Sensitive Detection Of Analytes Research Articles

Colorimetric Sensing of Gram-Negative and Gram-Positive Bacteria Using 4-Mercaptophenylboronic Acid-Functionalized Gold Nanoparticles in the Presence of Polyethylene Glycol.

Gold nanoparticles (GNPs) have been used as detection probes for rapid and sensitive detection of various analytes, including bacteria. Here, we demonstrate a simple strategy for bacterial detection using GNPs functionalized with 4-mercaptophenylboronic acid (4-MPBA). 4-MPBA can interact with peptidoglycan or lipopolysaccharides present in bacterial organelles. After the addition of a high concentration of sodium hydroxide (NaOH), the functionalization of the surface of 50 nm GNPs with 4-MPBA (4-MPBA@GNPs) in the presence of polyethylene glycol results in a color change because of the aggregation of 4-MPBA@GNPs. This color change is dependent on the amount of bacteria present in the tested samples. Escherichia coli (E. coli) K-12 and Staphylococcus aureus (S. aureus) are used as Gram-negative and Gram-positive bacterial models, respectively. The color change can be detected within an hour by the naked eye. A linear relationship is observed between bacterial concentrations and the absorbance intensity at 533 nm; R 2 values of 0.9152 and 0.8185 are obtained for E. coli K-12 and S. aureus, respectively. The limit of detection of E. coli K-12 is ∼2.38 × 102 CFU mL-1 and that of S. aureus is ∼4.77 × 103 CFU mL-1. This study provides a promising approach for the rapid detection of target Gram-negative and Gram-positive bacteria.

Enhancement of faradaic current in an electrochemical cell integrated into silicon microfluidic channels

Implantable electrochemical sensors enable fast and sensitive detection of analytes in biological tissue, but are hampered by bio-foulant attack and are unable to be recalibrated in-situ. Herein, an electrochemical sensor integrated into ultra-low flow (nL/min) silicon microfluidic channels for protection from foulants and in-situ calibration is demonstrated. The small footprint (5 µm radius channel cross-section) of the device allows its integration into implantable sampling probes for monitoring chemical concentrations in biological tissues. The device is designed for fast scan cyclic voltammetry (FSCV) in the thin-layer regime when analyte depletion at the electrode is efficiently compensated by microfluidic flow. A 3X enhancement of faradaic peak currents is observed due to the increased flux of analytes towards the electrodes. Numerical analysis of in-channel analyte concentration confirmed near complete electrolysis in the thin-layer regime below 10 nL/min. The manufacturing approach is highly scalable and reproducible as it utilizes standard silicon microfabrication technologies.

Recent Developments in the Design and Fabrication of Electrochemical Biosensors Using Functional Materials and Molecules.

Electrochemical biosensors are superior technologies that are used to detect or sense biologically and environmentally significant analytes in a laboratory environment, or even in the form of portable handheld or wearable electronics. Recently, imprinted and implantable biosensors are emerging as point-of-care devices, which monitor the target analytes in a continuous environment and alert the intended users to anomalies. The stability and performance of the developed biosensor depend on the nature and properties of the electrode material or the platform on which the biosensor is constructed. Therefore, the biosensor platform plays an integral role in the effectiveness of the developed biosensor. Enormous effort has been dedicated to the rational design of the electrode material and to fabrication strategies for improving the performance of developed biosensors. Every year, in the search for multifarious electrode materials, thousands of new biosensor platforms are reported. Moreover, in order to construct an effectual biosensor, the researcher should familiarize themself with the sensible strategies behind electrode fabrication. Thus, we intend to shed light on various strategies and methodologies utilized in the design and fabrication of electrochemical biosensors that facilitate sensitive and selective detection of significant analytes. Furthermore, this review highlights the advantages of various electrode materials and the correlation between immobilized biomolecules and modified surfaces.

Device integration of electrochemical biosensors.

