An origami microfluidic paper device based on core-shell Cu@Cu2S@N-doped carbon hollow nanocubes.

BACKGROUD: The global prevalence of diabetes mellitus, a serious chronic disease with fatal consequences for millions annually, is of utmost concern. The development of efficient and simple devices for monitoring glucose levels is of utmost significance in managing diabetes. The advancement of nanotechnology has resulted in the indispensable utilization of advanced nanomaterials in high-performance glucose sensors. Modulating the morphology and intricate composition of transition metals represents a viable approach to exploit their structure/function correlation, thereby achieving optimal electrocatalytic performance of the synthesized catalysts. RESULTS: Herein, a sensitive and rapid Cu-encapsulated Cu2S@nitrogen-doped carbon (Cu@Cu2S@N-C) hollow nanocubes-functionalized microfluidic paper-based analytical device (µ-PAD) was fabricated. Through a delicate sacrificial template/interface technique and thermal decomposition, inter-connected hollow networks were formed to boost the active sites, and the carbon shell was coated to protect Cu from being oxidation. For application, the constructed µ-PAD is used for glucose sensing utilizing an origami automated sample pretreatment system enabled by a simple application of strong alkaline solution on wax paper. Under optimal circumstances, the Cu@Cu2S@N-C electrochemical biosensor exhibits broad detection range of 2-7500 µM (R2 = 0.996) with low detection limit of 0.16 µM (S/N = 3) and high sensitivity of 1996 µA mM-1 cm-2. Additionally, the constructed µ-PAD also exhibited excellent selectivity, stability, and reproducibility. SIGNIFICANCE: By rationally designing the double-shell hollow nanostructure and introducing Cu-encapsulated inner layer, the synthesized Cu@Cu2S@N-C hollow nanocubes show large specific surface area, short diffusion channels, and high stability. The proposed origami µ-PAD has been successfully applied to serum samples without any additional sample preparation steps for glucose determination, offering a new perspective for early nonenzymatic glucose diagnosis.

Application of the Electrospinning Technique in Electrochemical Biosensors: An Overview.

Electrospinning is a cost-effective and flexible technology for producing nanofibers with large specific surface areas, functionalized surfaces, and stable structures. In recent years, electrospun nanofibers have attracted more and more attention in electrochemical biosensors due to their excellent morphological and structural properties. This review outlines the principle of electrospinning technology. The strategies of producing nanofibers with different diameters, morphologies, and structures are discussed to understand the regulation rules of nanofiber morphology and structure. The application of electrospun nanofibers in electrochemical biosensors is reviewed in detail. In addition, we look towards the future prospects of electrospinning technology and the challenge of scale production.

Dual-ligand lanthanide metal-organic framework based ratiometric fluorescent platform for visual monitoring of aminoglycoside residues in food samples.

Herein, a dual-emission Eu metal-organic framework (Eu-MOF) is prepared and used as the ratiometric fluorescence probe for ultrasensitive detection of aminoglycoside antibiotics (AGs). Due to the strong hydrogen bond interactions between AGs and Eu-MOF, the blue emission is enhanced while the red emission has little fluctuation in Eu-MOF with the addition of AGs, thus a good linear relationship with the logarithm of AGs concentrations from 0.001 to 100 µg/mL can be established for quantitative analysis. Good sensitivity with the detection limit of 0.33 ng/mL for apramycin, 0.32 ng/mL for amikacin and 0.30 ng/mL for kanamycin is achieved. The proposed assay demonstrates good selectivity and applicability for determination of AGs in real milk and honey samples. The Eu-MOF materials are further fabricated as fluorescent test papers for facile visual detection. The as-established ratio fluorescence platform offers a portable and economical way for rapid monitoring AGs residues in complex food samples.

Catalytic hairpin assembly-based AIEgen/graphene oxide nanocomposite for fluorescence-enhanced and high-precision spatiotemporal imaging of microRNA in living cells.

