Harnessing protein sensing ability of electrochemical biosensors via a controlled peptide receptor-electrode interface.

BACKGROUND: Cathepsin B, a cysteine protease, is considered a potential biomarker for early diagnosis of cancer and inflammatory bowel diseases. Therefore, more feasible and effective diagnostic method may be beneficial for monitoring of cancer or related diseases. RESULTS: A phage-display library was biopanned against biotinylated cathepsin B to identify a high-affinity peptide with the sequence WDMWPSMDWKAE. The identified peptide-displaying phage clones and phage-free synthetic peptides were characterized using enzyme-linked immunosorbent assays (ELISAs) and electrochemical analyses (impedance spectroscopy, cyclic voltammetry, and square wave voltammetry). Feasibilities of phage-on-a-sensor, peptide-on-a-sensor, and peptide-on-a-AuNPs/MXene sensor were evaluated. The limit of detection and binding affinity values of the peptide-on-a-AuNPs/MXene sensor interface were two to four times lower than those of the two other sensors, indicating that the peptide-on-a-AuNPs/MXene sensor is more specific for cathepsin B (good recovery (86-102%) and %RSD (< 11%) with clinical samples, and can distinguish different stages of Crohn's disease. Furthermore, the concentration of cathepsin B measured by our sensor showed a good correlation with those estimated by the commercially available ELISA kit. CONCLUSION: In summary, screening and rational design of high-affinity peptides specific to cathepsin B for developing peptide-based electrochemical biosensors is reported for the first time. This study could promote the development of alternative antibody-free detection methods for clinical assays to test inflammatory bowel disease and other diseases.

The Fabrication of Cesium Lead Bromide-Coated Cellulose Nanocomposites and Their Effect on the Detection of Nitrogen Gas.

In this work, we fabricate cesium lead bromide nanofibers (CsPbBr3 NFs) via the attachment of cesium lead bromide nanocrystals (CsPbBr3 NCs) on the surface of electrospun cellulose nanofibers (CNFs) and employ them in a sensor to effectively detect gaseous nitrogen. The CsPbBr3 NFs are produced initially by producing CsPbBr3 NCs through hot injection and dispersing on hexane, followed by dipping CNFs and ultrasonicate for 1 h. Morphological characterization through visual, SEM and TEM image, and crystalline structure analysis by XRD and FT-IR analysis of CsPbBr3 NFs and NCs show similar spectra except for PL due to unavoidable damage during the ultrasonication. Gaseous nitrogen is subsequently detected using the photoluminescence (PL) property of CsPbBr3 NFs, in which the PL intensity dramatically decreases under various flow rate. Therefore, we believe that the proposed CsPbBr3 NFs show significant promise for use in detection sensors in various industrial field and decrease the potential of fatal damage to workers due to suffocation.

Fabrication of Carbon Disulfide Added Colloidal Gold Colorimetric Sensor for the Rapid and On-Site Detection of Biogenic Amines.

Meat is often wasted due to the perceived concerns of its shelf life and preservation. Specifically, in meat formation, biogenic amines (BAs) are the major agents to spoil them. Herein, we have developed a carbon disulfide (CS2) added colloidal gold nanoparticles-based colorimetric sensor for the rapid and on-site detection of biogenic amines. Transmission electron microscopy is used to observe the morphological changes in colloidal gold nanoparticles and aggregation behavior of CS2 added to the colloidal gold nanoparticles' solution. Raman spectroscopic analysis is further used to characterize the peaks of CS2, Cad and CS2-Cad molecules. Absorption spectroscopy is used to estimate the colorimetric differences and diffuse reflectance spectra of the samples. The sensing analysis is performed systematically in the presence and absence of CS2. CS2 added colloidal gold nanoparticles colorimetric sensor detected the BAs with a limit of detection (LOD) value of 50.00 µM. Furthermore, the developed sensor has shown an LOD of 50.00 µM for the detection of multiple BAs at a single time. The observed differences in the colorimetric and absorption signals indicate that the structure of BAs is converted to the dithiocarbamate (DTC)-BA molecule, due to the chemical reactions between the amine groups of BAs and CS2. Significantly, the developed colorimetric sensor offers distinct features such as facile fabrication approach, on-site sensing strategy, rapid analysis, visual detection, cost-effective, possibility of mass production, availability to detect multiple BAs at a single time and appreciable sensitivity. The developed sensor can be effectively used as a promising and alternative on-site tool for the estimation of BAs.

