Analytical Methods最新文献

Due to their wide applications, occurrence and "PFAS-like" environmental behaviors, ionic liquids (ILs) represent a new challenge for the environmental monitoring community, who require robust analytical methods that can determine accurately and efficiently their environmentally relevant concentrations. A new passive sampling method based on the diffusive gradients in thin films (DGT) technique was developed for the measurement of imidazole-based ILs in waters using a mixed-mode cation exchange (MCX) resin as the adsorbent. The selected binding gel had a high binding capacity (>170 μg per disc) for ILs. Diffusion coefficients measured using a diffusion cell correlated well with alkyl chain lengths (r² = 0.95) and retention times (r² = 0.88), providing a simple and rapid prediction approach for other ILs. The assembled MCX-DGT sampler exhibited a linear accumulation for at least 120 h. MCX-DGT also showed good performance under typical freshwater conditions (pH 5-8, ionic strength 0.001-0.01 M, and humic acid 0-5 mg L^-1), while still being problematic for aquatic conditions with higher ionic strength (>0.1 M) or DOM (>10 mg L^-1). Laboratory deployment (for up to 3 days) in spiked natural freshwater (SNW) resulted in linear mass uptakes for the short-chain ILs (C2-C8), and their DGT-measured concentrations agreed well with solution concentrations. However, MCX-DGT significantly overestimated the concentrations of the long-chain ILs (C10-C12) when deployed in SNW for one day or more, which is attributed to the strong competitive adsorption of the long-chain ILs by natural organic matter. In situ field evaluation along with grab sampling found no target ILs in a wastewater treatment plant and its receiving river, implying that these new chemicals might not be widely used in South China now. This is the first report on the DGT technique for ILs and might provide an effective tool for monitoring short chain length ILs in the aquatic environment in the near future.

Mercury contamination is a global environmental issue due to its toxicity and persistence in ecosystems. It poses a particular risk in aquatic systems, where it bioaccumulates and biomagnifies, leading to serious health impacts on humans. Therefore, effective detection technologies for mercuric ions in natural water resources are highly desirable. However, most existing detection methods are time-consuming, require complicated sample pre-treatment, and rely on expensive equipment, which hinders their widespread use in real-time detection. Here, we present a convenient, rapid, portable, user-friendly, and cost-effective sensing system for detecting Hg²⁺ ion contamination in water. This system utilizes a highly selective, amphiphilic, and structurally simple molecular probe, N-dodecylamine-di-thiocarbamate (DDC). DDC molecules align at the interface between the liquid crystal (LC) and water, inducing a homeotropic LC orientation. In water samples contaminated with Hg²⁺, a bright optical texture is observed, indicating the alignment of the 5CB LC in a planar manner at the LC/aqueous boundary. The minimum detectable concentration (LOD) for Hg²⁺ ions is 5.0 μM in distilled water, with a broad detection range from 5.0 μM to 2 mM. The sensor selectively detects Hg²⁺ ions over other common interfering metal ions, including Pb²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺, Zn²⁺, Cr²⁺, Mg²⁺, Na⁺, K⁺, and Ca²⁺. Boolean logic gates, bar graphs, and truth tables are employed to explain the selectivity of this liquid crystal-based sensor. This work demonstrates the significant potential of the sensor for monitoring mercuric ions in natural water resources, offering a promising strategy for controlling mercury pollution.

Boldenone (BOL) has been frequently detected in doping and food safety over the past few decades. Researchers have studied BOL metabolism across various species, reporting significant differences even within the same species due to variations in experimental designs and analytical methods. Additionally, detection methods face challenges such as matrix interferences and the presence of endogenous structural analogs at low concentrations. This study aims to compile and analyze the development of chromatographic techniques for detecting BOL and its metabolites in biological matrices. An integrative review of literature from May 2000 to September 2024 was conducted using databases like PubMed, ScienceDirect, Elsevier, Springer, Scopus, Wiley, and Taylor & Francis. The MeSH terms ‘boldenone’ AND ‘detection,’ restricted to titles or abstracts, yielded 167 records, with 79 meeting the inclusion criteria. Hyphenated techniques (e.g., LC/MS/MS and GC/C/IRMS) were predominantly used and generally successful in identifying BOL, its precursors, and metabolites, particularly in characterizing their endogenous origin or differentiating isomers. Urine was the most commonly observed matrix, and solid-phase extraction (SPE) was the predominant extraction technique. Future research should aim to improve extraction and detection methods to address current discrepancies in controlling BOL use, as its pharmacological properties have led to negative repercussions in sports and concerns about food safety.