The low abundance, heterogeneous expression, and temporal changes of miRNA in different cellular locations pose significant challenges for both the detection sensitivity of miRNA liquid biopsy and intracellular imaging. In this work, we report an intelligently assembled biosensor based on catalytic hairpin assembly (CHA) and aggregation-induced emission (AIE), named as catalytic hairpin aggregation-induced emission (CHAIE), for the ultrasensitive detection and intracellular imaging of miRNA-155. To achieve such goal, tetraphenylethylene-N3 (TPE-N3) is used as AIE luminogen (AIEgen), while graphene oxide is introduced to quench the fluorescence. When the target miRNA is present, CHA reaction is triggered, causing the AIEgen to self-assemble with the hairpin DNA. This will restrict the intramolecular rotation of the AIEgen and produce a strong AIE fluorescence. Interestingly, CHAIE does not require any enzyme or expensive thermal cycling equipment, and therefore provides a rapid detection. Under optimal conditions, the proposed biosensor can determine miRNA in the concentration range from 2 pM to 200 nM within 30 min, with the detection limit of 0.42 pM. The proposed CHAIE biosensor in this work offers a low background signal and high sensitivity, making it applicable for highly precise spatiotemporal imaging of target miRNA in living cells.

Upgrading CO2 to sustainable aromatics via perovskite-mediated tandem catalysis.

The directional transformation of carbon dioxide (CO2) with renewable hydrogen into specific carbon-heavy products (C6+) of high value presents a sustainable route for net-zero chemical manufacture. However, it is still challenging to simultaneously achieve high activity and selectivity due to the unbalanced CO2 hydrogenation and C-C coupling rates on complementary active sites in a bifunctional catalyst, thus causing unexpected secondary reaction. Here we report LaFeO3 perovskite-mediated directional tandem conversion of CO2 towards heavy aromatics with high CO2 conversion (> 60%), exceptional aromatics selectivity among hydrocarbons (> 85%), and no obvious deactivation for 1000 hours. This is enabled by disentangling the CO2 hydrogenation domain from the C-C coupling domain in the tandem system for Iron-based catalyst. Unlike other active Fe oxides showing wide hydrocarbon product distribution due to carbide formation, LaFeO3 by design is endowed with superior resistance to carburization, therefore inhibiting uncontrolled C-C coupling on oxide and isolating aromatics formation in the zeolite. In-situ spectroscopic evidence and theoretical calculations reveal an oxygenate-rich surface chemistry of LaFeO3, that easily escape from the oxide surface for further precise C-C coupling inside zeolites, thus steering CO2-HCOOH/H2CO-Aromatics reaction pathway to enable a high yield of aromatics.

ZnO-CeO2 Hollow Nanospheres for Selective Determination of Dopamine and Uric Acid.

ZnO-CeO2 hollow nanospheres have been successfully synthesized via the hard templating method, in which CeO2 is used as the support skeleton to avoid ZnO agglomeration. The synthesized ZnO-CeO2 hollow nanospheres possess a large electrochemically active area and high electron transfer owing to the high specific surface area and synergistic effect of ZnO and CeO2. Due to the above advantages, the resulting ZnO-CeO2 hollow spheres display high sensitivities of 1122.86 µA mM-1 cm-2 and 908.53 µA mM-1 cm-2 under a neutral environment for the selective detection of dopamine and uric acid. The constructed electrochemical sensor shows excellent selectivity, stability and recovery for the selective analysis of dopamine and uric acid in actual samples. This study provides a valuable strategy for the synthesis of ZnO-CeO2 hollow nanospheres via the hard templating method as electrocatalysts for the selective detection of dopamine and uric acid.

Advances in miniature CRISPR-Cas proteins and their applications in gene editing.

The CRISPR-Cas system consists of Cas proteins and single-stranded RNAs that recruit Cas proteins and specifically target the nucleic acid. Some Cas proteins can accurately cleave the target nucleic acid under the guidance of the single-stranded RNAs. Due to its exceptionally high specificity, the CRISPR-Cas system is now widely used in various fields such as gene editing, transcription regulation, and molecular diagnosis. However, the huge size of the most frequently utilized Cas proteins (Cas9, Cas12a, and Cas13, which contain 950-1,400 amino acids) can limit their applicability, especially in eukaryotic gene editing, where larger Cas proteins are difficult to deliver into the target cells. Recently discovered miniature CRISPR-Cas proteins, consisting of only 400 to 800 amino acids, offer the possibility of overcoming this limitation. This article systematically reviews the latest research progress of several miniature CRISPR-Cas proteins (Cas12f, Cas12j, Cas12k, and Cas12m) and their practical applications in the field of gene editing.

One-Step Synthesis of 3D Graphene Aerogel Supported Pt Nanoparticles as Highly Active Electrocatalysts for Methanol Oxidation Reaction.

