Detection Of Analytes Research Articles

Xanthene-Based Dyes for Photoacoustic Imaging and their Use as Analyte-Responsive Probes.

Developing imaging tools that can report on the presence of disease-relevant analytes in multicellular organisms can provide insight into fundamental disease mechanisms as well as provide diagnostic tools for the clinic. Photoacoustic imaging (PAI) is a light-in, sound-out imaging technique that allows for high resolution, deep-tissue imaging with applications in pre-clinical and point-of-care settings. The continued development of near-infrared (NIR) absorbing small-molecule dyes promises to improve the capabilities of this emerging imaging modality. For example, new dye scaffolds bearing chemoselective functionalities are enabling the detection and quantification of disease-relevant analytes through activity-based sensing (ABS) approaches. Recently described strategies to engineer NIR absorbing xanthenes have enabled development of analyte-responsive PAI probes using this classic dye scaffold. Herein, we present current strategies for red-shifting the spectral properties of xanthenes via bridging heteroatom or auxochrome modifications. Additionally, we explore how these strategies, coupled with chemoselective spiroring-opening approaches, have been employed to create ABS probes for in vivo detection of hypochlorous acid, nitric oxide, copper (II), human NAD(P)H: quinone oxidoreductase isozyme 1, and carbon monoxide. Given the versatility of the xanthene scaffold, we anticipate continued growth and development of analyte-responsive PAI imaging probes based on this dye class.

Elucidating important factors and corresponding method optimization for sensitive detection of small peptide drugs in human urine by solid-phase extraction and UPLC-HRMS: The influence of MS scan modes, protein precipitants, and ammonium formate.

Small peptide hormones are widely used in sports as performance-enhancing substances, making it crucial to develop sensitive analytical methods for their detection in doping control analysis. Various factors significantly affect analytical sensitivity, such as the selection of ultra-performance liquid chromatography (UPLC) mobile phase, high-resolution mass spectrometry (HRMS) scanning modes, and extraction solvents for pretreatment. Herein, comparative study approach was utilized to investigate the sensitivity of each peptide analyte under both full scan and parallel reaction monitoring (PRM) modes of HRMS and assess the effects of some protein precipitants as a part of extraction solvents on solid-phase extraction (SPE). The results showed that full scan should be selected as the primary scan mode of HRMS, and the combination with PRM mode could effectively compensate for the limitations of full scan, and the addition of protein precipitants would adversely affect the detection of certain small peptide analytes. Meanwhile, influences of ammonium formate in reverse UPLC mobile phase on the charge state distribution of small peptides were investigated and elucidated. Based on these findings, a sensitive and reliable UPLC-HRMS analytical method combining full scan and PRM mode was validated for screening and confirmation of 63 small peptide analytes after SPE, with limits of detection (LODs) ranging between 0.010 and 0.473 ng/ml and limits of identification (LOIs) ranging between 0.015 and 1.512 ng/ml. Additionally, suggestions were provided for the detection of [Arg8]-vasopressin, dermorphin, and its analogues.

Development and validation of a method for analysis of 25 cannabinoids in oral fluid and exhaled breath condensate.

Currently, there is a significant demand in forensic toxicology for biomarkers of cannabis exposure that, unlike ∆9-tetrahydrocannabinol, can reliably indicate time and frequency of use, be sampled with relative ease, and correlate with impairment. Oral fluid (OF) and exhaled breath condensate (EBC) are alternative, non-invasive sample matrices that hold promise for identifying cannabis exposure biomarkers. OF, produced by salivary glands, is increasingly utilized in drug screening due to its non-invasive collection and is being explored as an alternative matrix for cannabinoid analysis. EBC is an aqueous specimen consisting of condensed water vapor containing water-soluble volatile and non-volatile components present in exhaled breath. Despite potential advantages, there are no reports on the use of EBC for cannabinoid detection. This study developed a supported liquid extraction approach and LC-QqQ-MS dMRM analytical method for quantification of 25 major and minor cannabinoids and metabolites in OF and EBC. The method was validated according to the ANSI/ASB 036 standard and other published guidelines. LOQ ranged from 0.5 to 6.0ng/mL for all cannabinoids in both matrices. Recoveries for most analytes were 60-90%, with generally higher values for EBC compared to OF. Matrix effects were observed with some cannabinoids, with effects mitigated by use of matrix-matched calibration. Bias and precision were within ± 25%. Method applicability was demonstrated by analyzing ten authentic OF and EBC samples, with positive detections of multiple analytes in both matrices. The method will facilitate comprehensive analysis of cannabinoids in non-invasive sample matrices for the development of reliable cannabis exposure biomarkers.

