Improved Sample Preparation Method for Protein and Peptide Identification from Human Hair.

A fast and sensitive direct extraction (DE) method developed in our group can efficiently extract proteins in 30 min from a 5 cm-long hair strand. Previously, we coupled DE to downstream analysis using gel electrophoresis followed by in-gel digestion, which can be time-consuming. In searching for a better alternative, we found that a combination of DE with a bead-based method (SP3) can lead to significant improvements in protein discovery in human hair. Since SP3 is designed for general applications, we optimized it to process hair proteins following DE and compared it to several other in-solution digestion methods. Of particular concern are genetically variant peptides (GVPs), which can be used for human identification in forensic analysis. Here, we demonstrated improved GVP discovery with the DE and SP3 workflow, which was 3 times faster than the previous in-gel digestion method and required significantly less instrument time depending on the number of gel slices processed. Additionally, it led to an increased number of identified proteins and GVPs. Among the tested in-solution digestion methods, DE combined with SP3 showed the highest sequence coverage, with higher abundances of the identified peptides. This provides a significantly enhanced means for identifying proteins and GVPs in human hair.

Sub-PPB Detection with Gas-Phase Multiphoton Electron Extraction Spectroscopy under Ambient Conditions.

Multiphoton electron extraction spectroscopy (MEES) is an advanced analytical technique that has demonstrated exceptional sensitivity and specificity for detecting molecular traces on solid and liquid surfaces. Building upon the solid-state MEES foundations, this study introduces the first application of MEES in the gas phase (gas-phase MEES), specifically designed for quantitative detection of gas traces at sub-part per billion (sub-PPB) concentrations under ambient atmospheric conditions. Our experimental setup utilizes resonant multiphoton ionization processes using ns laser pulses under a high electrical field. The generated photoelectron charges are recorded as a function of the laser's wavelength. This research showcases the high sensitivity of gas-phase MEES, achieving high spectral resolution with resonant peak widths less than 0.02 nm FWHM. We present results from quantitative analysis of benzene and aniline, two industrially and environmentally significant compounds, demonstrating linear responses in the sub-PPM and sub-PPB ranges. The enhanced sensitivity and resolution of gas-phase MEES offer a powerful approach to trace gas analysis, with potential applications in environmental monitoring, industrial safety, security screening, and medical diagnostics. This study confirms the advantages of gas-phase MEES over many traditional optical spectroscopic methods and demonstrates its potential in direct gas-trace sensing in ambient atmosphere.

SERS Detection of Trace Carcinogenic Aromatic Amines Based on Amorphous MoO3 Monolayers.

Aromatic amines are important commercial chemicals, but their carcinogenicity poses a threat to humans and other organisms, making their rapid quantitative detection increasingly urgent. Here, amorphous MoO3 (a-MoO3) monolayers with localized surface plasmon resonance (LSPR) effect in the visible region are designed for the trace detection of carcinogenic aromatic amine molecules. The hot-electron fast decay component of a-MoO3 decreases from 301 fs to 150 fs after absorption with methyl orange (MO) molecules, indicating the plasmon-induced hot-electron transfer (PIHET) process from a-MoO3 to MO. Therefore, a-MoO3 monolayers present high SERS performance due to the synergistic effect of electromagnetic enhancement (EM) and PIHET, proposing the EM-PIHET synergistic mechanism in a-MoO3. In addition, a-MoO3 possesses higher electron delocalization and electronic state density than crystal MoO3 (c-MoO3), which is conducive to the PIHET. The limit of detection (LOD) for o-aminoazotoluene (o-AAT) is 10-9 M with good uniformity, acid resistance, and thermal stability. In this work, trace detection and identification of various carcinogenic aromatic amines based on a-MoO3 monolayers is realized, which is of great significance for reducing cancer infection rates.

Functionalized MoS2: circular economy SERS substrate for label-free detection of bilirubin in clinical diagnosis.