Herein, we developed an easy-to-synthesize, simple colorimetric probe and demonstrated its potential for the detection of anions and amines. The probe was capable of detecting CN^- selectively among other anions and could detect the presence of all tested amines. It exhibited obvious colour and spectroscopic changes in the presence of the said analytes. The probe was highly sensitive to CN^- ions, which enabled the detection of trace amounts of the aforementioned anion. The detection limit for CN^- was found to be 3.98 × 10^-8 M, which is below most of the LOD values reported thus far. The sensing was further extended to the solid state by effectively immobilizing the probe in a hydrogel matrix. Moreover, upon exposure to ammonia vapour, noticeable colour changes were observed in a probe-coated paper chip within few minutes. Moreover, the practical application of the probe was demonstrated for both CN^- and amines. The probe can serve as a promising alternative for detection of CN^- content in food and monitoring of biogenic amines and food freshness.

A simple, accurate method for measuring ricin activity was developed by detecting depurinated nucleic acid stem-loops and adenine using a commercially available hydrophilic interaction liquid chromatography (HILIC) column and a quadrupole-Orbitrap tandem mass spectrometer. Ricin in beverages was isolated using magnetic beads conjugated with ricin B-chain antibodies, and then incubated with a 14 mer RNA or a 12 mer RNA/DNA chimera, in which adenosine at the depurination site of RNA was replaced by deoxyadenosine. The adenine and depurinated nucleic acids were separated by HILIC and both analytes were detected by high-resolution mass spectrometry. The depurinated RNA was detectable at concentrations as low as 100 pM (6.5 μg mL^-1) in orange juice and coffee, and 10 pM (0.65 μg mL^-1) in milk and sake after incubation with the RNA substrate for 4 h. Free adenine was detectable at 10 pM in all matrices, although free adenine was also detected in all blanks and could not be distinguished from the coffee and orange juice blanks at 10 pM. When using the chimera as the substrate, the depurinated chimera and adenine were detected up to concentrations of 10 pM as larger peaks. However, since the depurinated chimera and adenine were also detected in blanks, careful judgment was needed to determine whether they were active. Following the assay, the captured ricin could be analyzed by enzymatic digestion and nano liquid chromatography-high-resolution mass spectrometry. The ricin A chain-specific T7A peptide was detectable at 10 pM for sake and at 100 pM for milk, orange juice, and coffee. Using the present method, a toxicity assay and qualitative analysis of ricin were feasible with a 0.2 mL beverage sample.

Over the last several decades, multiple microfluidic platforms have been used for measurement of hormone secretion from islets of Langerhans. Most have used continuous flow systems where mixing of hormones with assay reagents is governed by diffusion, leading to long mixing times, especially for biomolecules like peptides and proteins which have large diffusion coefficients. Consequently, dispersion of rapidly changing signals can occur, reducing temporal resolution. Droplet microfluidic systems can be used to capture reagents into individual reactors, limiting dispersion and improving temporal resolution. In this study, we integrated a fluorescence anisotropy (FA) immunoassay (IA) for insulin into a droplet microfluidic system. Insulin IA reagents were mixed online with insulin and captured quickly into droplets prior to passing through a 200 mm incubation channel. Double etching of the glass device was used to increase the depth of the incubation channel compared to the IA channels to maintain proper flow of reagents. The droplet system produced highly precise FA results with relative standard deviations < 2% at all insulin concentrations tested, whereas the absolute fluorescence intensity precisions ranged between 5 and 6%. A limit of detection of 3 nM for insulin was obtained, similar to those found in conventional flow systems. The advantage of the system was in the increased temporal resolution using the droplet system where a 9.8 ± 2.6 s response time was obtained, faster than previously reported continuous flow systems. The improved temporal resolution aligns with continued efforts to resolve rapid signaling events in pancreatic islet biology.

Tuberculosis is a highly infectious bacterial disease caused by Mycobacterium tuberculosis. The spread of this agent has caused serious health problems worldwide, and the rapid and accurate detection of M. tuberculosis is essential for controlling the spread of infection and for preventing the emergence of multidrug-resistant strains. In this study, the trans cleavage ability of CRISPR-Cas12a against single-stranded DNA was combined with hybridization chain reaction and chemiluminescent signal to establish an imaging sensor for the hypersensitive detection of M. tuberculosis DNA. We observed linear relationships between the concentration of M. tuberculosis DNA and the output signal over the ranges of 10 to 200 pM and 200 to 800 pM DNA. The equations of the standard curves were y = 56.08x + 3303, with R² = 0.9916 for the lower range and y = 15.69x + 10 685, with R² = 0.9929 for the higher range. The limit of detection was as low as 0.83 pM for genomic DNA, and a plasmid containing an M. tuberculosis-specific sequence was detected at 1 copy per μL. A detection accuracy of 100% was achieved in the analysis of DNA isolated from sputum of hospitalized tuberculosis patients. The sensitivity and specificity of the proposed sensor is combined with a long shelf-life and a low cost of materials. This study introduces a new method for tuberculosis detection and broadens the application of CRISPR-Cas12a-based sensors in clinical diagnosis.