Electrochemical biosensors incorporate a recognition element and an electronic transducer for the highly sensitive detection of analytes in body fluids. Importantly, they can provide rapid readouts and they can be integrated into portable, wearable and implantable devices for point-of-care diagnostics; for example, the personal glucose meter enables at-home assessment of blood glucose levels, greatly improving the management of diabetes. In this Review, we discuss the principles of electrochemical biosensing and the design of electrochemical biosensor devices for health monitoring and disease diagnostics, with a particular focus on device integration into wearable, portable and implantable systems. Finally, we outline the key engineering challenges that need to be addressed to improve sensing accuracy, enable multiplexing and one-step processes, and integrate electrochemical biosensing devices in digital health-care pathways.

Nanogap-Rich Surface-Enhanced Raman Spectroscopy-Active Substrate Based on Double-Step Deposition and Annealing of the Au Film over the Back Side of Polished Si.

Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive and rapid detection technique that is used for detection of various analytes in trace quantities. We present a sensitive, large-area, and nanogap-rich SERS-active substrate by altering a thin gold (Au) film on the unpolished side of a single-side polished silicon wafer by repeated thermal deposition and annealing in an argon environment. The repeated thermal deposition and annealing process was compared on both sides of a one-side-polished silicon wafer; however, the rear side (etched/unpolished side) demonstrated a more enhanced Raman signal owing to the larger effective area. The proposed substrate can be fabricated easily, having a high density of hotspots distributed uniformly all over the substrate. This ensures easy, rapid, and sensitive detection of analytes with a high degree of reproducibility, repeatability, and acceptable uniformity. The optimized substrate shows a high degree of stability with time when exposed to the ambient environment for a longer duration of 148 days. The reported substrate can detect up to 10-11 M concentrations of 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (DNT), with limits of detection (LODs) of 1.22 and 1.26 ng/L, respectively. This work not only presents the efficient and sensitive SERS-active substrate but also shows the advantages of using the rear side of a one-side-polished silicon substrate as a SERS-active chip.

Determination of trace amount of iron cations using electrochemical methods at N, S doped GQD modified electrode

In this work, nitrogen and sulfur co-doped graphene quantum dot-modified glassy carbon electrodes (N, S-GQD/GCE) were used for the recognition of iron cations in aqueous solutions. The dissolved cations are detected based on the faradaic reduction or oxidation current of Fe(III) and Fe(II) obtained at the N, S-GQD/GCE surface. Cyclic voltammetry (CV), square wave voltammetry (SWV), and hydrodynamic amperometry are used as suitable electrochemical techniques for studying electrochemical behavior and determination of Fe cations. Based on the obtained results, it is concluded that the presence of free electrons in the structure of N, S-GQD could facilitate electron transfer reaction between Fe(III) and electrode surface which with increased surface area results in increased sensitivity and lower limit of detection. By performing suitable experiments, the best condition for preparing the modified electrode and determining Fe(III) was selected. Under optimized conditions, the amperometric response is linear from 1 to 100 nM of Fe(III) with a detection limit of 0.23 nM. The validity of the method and applicability of the sensor is successfully tested by the determination of Fe(III) in drug and water real samples. This sensor opened a new platform based on doped nanoparticles for highly sensitive and selective detection of analytes.

Thiol-grafted covalent organic framework-based electrochemical platforms for sensitive detection of Hg(II) ions.

Triazine-based covalent organic frameworks functionalized by thiol and thioether (COFS-CH3/COFS-SH) were designed and served as a platform that could bind with mercury ions specifically based on Hard-Soft-Acid-Base theory. As such, when employing COFs as a modifier in a carbon paste electrode (CPE), the COFS-CH3-modified CPE revealed an extraordinary performance (detection limit of 0.01 ppb; linear range of 0.1 to 1.0 ppb) and repeatability for electrochemical detection of trace mercury, even in real samples collected from tap or lake water. This innovative approach leverages the inherent properties of covalent organic frameworks (COFs) to enable highly sensitive and selective detection of target analytes.

Silver nanoparticles - laser induced graphene (Ag NPs - LIG) hybrid electrodes for sensitive electrochemical-surface enhanced Raman spectroscopy (EC-SERS) detection.