A one-pot hydrothermal synthesis of Fe-doped MoS2 nanoflowers (Fe-MoS2 NFs) has been developed as a surface-enhanced Raman spectroscopy (SERS) substrate. The Fe-MoS2 NFs display high reproducibility, stability, and recyclability, which is beneficial for the development of the sustainable ecological environment. The SERS substrate provides a high enhancement factor of 105, which can be ascribed to the inducing defects by doping Fe that can improve the charge transfer between probe molecules and MoS2. The Fe-MoS2 NFs have been used to detect bilirubin in serum. The Fe-MoS2 NF SERS substrate exhibits a linear detection range from 10-3 to 10-9 M with a low limit of detection (LOD) of 10-8 M. The substrate displays an excellent selectivity to bilirubin in the presence of other potentially interfering molecules (dextrose and phosphate). These results provide a novel concept to synthesize ultra-sensitive SERS substrates and open up a wide range of possibilities for new applications of MoS2 in clinical diagnosis.

High-Precision Trace Hydrogen Sensing by Multipass Raman Scattering.

Despite its growing importance in the energy generation and storage industry, the detection of hydrogen in trace concentrations remains challenging, as established optical absorption methods are ineffective in probing homonuclear diatomics. Besides indirect detection approaches using, e.g., chemically sensitized microdevices, Raman scattering has shown promise as an alternative direct method of unambiguous hydrogen chemical fingerprinting. We investigated the suitability of feedback-assisted multipass spontaneous Raman scattering for this task and examined the precision with which hydrogen can be sensed at concentrations below 2 parts per million. A limit of detection of 60, 30, and 20 parts per billion was obtained at a pressure of 0.2 MPa in a 10-min-long, 120-min-long, and 720-min-long measurement, respectively, with the lowest concentration probed being 75 parts per billion. Various methods of signal extraction were compared, including asymmetric multi-peak fitting, which allowed the resolution of concentration steps of 50 parts per billion, determining the ambient air hydrogen concentration with an uncertainty level of 20 parts per billion.

High-Quality Conjugated Polymers Achieving Ultra-Trace Detection of Cr2O72- in Agricultural Products.

In view of that conjugated polymers (CPs) are an attractive option for constructing high-sensitive Cr2O72- sensors but suffer from lacking a general design strategy, we first proposed a rational structure design of CPs to tailor their sensing properties while validating the structure-to-performance correlation. Short side chains decorated with N and O atoms as recognition groups were instructed into fluorene to obtain monomers Fmoc-Ala-OH and Fmoc-Thr-OH. Additionally, their polymers P(Fmoc-Ala-OH) and P(Fmoc-Thr-OH) were obtained through electrochemical polymerization. P(Fmoc-Ala-OH) and P(Fmoc-Thr-OH) with high polymerization degrees have an excellent selectivity towards Cr2O72- in comparison to other cations and anions. Additionally, their limit of detection could achieve 1.98 fM and 3.72 fM, respectively. Especially, they could realize the trace detection of Cr2O72- in agricultural products (red bean, black bean, and millet). All these results indicate that short side chains decorated with N and O atoms functionalizing polyfluorene enables the ultra-trace detection of Cr2O72-. Additionally, the design strategy will spark new ideas for the construction of highly selective and sensitive Cr2O72- sensors.

One-step preparation of red-emitting carbon dots for visual and quantitative detection of copper ions.

A one-step solvothermal method for the preparation of carbon dots with red fluorescence (R-CDs) was put forward, in which sodium citrate and formamide were chosen as precursors, while formamide was adopted as the solvent. The fluorescence emission peak of the as-prepared R-CDs remained the same (600 nm) when the excitation wavelength increased from 490 nm to 560 nm, and the fluorescence quantum yield is 35.3%. Furthermore, the fluorescence intensity of the as-prepared R-CDs could be selectively quenched by copper ions, and the mechanism of Cu2+ quenching R-CDs is the combination of static and dynamic quenching. As a result, the R-CDs were applied for the construction of a fluorescent sensor without any modification for the quantitative and visual detection of copper ions, which is a typical contaminant in water. The limit of detection for the fluorescent sensor was as low as 5 nmol/L, and it can be used to fast and directly confirm whether the content of copper ions in drinking water meets the criteria of the United States Environmental Protection Agency and the World Health Organization.

