Twisted DNA Origami-Based Chiral Monolayers for Spin Filtering.

DNA monolayers with inherent chirality play a pivotal role across various domains including biosensors, DNA chips, and bioelectronics. Nonetheless, conventional DNA chiral monolayers, typically constructed from single-stranded DNA (ssDNA) or double-stranded DNA (dsDNA), often lack structural orderliness and design flexibility at the interface. Structural DNA nanotechnology has emerged as a promising solution to tackle these challenges. In this study, we present a strategy for crafting highly adaptable twisted DNA origami-based chiral monolayers. These structures exhibit distinct interfacial assembly characteristics and effectively mitigate the structural disorder of dsDNA monolayers, which is constrained by a limited persistence length of ∼50 nm of dsDNA. We highlight the spin-filtering capabilities of seven representative DNA origami-based chiral monolayers, demonstrating a maximal one-order-of-magnitude increase in spin-filtering efficiency per unit area compared with conventional dsDNA chiral monolayers. Intriguingly, our findings reveal that the higher-order tertiary chiral structure of twisted DNA origami further enhances the spin-filtering efficiency. This work paves the way for the rational design of DNA chiral monolayers.

Construction of an Enzyme Cascade Based on the Accurate Adjacent Arrangement of Coupled Enzymes Using a Triblock PolyA DNA Probe.

Intracellular enzyme cascades are essential for various biological processes, and mimicking their functions in artificial systems has attracted significant research attention. However, achieving convenient and efficient spatial organization of enzymes on interfaces remains a critical challenge. In this work, we designed a simple single-DNA scaffold using triblock polyA single-stranded DNA for the arrangement of coupled enzymes. The scaffold was assembled onto a gold electrode through the affinity of polyA-Au, and two enzymes (glucose oxidase and horseradish peroxidase) were captured through hybridization. The molecular distance between the enzymes was regulated by changing the length of the polyA fragment. As a proof of concept, a glucose biosensor was constructed based on the enzyme cascade amplification. The biosensor exhibited excellent detection capability for glucose in human serum samples with a limit of detection of 1.6 µM. Additionally, a trienzyme cascade reaction was successfully activated, demonstrating the potential scalability of our approach for multienzyme reactions. This study provides a promising platform for the development of easy-to-operate, highly efficient, and versatile enzyme cascade systems using DNA scaffolds.

Functionalized-Graphene Field Effect Transistor-Based Biosensor for Ultrasensitive and Label-Free Detection of ß-Galactosidase Produced by Escherichia coli.

The detection of ß-galactosidase (ß-gal) activity produced by Escherichia coli (E. coli) can quickly analyze the pollution degree of seawater bodies in bathing and fishing grounds to avoid large-scale outbreaks of water pollution. Here, a functionalized biosensor based on graphene-based field effect transistor (GFET) modified with heat-denatured casein was developed for the ultrasensitive and label-free detection of the ß-gal produced by E. coli in real water samples. The heat-denatured casein coated on the graphene surface, as a probe linker and blocker, plays an important role in fabricating GEFT biosensor. The GFET biosensor response to the ß-gal produced by E. coli has a wide concentration dynamic range spanning nine orders of magnitude, in a concentration range of 1 fg·mL-1-100 ng·mL-1, with a limit of detection (LOD) 0.187 fg·mL-1 (1.61 aM). In addition to its attomole sensitivity, the GFET biosensor selectively recognized the ß-gal in the water sample and showed good selectivity. Importantly, the detection process of the ß-gal produced by E. coli can be completed by a straightforward one-step specific immune recognition reaction. These results demonstrated the usefulness of the approach, meeting environmental monitoring requirements for future use.

Methylation specific enzyme-linked oligonucleotide assays (MS-ELONA) for ultrasensitive DNA methylation analysis.