This paper presents a novel approach for the fabrication of low cost Electrochemical-Surface Enhanced Raman Scattering (EC-SERS) sensing platforms. Laser Induced Graphene (LIG) electrodes were readily fabricated by direct laser writing of polyimide tapes and functionalized with silver nanoparticles (Ag NPs) to obtain hybrid Ag NPs - LIG electrodes suitable for EC-SERS analysis. Detection was achieved by coupling a handheld potentiostat with a Raman spectrograph, enabling measurement of SERS spectra of target analytes generated during voltage sweeps in the 0.0 to -1.0 V interval range. The sensing capabilities of the fabricated system were first tested with model molecule 4-aminobenzenethiol (4-ABT). Following sensitive detection of 4-ABT, EC-SERS analysis of food contaminant melamine in milk and antibiotic difloxacin hydrochloride (DIF) in river water was demonstrated, achieving sensitive detection of both analytes without pre-treatment steps. The easiness of fabrication, versatility of design, rapid analysis time and potential miniaturization of the system make Ag NPs - LIG electrodes suitable for a large range of in situ applications in the field of food monitoring and for environmental analysis.

Advancements in Amperometric Biosensing Instruments for Creatinine Detection: A Critical Review

Kidney disease is one of the leading causes of the death for patients worldwide, and creatinine is a key biomarker for kidney diseases. Amperometric biosensors have gained significant attention in recent years due to their ability to provide rapid, sensitive, and selective detection of target analytes. And the miniaturized and portable amperometric biosensing systems offer a convenient solution for detecting in a variety of settings, making them an increasingly popular choice. Here, this review explores the current status for the development of amperometric biosensing instrumentation for creatinine, including the mechanism of amperometric creatinine biosensors, materials and fabrication methods for creatinine biosensors, as well as their practical applications and commercial status. This review can serve as a resource for future creatinine biosensor development and advance a wide range of practical applications in kidney patients.

The volatile release evaluation of nicotine from snus products under different storage conditions based on surface-enhanced Raman spectroscopy technology.

Surface enhanced Raman spectroscopy (SERS) is a highly sensitive analytical detection technique that provides unique chemical and structural information on target molecules. Snus is a type of tobacco product that can release nicotine and other components under certain humidity and temperature without burning, and the evaluation of its nicotine release under different storage conditions is very important for understanding its characteristics, regulating its components, and setting reasonable storage conditions. Herein, by means of an artificial climate box and suction extraction device, the volatile release evaluations of nicotine from snus products under different storage conditions were performed based on Fe3O4 microparticles coated with Au nanorods and Au nanoparticles (Fe3O4@AuNRsNPs) as SERS substrates combined with a capillary. The Fe3O4@AuNRsNPs assemblies can be fixed in the inner wall of the capillary with the aid of an external magnetic field, which improved the maneuverability of the SERS substrates. By comparing the intensities of the spectral peaks of the symmetrical breathing of the pyridine moiety of nicotine molecules with increasing temperature and humidity, which could significantly accelerate the volatile release of a small amount of nicotine, the nicotine release under different conditions could be evaluated. Based on this strategy, it was possible to obtain the storage or placement conditions of the product. The results of this study provide a reference to clarify the volatile release of nicotine under various storage conditions, which is helpful for better regulation of the levels of nicotine in snus. Moreover, such destruction-free evaluation of the volatile release of nicotine from snus products under different storage conditions opens up new perspectives for further research about the impact of nicotinoids on smokers' health and cessation programs.

Deep Learning‐Enhanced Potentiometric Aptasensing with Magneto‐Controlled Sensors

AbstractBioelectronic sensors that report charge changes of a biomolecule upon target binding enable direct and sensitive analyte detection but remain a major challenge for potentiometric measurement, mainly due to Debye Length limitations and the need for molecular‐level platforms. Here, we report on a magneto‐controlled potentiometric method to directly and sensitively measure the target‐binding induced charge change of DNA aptamers assembled on magnetic beads using a polymeric membrane potentiometric ion sensor. The potentiometric responses of the negatively charged aptamer, serving as a receptor and reporter, were dynamically controlled and modulated by applying a magnetic field. Based on a potentiometric array, this non‐equilibrium measurement technique combined with deep learning algorithms allows for rapidly and reliably classifying and quantifying diverse small molecules using antibiotics as models. This potentiometric strategy opens new modalities for sensing applications.