Magnesium Polymer Electrolytes Based on the Polycarbonate Poly(2-butyl-2-ethyltrimethylene-carbonate).

Magnesium electrolytes based on a polycarbonate with either magnesium tetrakis(hexafluoroisopropyloxy) borate (Mg(B(HFIP)4)2) or magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) for magnesium batteries were prepared and characterized. The side-chain-containing polycarbonate, poly(2-butyl-2-ethyltrimethylene carbonate) (P(BEC)), was synthesized by ring opening polymerization (ROP) of 5-ethyl-5-butylpropane oxirane ether carbonate (BEC) and mixed with Mg(B(HFIP)4)2 or Mg(TFSI)2 to form low- and high-salt-concentration polymer electrolytes (PEs). The PEs were characterized by impedance spectroscopy, differential scanning calorimetry (DSC), rheology, linear sweep voltammetry, cyclic voltammetry, and Raman spectroscopy. A transition from classical salt-in-polymer electrolytes to polymer-in-salt electrolytes was indicated by a significant change in glass transition temperature as well as storage and loss moduli. Ionic conductivity measurements indicated the formation of polymer-in-salt electrolytes for the PEs with 40 mol % Mg(B(HFIP)4)2 (HFIP40). In contrast, the 40 mol % Mg(TFSI)2 PEs showed mainly the classical behavior. HFIP40 was further found to have an oxidative stability window greater than 6 V vs Mg/Mg2+, but showed no reversible stripping-plating behavior in an Mg||SS cell.

Closed Bipolar Electrode-Enabled Electrochromic Sensing of Multiple Metabolites in Whole Blood.

We report a closed bipolar electrode (CBE)-based sensing platform for the detection of diagnostic metabolites in undiluted whole human blood. The sensor is enabled by electrode chemistry based on: (1) a mixed layer of blood-compatible adsorption-resistant phosphorylcholine (PPC) and phenylbutyric acid (PBA), (2) ferrocene (Fc) redox mediators, and (3) immobilized redox-active enzymes. This scheme is designed to overcome nonspecific protein adsorption and amplify sensing currents in whole human fluids. The scheme also incorporates a diffusing mediator to increase electronic communication between the immobilized redox enzyme and the working electrode. The use of both bound and freely diffusing mediators is synergistic in producing the electrochemical response. The sensor is realized by linking the analyte cell, containing the specific electrode surface architecture, through a CBE to a reporter cell containing the electrochromic reporter, methyl viologen (MV). The colorless-to-purple color change accompanying the 1e- reduction of MV2+ is captured using a smartphone camera. Subsequent red-green-blue analysis is performed on the acquired images to determine cholesterol, glucose, and lactate concentrations in whole blood. The CBE blood metabolite sensor produces a linear color change at clinically relevant concentration ranges for all metabolites with good reproducibility (∼5% or better) and with limits of detection of 79 µM for cholesterol, 59 µM for glucose, and 86 µM for lactate. Finally, metabolite concentration measurements from the CBE blood metabolite sensor are compared with results from commercially available FDA-approved blood cholesterol, glucose, and lactate meters, with an average difference of ∼3.5% across all three metabolites in the ranges studied.

Iron oxide (Fe3O4)-laden titanium carbide (Ti3C2Tx) MXene stacks for the efficient sequestration of cationic dyes from aqueous solution.

We prepared two-dimensional (2D) stack-structured magnetic iron oxide (Fe3O4) nanoparticle anchored titanium carbide (Ti3C2Tx) MXene material (Ti3C2Tx/Fe3O4). It was used as a potential adsorbent to remove carcinogenic cationic dyes, such as methylene blue (MB) and rhodamine B (Rh B), from aqueous solutions. Ti3C2Tx/Fe3O4 exhibited maximum adsorption capacities of 153 and 86 mg g-1 for MB and Rh B dyes, respectively. Batch adsorption experimental data fits the Langmuir model well, revealing monolayer adsorption of MB and Rh B onto the adsorption sites of Ti3C2Tx/Fe3O4. Additionally, Ti3C2Tx/Fe3O4 showed rapid MB/Rh B adsorption kinetics and attained equilibrium within 45 min. Moreover, Ti3C2Tx/Fe3O4 demonstrated recyclability over four cycles with high stability due to the presence of magnetic Fe3O4 nanoparticles. Furthermore, it exhibited remarkable selectivities of 91% and 88% in the presence of co-existing cationic and anionic dyes, respectively. Given the extraordinary adsorption capacities, Ti3C2Tx/Fe3O4 may be a promising material for the effective removal of cationic dyes from aqueous media.