Methylation of the promoter region of cancer related genes plays a crucial role in the occurrence and development of cancer, and the degree of methylation has great potential for the early cancer diagnosis. At present, the technology used to quantify DNA methylation is mainly based on the DNA sequencing which are time-consuming and high-cost in the relating application. We have developed an ultrasensitive method of methylation specific enzyme-linked oligonucleotide assays (MS-ELONA) to detect and quantify the level of DNA methylation. We could detect as little as 2 pg of methylated DNA in the 100000-fold excess of unmethylated genes, and discriminate prostate cancer from benign prostatic hyperplasia (BPH) and control with serum samples. We also demonstrate the reversibility of DNA methylation modification by treatment with demethylation drugs. With 16-channel electrochemical work station, our research reveals a simple and inexpensive method to quantify the methylation level of specially appointed genes, and have the potential to be applied in the clinical research.

A DNA framework-based dual signal amplification biosensor for portable detection of SARS-CoV-2 and its mutations.

We developed a rapid and accurate biosensor to detect SARS-CoV-2 and distinguish its mutations. Benefitting from a DNA framework-modified ordered interface and a dual signal amplification strategy, our biosensor could detect SARS-CoV-2 with a detection limit down to 10 fM. It performed well on pseudo virus and SARS-CoV-2 RNA standard materials, revealing the potential application in disease diagnosis and spread, in combination with a home-made smartphone.

Efficient H2 production in a ZnFe2O4/g-C3N4 photo-cathode single-chamber microbial electrolysis cell.

Photo-assisted single-chamber microbial electrolysis cells (MECs) incorporating semiconductor cathodes are attractively promising for exclusive hydrogen without CH4 and CO2. However, the unsustainable, high cost, and unstable metal catalysts on the cathodes along with the intricacies behind the interplay of circuital current, light illumination, and bacterial communities on both electrodes are poorly understood. Herein, photo-assisted single-chamber MECs incorporating ZnFe2O4/g-C3N4 cathodes are demonstrated to achieve efficient production of exclusive hydrogen (0.11 ± 0.01 m3/m2/day; 1.70 ± 0.04 m3/m3/day) with a solar-to-hydrogen conversion efficiency of 4.08 ± 0.17% and an energy efficiency relative to electrical input of 233 ± 5%. The ZnFe2O4/g-C3N4 structured cathodes exhibited appreciable higher photocurrents than the controls (g-C3N4: 4.3-fold; ZnFe2O4: 3.3-fold), and negligible leaking of Fe and Zn after the 4th-cycle operation. Circuital current and light illumination were proven to varying degree shape both electrodes for building up functional bacterial communities with metabolic regulation at the prolonged operation of 12 batch cycles. Energy metabolism and carbohydrate metabolism along with membrane transport, signal transduction, and cell motility based on PICRUSt functional prediction further confirmed the photo-assisted single-chamber MECs for efficient hydrogen production. This study provided a sustainable, cost-effective, and efficient approach for achieving high rates of exclusive hydrogen production and offered new insights for ingenious interplay of circuital current, light illumination, and bacterial communities for efficient hydrogen production in the photo-assisted single-chamber MECs. KEY POINTS: • ZnFe2O4/g-C3N4 cathodes of single-chamber MECs achieve efficient H2 production. • Light irradiation and circuit current shape bacterial communities on both electrodes. • Circuital current contributes to less leaking of Fe and Zn, and thus system stability.

DNA-Encoded Gold-Gold Wettability for Programmable Plasmonic Engineering.

Controlling the deposition and diffusion of adsorbed atoms (adatoms) on the surface of a solid material is vital for engineering the shape and function of nanocrystals. Here, we report the use of single-stranded DNA (oligo-adenine, oligo-A) to encode the wettability of gold seeds by homogeneous gold adatoms to synthesize highly tunable plasmonic nanostructures. We find that the oligo-A attachment transforms the nanocrystal growth mode from the classical Frank-van der Merwe to the Volmer-Weber island growth. Finely tuning the oligo-A density can continuously change the gold-gold contact angle (θ) from 35.1±3.6° to 125.3±8.0°. We further demonstrate the versatility of this strategy for engineering nanoparticles with different curvature and dimensions. With this unconventional growth mode, we synthesize a sub-nanometer plasmonic cavity with a geometrical singularity when θ>90°. Superfocusing of light in this nanocavity produces a near-infrared intraparticle plasmonic coupling, which paves the way to surface engineering of single-particle plasmonic devices.

