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Mass spectrometry (MS) is a formidable analytical tool for the analysis of non-polar to polar compounds individually and/or from mixtures, providing information on the molecular weights and chemical structures of the analytes. During the last more than one-decade, ambient ionization mass spectrometry (AIMS) has developed quickly, producing a wide range of platforms and proving scientific improvements in a variety of domains, from biological imaging to quick quality control. These methods have made it possible to detect target analytes in real time without sample preparation in an open environment, and they can be connected to any MS system with an atmospheric pressure interface. They also have the ability to analyze explosives, illicit drugs, disease diagnostics, drugs in biological samples, adulterants in food and agricultural products, reaction progress, and environmental monitoring. The development of novel ambient ionization techniques, such as probe electrospray ionization, paper spray ionization, and fiber spray ionization, employed even at picolitre to femtolitre solution levels to provide femtogram to attogram levels of the target analytes. The special characteristic of this ambient ion source, which has been extensively used, is the noninvasive property of PESI of examination of biological real samples. The results in the current review supports the idea that AIMS has emerged as a pioneer in MS-based approaches and that methods will continue to be developed along with improvements to existing ones in the near future.

Mass spectrometry (MS) has become an essential analytical method in every sector of science and technology. Because of its unique ability to provide direct molecular structure information on analytes, an extra method is rarely required. This review describes fabrication of a variable-pressure hollow cathode discharge (HCD) ion source for MS in detection, quantification and investigation of gas-phase ion molecule reactions of explosives and related compounds using air as a carrier gas. The HCD ion source has been designed in such a way that by altering the ion source pressures, the system can generate both HCD and conventional GD. This design enables for the selective detection and quantification of explosives at trace to ultra-trace levels. The pressure-dependent HCD ion source has also been used to investigate ion-molecule reactions in the gas phase of explosives and related compounds. The mechanism of ion formation in explosive reactions is also discussed.

The urgent threat of new psychoactive substances worldwide promotes rapid detection and identification demand for public security. Ambient ionization mass spectrometry (AIMS) has become mainstream among various detection techniques. Still, scant successful applications have been fulfilled toward dried blood spot (DBS) or plasma spot (DPS) as an easy-to-implement sampling format in AIMS. This work bridged the gap between dielectric barrier discharge ionization mass spectrometry (DBDI-MS) and DPS/DBS samples by thermal desorption (TD) assistance. It made the impossible mission of direct DBDI-MS measurement on DPS/DBS samples containing fentanyl analogs (FTNs) possible. Guided by finite element simulations and a customized three-dimensional printing interface, we constructed a semi-covered flat-TD surface for sufficient desorption and ionization of FTNs from DPS/DBS samples without any sample pretreatment or sample separation. We successfully quantified eight FTNs in DPS samples using deuterated fentanyl as internal standard by triple quadrupole tandem mass spectrometry (MS/MS) and proved its practical applicability in the fentanyl-exposed rat plasma samples. This DBDI-TD-MS method also fits well with DBS samples, and it only took 20 s to analyze each sample. Further, based on summarized fragmentation characteristics of twenty FTNs, we established a backbone alerting ion-guided screening rule for suspect screening of FTNs in DPS samples

In this work, a disposable and inexpensive bamboo stir bar containing an organic membrane was constructed to perform stir bar sorptive extraction (SBSE), followed by portable mass spectrometry to achieve on-site detection of four residual drugs (malachite green, crystal violet and their metabolites) in fishes. The entire method uses only microliter quantities of organic solvents, enabling environmentally friendly pretreatment. The portable mass spectrometer can simultaneously detect four target analytes in a sample in approximately ten seconds. Under the optimal conditions, the proposed method was successfully applied to simultaneously detect four drugs in fish samples with detection limits of 0.16-0.59 µg/kg. The spiked recoveries for mandarin fish and lateolabrax maculatus were 74.5-96.5%, with relative standard deviations (RSD) of 4.4-16%. In addition, the matrix effects of the four analytical targets in the method were experimentally verified to range from 7.30% to 20.62%. The method can potentially be extended to the on-site detection of other veterinary drug residues in foods.