Pushing the Limits of Capacitively Coupled Contactless Conductivity Detection for Capillary Electrophoresis.

Capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D) has proven to be an efficient technique for the separation and detection of charged inorganic, organic, and biochemical analytes. It offers several advantages, including cost-effectiveness, nanoliter injection volume, short analysis time, good separation efficiency, suitability for miniaturization, and portability. However, the routine determination of common inorganic cations (NH4+, K+, Na+, Ca2+, Mg2+, and Li+) and inorganic anions (F-, Cl-, Br-, NO2-, NO3-, PO43-, and SO42-) in water quality monitoring typically exhibits limits of detection of about 0.3-1 μM without preconcentration. This sensitivity often proves insufficient for the applications of CE-C4D in trace analysis situations. Here, we explore methods to push the detection limits of CE-C4D through a comprehensive consideration of signal and noise sources. In particular, we (i) studied the model of C4D and its guiding roles in C4D and CE-C4D, (ii) optimized the bandwidth and noise performance of the current-to-voltage (I-V) converter, and (iii) reduced the noise level due to the strong background signal of the background electrolyte by adaptive differential detection. We characterized the system with Li+; the 3-fold signal-to-noise (S/N) detection limit for Li+ was determined at 20 nM, with a linear range spanning from 60 nM to 1.6 mM. Moreover, the optimized CE-C4D method was applied to the analysis of common mixed inorganic cations (K+, Na+, Ca2+, Mg2+, and Li+), anions (F-, Cl-, Br-, NO2-, NO3-, PO43-, and SO42-), toxic halides (BrO3-) and heavy metal ions (Pb2+, Cd2+, Cr3+, Co2+, Ni2+, Zn2+, and Cu2+) at trace concentrations of 200 nM. All electropherograms showed good S/N ratios, thus proving its applicability and accuracy. Our results have shown that the developed CE-C4D method is feasible for trace ion analysis in water quality control.

Plasmonic AgNPs reinforced flexible hydrogel Surface-Enhanced Raman scattering (SERS) sensor for in-situ detection of curved samples

In-situ detection of analytes on curved surfaces is a persistent and great challenge in the application of SERS technique. A hydrogel-based flexible SERS substrate demonstrates a unique charm for providing close contact to the real-sample surface but limited by its weak enhancement capability in the quantitative analysis. Herein, we report a reinforced hydrogel by reduction of plasmonic silver nanoparticles (AgNPs) on a PNIPAM membrane with the aid of polyvinylpyrrolidone (PVP) surfactant. The modification of AgNPs on PNIPAM endows the AgNPs/PNIPAM composite hydrogel with good mechanical properties and reinforced swelling property. Moreover, the AgNPs/PNIPAM hydrogel-based SERS sensor exhibits an enhanced SERS sensitivity as well as improved signal uniformity (RSD ＜10 %), and the detection concentration for pesticide molecules can be down to 10-9 M. Due to the fingerprint feature of SERS, multicomponent detection of pesticide mixtures was readily realized. In addition, the flexible AgNPs/PNIPAM hydrogel was successfully applied to the curved apple surface for SERS detection. Notably, it is capable of achieving qualitative and quantitative analyses of different pesticides, which has lower analytical concentrations than European Union (EU) standards, indicating the potential applications in rapid in-situ pesticide analysis.

