Chemical Detection Research Articles

Development of a Rapid and Accurate Vapor Generation System for Real-Time Monitoring of a Chemical Warfare Agent (CWA) by Coupling Fourier Transform Infrared (FT-IR) Spectroscopy.

Developing an accurate chemical warfare agent (CWA) vapor generator is critical for homeland security because it enables real-time monitoring of target agent concentration for testing and evaluation. We designed and built an elaborate CWA vapor generator that offers reliable long-term stability and real-time monitoring capabilities by coupling it with Fourier transform infrared (FT-IR) spectroscopy. We evaluated the reliability and stability of the vapor generator using a gas chromatography-flame ion detector (GC-FID) and conducted a comparison between the experimental and theoretical results of sulfur mustard (HD, bis-2-chloroethylsulfide), a real CWA, at concentrations ranging from 1 to 5 ppm. Our FT-IR-coupled vapor generation system showed real-time monitoring ability, which enables rapid and accurate evaluation of chemical detectors. The vapor generation system was able to generate CWA vapor continuously for over 8 h, demonstrating its long-term vapor generation capability. In addition, we vaporized another representative CWA, viz., GB (Sarin, propan-2-yl ethylphosphonofluoridate), and conducted real-time monitoring of GB vapor concentration with high accuracy. This versatile vapor generator approach can enable the rapid and accurate evaluation of CWAs for homeland security against chemical threats and can be used in constructing a versatile real-time monitoring vapor generation system for CWAs.

13C Radiofrequency Amplification by Stimulated Emission of Radiation Threshold Sensing of Chemical Reactions.

Conventional nuclear magnetic resonance (NMR) enables detection of chemicals and their transformations by exciting nuclear spin ensembles with a radio-frequency pulse followed by detection of the precessing spins at their characteristic frequencies. The detected frequencies report on chemical reactions in real time and the signal amplitudes scale with concentrations of products and reactants. Here, we employ Radiofrequency Amplification by Stimulated Emission of Radiation (RASER), a quantum phenomenon producing coherent emission of 13C signals, to detect chemical transformations. The 13C signals are emitted by the negatively hyperpolarized biomolecules without external radio frequency pulses and without any background signal from other, nonhyperpolarized spins in the ensemble. Here, we studied the hydrolysis of hyperpolarized ethyl-[1-13C]acetate to hyperpolarized [1-13C]acetate, which was analyzed as a model system by conventional NMR and 13C RASER. The chemical transformation of 13C RASER-active species leads to complete and abrupt disappearance of reactant signals and delayed, abrupt reappearance of a frequency-shifted RASER signal without destroying 13C polarization. The experimentally observed "quantum" RASER threshold is supported by simulations.

Identification of antimicrobial and glucocorticoid compounds in wastewater effluents with effect-directed analysis

Pharmaceuticals, such as glucocorticoids and antibiotics, are inadequately removed from wastewater and may cause unwanted toxic effects in the receiving environment. This study aimed to identify contaminants of emerging concern in wastewater effluent with antimicrobial or glucocorticoid activity by applying effect-directed analysis (EDA). Effluent samples from six wastewater treatment plants (WWTPs) in the Netherlands were collected and analyzed with unfractionated and fractionated bioassay testing. Per sample, 80 fractions were collected and in parallel high-resolution mass spectrometry (HRMS) data were recorded for suspect and nontarget screening. The antimicrobial activity of the effluents was determined with an antibiotics assay and ranged from 298 to 711 ng azithromycin equivalents·L−1. Macrolide antibiotics were identified in each effluent and found to significantly contribute to the antimicrobial activity of each sample. Agonistic glucocorticoid activity determined with the GR-CALUX assay ranged from 98.1 to 286 ng dexamethasone equivalents·L−1. Bioassay testing of several tentatively identified compounds to confirm their activity revealed inactivity in the assay or the incorrect identification of a feature. Effluent concentrations of glucocorticoid active compounds were estimated from the fractionated GR-CALUX bioassay response. Subsequently, the biological and chemical detection limits were compared and a sensitivity gap between the two monitoring approaches was identified. Overall, these results emphasize that combining sensitive effect-based testing with chemical analysis can more accurately reflect environmental exposure and risk than chemical analysis alone.