Deep Learning-Enhanced Potentiometric Aptasensing with Magneto-Controlled Sensors.

Bioelectronic sensors that report charge changes of a biomolecule upon target binding enable direct and sensitive analyte detection but remain a major challenge for potentiometric measurement, mainly due to Debye Length limitations and the need for molecular-level platforms. Here, we report on a magneto-controlled potentiometric method to directly and sensitively measure the target-binding induced charge change of DNA aptamers assembled on magnetic beads using a polymeric membrane potentiometric ion sensor. The potentiometric responses of the negatively charged aptamer, serving as a receptor and reporter, were dynamically controlled and modulated by applying a magnetic field. Based on a potentiometric array, this non-equilibrium measurement technique combined with deep learning algorithms allows for rapidly and reliably classifying and quantifying diverse small molecules using antibiotics as models. This potentiometric strategy opens new modalities for sensing applications.

Terahertz Spectroscopic Molecular Sensor for Rapid and Highly Specific Quantitative Analytical Gas Sensing

Quantitative analytical gas sampling is of great importance in a range of environmental, safety, and scientific applications. In this article, we present the design, operation, and performance of a recently developed tabletop terahertz (THz) spectroscopic molecular sensor capable of rapid (minutes) and sensitive detection of polar gaseous analytes with near "absolute" specificity. A novel double-coil absorption cell design and an array of room-temperature sorbent-based preconcentration modules facilitate quantitative THz detection of light polar volatile compounds, which often challenge the capabilities of established gas sensing techniques. Acetone, ethanol, methanol, acetaldehyde, formaldehyde, and isoprene are detected at low parts-per-billion to high parts-per-trillion levels. This work evaluates performance-limiting factors for THz spectroscopy-based chemical identification: (1) spectral signal to noise and (2) preconcentrator efficiency.

Ni2P nanocrystallines anchored on black phosphorus nanosheets enable highly selective and sensitive non-enzymatic electrochemical detection of L-cysteine over glutathione

Selective and sensitive determination of L-cysteine (L-Cys) plays an important role in clinical diagnoses and regulation of L-Cys level. However, glutathione (GSH) interferes greatly with the L-Cys detection due to their similar electrochemically active functional sulfhydryl groups and the high abundance of GSH in biological samples. Herein, Ni2P nanocrystallines anchored on black phosphorus nanosheets (Ni2P @ BPNSs) electrocatalysts were prepared by an in-situ solvothermal method using BPNSs as phosphorus sources and substrate. The electrochemical behaviors of Ni2P @ BPNSs with different Ni2P contents were studied for L-Cys determination. The experimental and DFT calculation results reveal the extraordinary electrocatalytic and selective sensing mechanism of Ni2P @ BPNSs toward L-Cys is attributed to the high selective adsorption and electrocatalytic activity of Ni active sites, and BPNSs matrix. The electrochemical sensor displays low detection limit (2 nM), more negative oxidation potential (+0.30 V), extremely broad linear range (0.02 −1000 μM), excellent sensitivity (396.00 μA mM−1 cm−2), and extraordinary selectivity. The sensor has been practically applied in detection of L-Cys concentrations in serum and urine samples. This work opens the avenues for the engineering design of metal atoms decorated BP materials in biosensors with enhanced sensing performance by adjusting the properties of materials, allowing for more selective and sensitive analyte detection.

