Smartphone-Assisted Flexible Electrochemical Sensor Platform by a Homology DNA Nanomanager Tailored for Multiple Cancer Markers Field Inspection.

In this work, an ingenious sensor technology was established by integrating the EBFCs on a flexible paper strip carrier (PE) that was used for simultaneous detection of tumor markers in complex samples. Adopting high performance ultrathin graphdiyne (U-GDY) as the substrate can increase the enzyme load, accelerate the electron transfer rate, and significantly enhance the detection sensitivity. A homologous DNA nanomanager strategy cleverly uses signal switches to recycle and amplify target miRNAs, while the smartphone receives real-time instantaneous current values to realize multivariate detection. Electrochemical data show that the detection limits (LODs) of miRNA-21 and miRNA-155 are 0.09 and 0.15 fM in the wide concentration range. The results confirm that the tailored sensor platform provides a strategy for the early cancer diagnosis and lays the foundation for the construction of a flexible wearable platform.

Flexible Self-Powered Sensing System Based on Novel DNA Circuit Strategy and Graphdiyne for Thalassemia Gene by Rapid Naked-Eye Tracking and Open-Circuit Voltage.

Based on the controllable instantaneous self-assembly ability of long-chain branched DNA nanostructures and the synergistic effect between nucleic acid amplification without enzymes, a highly sensitive and highly specific self-powered biosensing platform is developed. Two-dimensional graphdiyne is prepared, modified on flexible carbon cloth, and then functionalized with gold nanoparticles. When DNA mi-tubes are applied on it, target thalassemia gene CD122 triggers a dual-catalytic hairpin assembly reaction. The generated nanoscale DNA is precisely captured by the DNA mi-tube, exposing binding sites and activating the hybridization chain reaction to form long-chain branched DNA. Double-stranded DNA, along with dendritic DNA carrying a large number of guanine bases, precisely captures the signal molecule methylene blue (MB), generating a significant electrochemical signal. The redox reaction of MB also causes a proportional change in the system's color, achieving a colorimetric detection functionality. An efficient dual-mode self-powered sensing platform, therefore, is established for detecting the thalassemia gene CD122. The linear response range of target concentration to open-circuit voltage and RGB Blue value is 0.0001-10,000 pM. The detection limit under electrochemical mode is 36.3 aM (S/N = 3), and under colorimetric mode, it is as low as 12.1 aM (S/N = 3). The new method exhibits high sensitivity, excellent selectivity, and high accuracy, providing a universal strategy for designing novel biosensing platforms that can be extended to the detection of other biomolecules.

Smart Target-Initiated Catalytic DNA Junction Circuit Amplification Strategy for the Ultrasensitive Electrochemiluminescence Detection of MicroRNA.

One of the highly attractive research directions in the electrochemiluminescence (ECL) field is how to regulate and improve ECL efficiency. Quantum dots (QDs) are highly promising ECL materials due to their adjustable luminescence size and strong luminous efficiency. MoS2 NSs@QDs, an ECL emitter, is synthesized via hydrothermal methods, and its ECL mechanism is investigated using cyclic voltammetry and ECL-potential curves. Then, a stable and vertical attachment of a triplex DNA (tsDNA) probe to the MoS2 nanosheets (NSs) is applied to the electrode. Next, an innovative ECL sensor is courageously empoldered for precise and ultrasensitive detection of target miRNA-199a through the agency of ECL-resonance energy transfer (RET) strategy and a dextrous target-initiated catalytic three-arm DNA junction assembly (CTDJA) based on a toehold strand displacement reaction (TSDR) signal amplification approach. Impressively, the ingenious system not only precisely regulates the distance between energy donor-acceptor pairs leave energy less loss and more ECL-RET efficiency, but also simplifies the operational procedure and verifies the feasibility of this self-assembly process without human intervention. This study can expand MoS2 NSs@QDs utilization in ECL biosensing applications, and the proposed nucleic acid amplification strategy can become a miracle cure for ultrasensitive detecting diverse biomarkers, which helps researchers to better study the tumor mechanism, thereby unambiguously increasing cancer cure rates and reducing the risk of recurrence.