Nowadays, two of the biggest obstacles restricting the further development of methanol fuel cells are excessive cost and insufficient catalytic activity of platinum-based catalysts. Herein, platinum nanoparticle supported graphene aerogel (Pt/3DGA) was successfully synthesized by a one-step hydrothermal self-assembly method. The loose three-dimensional structure of the aerogel is stabilized by a simple one-step method, which not only reduces cost compared to the freeze-drying technology, but also optimizes the loading method of nanoparticles. The prepared Pt/3DGA catalyst has a three-dimensional porous structure with a highly cross-linked, large specific surface area, even dispersion of Pt NPs and good electrical conductivity. It is worth noting that its catalytic activity is 438.4 mA/mg with long-term stability, which is consistent with the projected benefits of anodic catalytic systems in methanol fuel cells.. Our study provides an applicable method for synthesizing nano metal particles/graphene-based composites.

A paper-based ratiometric fluorescence sensor based on carbon dots modified with Eu3+ for the selective detection of tetracycline in seafood aquaculture water.

Paper-based ratiometric fluorescence sensors are normally prepared using two or more types of fluorescent materials on a paper chip for simple, low-cost and fast detection. However, the choice of multi-step and one-step modifications on the paper chip affects the analytical performance. Herein, a novel paper-based dual-emission ratiometric fluorescence sensor was designed for the selective detection of tetracycline (TC). Carbon dots (CDs) modified with Eu3+ were combined with a sealed paper-based microfluidic chip by two methods: one-step grafting of CDs-Eu3+ on paper and step-by-step grafting of CDs and Eu3+ on paper. The analytical performance was studied and optimized respectively. The red fluorescence of Eu3+ at 450 nm is enhanced and the blue fluorescence of CDs at 617 nm is quenched by energy transfer in the presence of TC. Under optimal conditions, TC is selectively determined in the linear range from 0.1 µM to 100 µM with a detection limit of 0.03 µM by the step-by-step grafting method. In addition, the sealed paper chip could effectively prevent pollution and volatilization from the reagent. This technique has been used to analyze TC in seafood aquaculture water with satisfactory results.

Synthesis of Superelastic, Highly Conductive Graphene Aerogel/Liquid Metal Foam and its Piezoresistive Application.

Graphene aerogel (GA) has important application potential as piezoresistive sensors due to its low density, high conductivity, high porosity, and good mechanical properties. However, the fabrication of GA-based sensors with good mechanical properties and excellent sensing performance is still challenging. Herein, liquid- metal-modified GAs (GA/LM) are proposed for the development of an excellent GA-based sensor. GA/LM with three-dimensional interconnected layered structure exhibits excellent compressive stress of 41 KPa and fast response time (<20 ms). While generally flexible GA composites cannot be compressed beyond 80 % strain without plastic deformation, GA/LM demonstrates a high compressive strength of 60 kPa under a strain of 90 %. A real-time pressure sensor was fabricated based on GA/LM-2 to monitor swallowing, pulse beating, finger, wrist and knee bending, and even plantar pressure during walking. These excellent features enable potential applications in health detection.

Recent Advances in Functional Nanomaterials for Electrochemical Sensors and Biosensors.

Considering the unique advantages of the quantum size, volume, surface, and macroscopical quantum tunnel effects, nanomaterials have been paid increasing attention for various applications in environmental, medical, biological, and chemical analyses in recent decades [...].

Pb speciation and elemental distribution in leeks by micro X-ray fluorescence and X-ray absorption near-edge structure.

Vegetables are crucial to a human diet as they supply the body with essential vitamins, minerals, etc. Heavy metals that accumulate in plants consequently enter the food chain and endanger people's health. Studying the spatial distribution and chemical forms of elements in plant/vegetable tissues is vital to comprehending the potential interactions between elements and detoxification mechanisms. In this study, leek plants and soil from vegetable gardens near lead-zinc mines were collected and cultivated with 500 mg L-1 PbNO3 solutions for three weeks. Micro X-ray fluorescence was used to map the distribution of Pb and other chemical elements in leek roots, and X-ray absorption near-edge spectroscopy was used to assess the Pb speciation in leek roots and leaves. These findings demonstrated that Pb, Cu, Mn, Cr, Ti and Fe were detected in the outer rings of the root's cross section, and high-intensity points were observed in the epidermis. Zn, K and Ca, on the other hand, were distributed throughout the root's cross section. Leek root and leaf contained significant quantities of lead phosphate and basic lead carbonate at more than 80%, followed by lead sulfide (19%) and lead stearate (11.1%). The capacity of leek roots to convert ambient lead into precipitated lead and fix it on the root epidermis and other inner surfaces is a key mechanism for reducing the toxic effects of Pb.