A specific SNP-based multiplex PCR assay for the simultaneous identification of two biological ingredients for the Chinese patent medicine, Danggui Buxue pill.

Background: An increasing number of Chinese patent medicines (CPM) have been widely used in East Asian and North American countries, and the safety and efficacy of CPM have highly attracted public attention. However, it is difficult to supervise the authenticity of multiple biological ingredients within CPM based on microscopic inspection and physical and chemical detection. The raw materials may have similar characteristics of tissue structures and ergastic substances or similar chemical composition and contents when substitutes and/or adulterants are added. DNA molecular markers have been used to distinguish the biological ingredients within CPM based on conventional PCR assay. However, it was proved to be time- and labor-consuming and reagent-wasting, as multiple PCR amplification strategies were required for identifying the complex species composition within CPM. Here, we took the CPM (Danggui Buxue pill) as an example and aimed to establish a specific SNP-based multiplex PCR assay and simultaneously determine the authenticity of the two biological ingredients (Angelicae Sinensis Radix and Astragali Radix) within this CPM. Methods: We, respectively, designed the species-specific primers based on highly variable nrITS for discriminating Angelicae Sinensis Radix and Astragali Radix from their common substitutes and adulterants. The specificity of the primers was checked through conventional PCR assay and multiplex PCR assay. Furthermore, we used a handcrafted Danggui Buxue pill sample (DGBXP) to optimize annealing temperatures for the primers with multiplex PCR, and the sensitivity was also assessed. Finally, fourteen batches of commercial Danggui Buxue pills were used to verify the stability and practicability of the established multiplex PCR assay. Results: Two pairs of highly species-specific primers for amplifying Angelicae Sinensis Radix and Astragali Radix were screened, and our established multiplex PCR assay showed high specificity and sensitivity (lowest detection concentration: 4.0 × 10-3ng/μL) at an optimal annealing temperature of 65°C. The method could simultaneously identify both biological ingredients within the Danggui Buxue pill. Conclusion: The specific SNP-based multiplex PCR provided a simple, time-, and labor-saving method for the simultaneous identification of the two biological ingredients within Danggui Buxue pills. This study was expected to provide a novel qualitative quality control strategy for CPM.

Development of Taper-in-Taper-Based Optical Fiber Sensors for Chemical and Biological Sensing

This paper presents the development of taper-in-taper fiber (TITF)–optical fiber-based sensors for chemical and biological detection. TITF structure is a fiber structure formed by fabricating a taper again on the taper region of the traditional taper fiber. The experimental results show that the TITF structure has a lower transmitted intensity than the common taper fiber structure. It is demonstrated that the structure of TITF is more conducive to evanescent waves, thereby making it more sensitive to changes in the refractive index (RI) of the external environment. To confirm this, measurements of ethanol solutions with different water contents are taken using the TITF structure to showcase the chemical sensing, thus verifying its sensitivity to RI changes in the external environment. The sensor can measure ethanol solutions from 0 to 100% with a sensitivity of 4.06 a.u./%. Thereafter, the TITF sensor is modified with ZnO-NPs to enhance its sensitivity for biological sensing (creatinine detection). The transmitted intensity of different concentrations of creatinine solution (0–2000 μM) is measured using the proposed sensor. The sensor showed good linearity and a high sensitivity of 0.11 a.u./μM for creatinine solution. Therefore, it is demonstrated that the TITF sensor with ZnO-NPs can be used for effective biological sensing.

Strong coupling of localized surface plasmons and intermolecular vibration mode at terahertz frequencies

Organic molecular vibrations, typically occurring in the terahertz (THz) regime, can resonate with a metastructure. A hallmark Rabi splitting occurs when the coupling strength is sufficiently strong. In this work, we observe the strong coupling of localized surface plasmons (LSPs) and intermolecular vibration mode at THz on a metasurface spin-coated with organic molecule α-lactose monohydrate. Excited by transverse-electric THz waves, dispersive localized surface plasmons interact with nondispersive intermolecular vibrations and form two vibro-polariton modes. The angle-resolved transmission spectra of the coupled system are detected by using a terahertz time-domain spectrometer, demonstrating an anti-crossing effect with a clear Rabi splitting. By retrieving the coupling strength and Hopfield coefficients of polariton bands from the measured data, we further verify that these two bands originate from the strong coupling between LSPs and molecular vibration mode. Moreover, we show that it is possible to implement molecular concentration sensing based on this strong coupling effect. This study demonstrates a unique approach to investigate vibro-polaritons at the terahertz regime and provides a testbed for future applications of strong coupling effects in chemical detection and biosensing.