Fast Sensing of Hydrogen Cyanide (HCN) Vapors Using a Hand-Held Ion Mobility Spectrometer with Nonradioactive Ionization Source.

Sensitive real-time detection of vapors produced by toxic industrial chemicals (TICs) always represents a stringent priority. Hydrogen cyanide (HCN) is definitely a TIC, being widely used in various industries and as an insecticide; it is a reactive, very flammable, and highly toxic compound that affects the central nervous system, cardiovascular system, eyes, nose, throat, and also has systemic effects. Moreover, HCN is considered a blood chemical warfare agent. This study was focused toward quick detection and quantification of HCN in air using time-of-flight ion mobility spectrometry (ToF IMS). Results obtained clearly indicate that IMS can rapidly detect HCN at sub-ppmv levels in air. Ion mobility spectrometric response was obtained in the negative ion mode and presented one single distinct product ion, at reduced ion mobility K0 of 2.38 cm2 V-1 s-1. Our study demonstrated that by using a miniaturized commercial IMS system with nonradioactive ionization source model LCD-3.2E (Smiths Detection Ltd., London, UK), one can easily measure HCN at concentrations of 0.1 ppmv (0.11 mg m-3) in negative ion mode, which is far below the OSHA PEL-TWA value of 10 ppmv. Measurement range was from 0.1 to 10 ppmv and the estimated limit of detection LoD was ca. 20 ppbv (0.02 mg m-3).

In situ synthesis of graphene oxide/gold nanocomposites as ultrasensitive surface-enhanced Raman scattering substrates for clenbuterol detection.

A highly sensitive approach to detect trace amount of clenbuterol (CB) based on graphene oxide/gold nanoparticles (GO/Au NPs) by surface-enhanced Raman spectroscopy (SERS) was presented. To be specific, the GO/Au nanocomposites were formed by depositing Au NPs onto the surface of GO through an in situ reduction process, where a high density of inherent hot spots was created between Au NPs. By optimizing the depositing density of Au NPs, the strongest electromagnetic coupling effect originating from highly dense hot spots was obtained. The optimized GO/Au was demonstrated to enhance the Raman signals of CB by 4.8 times more than that of CB enhanced by Au NPs. Moreover, GO/Au nanocomposites exhibit good biocompatibility and accessible surface for high adsorption of target molecules through the pi-pi stacking with graphene oxide. Hence, the proposed GO/Au nanocomposites were utilized to capture aromatic molecules like CB and served as excellent sensitive SERS-active substrates for sensing of it, which exhibited an excellent linear performance in the range of 5 × 10-8 to 1 × 10-6 mol/L with a limit of detection (LOD) of 3.34 × 10-8 mol/L (S/N = 3). Due to high-density hot spots with easy operation, this proposed GO/Au nanocomposite-based SERS technique holds great potential in the application of food safety analysis and biomedical science.

Preparation and application of a novel magnetic molecularly imprinted polymer for simultaneous and rapid determination of three trace endocrine disrupting chemicals in lake water and milk samples.

Exposure to endocrine disruptor substances will alter the function of the endocrine system and then cause adverse effects on human health. Among these endocrine disrupting chemicals, hexestrol, nonylphenol, and bisphenol A are most commonly used worldwide. In this study, we aim to develop a simple, rapid, and efficient analytical method for the simultaneous determination of trace hexestrol, nonylphenol, and bisphenol A in lake water and milk samples. A magnetic molecularly imprinted polymer-assisted magnetic solid-phase extraction technique was applied. The magnetic molecularly imprinted polymer was prepared and characterized by electron scanning microscopy and Fourier transform infrared spectroscopy. Subsequently, different experiments were conducted to optimize the magnetic solid-phase extraction conditions. High-performance liquid chromatography with UV detection was employed to determine hexestrol, nonylphenol, and bisphenol A. Limits of detection of the developed method were from 0.1 to 0.3 µg L-1 and spiked recoveries ranged from 89.9 to 102.5%, with a relative standard deviation of < 2.5% (intraday). Results obtained from this study showed that the proposed magnetic solid-phase extraction method was a simple, rapid, and sensitive sample pre-treatment method for the determination of trace hexestrol, nonylphenol, and bisphenol in different aqueous samples.