According to the Report of Drug Situation in China (2020), the growth rate of the number of drug abusers in China has decreased, but the number of drug abusers is still large. An efficient screening method is necessary for controlling drug abuse. As an important type of biological sample, urine is widely used for the rapid screening of drug addicts. However, because of the complex composition, low content, and strong interference from the body's metabolism, the detection of drugs in urine remains a challenge. Traditional rapid screening techniques such as immunocolloidal gold analysis have a high false positive rate and insufficient quantitative capability. In addition, laboratory mass spectrometry methods require complicated time-consuming sample pre-processing and strict environmental conditions, and hence, are unsuitable for on-site rapid analysis. In recent years, various direct ionization mass spectrometry techniques such as direct analysis in real time (DART), desorption electrospray ionization (DESI), and dielectric barrier discharge ionization (DBDI) have advanced rapidly. These techniques have been applied to public safety, food safety, environmental detection, etc. In contrast to traditional ionization mass spectrometry methods, these direct ionization techniques allow for the

Inspired by molecular self-assemblies in nature, this article reports a versatile strategy for confined encapsulation of single-atomic metal into high-quality rGO nanosheets by the microwave-assisted emulsion micelle method. Multilayer self-assembly of organometallics-surfactants micelles into the interlayer of nanosheets can not only promote microwave exfoliation and reduction of GO but also precisely control loading and distribution of single-metal atoms. With this synthetic strategy, the simultaneous trinity of exfoliation, reduction, and composition are achieved for 1 min. Experimental results and density functional theory calculations demonstrate that graphene-supported FeN

The controllable preparation of crystals is a prerequisite for exploring their shape-dependent physicochemical properties. Herein, AgCl crystals with different morphologies including octahedron, trapezohedron (TPH), 12-pod and hexapods with mace pods were successfully prepared by a one-pot synthesis method. In the preparation process, ethylene glycol (EG) was used as a solvent and AgNO3 was used as a precursor of Ag+. In particular, the ionic liquid poly(diallyldimethylammonium chloride) (PDDA) not only acted as a Cl− ion precursor but also as a morphology-controlled stabilizer. We further explored the effects of temperature, ligand and precursor concentration on AgCl crystal growth. Moreover, we investigated the effect of Cl− concentration on the morphology of AgCl by adding different amounts of NaCl. We found that under the condition of the lower concentrations of Cl−, {111}-bound octahedral AgCl crystals will transform into TPH enclosed with the {311} facet as the concentration of Cl− ions increases. However, at medium concentrations of Cl−, {111}-bound octahedral AgCl crystals will transform into 3D 12-pod AgCl crystals as the concentration of Cl− ions increases. Under the condition of higher concentrations of Cl−, {111}-bound octahedral AgCl crystals will transform into hexapods with mace pods AgCl crystals as the concentration of Cl− ions increases. According to the experimental results, we proposed the growth mechanism of AgCl microcrystals. This work not only provides a new method for the synthesis of AgCl crystals with a tunable shape, but also helps to understand the crystal growth mechanism.

In food safety monitoring, on-site and simultaneous detection of a variety of insecticides with different concentrations in the same matrix is necessary. However, the task remains challenging. In this study, a novel nitrogen and sulfur co-doped carbon dot (N, S-CD) was synthesized and used as a QuEChERS clean-up reagent to reduce matrix interferences in the determination of insecticides in vegetables. In addition, a portable mass spectrometer (µ-MS) was employed, without chromatography separation, to directly determine neonicotinoids, carbamates, and benzopyrazole insecticides (with acetamiprid, imidacloprid, thiamethoxam, fipronil, and carbofuran as models) in the pretreated samples. The N,S-CD µ-MS method exhibited effective clean-up performance with satisfactory matrix effects between -15.2% and 15.7%. The recoveries of spiked vegetable samples ranged from 82.2% to 109.7% for the five target insecticides, and the relative standard deviations (RSDs) ranged from 3.8% to 16.5%. The linear ranges were from 2.0 to 5.0 ng/g, with low detection limits (LOD) from 0.5 to 1.0 ng/g. Moreover, the total pretreatment and detection time was within 20 min. Thus, the incorporation of N,S-CD with QuEChERS extraction, together with the portable µ-MS system, could be a promising and feasible strategy for on-site, rapid, and simultaneous detection of various insecticides in vegetables.