Beyond the Passive Diffusion: Core@Satellite Magneto‐Plasmonic Particles for Rapid and Sensitive Colorimetric Immunosensor Response

AbstractMagneto‐plasmonic particles, comprising gold and iron oxide, exhibit substantial potential for biosensing applications due to their distinct properties. Gold nanoparticles (AuNPs) provide plasmonic features, while iron oxide composites, responsive to an external magnetic field, significantly reduce detection time compared to passive diffusion. This study explores core@satellite magneto‐plasmonic particles (CSMPs), featuring magnetic nanoparticle clusters and numerous satellite‐like AuNPs, to amplify the optical response on a nanostructured gold surface. Using a sandwich scheme, target analytes are detected as hybrid nanoparticles bind to the pre‐immobilized target on the AuNPs surface, inducing changes in the immunosensor's extinction spectrum. Application of an external magnetic field notably enhances biosensor response and sensitivity, reducing assay time from hours to minutes. Leveraging the properties of CSMPs, the immunosensor detects specific immune protein at low concentrations within minutes. CSMPs hold considerable promise for precise and sensitive analyte detection, offering potential applications in rapid testing and mass screening.

Electrifying Fruit Juice: Integrating Applied Electroanalytical Chemistry into the Undergraduate Curriculum.

Electroanalytical chemistry has been advanced through portable devices, providing methods and sensors for the detection of analytes with high sensitivity and accuracy. This subfield of electrochemistry has the potential to be utilized in industry and analytical quality control, in general. This results in an increasing demand for trained personnel, capable of operating benchtop and portable electroanalytical equipment. Although electrochemical techniques are routinely taught in theoretical undergraduate courses, they need to be more often incorporated into experimental didactic activities. Herein, we describe the application of an effective, hands-on, and low-maintenance experiment that can enhance the learning experience of electroanalytical methods and their use in industrial quality control settings. This activity is based on the detection of ascorbic acid (vitamin C) by employing cyclic voltammetry at unmodified glassy carbon electrodes (GCE) in real juice samples. This didactic experiment teaches students about the theoretical concepts of cyclic voltammetry, three-electrode cell setup, chemical reversibility, data treatment, and quantitative analysis. This teaching approach was conducted in a second-year analytical chemistry course and was easily adapted to social distancing measures imposed by the COVID-19 pandemic.

Novel Multifunctional Meta-Surface Plasmon Resonance Chip Microplate for High-Throughput Molecular Screening.

The utilization of surface plasmon resonance (SPR) sensors for real-time label-free molecular interaction analysis is already being employed in the fields of in vitro diagnostics and biomedicine. However, the widespread application of SPR technology is hindered by its limited detection throughput and high cost. To address this issue, this study introduces a novel multifunctional MetaSPR high-throughput microplate biosensor featuring 3D nanocupsarray structure, aiming to achieve high-throughput screeningwith a reduced cost and enhanced speed. Different types of MetaSPR sensors and analytical detection methods have been developed for accurateantibody subtype identification, epitope binding, affinity determination, antibody collocation, and quantitative detection， greatly promoting the screening and analysis ofearly-stageantibody drugs. The MetaSPR platform combined with nano-enhanced particles amplifies the detection signal and improves the detection sensitivity, making it more convenient, sensitive, and efficient than traditional ELISA. The findings demonstrate that the MetaSPR biosensor is a new practical technology detection platform that can improve the efficiency of biomolecular interaction studies with unlimited potential for new drug development.

A gas sensor based on free-standing SWCNT film for selective recognition of toxic and flammable gases under thermal cycling protocols

The widespread adoption of e-nose devices based on chemiresistive materials has been hindered by issues related to sensor device complexity and reliability, specifically sensor drift, necessitating frequent recalibration and retraining of pattern recognition models. This study introduces a method for thermocycling a single sensor based on a free-standing network of single-walled carbon nanotubes (SWCNTs) to acquire signal patterns for selective analyte detection. Additionally, it employs a data filtering technique to compensate for the sensor drift. A free-standing SWCNT film, only a few nanometers thick, is thermally cycled via Joule heating between room temperature and 120 °C. Under these conditions, the sensitivity was tested towards NO2, H2S, and acetone vapors (10–25 ppm) in the mixture with dry air. Signal patterns produced through thermocycling were processed using CatBoost and LSTM algorithms. The accuracy of detection reached 90 % in the classification task, and the average root mean squared error of analyte concentration detection in the multioutput regression task was below 4 ppm. By combining original sensor design, thermocycling, signal filtering for drift compensation, and advanced pattern recognition models, this work contributes to overcoming the challenges in multivariate sensing systems, paving the way for practical applications of the more reliable chemiresistive sensors.