Photoacoustic trace detection of gases at the parts-per-quadrillion level with a moving optical grating.

The amplitude of the photoacoustic effect for an optical source moving at the sound speed in a one-dimensional geometry increases linearly in time without bound in the linear acoustic regime. Here, use of this principle is described for trace detection of gases, using two frequency-shifted beams from a CO2 laser directed at an angle to each other to give optical fringes that move at the sound speed in a cavity with a longitudinal resonance. The photoacoustic signal is detected with a high-[Formula: see text], piezoelectric crystal with a resonance on the order of [Formula: see text] kHz. The photoacoustic cell has a design analogous to a hemispherical laser resonator and can be adjusted to have a longitudinal resonance to match that of the detector crystal. The grating frequency, the length of the resonator, and the crystal must all have matched frequencies; thus, three resonances are used to advantage to produce sensitivity that extends to the parts-per-quadrillion level.

Sensing Precursors of Illegal Drugs-Rapid Detection of Acetic Anhydride Vapors at Trace Levels Using Photoionization Detection and Ion Mobility Spectrometry.

Sensitive real-time detection of vapors produced by the precursors, reagents and solvents used in the illegal drugs manufacture represents a priority nowadays. Acetic anhydride (AA) is the key chemical used as acetylation agent in producing the illegal drugs heroin and methaqualone. This study was directed towards quick detection and quantification of AA in air, using two fast and very sensitive analytical techniques: photoionization detection (PID) and ion mobility spectrometry (IMS). Results obtained indicated that both PID and IMS can sense AA at ultra-trace levels in air, but while PID produces a non-selective response, IMS offers richer information. Ion mobility spectrometric response in the positive ion mode presented one product ion, at reduced ion mobility K0 of 1.89 cm2 V-1 s-1 (almost overlapped with positive reactant ion peak), while in the negative ion mode two well separated product ions, with K0 of 1.90 and 1.71 cm2 V-1 s-1, were noticed. Our study showed that by using a portable, commercial IMS system (model Mini IMS, I.U.T. GmbH Berlin) AA can be easily measured at concentrations of 0.05 ppmv (0.2 mg m-3) in negative ion mode. Best selectivity and sensitivity of the IMS response were therefore achieved in the negative operation mode.

Rapid determination of antiviral medication ribavirin in different feedstuffs using a novel magnetic molecularly imprinted polymer coupled with high-performance liquid chromatography.

A novel magnetic molecularly imprinted polymer adsorbing material was successfully synthesized to detect ribavirin in animal feedstuff. Molecularly imprinted polymer was prepared through surface polymerization by using ribavirin as template molecule, methyl methacrylate, and γ-methacryloxypropyl trimethoxy silane functionalized magnetic mesoporous silica as bifunctional monomers, and ethylene diglycidyl ether as crosslinking agent. The prepared magnetic molecularly imprinted polymer was characterized by scanning electron microscopy and infrared spectroscopy. Static and dynamic adsorption experiments and selective adsorption analysis were performed to evaluate the adsorption and selectivity of magnetic molecularly imprinted polymer. Different experiments were conducted to optimize the magnetic solid-phase extraction conditions. Under optimal experimental conditions, a magnetic molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography method was successfully developed for ribavirin detection. The established method achieved a satisfactory linear range of 0.20-50 mg/L (R2  > 0.99) and a low detection limit (0.081 mg/kg). An average recovery of 92-105% with relative standard deviation of <6.5% was obtained upon the application of the developed method to detect ribavirin in real feedstuff samples. Thus, established method can be used for the rapid and simple separation and detection of added ribavirin in feedstuff.

