nanocomposite modified electrode was successively incubated with antibody against urokinase-type plasminogen activator and the blocking agent BSA to produce a photoelectrochemical biosensor for u-PA. In the presence of target u-PA antigen, the photocurrent response of the prepared biosensor electrode decreased significantly. The proposed novel photoelectrochemical biosensor exhibited good sensitivity, specificity, and reproducibility for u-PA detection, and a low detection limit of 33 fg mL-1, ranging from 1 µg mL-1-0.1 pg mL-1. The proposed strategy should provide a promising method for detection of other biomarkers.

Direct Electrochemiluminescence Imaging of a Single Cell on a Chitosan Film Modified Electrode.

Single-cell imaging is essential for elucidating the biological mechanism of cell function because it accurately reveals the heterogeneity among cells. The electrochemiluminescence (ECL) microscopy technique has been considered a powerful tool to study cells because of its high throughput and zero cellular background light. However, since cells are immobilized on the electrode surface, the steric hindrance and the insulation from the cells make it difficult to obtain a luminous cell ECL image. To solve this problem, direct ECL imaging of a single cell was investigated and achieved on chitosan and nano-TiO2 modified fluoride-doped tin oxide conductive glass (FTO/TiO2/CS). The permeable chitosan film is not only favorable for cell immobilization but also increases the space between the bottom of cells and the electrode; thus, more ECL reagent can exist below the cells compared with the cells on a bare electrode, which guarantees the high sensitivity of quantitative analysis. The modification of nano-TiO2 strengthens the ECL visual signal in luminol solution and effectively improves the signal-to-noise ratio. The light intensity is correlated with the H2O2 concentration on FTO/TiO2/CS, which can be applied to analyze the H2O2 released from cells at the single-cell level. As far as we know, this is the first work to achieve cell ECL imaging without the steric hindrance effect of the cell, and it expands the applications of a modified electrode in visualization study.