3D Paper-Based Origami Device for Programmable Multifold Analyte Preconcentration.

In analytical chemistry, preconcentration represents a critical step able to enhance the accuracy of detection; however, the experimental procedures needed to preconcentrate samples might be characterized by drawbacks regarding the whole analytical process, e.g., being complex, invasive, and/or time-consuming. In this study, a novel 3D paper-based origami device is introduced for multifold analyte preconcentration. Leveraging the benefits of paper-based substrates, the proposed architecture boosts sample preconcentration while minimizing time and tasks for measurements, solely by exploiting the porous and versatile nature of paper-based substrates. In comparison with other paper-based approaches reported in the literature for preconcentration, the present architecture offers the ability to be programmed for obtaining the needed sensitivity increase without sacrificing measurement time. To demonstrate the efficacy of the novel approach, the 3D paper-based origami device was deeply characterized, including the most relevant parameters, i.e., disk size and number, unfolding time, and volume, and subsequently applied for the preconcentration and the detection of various analytes in real matrices, namely, mercury in tap water and glucose in sweat, resulting in a 400% and 300% sensitivity enhancement, respectively. This innovative preconcentration tool addresses the limitations of existing conventional methods, providing increased sensitivity without the use of expensive and time-consuming procedures through only exploiting the intrinsic properties of paper-based substrates and a rationale design. The proposed architecture emerges as a universal tool to be adopted and programmed for various analytical systems and fields of application.

Bimetallic Nanoparticles as Electrochemical Labels in Immunosensors for the Detection of Biomarkers of Clinical Interest

AbstractElectrochemical immunosensors have emerged in the last years as outstanding analytical systems for the detection of analytes of clinical interest. As alternative to the traditional enzymatic labels, the use of nanoparticles and especially bimetallic ones has gained increased attention thanks to their advantages related to the higher simplicity, stability and sensitivity offered. Main routes for the detection of such nanoparticle labels are based on i) dissolution of the nanoparticle into the corresponding metal ions followed by voltammetric detection; ii) taking advantage of the electrocatalytic effect of the metals towards secondary reactions; and iii) taking advantage of their electrochemiluminescence properties.

Colorimetric Glucose Biosensor Based on Chitosan Films and Its Application for Glucose Detection in Beverages Using a Smartphone Application.

Nowadays, biosensors are gaining increasing interest in foods' and beverages' quality control, owing to their economic production, enhanced sensitivity, specificity, and faster analysis. In particular, colorimetric biosensors can be combined with color recognition applications on smartphones for the detection of analytes, rendering the whole procedure more applicable in everyday life. Herein, chitosan (CS) films were prepared with the deep eutectic solvent (DES) choline chloride/urea/glycerol (ChCl:U:Gly). Glucose oxidase (GOx), a widely utilized enzyme in quality control, was immobilized within CS films through glutaraldehyde (GA), leading to the formation of CS/GOx films. The optimized GOx concentration and DES content were determined for the films. Moreover, the effect of the pH and temperature of the glucose oxidation reaction on the enzymatic activity of GOx was studied. The structure, stability, and specificity of the CS/GOx films as well as the Km values of free and immobilized GOx were also determined. Finally, the analytical performance of the films was studied by using both a spectrophotometer and a color recognition application on a smartphone. The results demonstrated that the films were highly accurate, specific to glucose, and stable when stored at 4 °C for 4 weeks and when reused 10 times, without evident activity loss. Furthermore, the films displayed a good linear response range (0.1-0.8 mM) and a good limit of detection (LOD, 33 μM), thus being appropriate for the estimation of glucose concentration in real samples through a smartphone application.

Colorimetric detection of the potent carcinogen aflatoxin B1 based on the aggregation of L-lysine-functionalized gold nanoparticles in the presence of copper ions.