Correction: A smartphone-based three-in-one biosensor for co-detection of SARS-CoV-2 viral RNA, antigen and antibody.

Correction for 'A smartphone-based three-in-one biosensor for co-detection of SARS-CoV-2 viral RNA, antigen and antibody' by Yanzhi Dou et al., Chem. Commun., 2022, DOI: https://doi.org/10.1039/d2cc01297a.

A smartphone-based three-in-one biosensor for co-detection of SARS-CoV-2 viral RNA, antigen and antibody.

Rapid and comprehensive diagnostic methods are necessary for early identification and monitoring of SARS-CoV-2. Here, we have developed a universal and portable three-in-one biosensor linked to a smartphone for co-detection of SARS-CoV-2 viral RNA, antigen, and antibody. In combination with a smartphone, the online monitoring of SARS-CoV-2 virus-infected patients from infection to immunization could be intelligently achieved.

A Portable Biosensor Based on Au Nanoflower Interface Combined with Electrochemical Immunochromatography for POC Detection of Prostate-Specific Antigen.

Serum prostate-specific antigen (PSA) is a widely used for the detection of prostate cancer and is considered the most reliable biomarker. However, the currently reported detection methods cannot achieve rapid monitoring. Here, we report a novel electrochemical immunochromatography (EIC) system for clinically accurate PSA detection. First, we constructed a carbon interface modified with gold nanoflowers (Au NFs) based on screen-printed carbon electrodes (SPCE), which acted as nanostructures with larger specific surface area that increased the number of PSA capture antibodies and can further improve detection signal-to-noise (S/N) ratio. Then, we fabricated detection chips by combining the SPCE/Au NFs with EIC. Under optimized conditions, the proposed biosensor exhibits high accuracy, taking only 15 minutes to complete detection. By measuring the levels of PSA in clinical blood samples, the biosensor can successfully discriminate clinically diagnosed prostate cancer patients from healthy controls.

Smartphone-Based Electrochemical Biosensors for Directly Detecting Serum-Derived Exosomes and Monitoring Their Secretion.

Exosomes are potential biomarkers, which play an important role in early diagnosis and prognosis prediction of cancer-related diseases. Nevertheless, direct quantification of exosomes in biological fluid, especially in point-of-care tests (POCTs), remains extremely challenging. Herein, we developed a sensitive and portable electrochemical biosensor in combination with smartphones for quantitative analysis of exosomes. The improved double-antibody sandwich method-based poly-enzyme signal amplification was adopted to detect exosomes. We could detect as low as 7.23 ng of CD63-positive exosomes in 5 µL of serum within 2 h. Importantly, we demonstrated that the biosensor worked well with microliter-level serum and cell culture supernatant. The biosensor holds great potential for the detection of CD-63-expressing exosomes in early diagnosis of prostate disease because CD63-positive exosomes were less detected from the prostate patient serum. Also, the biosensor was used to monitor the secretion of exosomes with the drug therapy, showing a close relationship between the secretion of exosomes and the concentration of cisplatin. The biosensing platform provides a novel way toward POCT for the diagnosis and prognosis prediction of prostate disease and other diseases via biomarker expression levels of exosomes.

CRISPR/Cas12a Powered DNA Framework-Supported Electrochemical Biosensing Platform for Ultrasensitive Nucleic Acid Analysis.