Real-Time Biosensor Platform Based on Novel Sandwich Graphdiyne for Ultrasensitive Detection of Tumor Marker.

Realization of a highly sensitive analysis and sensing platform is important for early-stage tumor diagnosis. In this work, a self-powered biosensor with a novel sandwich graphdiyne (SGDY) combined with an aptamer-specific recognition function was developed to sensitively and accurately detect tumor markers. Results indicated that the detection limits of microRNA (miRNA)-21 and miRNA-141 were 0.15 and 0.30 fM (S/N = 3) in the linear range of 0.05-10000 and 1-10000 fM, respectively. The newly designed platform has great promise for early-stage tumor diagnosis.

Recent advances in biological detection with rolling circle amplification: design strategy, biosensing mechanism, and practical applications.

Rolling circle amplification (RCA) is a simple and isothermal DNA amplification technique that is used to generate thousands of repeating DNA sequences using circular templates under the catalysis of DNA polymerase. Compared to alternating temperature nucleic acid amplification such as polymerase chain reaction (PCR) amplification, RCA is more suitable for on-spot detection without the need for an expensive thermal cycler. In this study, the principle and classification of RCA are introduced, and the applications of RCA in the detection of pathogenic bacteria, nucleic acid tumor markers, viruses, and proteins are reviewed. Finally, the perspectives of RCA in biological detection are anticipated. The RCA method has a great potential for biological detection. This review aims to provide references for the further development and application of the RCA technique in biosensors.

Superior performance of a graphdiyne self-powered biosensor with exonuclease III-assisted signal amplification for sensitive detection of microRNAs.

Graphdiyne (GDY) is an sp and sp2 co-hydrocarbon allotrope whose particular structure endows it with many fascinating properties, including abundant chemical bonds, high conjugation, natural pores, high carrier mobility, high conductivity and stability, etc. In this work, two-dimensional graphdiyne is prepared as an electrode substrate material coupling with an exonuclease III-assisted amplification strategy to construct a superior-performance self-powered biosensor based on enzymatic biofuel cells for highly sensitive detection of the tumour marker miRNA-21. Glucose oxidase (GOD) is first immobilized on the GDY/AuNP composite to prepare a bioconjugate. GDY/AuNP modified carbon cloth is used as an enzyme biofuel cell electrode, which is then modified with bilirubin oxidase as a biocathode. The bioconjugate binds to GOD through specific binding to the bioanode. When miRNA-21 is present, specific recognition by exonuclease III in the system results in cleavage of the capture probe, and miRNA-21 is recovered and involved in the cycle. The target miRNA-21 then causes corresponding changes in the open-circuit voltage of the self-powered system. Based on this, a sensitive detection method was constructed, within the scope from 0.1 fM to 0.1 nM with a shallow detection limit of 55.2 aM (S/N = 3). The new approach triumphantly has been used to detect miRNA-21 in serum, which provides a compelling new way for early diagnosis of related cancers.

Construction of an Integrated Device of a Self-Powered Biosensor and Matching Capacitor Based on Graphdiyne and Multiple Signal Amplification: Ultrasensitive Method for MicroRNA Detection.

The detection of microRNA (miRNA) in human serum has great significance for cancer prevention. Herein, a novel self-powered biosensing platform is developed, which effectively integrates an enzymatic biofuel cell (EBFC)-based self-powered biosensor with a matching capacitor for miRNA detection. A catalytic hairpin assembly and hybrid chain reaction are used to improve the analytical performance of EBFC. Furthermore, the matching capacitor is selected as an auxiliary signal amplifying device, and graphdiyne is applied as substrate material for EBFC. The results confirm that the developed method obviously increases the output current of EBFC, and the sensitivity can reach 2.75 µA/pM, which is 786% of pure EBFC. MiRNA can be detected in an expanded linear range of 0.1-100000 fM with a detection limit of 0.034 fM (S/N = 3). It can offer a selective and sensitive platform for nucleotide sequence detection with great potential in clinical diagnostics.