L-lysine functionalized gold nanoparticles (AuNPs-Lys) have been widely used for the detection of worldwide interest analytes. In this work, a colorimetric assay for the detection of the carcinogen aflatoxin B1 (AFB1) based on the aggregation of AuNPs-Lys in the presence of copper ions was developed. For this purpose, AuNPs were synthesized in citrate aqueous solution, functionalized, and further characterized by UV-Vis, fluorescence, Fourier transform infrared spectroscopy (FTIR), nanoparticle tracking analysis (NTA), dynamic light scattering (DLS), and transmission electron microscopy (TEM). In general, AuNPS-Lys (~2.73 × 1011 particles) offered a clear colorimetric response in the presence of AFB1 and Cu2+ ions showing linearity in the range of 6.25 to 200 ng AFB1/mL, with a detection limit of 4.18 ng AFB1/mL via photometric inspection. Moreover, the performance of the proposed methodology was tested using the 991.31 AOAC official procedure based on monoclonal antibodies in maize samples artificially contaminated with AFB1. There was a good agreement between the measured AFB1 concentrations in both assays, the average recoveries for the colorimetric and immunoaffinity assays were between 91.2-98.4% and 96.0-99.2%, respectively. These results indicated that the colorimetric assay could be used as a rapid, eco-friendly, and cost-effective platform for the quantification of AFB1 in maize-based products.

Architecture of Molecular Logic Gates: From Design to Application as Optical Detection Devices

Three decades after A. P. de Silva’s seminal paper introduced the concept of logic gates at the molecular level, the field of molecular logic gates (MLGs) has witnessed significant advancements. MLGs are devices designed to perform logical operations, utilizing one or more physical or chemical stimulus signals (inputs) to generate an output response. Notably, MLGs have found diverse applications, with optical detection of analytes emerging as a notable evolution of traditional chemosensors. Organic synthesis methods are pivotal in crafting molecular architectures tailored as optical devices capable of analyte detection through logical functions. This review delves into the fundamental aspects and physical–chemical properties of MLGs, with a particular emphasis on synthetic strategies driving their design.

Multi-analyte responsive luminescent probes for the detection of biochemical targets in cell models

Luminescence has found wide application in biology, biotechnology and medicine. Particularly, fluorescent and bioluminescent probes allow visualization of molecular targets at the cellular level and even macromolecules or single small-molecule analytes. Among the most reliable tools for visualization of molecular targets are so-called responsive probes, which change the intensity and colour of the emitted signal after interaction with a molecular target. The majority of such probes allow detection of a single analyte. Meanwhile, most of the processes in the human body involve multiple elements. To better understand these mechanisms, it is possible to use several responsive probes simultaneously. However, this poses a risk of their different uptake by cells or different metabolism. In order to provide a more reliable response, so-called multi-analyte and multi-responsive probes are being developed. Examples of such probes will be discussed in the article, divided based on their response mechanism and detected changes within the cell.

Utilization of Spontaneous Alkyne-Gold Self-Assembly Chemistry as an Alternative Method for Fabricating Electrochemical Aptamer-Based Sensors.

Electrochemical aptamer-based (E-AB) sensors are a promising class of biosensors which use structure-switching redox-labeled oligonucleotides (aptamers) codeposited with passivating alkanethiol monolayers on electrode surfaces to specifically bind and detect target analytes. Signaling in E-AB sensors is an outcome of aptamer conformational changes upon target binding, with the sequence of the aptamer imparting specificity toward the analyte of interest. The change in conformation translates to a change in electron transfer between the redox label attached to the aptamer and the underlying electrode and is related to analyte concentration, allowing specific electrochemical detection of nonelectroactive analytes. E-AB sensor measurements are reagentless with time resolutions of seconds or less and may be miniaturized into the submicron range. Traditionally these sensors are fabricated using thiol-on-gold chemistry. Here we present an alternate immobilization chemistry, gold-alkyne binding, which results in an increase in sensor lifetimes under ideal conditions by up to ∼100%. We find that gold-alkyne binding is spontaneous and supports efficient E-AB sensor signaling with analytical performance characteristics similar to those of thiol generated monolayers. The surface modification differs from gold-thiol binding only in the time and aptamer concentration required to achieve similar aptamer surface coverages. In addition, alkynated aptamers differ from their thiolated analogues only by their chemical handle for surface attachment, so any existing aptamers can be easily adapted to utilize this attachment strategy.