Preparation and application of a magnetic plasticizer as a molecularly imprinted polymer adsorbing material for the determination of phthalic acid esters in aqueous samples.

A novel magnetic plasticizer molecularly imprinted polymer adsorbing material (MIP@mSiO2 -ß-CD@Fe3 O4 ) was successfully synthesized for the determination of six phthalic acid esters in water, milk, and wine samples. The molecularly imprinted polymers were prepared via precipitation polymerization and a surface molecular imprinting technique, using a cyclodextrin-modified magnetic meso-porous material (mSiO2 -ß-CD@Fe3 O4 ) as a magnetic supporter, dibutyl phthalate and butyl benzyl phthalate as the dual template molecules, methacrylic acid as the functional monomer, and ethyleneglycol dimethacrylate as the cross-linking agent. The polymers were characterized by scanning electron microscopy, IR spectroscopy, and X-ray powder diffraction. Thermogravimetric analysis and static and dynamic adsorption experiments were carried out to assay its stability and selectivity. Under optimal experimental conditions, a magnetic solid-phase extraction with MIP@mSiO2 -ß-CD@Fe3 O4 coupled to gas chromatography and mass spectrometry method was successfully developed for the determination of phthalic acid esters. The established method achieved a good linear range of 0.10∼8.00 µg/mL (R > 0.99) and a low detection limit within the range of 1.0∼5.0 µg/L. An average recovery rate of 80.2∼103% with relative standard deviation < 6.7% was obtained upon the application of the developed method to detect phthalic acid esters in actual aqueous samples.

A Cu(II)-anchored unzipped covalent triazine framework with peroxidase-mimicking properties for molecular imprinting-based electrochemiluminescent detection of sulfaquinoxaline.

The authors describe a method of electrochemiluminescent quantitation of the antibiotic sulfaquinoxaline (SQX). It relies on the use of a molecularly imprinted polymer and a Cu(II)-anchored unzipped covalent triazine framework (UnZ-CCTF) with excellent dispersibility, electrical conductivity, and peroxidaze-like activity. The framework was prepared by unzipping a covalent triazine framework under retention of basic triazine units. It was morphologically and structurally characterized by a range of instrumental techniques. The excellent peroxidase-mimicking effect of UnZ-CCTF on the electrochemiluminescence of the luminol/H2O2 system was exploited to design an ultrasensitive SQX assay with a 1.0-20 pM detection range and a detection limit of 0.76 pM (at 3δ/m). The technique was used for SQX quantitation in spiked milk samples, achieving recoveries of 94.0-104.8%. Graphical abstract Scheme of the sulfaquinoxaline molecularly imprinted electrochemiluminescence sensor based on Cu-anchored unzipped covalent triazine frameworks.

Non-Destructive Trace Detection of Explosives Using Pushbroom Scanning Hyperspectral Imaging System.

The aim of this study was to investigate the potential of the non-destructive hyperspectral imaging system (HSI) and accuracy of the model developed using Support Vector Machine (SVM) for determining trace detection of explosives. Raman spectroscopy has been used in similar studies, but no study has been published which is based on measurement of reflectance from hyperspectral sensor for trace detection of explosives. HSI used in this study has an advantage over existing techniques due to its combination of imaging system and spectroscopy, along with being contactless and non-destructive in nature. Hyperspectral images of the chemical were collected using the BaySpec hyperspectral sensor which operated in the spectral range of 400⁻1000 nm (144 bands). Image processing was applied on the acquired hyperspectral image to select the region of interest (ROI) and to extract the spectral reflectance of the chemicals which were stored as spectral library. Principal Component Analysis (PCA) and first derivative was applied to reduce the high dimensionality of the image and to determine the optimal wavelengths between 400 and 1000 nm. In total, 22 out of 144 wavelengths were selected by analysing the loadings of principal components (PC). SVM was used to develop the classification model. SVM model established on the whole spectrum from 400 to 1000 nm achieved an accuracy of 81.11%, whereas an accuracy of 77.17% with less computational load was achieved when SVM model was established on the optimal wavelengths selected. The results of the study demonstrate that the hyperspectral imaging system along with SVM is a promising tool for trace detection of explosives.