Highly Specific Peptide-Mediated Cuvette-Form Localized Surface Plasmon Resonance (LSPR)-Based Fipronil Detection in Egg.

Herein, we have developed peptide-coated gold nanoparticles (AuNPs) based on localized surface plasmon resonance (LSPR) sensor chips that can detect fipronil with high sensitivity and selectivity. The phage display technique has been exploited for the screening of highly specific fipronil-binding peptides for the selective detection of the molecule. LSPR sensor chips are fabricated initially by attaching uniformly synthesized AuNPs on the glass substrate, followed by the addition of screened peptides. The parameters, such as the peptide concentration of 20 µg mL-1 and the reaction time of 30 min, are further optimized to maximize the efficacy of the fabricated LSPR sensor chips. The sensing analysis is performed systematically under standard fipronil solutions and spike samples from eggs. The developed sensor has shown excellent sensitivity towards both standard solutions and spike samples with limit of detection (LOD) values of 0.01 ppb, respectively. Significantly, the developed LSPR sensor chips offer distinct features, such as a facile fabrication approach, on-site sensing, rapid analysis, cost-effectiveness, and the possibility of mass production, in which the chips can be effectively used as a promising and potential on-site detection tool for the estimation of fipronil.

Electrochemical Immunosensing of Interleukin-6 in Human Cerebrospinal Fluid and Human Serum as an Early Biomarker for Traumatic Brain Injury.

In this work, we develop a label-free electrochemical immunosensor for the detection of interleukin-6 (IL-6) in human cerebrospinal fluid (CSF) and serum for diagnostic and therapeutic monitoring. The IL-6 immunosensor is fabricated from gold interdigitated electrode arrays (IDEAs) that are modified with IL-6 antibodies for direct antigen recognition and capture. A rigorous surface analysis of the sensor architecture was conducted to ensure high structural fidelity and performance. Electrochemical characterization was conducted by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and sensing was performed using differential pulse voltammetry (DPV). The DPV peak current was used to quantify IL-6 in buffer, CSF, and serum in the range 1 pg mL-1 < [IL-6] < 1 µg mL-1. The IL-6 IDEA sensor achieved a limit of detection (LOD) of 1.63 pg mL-1 in PBS, 2.34 pg mL-1 in human CSF, and 11.83 pg mL-1 in human serum. The sensor response is linear in the concentration range 10 pg mL-1 < [IL-6] < 10 ng mL-1, and the sensor is selective for IL-6 over other common cytokines, including IL-10 and TNF-α. EIS measurements showed that the resistance to charge transfer, R CT, decreases upon IL-6 binding, an observation attributed to a structural change upon Ab-Ag binding that opens up the architecture so that the redox probe can more easily access the electrode surface. The IL-6 IDEA sensor can be used as a point-of-care diagnostic tool to deliver rapid results (∼3 min) in clinical settings for traumatic brain injury, and potentially address the unmet need for effective diagnostic and prognostic tools for other cytokine-related illnesses, such as sepsis and COVID-19 induced cytokine storms. Given the interdigitated electrode form factor, it is likely that the performance of the sensor can be further improved through redox cycling.

Dual-functional micro-adsorbents: Application for simultaneous adsorption of cesium and strontium.

In current work, Prussian blue (PB)- and hydroxyapatite (HAp)-embedded micro-adsorbents (PB-HAp-MAs) were rationally fabricated through an easy and flexible custom-made micronozzle system as a novel bifunctional adsorbent. The adsorption performance of the as-prepared samples was conducted based on the removal of cesium (Cs+) and strontium (Sr2+) ions. Adsorption behaviors of the PB-HAp-MAs were also evaluated as function extrusion dimensions and adsorbate concentration. The adsorption isotherm was well fitted by the Langmuir model with adsorption capacities of 24.688 mg g-1 and 29.254 mg g-1 for Cs+ and Sr2+, respectively. Specially, the enhanced adsorption activity can be synergistically attributed to the porous nature of the developed alginate backbone with a high surface area of encapsulated functional nanoparticles, thus leading to rapid saturation within 1 min. In addition, the as-synthesized PB-HAp-MAs were successfully separated from the aqueous solution within 10 s by applying a magnetic field. We expect that our findings will provide valuable guidelines towards developing highly efficient adsorbents for environmental remediation.