Stimulating the Reversibility of Sb2 S3 Anode for High-Performance Potassium-Ion Batteries.

Conversion-alloy sulfide materials for potassium-ion batteries (KIBs) have attracted considerable attention because of their high capacities and suitable working potentials. However, the sluggish kinetics and sulfur loss result in their rapid capacity degeneration as well as inferior rate capability. Herein, a strategy that uses the confinement and catalyzed effect of Nb2 O5 layers to restrict the sulfur species and facilitate them to form sulfides reversibly is proposed. Taking Sb2 S3 anode as an example, Sb2 S3 and Nb2 O5 are dispersed in the core and shell layers of carbon nanofibers (C NFs), respectively, constructing core@shell structure Sb2 S3 -C@Nb2 O5 -C NFs. Benefiting from the bi-functional Nb2 O5 layers, the electrochemical reversibility of Sb2 S3 is stimulated. As a result, the Sb2 S3 -C@Nb2 O5 -C NFs electrode delivers the rapidest K-ion diffusion coefficient, longest cycling stability, and most excellent rate capability among the controlled electrodes (347.5 mAh g-1 is kept at 0.1 A g-1 after 100 cycles, and a negligible capacity degradation (0.03% per cycle) at 2.0 A g-1 for 2200 cycles is delivered). The enhanced K-ion storage properties are also found in SnS2 -C@Nb2 O5 -C NFs electrode. Encouraged by the stimulated reversibility of Sb2 S3 and SnS2 anodes, other sulfides with high electrochemical performance also could be developed for KIBs.

Synthesis and modification of carbon dots for advanced biosensing application.

There has been an explosion of interest in the use of nanomaterials for biosensing applications, and carbonaceous nanomaterials in particular are at the forefront of this explosion. Carbon dots (CDs), a new type of carbon material, have attracted extensive attention due to their fascinating properties, such as small particle size, tunable optical properties, good conductivity, low cytotoxicity, and good biocompatibility. These properties have enabled them to be highly promising candidates for the fabrication of various high-performance biosensors. In this review, we summarize the top-down and bottom-up synthesis routes of CDs, highlight their modification strategies, and discuss their applications in the fields of photoluminescence biosensors, electrochemiluminescence biosensors, chemiluminescence biosensors, electrochemical biosensors and fluorescence biosensors. In addition, the challenges and future prospects of the application of CDs for biosensors are also proposed.

Stabilizing Metallic Iron Nanoparticles by Conformal Graphitic Carbon Coating for High-Rate Anode in Ni-Fe Batteries.

Nickel-iron (Ni-Fe) batteries are promising candidates for large-scale energy storage due to their high safety and low cost. However, their power density and cycling efficiency remain limited by the poor kinetics of the Fe anode. Herein, we report high-performance Fe anodes based on active Fe nanoparticles conformally coated with carbon shells, which were synthesized from low-cost precursors using a scalable process. Such core-shell structured C-Fe anodes offer high electrochemical activity and stability. Specifically, a high specific capacity of 208 mAh g-1 at a current density of 1 A g-1 (based on the total weight of Fe and C) and a capacity retention of 93% after 2000 cycles at 4 A g-1 can be achieved. When coupled with a Ni cathode, such a full cell battery can deliver a high energy density of 101.0 Wh kg-1 at power density of 0.81 kW kg-1 and 51.6 Wh kg-1 at 8.2 kW kg-1 (based on the mass of the electrode materials), among the best energy and power performance among Ni-Fe batteries reported results. Thus, this work may provide an effective and scalable route toward high-performance anodes for high-power and long-life Ni-Fe batteries.

A highly sensitive electrochemical biosensor for protein based on a tetrahedral DNA probe, N- and P-co-doped graphene, and rolling circle amplification.