Carbon coating of GaN nanostructures for enhanced sensitivity and selectivity of chemical vapours

The chemical vapour sensing behaviour of pristine gallium nitride (GaN) and variously carbon coated GaN (C-GaN) nanostructures towards polar protic (methanol, lactic acid, ammonia, water), polar aprotic (acetone) and apolar (toluene) analytes is investigated. The thickness of the carbon layer on GaN was controlled by using argon or nitrogen as carrier gases for toluene. TEM micrographs revealed dependence of the carbon layer on the carrier gas; with nitrogen (~2.6 ± 0.6 nm) leading to a thinner layer than argon (~3.4 ± 0.7 nm). Interestingly, chemical sensing performance studies showed that the carbon coating improved the sensitivity of GaN to polar protic analytes, especially to the toxic ammonia. Most importantly, enhanced sensitivity was observed for water molecules on the C-GaN based devices in comparison to water sensitivity on bare GaN devices. In contrast, the carbon coating was observed to have little or no influence on the sensitivity towards polar aprotic and apolar analytes. In summary, the study demonstrates the importance of coating GaN nanoparticles with a thin carbonaceous layer for enhanced room temperature sensitive and selective detection of chemical vapour analytes. • GaN and carbon coated GaN nanostructured resistive sensors were studied • Studied analytes were methanol, lactic acid, ammonia, water, acetone and toluene • Carbon coating improves sensitivity of GaN nanostructures to polar protic analytes • The sensors operate at room temperature

Paper-Based Electrochemical Biosensors for Food Safety Analysis.

Nowadays, foodborne pathogens and other food contaminants are among the major contributors to human illnesses and even deaths worldwide. There is a growing need for improvements in food safety globally. However, it is a challenge to detect and identify these harmful analytes in a rapid, sensitive, portable, and user-friendly manner. Recently, researchers have paid attention to the development of paper-based electrochemical biosensors due to their features and promising potential for food safety analysis. The use of paper in electrochemical biosensors offers several advantages such as device miniaturization, low sample consumption, inexpensive mass production, capillary force-driven fluid flow, and capability to store reagents within the pores of the paper substrate. Various paper-based electrochemical biosensors have been developed to enable the detection of foodborne pathogens and other contaminants that pose health hazards to humans. In this review, we discussed several aspects of the biosensors including different device designs (e.g., 2D and 3D devices), fabrication techniques, and electrode modification approaches that are often optimized to generate measurable signals for sensitive detection of analytes. The utilization of different nanomaterials for the modification of electrode surface to improve the detection of analytes via enzyme-, antigen/antibody-, DNA-, aptamer-, and cell-based bioassays is also described. Next, we discussed the current applications of the sensors to detect food contaminants such as foodborne pathogens, pesticides, veterinary drug residues, allergens, and heavy metals. Most of the electrochemical paper analytical devices (e-PADs) reviewed are small and portable, and therefore are suitable for field applications. Lastly, e-PADs are an excellent platform for food safety analysis owing to their user-friendliness, low cost, sensitivity, and a high potential for customization to meet certain analytical needs.

An ultrasensitive electrochemical immunosensor for carcinoembryonic antigen detection based on two-dimensional PtPd/Cu-TCPP(Fe) nanocomposites.

Establishing an effective signal amplification strategy is the key to achieving sensitive detection of analytes by electrochemical immunoassay. In this work, a novel sandwich-type electrochemical immunosensor with dual-signal amplification was successfully constructed using PtPd/Cu-TCPP(Fe) as the sensing platform and mesoporous silicon dioxide as the signal amplifier. Firstly, two-dimensional wrinkled Cu-TCPP(Fe) nanomaterials loaded with PtPd nanoparticles have strong affinity for the immobilization of capture antibodies and can generate excellent electrochemical signals. Meanwhile, the mesoporous silicon dioxide with large steric hindrance was used as signal label to further improve the sensitivity of the immunosensor by increasing the difference of the current response signal. Under optimal experimental conditions, the electrochemical immunosensor exhibited a wide linear detection range from 0.1pg/mL to 1.0μg/mL, with a detection limit as low as 0.166fg/mL. The experimental results showed that the constructed immunosensor has a great application prospect in clinical biomarker detection.