Chemical-imaging-guided optical manipulation of biomolecules.

Chemical imaging via advanced optical microscopy technologies has revealed remarkable details of biomolecules in living specimens. However, the ways to control chemical processes in biological samples remain preliminary. The lack of appropriate methods to spatially regulate chemical reactions in live cells in real-time prevents investigation of site-specific molecular behaviors and biological functions. Chemical- and site-specific control of biomolecules requires the detection of chemicals with high specificity and spatially precise modulation of chemical reactions. Laser-scanning optical microscopes offer great platforms for high-speed chemical detection. A closed-loop feedback control system, when paired with a laser scanning microscope, allows real-time precision opto-control (RPOC) of chemical processes for dynamic molecular targets in live cells. In this perspective, we briefly review recent advancements in chemical imaging based on laser scanning microscopy, summarize methods developed for precise optical manipulation, and highlight a recently developed RPOC technology. Furthermore, we discuss future directions of precision opto-control of biomolecules.

Detection of hazardous greenhouse gases and chemicals with topological edge state using periodically arranged cross-sections

This study investigates a sensitive chemical and hazardous greenhouse gas sensor using ternary phononic crystals composed of periodic tubes. The sensing mechanism depends on the localization of the topological edge state at the interface between phononic crystals. The impact of the structure’s geometry and concentration of a specific gas in air are discussed. Further, the effect of temperature on the position of topological edge state and the sensitivity of the proposed sensor will be studied. This model has shown good sensitivity of 1.58 Hz m−1 s and a figure of merit of 33.7 m−1 s to distinguish different chemical and hazardous greenhouse gas. Furthermore, the proposed detector is low-cost and simple because it does not require a complicated procedure to fabricate multilayers with different mechanical properties.

Electromagnetic Analysis of Water Spectra in Bulk and Film Forms at Terahertz Frequencies in a Modified Attenuated Total Reflection Configuration

Terahertz attenuated total reflectance (THz-ATR) is being extensively used for spectroscopy and imaging applications in materials science, chemistry, and biomedical research. One of the driving motivations is its potential for studying protein dynamics, identifying living tissues, or detecting herbicide traces, as a non-destructive and non-ionizing technique. It is well known that studying biological and chemical samples in the terahertz range represents a real challenge because of the presence of water, which is highly absorbing. In this work, we present experimental data from THz-ATR spectroscopy of water in the 1-15 THz frequency range and propose an insightful interpretation of the optical phenomenon that is taking place in this experiment, supported by finite-element-method simulations and an analytical model. Interestingly, this study reveals that there is no evanescent field at the interface between the ATR prism and water, but that a refracted beam is propagating through the water, independently from the value of the angle of incidence. These findings allowed an important improvement in the signal intensity after a simple modification of the accessory, by creating a thin film of micrometer thickness with a top mirror. We believe that this technique could lead to highly sensitive terahertz microfluidic systems for chemical and biomolecular detection.

Effect of tannin fruit extracts on Candida albicans yeast

Background: The results of the chemical detection showed that the active groups in the fruit extracts of the tannin plant contained glycosides, saponins, flavonoids, tannins, terpene and phenols.
 Aim: To evaluate Tannins inhibition activity against Candida albicans. 
 Materials and methods: A number of aqueous, alcoholic and acetone fruit extracts of Tannins were prepared, and their effect on inhibition of Candida albicans was tested. Four concentrations were used [10, 20, 30, 40 (mg / ml)].
 Results: The effect of tested extracts on yeast varied in terms of concentration and type of extract. The inhibition diameter was positively correlated to the increase in extract concentration. The results showed that the acetone extract was with a very high effectiveness and demonstrate higher inhibition effect against C. albicans, with an average inhibition diameter of 15.5 and 20 mm at a concentration of 10 and 20 mg / ml, respectively, while it was increased to reach 24.5 and 28 mm at a concentration 30 and 40 mg/ml, respectively. The alcoholic extract came in the second inhibition effect.
 Conclusion: The acetone extract shows a higher inhibitory activity than alcoholic and aqueous extracts. The interesting finding of this study was the inhibition against C. albicans was exhibited in the first 24 hours, while the nystatin inhibitory effect started in after 48 hours. The inhibition timing was vital as it lead to short course of treatment and less possibility for resistance induction