Dual-Mode Undistorted Visual Fluorescent Sensing Strategy through Manipulating the Coffee-Ring Effect on Microfluidic Paper-Based Chip.

To overcome the insufficient sensitivity due to distortion of the fluorescent images by mobile devices, we first developed a novel dual-mode strategy for undistorted visual fluorescent sensing on µPAD by technically manipulating the coffee-ring effect of the fluid sample. Based on the manipulating coffee-ring effect, we divided the horizontal direction of the resulting fluorescence image into 600 pixels and obtained more accurate quantitative information to avoid image distortion. The bovine serum albumin-stabilized gold nanoclusters-copper ion complex was used as the fluorescent probe, combined with a small imaging box and a smartphone, to achieve a rapid testing of histidine in human urine. The output image was analyzed in dual mode: RGB numerical analysis in pixel units and the direct measurement of the fluorescent strips length (limit of detection (LOD) is 0.021 and 0.5 mM, respectively), and improved antidistortion for visual fluorescent sensing. This strategy can overcome the distortion of a smartphone-visualized fluorescent image and shows great potential for rapid and convenient analysis.

Colorimetric and visual sensing of ferrous ion by Fenton reaction-stimulated etching of triangular gold nanoplates.

In this study, a method for ultrasensitive sensing of Fe2+ based on Fenton reaction mediated etching of triangular gold nanoplates (Au NPLs) was developed. In this assay, the etching of Au NPLs by H2O2 was accelerated in the presence of Fe2+ due to the generation of superoxide free radical (O2·-) via Fenton reaction. With the concentration of Fe2+ increased, the shape of Au NPLs changed from triangular to sphere with the blue shifted localized surface plasmon resonance, accompanying a series of consecutive color changes from blue, bluish purple, purple, reddish purple and finally to pink. The rich color variations enable rapid visual quantitative determination of Fe2+ within 10 min. A good linear relationship between the peak shifts and the concentration of Fe2+ was obtained in the range of 0.035 to 1.5 µM (R2 = 0.996). Favorable sensitivity and selectivity in the presence of other tested metal ions were achieved in the proposed colorimetric assay. The detection limits (3Æ¡/k) for Fe2+ was 26 nM by UV-vis spectroscopy, and the clearly discernible concentration of Fe2+ was as low as 0.07 µM by naked eyes. The recoveries of fortified samples in pond water and serum samples ranged from 96% to 106% with interday relative standard deviations <3.6% in all cases, demonstrating the applicability of the assay for measuring Fe2+ in real samples.

The Applications of Electrochemical Immunosensors in the Detection of Disease Biomarkers: A Review.

Disease-related biomarkers may serve as indicators of human disease. The clinical diagnosis of diseases may largely benefit from timely and accurate detection of biomarkers, which has been the subject of extensive investigations. Due to the specificity of antibody and antigen recognition, electrochemical immunosensors can accurately detect multiple disease biomarkers, including proteins, antigens, and enzymes. This review deals with the fundamentals and types of electrochemical immunosensors. The electrochemical immunosensors are developed using three different catalysts: redox couples, typical biological enzymes, and nanomimetic enzymes. This review also focuses on the applications of those immunosensors in the detection of cancer, Alzheimer's disease, novel coronavirus pneumonia and other diseases. Finally, the future trends in electrochemical immunosensors are addressed in terms of achieving lower detection limits, improving electrode modification capabilities and developing composite functional materials.

Cultureless enumeration of live bacteria in urinary tract infection by single-cell Raman spectroscopy.