Development and validation of a simultaneous quantitative analytical method for two Alternaria toxins and their metabolites in plasma and urine using ultra-high-performance liquid chromatography-tandem mass spectrometry.

Much more attention has been paid to the contamination of Alternaria toxins because of food contamination and the threat to human health. In this study, an ultra-high-performance liquid chromatography-tandem mass spectrometry method was developed for the simultaneous detection of the prototypical alternariol, alternariol monomethylether, and the metabolites 4-oxhydryl alternariol, and alternariol monomethylether 3-sulfate ammonium salt of Alternaria toxins. The positive samples were used as matrix samples to optimize the different experimental conditions. 0.01% formic acid solution and acetonitrile were used as the mobile phase, and analytes were scanned in negative electron spray ionization under multiple reaction monitoring, and quantitative determination by isotope internal standard method. Application of this method to samples of human plasma and urine showed the detection of the above analytes. The results showed that the recoveries were from 80.40% to 116.4%, intra-day accuracy was between 0.6% and 8.0%, and inter-day accuracy was between 1.1% and 12.1%. The limit of detection of the four analytes ranged from 0.02 to 0.6µg/L in urine, and 0.02 to 0.5µg/L in plasma, respectively. Thus, the developed method was rapid and accurate for the simultaneous detection of analytes and provided a theoretical basis for the risk assessment of Alternaria toxins for human exposure.

Pyrene Appendant Triazole-based Chemosensors for Sensing Applications.

Over the last two decades, the design and development of fluorescent chemosensors for the targeted detection of Heavy Transition-metal (HTM) ions, anions, and biological analytes, have drawn much interest. Since the introduction of click chemistry in 2001, triazole moieties have become an increasingly prominent theme in chemosensors. Triazoles generated via click reactions are crucial for sensing various ions and biological analytes. Recently, the number of studies in the field of pyrene appendant triazole moieties has risen dramatically, with more sophisticated and reliable triazole-containing chemosensors for various analytes of interest described. This tutorial review provides a general overview of pyrene appendant-triazole-based chemosensors that can detect a variety of metal cations, anions, and neutral analytes by using modular click-derived triazoles.

Strategic framework for harnessing luminescent metal nanocluster assemblies in biosensing applications.

The distinctive physicochemical attributes of ultra-small metal nanoclusters (MNCs) resembling those of molecules make them versatile constituents for self-assembled frameworks. This critical review scrutinizes the influence of assembly on the photoluminescence (PL) properties of MNCs and investigates their utility in biosensing applications. The investigation isinitiated with an assessment of the shift from individual MNCs to assemblies and its repercussions on PL efficacy. Subsequently, two distinct biosensing modalities are explored: assembly-driven detection mechanisms and detection predicated on structural modifications in assembled MNCs. Through meticulous examination, we underscore the potential of self-assembly methodologies in tailoring the PL behavior of MNCs for the detection of diverse biological analytes and diseases.

Design of a high-resolution magneto-plasmonic biosensor for analyte detection

This paper introduces the design of a magneto-plasmonic refractometric sensor aimed at achieving high resolution. This sensor consists of arrays of gold nanowires and layers of SiO2 and Co6Ag94, where the analyte is placed on the gold nanowires. A p-polarized optical field with a wavelength of 631 nm is used to excite the structure, which is applied in the range of 1° to 45°. A magnetic field is applied to z-axis to create the magneto-optical effect. The reflected optical field of the samples is used to calculate the signal of the transverse magneto-optical Kerr effect, which shows significant changes in the refractive index of the samples and the direction of the magnetic field. The highest displacement is 4°. The highest value of the figure of merit is 3611 RIU−1, and the maximum sensitivity is obtained as 71 °/RIU.