Nucleic acid analysis using ultrasensitive and simple methods is critically important for the early-stage diagnosis and treatment of diseases. The CRISPR/Cas proteins, guided by a single-stranded RNA have shown incredible capability for sequence-specific targeting and detection. Herein, in order to improve and expand the application of CRISPR/Cas technology to the electrochemical interface-based nucleic acids analysis, the authors develop a CRISPR/Cas12a powered DNA framework-supported electrochemical biosensing platform via the cis and trans cleavage of Cas12a on the heterogeneous carbon interface (the existing publications which commonly adopted trans-cleavage). Their solid-liquid interface is first immobilized by 3D tetrahedral framework nucleic acids (FNAs) with specific DNA recognition probe. Based on the recognition of the complementary target through protospacer adjacent motif (PAM) confirmation and CRISPR-derived RNA (crRNA) matching, the easily formed Cas12a/crRNA duplex can get access to the interface, and the cis and trans cleavage of Cas12a can be easily activated. In combination with the enzyme catalyzed reaction, they achieved an ultralow limit of detection (LOD) of 100 fm in HPV-16 detection without pre-amplification. Furthermore, the platform is compatible with a spike-in human serum sample and has superior stability. Thus, their reported platform offers a practical, versatile, and amplification-free toolbox for ultrasensitive nucleic acid analysis.

Ultrasensitive pathogen detection with a rolling circle amplification-empowered multiplex electrochemical DNA sensor.

We report a highly sensitive and selective multiplex assay by empowering an electrochemical DNA sensor with isothermal rolling circle amplification. The assay could simultaneously detect and discriminate three common entero-pathogens in a single reaction, with femtomolar sensitivity. It is useful for field- or resource-limited settings.

Fabrication of PVDF/BaTiO3/CNT Piezoelectric Energy Harvesters with Bionic Balsa Wood Structures through 3D Printing and Supercritical Carbon Dioxide Foaming.

Piezoelectric energy harvesters have received widespread attention in recent decades due to their inimitable electrical energy conversion methods. However, traditional polymer/piezoceramic materials and 2D thin-film structures have limited output performance, making them difficult to be efficiently applied in the collection of discrete mechanical energy. Here, new ternary composite powders were successfully developed by the ultrasonic coating method, and array structural devices with the construction of micropores were prepared using selective laser sintering (SLS) and supercritical carbon dioxide foaming (Sc-CO2) technologies. Coating carbon nanotubes improved the polarization efficiency of poly(vinylidene fluoride)/barium titanate (PVDF/BaTiO3) composites, which made it easy to perfectly combine the BaTiO3 piezoelectric constant and the flexibility of PVDF, promoting d33 from 0.7 to 2.6 pc/N. In addition, simulations and experiments simultaneously proved that SLS parts with high array densities amplified piezoelectric outputs because of a greater compression deformation in the vertical direction. Meanwhile, under the synergistic effect of SLS and Sc-CO2, 3D bionic balsa wood structure foams were successfully fabricated, which took advantage of the normal space, expanded the stress-strain effect, and improved the piezoelectric output capability. Excitingly, the prepared foam could directly produce 19.3 V and 415 nA piezoelectric output to charge a 1 µF commercial capacitor to 5.03 V within 180 s, which surpassed most of the PVDF piezoelectric energy harvesters reported thus far. This work has an excellent innovative and practical value in enriching the types of piezoelectric materials for SLS 3D printing and the design of 3D piezoelectric structures.

Multichannel Immunosensor Platform for the Rapid Detection of SARS-CoV-2 and Influenza A(H1N1) Virus.