Urinary tract infections (UTIs) are the most common outpatient infections. Obtaining the concentration of live pathogens in the sample is crucial for the treatment. Still, the enumeration depends on urine culture and plate counting, which requires days of turn-around time (TAT). Single-cell Raman spectra combined with deuterium isotope probing (Raman-DIP) has been proven to identify the metabolic-active bacteria with high accuracy but is not able to reveal the number of live pathogens due to bacteria replication during the Raman-DIP process. In this study, we established a new approach of using sodium acetate to inhibit the replication of the pathogen and applying Raman-DIP to identify the active single cells. By combining microscopic image stitching and recognition, we could further improve the efficiency of the new method. Validation of the new method on nine artificial urine samples indicated that the exact number of live pathogens obtained with Raman-DIP is consistent with plate-counting while shortening the TAT from 18 h to within 3 h, and the potential of applying Raman-DIP for pathogen enumeration in clinics is promising.

A sensitive fluorescence nanoplatform for monitoring benzoyl peroxide in food using carbon dots coupled with glutathione capped gold nanoparticles as FRET probe.

Herein, a sensitive fluorescence nanoplatform for benzoyl peroxide (BPO) detection is constructed from carbon dots (CDs) and glutathione capped gold nanoparticles (GSH-AuNPs). The fluorescence of CDs is first quenched due to the fluorescence resonance energy transfer (FRET) effect in the presence of GSH-AuNPs, and then effectively recovered when adding BPO. The detection mechanism lies in the aggregation of AuNPs in a high salt background due to oxidation of GSH caused by BPO, thus the amount of BPO is reflected by the variations of the recovered signals. The linear range and detection limit in this detection system is found to be 0.05-200 µM (R2 = 0.994) and 0.1 µg g-1 (3σ/K), respectively. Several possible interferents with high concentration show little influence on BPO detection. The proposed assay exhibits good performance for BPO determination in wheat flour and noodles, demonstrating its applicability for facile monitoring BPO additive amount in real foods.

Current Progress of Ratiometric Fluorescence Sensors Based on Carbon Dots in Foodborne Contaminant Detection.

Carbon dots (CDs) are widely used in the detection of foodborne contaminants because of their biocompatibility, photoluminescence stability, and ease of chemical modification. In order to solve the interference problem of complexity in food matrices, the development of ratiometric fluorescence sensors shows great prospects. In this review, the progress of ratiometric fluorescence sensors based on CDs in foodborne contaminant detection in recent years will be summarized, focusing on the functionalized modification of CDs, the fluorescence sensing mechanism, the types of ratiometric fluorescence sensors, and the application of portable devices. In addition, the outlook on the development of the field will be presented, with the development of smartphone applications and related software helping to better enable the on-site detection of foodborne contaminants to ensure food safety and human health.

Mn3O4/NiO Nanoparticles Decorated on Carbon Nanofibers as an Enzyme-Free Electrochemical Sensor for Glucose Detection.

Transition metal oxides have garnered a lot of attention in the field of electrocatalysis along with their unique crystal structure and excellent catalytic properties. In this study, carbon nanofibers (CNFs) decorated with Mn3O4/NiO nanoparticles were made using electrospinning and calcination. The conductive network constructed by CNFs not only facilitates electron transport, but also provides landing sites for nanoparticles, thus reducing nanoparticle aggregation and exposing more active sites. Additionally, the synergistic interaction between Mn3O4 and NiO improved electrocatalytic capacity for glucose oxidation. The Mn3O4/NiO/CNFs modified glassy carbon electrode shows satisfactory results in terms of linear range and anti-interference capability for glucose detection, suggesting that the constructed enzyme-free sensor has a promising application in clinical diagnosis.

Simultaneous Determination of Xanthine and Hypoxanthine Using Polyglycine/rGO-Modified Glassy Carbon Electrode.

A novel electrochemical sensor was developed for selective and sensitive determination of xanthine (XT) and hypoxanthine (HX) based on polyglycine (p-Gly) and reduced graphene oxide (rGO) modified glassy carbon electrode (GCE). A mixed dispersion of 7 µL of 5 mM glycine and 1 mg/mL GO was dropped on GCE for the fabrication of p-Gly/rGO/GCE, followed by cyclic voltammetric sweeping in 0.1 M phosphate buffer solution within -0.45~1.85 V at a scanning rate of 100 mV·s-1. The morphological and electrochemical features of p-Gly/rGO/GCE were investigated by scanning electron microscopy and cyclic voltammetry. Under optimal conditions, the linear relationship was acquired for the simultaneous determination of XT and HX in 1-100 µM. The preparation of the electrode was simple and efficient. Additionally, the sensor combined the excellent conductivity of rGO and the polymerization of Gly, demonstrating satisfying simultaneous sensing performance to both XT and HX.