Improved conductivity of flower-like MnWO4 on defect engineered graphitic carbon nitride as an efficient electrocatalyst for ultrasensitive sensing of chloramphenicol.

Environmental hazards caused by chloramphenicol has attained special attention. Fast, accurate and reliable detection of chloramphenicol in foodstuffs and water samples is of utmost importance. Herein, we developed a g-C3N4/MnWO4 composite for the selective and sensitive detection of chloramphenicol. Successful fabrication of g-C3N4/MnWO4 composite was verified by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), x-ray diffraction (XRD) and x-ray photo electron spectroscopy (XPS) techniques. Electrochemical characteristics were evaluated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV). The g-C3N4/MnWO4 modified glassy carbon electrode has shown the highest electrocatalytic activity towards chloramphenicol with a decreased reduction potential of -0.547 V and increased cathodic peak current. The developed sensor has shown excellent performance for the detection of chloramphenicol with a sensitivity of 0.9986 µA nM-1 cm-2 and LOD of 1.03 nM in a broad linear range of 4.0-71 nM. In addition, the fabricated sensor has achieved anti-interference ability, good stability, excellent repeatability and remarkable reproducibility for the detection of chloramphenicol. The fabricated sensor applied for the determination of chloramphenicol in milk, human blood serum and sewage samples, in which significant and satisfactory results were achieved.

Silver grass-derived activated carbon with coexisting micro-, meso- and macropores as excellent bioanodes for microbial colonization and power generation in sustainable microbial fuel cells.

In this study, highly biocompatible three-dimensional hierarchically porous activated carbon from the low-cost silver grass (Miscanthus sacchariflorus) has been fabricated through a facile carbonization approach and tested it as bioanode in microbial fuel cell (MFC) using Escherichia coli as biocatalyst. This silver grass-derived activated carbon (SGAC) exhibited an unprecedented specific surface area of 3027 m2 g-1 with the coexistence of several micro-, meso-, and macropores. The synergistic effect from pore structure (macropores - hosting E. coli to form biofilm and facilitates internal mass transfer; mesopores - favors fast electron transfer; and micropores - promotes nutrient transport to the biofilm) with very high surface area facilitates excellent extracellular electron transfer (EET) between the anode and biofilm which resulted in higher power output of 963 mW cm-2. Based on superior biocompatibility, low cost, environment-friendliness, and facile fabrication, the proposed SGAC bioanode could have a great potential for high-performance and cost-effective sustainable MFCs.

Efficient electron-mediated electrochemical biosensor of gold wire for the rapid detection of C-reactive protein: A predictive strategy for heart failure.

C-reactive protein (CRP) is considered a promising biomarker for the rapid and high-throughput real-time monitoring of cardiovascular disease and inflammation in unprocessed clinical samples. Implementation of this monitoring would enable various transformative biomedical applications. We have fabricated a highly specific sensor chip to detect CRP with a detection limit of 2.25 fg/mL. The protein was immobilized on top of a gold (Au) wire/polycarbonate (PC) substrate using 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride/N-hydroxy succinimide-activated 3-mercaptoproponic acid (MPA) as a self-assembled monolayer agent and bovine serum albumin (BSA) as a blocking agent. In contrast to the bare PC substrate, the CRP/BSA/anti-CRP/MPA/Au substrate exhibited a considerably high electrochemical signal toward CRP. The influence of the experimental parameters on CRP detection was assessed via various analysis methods, and these parameters were then optimized. The linear dynamic range of the CRP was 5-220 fg/mL for voltammetric and impedance analysis. Morever, the strategy exhibited high selectivity against various potential interfering species and was capable of directly probing trace amounts of the target CRP in human serum with excellent selectivity. The analytical assay based on the CRP/BSA/anti-CRP/MPA/Au substrate could be exploited as a potentially useful tool for detecting CRP in clinical samples.