A tetrahedral DNA probe can effectively overcome the steric effects of a single-stranded probe to obtain well-controlled density and minimize nonspecific adsorption. Herein, a highly sensitive electrochemical biosensor is fabricated for determination of protein using a tetrahedral DNA probe and rolling circle amplification (RCA). N- and P-co-doped graphene (NP-rGO) is prepared, and AuNPs are then electrodeposited on it for DNA probe immobilization. Benefitting from the synergistic effects of the excellent electrical conductivity of NP-rGO, the stability of the tetrahedral DNA probe and the signal amplification of RCA, the biosensor achieves a low limit of 3.53 × 10-14 M for thrombin and a wide linear range from 1 × 10-13 to 1 × 10-7 M. This study provides a sensitive and effective method for the detection of protein in peripheral biofluids, and paves the way for future clinical diagnostics and treatment of disease. Graphical abstract.

Recent advances in nanomaterial-based electrochemical and optical sensing platforms for microRNA assays.

MicroRNA (MiRNA) plays a crucial role in biological cells to enable assessment of a cancer's development stage. Increasing evidence has shown that the accurate and sensitive detection of miRNA holds the key toward correct disease diagnosis. However, some characteristics of miRNAs, such as their short chains, low concentration, and similar sequences, make it difficult to detect miRNA in biological samples. Nanomaterials usually have good optical, electronic, and mechanical properties and therefore provide new possibilities for improving the performance of miRNA assays. Many different sorts of nanomaterials, including metal nanomaterials, carbon nanomaterials, quantum dots, and transition-metal dichalcogenides, have been used to construct optical and electrochemical assays for miRNA and have shown attractive results. This review describes recent efforts in the application of nanomaterials as sensing elements in electrochemical and optical miRNA assays. The analytical figures of merit of various methods for the detection of miRNA are compared in the present article. The current capabilities, limitations, and future challenges in miRNA detection and analysis based on nanomaterials are also addressed.

Ultrasensitive determination of thrombin by using an electrode modified with WSe2 and gold nanoparticles, aptamer-thrombin-aptamer sandwiching, redox cycling, and signal enhancement by alkaline phosphatase.

A sensitive aptamer/protein binding-triggered sandwich assay for thrombin is described. It is based on electrochemical-chemical-chemical redox cycling using a glassy carbon electrode (GCE) that was modified with WSe2 and gold nanoparticles (AuNPs). The AuNPs are linked to thrombin aptamer 1 via Au-S bonds. Thrombin is first captured by aptamer 1 and then sandwiched through the simultaneous interaction with AuNPs modified with thrombin-specific aptamer 2 and signalling probe. Subsequently, the DNA-linked AuNP hybrids result in the capture of streptavidin-conjugated alkaline phosphatase onto the modified GCE through the specific affinity reaction for further signal enhancement. As a result, a linear range of 0-1 ng mL-1 and a detection limit as low as 190 fg mL-1 are accomplished. The specificity for thrombin is excellent. Conceivably, this strategy can be easily expanded to other proteins by using the appropriate aptamer. Graphical abstract Schematic presentation of an electrochemical biosensor for thrombin based on WSe2 and gold nanoparticles, aptamer-thrombin-aptamer sandwiching, redox cycling, and signal enhancement by alkaline phosphatase.

An electrochemical microRNA sensing platform based on tungsten diselenide nanosheets and competitive RNA-RNA hybridization.

In this work, we report an ultrasensitive electrochemical biosensor for microRNA-21 (miRNA-21) detection by using a competitive RNA-RNA hybridization configuration. A biotinylated miRNA of the self-same sequence with the target miRNA is mixed with the samples, and allowed competition with the target miRNA for a thiolated RNA probe immobilized onto a tungsten diselenide (WSe2) nanosheet modified electrode. Thereafter the current response is obtained by forming the hybridized biotinylated miRNA with streptavidin-horseradish peroxidase (HRP) conjugates to catalyze the H2O2 + hydroquinone (HQ) system. Benefiting from the high specific surface area of WSe2 nanosheets, the competitive hybridization configuration and the signal amplification of the H2O2 + HQ detection system, the proposed assay exhibits a wide linear range of 0.0001-100 pM towards target miRNA with a detection limit of 0.06 fM (S/N = 3), and shows excellent discrimination ability for base-mismatched miRNA sequences. Therefore, the designed platform has promising prospects for the detection of miRNA in biomedical research and early clinical diagnosis.