Application of Luminescent Bacteria Bioassay in the Detection of Pollutants in Soil

The luminescent bacteria bioassay has been commonly used in the detection of environmental pollutants. Compared with traditional chemical and other biological detection methods, the luminescent bacteria bioassay has many demonstrated advantages such as a sensitive response, low cost, high efficiency, and environmental friendliness. The traditional luminescent bacteria bioassay has poor reproducibility and cannot achieve undisturbed soil testing, and the use of leach liquor also affects the results. This paper reviews the research progress and existing issues for the traditional luminescent bacteria bioassay used in the detection of soil pollutants. The luminescence mechanisms and detection principles of three commonly used luminescent bacteria, i.e., Vibrio fischeri, Photobacterium phosphoreum, and Vibrio qinghaiensis, are discussed and compared. In addition, two new luminescent bacteria bioassays are introduced to detect soil pollutants. One method is based on recombinant luminescent bacteria obtained with a gene-modification technique. This method can realize specific detection and enhance sensitivity, but it still cannot achieve undisturbed soil detection. The other method involves using magnetic nanoparticle (MNP)-based biosensors made from luminescent bacteria and MNPs. It can realize the accurate detection of the biological toxicity of the combined pollutants in soil without disturbing the soil’s integrity. This study shows that MNP-based biosensors have good application prospects in soil pollution detection, but the mechanism behind their utility still needs to be investigated to realize their popularization and application.

Non-Destructive Detection of Different Pesticide Residues on the Surface of Hami Melon Classification Based on tHBA-ELM Algorithm and SWIR Hyperspectral Imaging.

In the field of safety detection of fruits and vegetables, how to conduct non-destructive detection of pesticide residues is still a pressing problem to be solved. In response to the high cost and destructive nature of existing chemical detection methods, this study explored the potential of identifying different pesticide residues on Hami melon by short-wave infrared (SWIR) (spectral range of 1000-2500 nm) hyperspectral imaging (HSI) technology combined with machine learning. Firstly, the classification effects of classical classification models, namely extreme learning machine (ELM), support vector machine (SVM), and partial least squares discriminant analysis (PLS-DA) on pesticide residues on Hami melon were compared, ELM was selected as the benchmark model for subsequent optimization. Then, the effects of different preprocessing treatments on ELM were compared and analyzed to determine the most suitable spectral preprocessing treatment. The ELM model optimized by Honey Badger Algorithm (HBA) with adaptive t-distribution mutation strategy (tHBA-ELM) was proposed to improve the detection accuracy for the detection of pesticide residues on Hami melon. The primitive HBA algorithm was optimized by using adaptive t-distribution, which improved the structure of the population and increased the convergence speed. Compared the classification results of tHBA-ELM with HBA-ELM and ELM model optimized by genetic algorithm (GA-ELM), the tHBA-ELM model can accurately identify whether there were pesticide residues and different types of pesticides. The accuracy, precision, sensitivity, and F1-score of the test set was 93.50%, 93.73%, 93.50%, and 0.9355, respectively. Metaheuristic optimization algorithms can improve the classification performance of classical machine learning classification models. Among all the models, the performance of tHBA-ELM was satisfactory. The results indicated that SWIR-HSI coupled with tHBA-ELM can be used for the non-destructive detection of pesticide residues on Hami melon, which provided the theoretical basis and technical reference for the detection of pesticide residues in other fruits and vegetables.

Enzymatic Electrochemical/Fluorescent Nanobiosensor for Detection of Small Chemicals.