Rapid detection of trace level amphetaminic drug compounds in urine is essential to monitor consumption of these abuse drugs by athletes. In this work, the amphetaminic drug compounds were spiked in human urine and analyzed using headspace – dielectric barrier discharge (DBD) ionization-mass spectrometry method. In the headspace method, the urine spiked drug compound was treated with alkali solution, thus the free base amphetaminic molecules were released into the gas phase. The gaseous molecules were then ionized by the DBD ion source placed in front of the mass spectrometer inlet under ambient condition. This method provided comparable sensitivity with the solid-phase microextraction (SPME) in analysis of the amphetaminic compounds where no derivatization or adduct formation was required. The present method also facilitated the sensitivity enhancement with about one order of magnitude in urine compared to standard solution. Carbonate alkali solution showed the highest sensitivity for detection of the drug compounds in urine and the sensitivity was enhanced by using NH3. The limits of detection (LODs) of the various amphetaminic molecules were found to be in the range of 0.10–0.80 ng/mL for standard solutions while those for urine were in the range of 0.04–0.40 ng/mL. The analytical figures of merit of this method were evaluated under ambient condition using suitable internal standard. Results suggested the suitability of this method for analytical routine work in detection of amine-based drugs in doping test and/or in forensic laboratories. A mechanism of enhanced sensitivity by the ammoniated carbonate alkali solution in urine is also discussed. Keywords: Amphetaminic drugs, Headspace method, Ambient mass spectrometry, Urine analysis, Enhanced sensitivity

Sulfanilamide is a common antibacterial drug that is used in clinical practice and in the industry. However, its abuse has emerged as a serious problem in the aquaculture industry, and more predominantly in the poultry industry, where it is administered for therapeutic purposes or as a growth promoter. In this study, a novel technical platform, heat-assisted desorption-dielectric barrier discharge ionization mass spectrometry (HAD-DBDI-MS), was used to detect sulfanilamide

ObjectiveThe increasing demand for unraveling cellular heterogeneity has boosted single cell metabolomics studies. However, current analytical methods are usually labor-intensive and hampered by lack of accuracy and efficiency. Methods: we developed a first-ever automated single cell mass spectrometry system (named SCMS) that facilitated the metabolic profiling of single cells. In particular, extremely small droplets of sub nano-liter were generated to extract the single cells, and the underlying mechanism was verified theoretically and experimentally. This was crucial to minimize the dilution of the trace cellular contents and enhance the analytical sensitivity. Based on the precise 3D positioning of the pipette tip, we established a visual servoing robotic micromanipulation platform on which single cells were sequentially extracted, aspirated, and ionized, followed by the mass spectrometry analyses. Results: With the SCMS system, inter-operator variability was eliminated and working efficiency was improved. The performance of the SCMS system was validated by the experiments on bladder cancer cells. MS and MS2 analyses of single cells enable us to identify several cellular metabolites and the underlying inter-cell heterogeneity. Conclusion: In contrast to traditional methods, the SCMS system functions without human intervention and realizes a robust single cell metabolic analysis. Significance: the SCMS system upgrades the way how single cell metabolites were analyzed, and has the potential to be a powerful tool for single cell metabolomics studies.

In this study, we have developed a variable pressure operating hollow cathode discharge (HCD) ion source to investigate the gas phase ion-molecule reactions of nitroaromatic explosive compounds. The developed HCD ion source coupled MS system has also been validated as an analytical method to analyze explosives at trace levels. The ion source was designed in such a way that the plasma can be generated alternatively at high pressure (~30 Torr), medium pressure (~5 Torr) and low pressure (~1 Torr) regions. The plasma contains a sufficient amount of reactant ions, electrons and excited species, thus the gaseous analyte molecules were efficiently ionized when they passed through the plasma. In the ion-molecule reactions of the nitroaromatic explosives, the discharge products of NOx− (x = 2,3), O3 and HNO3 originating from the plasma-excited air were suggested to contribute to the formation of mostly [M − H]-, [M − NO]-, [M+NO3–HNO2]- and [M-NO+HNO3]- adduct ions at the higher ion source pressures (~5 and 28 Torr) while the electron rich plasma leads to the formation of molecular ion, M−•, at the lower ion source pressure (~1 Torr). Formation of the hydride-adduct ions of the nitroaromatic compounds reveals the surface-assisted Birch type reduction in the HCD plasma. The variety of spectral patterns in the air-assisted glow discharge would be useful for high through-put detection of TNT and TNT-related explosives. An ambient helium dielectric barrier discharge (DBD) ion source was also used and gave identical mass spectra of the nitroaromatic explosive compounds to those observed by the HCD ion source, but did not give any hydride-adduct ions of the explosive compounds. Ion formation mechanism of these ions is also discussed.