Aptamer-based detection and quantitative analysis of human immunoglobulin E in capillary electrophoresis with chemiluminescence detection.

A novel aptamer-based CE with chemiluminescence (CL) assay was developed for highly sensitive detection of human immunoglobulin E (IgE). The IgE aptamer was conjugated with gold nanoparticles (AuNPs) to form AuNPs-aptamer that could specifically recognize the IgE to produce an AuNPs-aptamer-IgE complex. The mixture of the AuNPs-aptamer-IgE complex and the unbounded AuNPs-aptamer could be effectively separated by CE and sensitively detected with luminol-H2 O2 CL system. By taking the advantage of the excellent catalytic behavior of AuNPs on luminol-H2 O2 CL system, the ultrasensitive detection of IgE was achieved. The detection limit of IgE is 7.6 fM (S/N = 3) with a linear range from 0.025 to 250 pM. Successful detection of IgE in human serum samples was demonstrated and the recoveries of 94.9-103.2% were obtained. The excellent assay features of the developed approach are its specificity, sensitivity, adaptability, and very small sample consumption. Our design provides a methodology model for determination of rare proteins in biological samples.

Highly sensitive capillary electrophoretic immunoassay of rheumatoid factor in human serum with gold nanoparticles enhanced chemiluminescence detection.

A new CE-based immunoassay method for the determination of rheumatoid factor was developed using chemiluminescent reaction of luminol and hydrogen peroxide catalyzed by gold nanoparticles (AuNPs). In this method, AuNPs were synthesized and conjugated with anti-RF (antibody, Ab) to form tagged Ab (AuNPs-Ab, Ab*), which subsequently linked to limited amount of RF (antigen, Ag) to produce Ab*-Ag complex by a noncompetitive immunoreaction. AuNPs were used to label antibody and amplify chemiluminescent signal. Under the optimized conditions, the mixture of free Ab* and Ab*-Ag complex was well separated and detected. This method yields a wide linear range of 0.01-20 µg/mL with a correlation coefficient of 0.997, and the detection limit of RF reaches 5.95 ng/mL (ca. 6.0 pmol/L, S/N = 3). The proposed method was successfully applied for the quantification of RF in human sera from patients with rheumatoid arthritis. This highly sensitive and selective method could be developed into a promising and useful technique for biological molecules determination in clinical analysis.

Aptasensor based on tripetalous cadmium sulfide-graphene electrochemiluminescence for the detection of carcinoembryonic antigen.

A facile label-free electrochemiluminescence (ECL) aptasensor, based on the ECL of cadmium sulfide-graphene (CdS-GR) nanocomposites with peroxydisulfate as the coreactant, was designed for the detection of carcinoembryonic antigen (CEA). Tripetalous CdS-GR nanocomposites were synthesized through a simple onepot solvothermal method and immobilized on the glassy carbon electrode surface. L-Cystine (L-cys) could largely promote the electron transfer and enhance the ECL intensity. Gold nanoparticles (AuNPs) were assembled onto the L-cys film modified electrode for aptamer immobilization and ECL signal amplification. The aptamer modified with thiol was adsorbed onto the surface of the AuNPs through a Au-S bond. Upon hybridization of the aptamer with the target protein, the sequence could conjugate CEA to form a Y architecture. With CEA as a model analyte, the decreased ECL intensity is proportional to the CEA concentration in the range of 0.01-10.0 ng mL(-1) with a detection limit of 3.8 pg mL(-1) (S/N = 3). The prepared aptasensor was applied to the determination of CEA in human serum samples. The recoveries of CEA in the human serum samples were between 85.0% and 109.5%, and the RSD values were no more than 3.4%.

A novel electrochemical DNA biosensor construction based on layered CuS-graphene composite and Au nanoparticles.