The detection of small molecules has attracted enormous interest in various fields, including the chemical, biological, and healthcare fields. In order to achieve such detection with high accuracy, up to now, various types of biosensors have been developed. Among those biosensors, enzymatic biosensors have shown excellent sensing performances via their highly specific enzymatic reactions with small chemical molecules. As techniques used to implement the sensing function of such enzymatic biosensors, electrochemical and fluorescence techniques have been mostly used for the detection of small molecules because of their advantages. In addition, through the incorporation of nanotechnologies, the detection property of each technique-based enzymatic nanobiosensors can be improved to measure harmful or important small molecules accurately. This review provides interdisciplinary information related to developing enzymatic nanobiosensors for small molecule detection, such as widely used enzymes, target small molecules, and electrochemical/fluorescence techniques. We expect that this review will provide a broad perspective and well-organized roadmap to develop novel electrochemical and fluorescent enzymatic nanobiosensors.

All‐Polymer Fiber Organic Electrochemical Transistor for Chronic Chemical Detection in the Brain

AbstractContinuous and precise monitoring of chemicals in the brain can assist in understanding the working mechanism of the brain and exploring therapeutics for nerve disorders. Organic electrochemical transistors (OECTs) are employed for this purpose due to their high sensitivity from the in situ amplification effect. However, the chronic and stable detection of chemicals in the brain is rarely reported for OECTs. It is possibly due to the chronic inflammation from mechanical mismatch between the device and soft brain tissue as well as the biofouling that hinder the diffusion of chemicals to decrease the sensitivity similar to other implanted devices. Therefore, an all‐polymer fiber OECT (PF‐OECT) is designed, composed solely of conductive polymers and fluorine rubber. The PF‐OECT shows matching modulus with the soft brain tissue and good anti‐biofouling performance. It also demonstrates both high sensitivity and electrochemical stability under dynamic deformations and in complex protein solutions. Finally, the PF‐OECT is implanted into the mouse brain, achieving a stable 14‐day ascorbic acid monitoring. The design strategy of PF‐OECT presents a potential avenue for developing more biomedical devices.

Detection of Drug-Producing Chemicals Based on Gas Sensor Array With Dynamic Temperature Modulation

This paper aims to study how to use gas sensor array detection system to realize the remote contactless identification of drug-producing chemicals in the external environment. The dynamic temperature modulation method of semiconductor sensor array is used to prove the feasibility and practicality of the method. In this paper, the influence of heating period on sensor stability under rectangular wave heating condition is studied. The hardware system of gas sensor array is established, and the data is collected by the data acquisition system. In the simulated external environment, acetone, toluene, ether and 2-butanone are qualitative analysis and identification. The data are dimensionally reduced by principal component analysis (PCA) algorithm and combined with decision tree algorithm to identify the data dynamic temperature modulation and array, which provides a research direction for more accurate qualitative identification and quantitative analysis of drug-producing chemicals.

Enantioseparation/Recognition based on nano techniques/materials.

Enantiomers show different behaviors in interaction with the chiral environment. Due to their identical chemical structure and their wide application in various industries, such as agriculture, medicine, pesticide, food, and so forth, their separation is of great importance. Today, the term "nano" is frequently encountered in all fields. Technology and measuring devices are moving towards miniaturization, and the usage of nanomaterials in all sectors is expanding substantially. Given that scientists have recently attempted to apply miniaturized techniques known as nano-liquid chromatography/capillary-liquid chromatography, which were originally accomplished in 1988, as well as the widespread usage of nanomaterials for chiral resolution (back in 1989), this comprehensive study was developed. Searching the terms "nano" and "enantiomer separation" on scientific websites such as Scopus, Google Scholar, and Web of Science yields articles that either use miniaturized instruments or apply nanomaterials as chiral selectors with a variety of chemical and electrochemical detection techniques, which are discussed in this article.

High stability with low polarization and confinement loss based new structure of photonic crystal fiber waveguide profile

Abstract Nowadays ethanol is broadly used chemical item in various industrial purpose. So, detection of this organic chemical has become very important task in industrial basis. In this paper, a hexagonal core PCF has constructed in which silica is used as base material. A finite element method is applied and mesh analysis has been done for investigating boundary conditions of proposed PCF sensor. After simulation, 59.48 % sensitivity and an ignorable loss of confinement which is 8·956020 × 10−13 cm−1 at 2.5 THz frequency has been gained. Focusing on easy construction of fiber, conventional fabrication procedures are attainable. Having satisfactory waveguiding attributes, the proposed sensor can be applicable effectively for sensing ethanol and also polarization-based applications of terahertz waves.