This article presents a numerical platform for predicting the performance of paper-based analytical devices. The capillary flow, reaction, dissolution, and other physicochemical phenomena associated with device operation are accounted for using Darcy's law, Richard's equation and other transport equations. The platform can be used for different paper substrates, biorecognition methods, detection systems (such as optical and electrochemical detection), device patterns and dimensions, and ways in which the device is operated such as the input method of the body fluid. The device performance is quantified using indicators such as assay time, signal strength and product cost. The predictive capability of this numerical tool is verified with devices reported in the literature. It is shown that the platform can be used to identify possible improvements to these existing devices. More importantly, it can also serve as a numerical tool for synthesizing new paper-based analytical devices with minimum experimental effort.

The accurate and sensitive detection of foodborne pathogens is critical for timely food quality supervision and human health. To address this issue, herein, we developed a simple and novel surface-enhanced Raman scattering (SERS) assay using p-mercaptobenzoic acid (MBN)-modified gold nanoparticles (Au NPs) and magnetic beads for interference-free detection of Escherichia coli (E. coli). This assay technique cleverly reduced silver ions (Ag⁺) on the surface of E. coli (bacteria@Ag NPs), and the functionalized magnetic beads (capture probes) captured and enriched bacteria@Ag NPs, forming the structure of the capture probes–bacteria@Ag NPs. Then, the capture probes–bacteria@Ag NPs were dissolved in the acidic medium, and the Ag NPs on the surface of E. coli was converted to Ag⁺ again. Due to the special coordination between Ag⁺ and MBN-modified Au NPs (functionalized Au NPs), the SERS intensity of MBN exhibited a positive correlation with the E. coli concentration, and the SERS detection assay of E. coli was established. The signal of the functionalized Au NPs located at 2228 cm⁻¹ perfectly avoided the spectral overlap with coexisting materials in the Raman fingerprint region, which ensured the accuracy of the technique. The controlled aggregation of the functionalized Au NPs ensured the reproducibility and reliability of the detection system; the emergence of MBs greatly reduced the reaction time and made sure the operation was rapid, simple and portable. The limit of detection (LOD) for E. coli was as low as 10 cfu mL⁻¹, and the detection assay was successfully applied for the detection of E. coli in bottled water and milk. As a sensitive and accurate analytical technique for the detection of pathogens, this SERS-based method has great potential to be applied in the field of food safety.

The isolation and analysis of chiral isomers are critical parts of the drug development process to ensure effective and safe drug administration to patients. Indirect chiral ligand exchange chromatography (ICLEC) was developed to separate and determine tenofovir alafenamide fumarate (TAF) and its diastereoisomer GS-7339, with a hypothesized separation mechanism. The effect of using a chiral column versus a standard C18 column on the separation of the TAF chiral isomer mixture was investigated. Various factors in ICLEC, including ligand type, ligand ratio, mobile phase composition, and column temperature, were optimized. The separation of TAF and GS-7339 was successfully achieved by selecting L-phenylalanine as the chiral selective agent and Cu(II) as the central metal ion, using a C18 column as the analytic column and a mobile phase of 20 mM ammonium dihydrogen phosphate buffer (pH = 4.0)-acetonitrile (79 : 21, v/v). The corresponding linearity range for TAF and GS-7339 indicated a good correlation with R² > 0.9960. The average recoveries of TAF and GS-7339 ranged from 98.2% to 106.9%. None of the eight manufacturers detected GS-7339, and the percentage of TAF-labeled amounts in the drugs ranged from 95.0% to 98.5%. TAF tablets from eight manufacturers were of satisfactory quality. The separation mechanism of TAF and GS-7339 by ICLEC is due to the different spatial configurations of the two ternary complexes formed by the two chiral isomers, leading to differences in their thermodynamic stability and retention behavior. The established ICLEC method is economical, simple, and flexible, providing an effective strategy for studying chiral drug separation and analysis.