The Trace Detection of Nitrite Ions Using Neutral Red Functionalized SH-ß-Cyclodextrin @Au Nanoparticles.

A novel fluorescence sensor of NR-ß-CD@AuNPs was prepared for the trace detection of nitrite in quantities as low as 4.25 × 10-3 µg∙mL-1 in an aqueous medium. The fluorescence was due to the host-guest inclusion complexes between neutral red (NR) molecules and gold nanoparticles (AuNPs), which were modified by per-6-mercapto-beta-cyclodextrins (SH-ß-CDs) as both a reducing agent and a stabilizer under microwave radiation. The color of the NR-ß-CD@AuNPs changed in the presence of nitrite ions. A sensor was applied to the determination of trace nitrites in environmental water samples with satisfactory results.

Research Progress of Raman Spectroscopy in Drug Analysis.

Raman spectroscopy is a spectroscopic analysis technique that enables rapid qualitative and quantitative detection based on inelastic collision and Raman scattering intensity. This review detailed the generation principle, instrument composition, influencing factors, and common classifications of Raman spectrum. Furthermore, it summarized and forecast the research progress of Raman spectroscopy in the field of drug analysis simultaneously over the past decade, including the identification of active pharmaceutical ingredients (APIs), qualitative and quantitative studies of pharmaceutical preparations, detection of illicit drugs, the identification of Chinese herbal medicines, and the combination with other technologies. The development of Raman spectroscopy in other fields is additionally summarized.

A Zinc Oxide Nanoflower-Based Electrochemical Sensor for Trace Detection of Sunset Yellow.

Zinc oxide nanoflower (ZnONF) was synthesized by a simple process and was used to construct a highly sensitive electrochemical sensor for the detection of sunset yellow (SY). Due to the large surface area and high accumulation efficiency of ZnONF, the ZnONF-modified carbon paste electrode (ZnONF/CPE) showed a strong enhancement effect on the electrochemical oxidation of SY. The electrochemical behaviors of SY were investigated using voltammetry with the ZnONF-based sensor. The optimized parameters included the amount of ZnONF, the accumulation time, and the pH value. Under optimal conditions, the oxidation peak current was linearly proportional to SY concentration in the range of 0.50-10 µg/L and 10-70 µg/L, while the detection limit was 0.10 µg/L (signal-to-noise ratio = 3). The proposed method was used to determine the amount of SY in soft drinks with recoveries of 97.5%-103%, and the results were in good agreement with the results obtained by high-performance liquid chromatography.

Chemical Selectivity and Sensitivity of a 16-Channel Electronic Nose for Trace Vapour Detection.

Good chemical selectivity of sensors for detecting vapour traces of targeted molecules is vital to reliable detection systems for explosives and other harmful materials. We present the design, construction and measurements of the electronic response of a 16 channel electronic nose based on 16 differential microcapacitors, which were surface-functionalized by different silanes. The e-nose detects less than 1 molecule of TNT out of 10+12 N2 molecules in a carrier gas in 1 s. Differently silanized sensors give different responses to different molecules. Electronic responses are presented for TNT, RDX, DNT, H2S, HCN, FeS, NH3, propane, methanol, acetone, ethanol, methane, toluene and water. We consider the number density of these molecules and find that silane surfaces show extreme affinity for attracting molecules of TNT, DNT and RDX. The probability to bind these molecules and form a surface-adsorbate is typically 10+7 times larger than the probability to bind water molecules, for example. We present a matrix of responses of differently functionalized microcapacitors and we propose that chemical selectivity of multichannel e-nose could be enhanced by using artificial intelligence deep learning methods.