Risk assessment based on dose-responsive and time-responsive genes to build PLS-DA models for exogenously induced lung injury

Xenobiotics can easily harm human lungs owing to the openness of the respiratory system. Identifying pulmonary toxicity remains challenging owing to several reasons: 1) no biomarkers for pulmonary toxicity are available that might help to detect lung injury; 2) traditional animal experiments are time-consuming; 3) traditional detection methods solely focus on poisoning accidents; 4) analytical chemistry methods hardly achieve universal detection. An in vitro testing system able to identify the pulmonary toxicity of contaminants from food, the environment, and drugs is urgently needed. Compounds are virtually infinite, whereas toxicological mechanisms are countable. Therefore, universal methods to identify and predict the risks of contaminants can be designed based on these well-known toxicity mechanisms. In this study, we established a dataset based on transcriptome sequencing of A549 cells upon treatment with different compounds. The representativeness of our dataset was analyzed using bioinformatics methods. Artificial intelligence methods, namely partial least squares discriminant analysis (PLS-DA) models, were employed for toxicity prediction and toxicant identification. The developed model predicted the pulmonary toxicity of compounds with a 92 % accuracy. These models were submitted to an external validation using highly heterogeneous compounds, which supported the accuracy and robustness of our developed methodology. This assay exhibits universal potential applications for water quality monitoring, crop pollution detection, food and drug safety evaluation, as well as chemical warfare agent detection.

Long-Term Flexible Neural Interface for Synchronous Recording of Cross-Regional Sensory Processing along the Olfactory Pathway.

Humans perceive the world through five senses, of which olfaction is the oldest evolutionary sense that enables the detection of chemicals in the external environment. Recent progress in bioinspired electronics has boosted the development of artificial sensory systems. Here, a biohybrid olfactory system is proposed by integrating living mammals with implantable flexible neural electrodes, to employ the outstanding properties of mammalian olfactory system. In olfactory perception, the peripheral organ-olfactory epithelium (OE) projects axons into the olfactory relay station-olfactory bulb (OB). The olfactory information encoded in the neural activity is recorded from both OE and OB simultaneously using flexible neural electrodes. Results reveal that spontaneous slow oscillations (<12Hz) in both OE and OB closely follow respiration. This respiration-locked rhythm modulates the amplitude of fast oscillations (>20Hz), which are associated with odor perception. Further, by extracting the characteristics of odor-evoked oscillatory signals, responses of different odors are identified and classified with 80% accuracy. This study demonstrates for the first time that the flexible electrode enables chronic stable electrophysiological recordings of the peripheral and central olfactory system in vivo. Overall, the method provides a novel neural interface for olfactory biosensing and cognitive processing.

Selective Detection of Toxic C1 Chemicals Using a Hydroxylamine-Based Chemiresistive Sensor Array.

Formaldehyde (FA) is a deleterious C1 pollutant commonly found in the interiors of modern buildings. C1 chemicals are generally more toxic than the corresponding C2 chemicals, but the selective discrimination of C1 and C2 chemicals using simple sensory systems is usually challenging. Here, we report the selective detection of FA vapor using a chemiresistive sensor array composed of modified hydroxylamine salts (MHAs, ArCH2ONH2·HCl) and single-walled carbon nanotubes (SWCNT). By screening 32 types of MHAs, we have identified an ideal sensor array that exhibits a characteristic response pattern for FA. Thus, trace FA (0.02-0.05 ppm in air) can be clearly discriminated from the corresponding C2 chemical, acetaldehyde (AA). This system has been extended to discriminate methanol (C1) from ethanol (C2) in combination with the catalytic conversion of these alcohols to their corresponding aldehydes. Our system offers portable and reliable chemical sensors that discriminate the subtle differences between C1 and C2 chemicals, enabling advanced environmental monitoring and healthcare applications.