Tunable SERS activity of Ag@Fe3O4 core-shell nanoparticles: Effect of shell thickness on the sensing performance

Surface enhanced Raman spectroscopy (SERS) with enormous advantages has emerged as a powerful tool for both highly sensitive structural detection of analytes and imaging applications. Among various multifunctional nanomaterials for SERS substrate, nanocomposites of magnetic and plasmonic materials deliver both SERS effect and magnetic manipulation capacity, and thereby, have practical advantages for trace analysis in a broad range of fields. Herein, we investigate the SERS performance of different-sized Ag@Fe3O4 core-shell nanoparticles (NPs) obtained by controlling the Fe precursor concentration in a facile one-pot solvothermal synthesis method. The surface morphology, composition, structure, optical and magnetic properties are characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-Vis spectroscopy, and electrochemical techniques. The small shell thickness and high shell porosity of the smallest NPs significantly improve the mass diffusion and therefore SERS performance, making it an ideal substrate for highly sensitive detection of methylene blue (MB) and crystal violet (CV) organic pollutants. Quantitative SERS measurements using the Ag@Fe3O4 NPs are successfully demonstrated with MB as probe analytes. Due to the presence of a porous Fe3O4 shell, the Ag@Fe3O4 NPs showed outstanding SERS sensing performance with a linear concentration range from 10−7 to 10−10 M and the limit of detection (LOD) of 3 × 10−10 M. Moreover, the Ag@Fe3O4 core-shell nanocomposite exhibits high reproducibility and reliability and can be a promising candidate for SERS sensing systems.

Nanostructured Silicon Enabled HR-MS for the Label-Free Detection of Biomarkers in Colorectal Cancer Plasma Small Extracellular Vesicles

Despite improvements in treatment options for advanced colorectal cancer (CRC), survival outcomes are still best for patients with non-metastasised disease. Diagnostic tools to identify blood-based biomarkers and assist in CRC subtype classification could afford a means to track CRC progression and treatment response. Cancer cell-derived small extracellular vesicles (EVs) circulating in blood carry an elevated cargo of lipids and proteins that could be used as a signature of tumour suppressor/promoting events or stages leading up to and including metastasis. Here, we used pre-characterised biobanked plasma samples from surgical units, typically with a low volume (~100 µL), to generate and discover signatures of CRC-derived EVs. We employed nanostructured porous silicon (pSi) surface assisted-laser desorption/ionisation (SALDI) coupled with high-resolution mass spectrometry (HR-MS), to allow sensitive detection of low abundant analytes in plasma EVs. When applied to CRC samples, SALDI-HR-MS enabled the detection of the peptide mass fingerprint of cancer suppressor proteins, including serine/threonine phosphatases and activating-transcription factor 3. SALDI-HR-MS also allowed the detection of a spectrum of glycerophospholipids and sphingolipid signatures in metastatic CRC. We observed that lithium chloride enhanced detection sensitivity to elucidate the structure of low abundant lipids in plasma EVs. pSi SALDI can be used as an effective system for label-free and high throughput analysis of low-volume patient samples, allowing rapid and sensitive analysis for CRC classification.

Strategies for Enhancing the Sensitivity of Electrochemiluminescence Biosensors.

Electrochemiluminescence (ECL) has received considerable attention as a powerful analytical technique for the sensitive and accurate detection of biological analytes owing to its high sensitivity and selectivity and wide dynamic range. To satisfy the growing demand for ultrasensitive analysis techniques with high efficiency and accuracy in complex real sample matrices, considerable efforts have been dedicated to developing ECL strategies to improve the sensitivity of bioanalysis. As one of the most effective approaches, diverse signal amplification strategies have been integrated with ECL biosensors to achieve desirable analytical performance. This review summarizes the recent advances in ECL biosensing based on various signal amplification strategies, including DNA-assisted amplification strategies, efficient ECL luminophores, surface-enhanced electrochemiluminescence, and ratiometric strategies. Sensitivity-enhancing strategies and bio-related applications are discussed in detail. Moreover, the future trends and challenges of ECL biosensors are discussed.