A novel CuS-graphene (CuS-Gr) composite was synthesized to achieve excellent electrochemical properties for application as a DNA electrochemical biosensor. CuS-Gr composite was prepared by a hydrothermal method, in which two-dimensional graphene served as a two-dimensional conductive skeleton to support CuS nanoparticles. A sensitive electrochemical DNA biosensor was fabricated by immobilizing single-stranded DNA (ss-DNA) labeled at the 5' end using 6-mercapto-1-hexane (HS-ssDNA) on the surface of Au nanoparticles (AuNPs) to form ssDNA-S-AuNPs/CuS-Gr, and hybridization sensing was done in phosphate buffer. Cyclic voltammetry and electrochemical impedance spectroscopy were performed for the characterization of the modified electrodes. Differential pulse voltammetry was applied to monitor the DNA hybridization using an [Fe(CN)6](3-/4-) solution as a probe. Under optimum conditions, the biosensor developed exhibited a good linear relationship between the current and the logarithm of the target DNA concentration ranging from 0.001 to 1 nM, with a low detection limit of 0.1 pM (3σ/S). The biosensor exhibited high selectivity to differentiate one-base-mismatched DNA and three-base-mismatched DNA. The results indicated that the sensing platform based on CuS-Gr provides a stable and conductive interface for electrochemical detection of DNA hybridization, and could easily be extended to the detection of other nucleic acids.

A sandwich-type dual-mode biosensor based on graphdiyne and DNA nanoframework for ultra-sensitive detection of CD142 gene.

Thalassemia is a globally prevalent single-gene blood disorder, with nearly 7% of the world's population being carriers. Therefore, the development of specific and sensitive methods for thalassemia detection holds significant importance. Herein, a sandwich-type electrochemical/colorimetric dual-mode biosensor is developed based on gold nanoparticles (AuNPs)/graphdiyne (GDY) and DNA nanoframeworks for ultra-sensitive detection of CD142 gene associated with sickle cell anemia. Utilizing AuNPs/GDY as the substrate electrode, the fabricated sandwiched DNA nanoframework not only improves selectivity but also introduces numerous signal probes to further amplify the output signal. In the electrochemical mode, glucose oxidase catalyzes the oxidation of glucose, generating electrons that are transferred to the biocathode for a reduction reaction, resulting in an electric signal proportional to the target concentration. In the colorimetric mode, glucose oxidase catalyzes the generation of H2O2 from glucose, and with the aid of horseradish peroxidase, H2O2 oxidizes 3,3',5,5'-tetramethylbenzidine to produce a colored product, enabling colorimetric detection of the target. The dual-mode biosensor demonstrates a detection range of 0.0001-100 pM in the electrochemical mode and a detection range of 0.0001-10,000 pM in the colorimetric mode. The detection limit in the electrochemical mode is determined to be 30.4 aM (S/N=3), while in the colorimetric mode is of 35.6 aM (S/N=3). This dual-mode detection achieves ultra-sensitive detection of CD142, demonstrating broad prospects for application.

MoS2/ReS2 Hollow Heterojunction for Enhanced Aqueous Zinc-Ion Storage Performance.

The research of cathode materials for water-based zinc ion batteries (ZIBs) is very hot because the current mainstream electrode makes it difficult to meet the requirements of high specific discharge capacity and maintain a stable structure in the electrochemical process. In this work, the cathode properties are adjusted by the modification idea of morphology regulation and heterojunction construction. The simple hydrothermal method is used to prepare the hollow bimetallic heterojunction nanospheres, and their electrochemical properties as cathode materials for ZIBs are studied for the first time. Herein, the optimized cathode delivers high-rate performance and long-term cycling stability (∼98.9% Coulombic efficiency at 0.1 A g-1 after 200 cycles). The results indicate that the hollow bimetallic heterojunction nanospheres can support the material structure and provide a wide Zn2+ migration channel. The excellent performance is because hollow heterojunction bimetallic sulfides can provide abundant catalytic active sites, improve the mobility of electrons, and enhance the battery performance fundamentally. Therefore, we firmly believe that the combination of the different modification ideas can coordinate to adjust the electrode performance of ZIBs, enriching the electrode types and expanding the energy system application range.