The coronavirus disease 2019 (COVID-19) can present a similar syndrome to an influenza infection, which may complicate diagnosis and clinical management of these two important respiratory infectious diseases, especially during the peak season of influenza. A rapid and convenient point-of-care test (POCT) for severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and influenza virus is of great importance for prompt and efficient control of these respiratory epidemics. Herein, a multichannel electrochemical immunoassay (MEIA) platform was developed based on a disposable screen-printed carbon electrode (SPCE) array for the on-site detection of SARS-CoV-2 and A(H1N1). The developed MEIA was constructed with eight channels and allowed rapid detection on a single array. On the SPCE surface, monoclonal antibodies against influenza A(H1N1) hemagglutinin (HA) protein or SARS-CoV-2 spike protein were coated to capture the target antigens, which then interacted with a horseradish peroxidase (HRP)-labeled detection antibody to form an immuno-sandwich complex. The results showed that the MEIA exhibited a broader linear range than ELISA and comparable sensitivity for A(H1N1) HA and SARS-CoV-2 spike protein. The detection results on 79 clinical samples for A(H1N1) suggested that the proposed MEIA platform showed comparable results with ELISA in sensitivity (with a positive rate of 100% for positive samples) but higher specificity, with a false-positive rate of 5.4% for negative samples versus that of 40.5% with ELISA. Thus, it offers great potential for the on-the-spot differential diagnosis of infected patients, which would significantly benefit the efficient control and prevent the spread of these infectious diseases in communities or resource-limited regions in the future.

A nano-integrated microfluidic biochip for enzyme-based point-of-care detection of creatinine.

A nano-integrated portable enzymatic microfluidic electrochemical biochip was developed for single-step point-of-care testing of creatinine. The biochip could automatically eliminate a lot of interferences from practical biological samples and enzymatic intermediate products. Gold nanostructure- and carbon nanotube-based screen-printed carbon electrodes were integrated into microfluidic structures to improve the detection performance for creatinine. The microfluidic electrochemical biochip holds promise to become a practical device for medical diagnosis, especially POCT.

A Carbon-Based Antifouling Nano-Biosensing Interface for Label-Free POCT of HbA1c.

Electrochemical biosensing relies on electron transport on electrode surfaces. However, electrode inactivation and biofouling caused by a complex biological sample severely decrease the efficiency of electron transfer and the specificity of biosensing. Here, we designed a three-dimensional antifouling nano-biosensing interface to improve the efficiency of electron transfer by a layer of bovine serum albumin (BSA) and multi-walled carbon nanotubes (MWCNTs) cross-linked with glutaraldehyde (GA). The electrochemical properties of the BSA/MWCNTs/GA layer were investigated using both cyclic voltammetry and electrochemical impedance to demonstrate its high-efficiency antifouling nano-biosensing interface. The BSA/MWCNTs/GA layer kept 92% of the original signal in 1% BSA and 88% of that in unprocessed human serum after a 1-month exposure, respectively. Importantly, we functionalized the BSA/MWCNTs/GA layer with HbA1c antibody (anti-HbA1c) and 3-aminophenylboronic acid (APBA) for sensitive detection of glycated hemoglobin A (HbA1c). The label-free direct electrocatalytic oxidation of HbA1c was investigated by cyclic voltammetry (CV). The linear dynamic range of 2 to 15% of blood glycated hemoglobin A (HbA1c) in non-glycated hemoglobin (HbAo) was determined. The detection limit was 0.4%. This high degree of differentiation would facilitate a label-free POCT detection of HbA1c.

Facile preparation of high loading filled PVDF/BaTiO3 piezoelectric composites for selective laser sintering 3D printing.

3D printed piezoelectric devices, due to their sufficient multidimensional deformation and excellent piezoelectric properties, are one of the most promising research directions. However, the lack of high loaded piezoelectric composites is the key bottleneck restricting the enhancement of the piezoelectric output. In this work, we successfully prepared a novel high loaded polyvinylidene fluoride (PVDF)/barium titanate (BaTiO3) piezoelectric composite suitable for selective laser sintering (SLS) 3D printing via solid state shear milling (S3M) technology. The 50 wt% BaTiO3 filling made the most outstanding contribution to the piezoelectric properties of the composites. The 3D printed cymbal parts with a stress amplification effect exhibited outstanding piezoelectric conversion efficiency and responsiveness, whose open circuit voltage and short circuit current could reach 20 V and 1.1 µA, respectively. This work not only contributed a new high loaded piezoelectric composite for SLS processing, but also provided a novel piezoelectric performance enhancement strategy by the construction of 3D structure.