Detection of explosives at trace levels is crucial for security purposes because of increasing worldwide terrorist threats at public places. Previously, a hollow cathode discharge (HCD) ion source has been fabricated for detection of explosives. Recently, the HCD ion source has been modified for a dual pressures operating system and coupled to a linear ion trap MS to analyze explosives simultaneously. Here, trinitrotoluene (TNT), nitroglycerin (NG), pentaerythritol tetranitrate (PETN) and 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) were taken as model explosive compounds and the mass spectra were recorded in the negative mode ionization. At the higher ion source pressure (~28.0–30.0 Torr), NG, PETN and RDX gave adduct ions with the NO3− ion while TNT showed the [TNT + NO3–HNO2]- (m/z 242) simultaneously. However, NG and PETN did not give any ion signals at the lower ion source pressure (~0.8–1.0 Torr) while TNT exhibited its molecular ion, [TNT]-• (m/z 227), as a major ion through electron attachment and RDX showed fragment ions that followed electron capture dissociation concurrently. The modified HCD ion source exhibited better sensitivity in simultaneous detection and quantification of the explosives. The NO3− and NO2− as reagent ions in the air HCD plasma form stable adduct ions with the NG, PETN and RDX even with TNT at the higher temperature (140–200 °C). The formation of the NO3−, NO2− in the HCD plasma also causes the formation of [TNT-H]- (m/z 226) at the higher ion source pressure. The inner metallic surface of the hollow tube assists the Birch reduction type reaction that results in the formation of hydride ion of the TNT, [TNT + H]- (m/z 228). No significant difference in the spectral pattern for simultaneous and individual measurements for the explosives was observed at the higher ion source pressure. Therefore, it may conclude that the present modified HCD ion source can be used for simultaneous detection and quantification of the explosive compounds at trace and/or ultra-trace levels using air as a carrier gas.

Variation within the C1QTNF6 gene at 22q12.3, the RAC2 gene at 22q13.1, and an intergenic region at 14q32.2 were found to be associated with risk to Graves' disease (GD) in a recent study. We aimed to validate these associations with GD in an independent sample set of Han Chinese population.We investigated these associations by genotyping the most significantly associated single nucleotide polymorphisms (SNPs) located in these three regions. Rs1456988 within the intergenic region at 14q32.2, rs229527 within C1QTNF6 at 22q12.3, and rs2284038 within RAC2 at 22q13.1 were selected for genotyping. These three SNPs were genotyped using a case-control study that included 2382 GD patients and 3092 unrelated healthy controls from Northern Han Chinese ancestry. The genotyping was performed using TaqMan assays on the ABI7900 platform.We found both the rs229527 allele within C1QTNF6 (odds ratio [OR] = 1.23, confidence interval [95% CI]: 1.12-1.33, pOur findings confirmed that chromosome 22q12.3 and 22q13.1 variants are associated with GD in an independent Han Chinese population; however, 14q32.2 showed no association with GD.

The online combination of surface plasmon resonance (SPR) with mass spectrometry (MS) could be beneficial for accurately acquiring molecular interaction data simultaneously with their structural information at high throughputs. In this work, a novel SPR-MS interface was developed using a dielectric barrier discharge ionization (DBDI) source. The DBDI source was placed in front of the MS inlet, generating an ionization plasma jet. A spray tip was set between the DBDI source outlet and the MS inlet, nebulizing the SPR sample solution. Using this interface, samples could first be studied by SPR, then sprayed and ionized, finally analyzed by MS. By analyzing model samples containing small-molecule drugs dissolved in salt containing solutions, the practicability of this SPR-DBDI-MS interface was proved, observing the consistent change of SPR and MS signals. Compared with our previously developed direct analysis in real time (DART) based SPR-MS interface, this new interface exhibited a higher and better tolerance to non-volatile salts, and different ionization capabilities for various samples. These results indicated that the interface could find further utilization in SPR-MS studies especially when physiological conditions were needed.

In this study, a rapid analytical method has been developed for the identification of nine representative perfluorinated carboxylic acids (PFCAs) in textiles using dielectric barrier discharge ionization (DBDI) coupled with a benchtop ion trap mass spectrometer. Key parameters affecting DBDI efficiency, including ion source temperature, gas flow rate, and horizontal distance between the DBDI outlet and ceramic tube inlet, were systematically optimized based on both single factor test and response surface methodology. The developed method allowed direct analysis of textiles bypassing conventional sample preparation and chromatographic separation. The applicability of the protocol was demonstrated through the analysis of 15 real textile samples of different fabrics.

The overlap factor is used to evaluate the LiDAR light collection ability. Ranging LiDAR is mainly determined by the optical configuration. However, scanning LiDAR, equipped with a scanning mechanism to acquire a 3D coordinate points cloud for a specified target, is essential in considering the scanning effect at the same time. Otherwise, scanning LiDAR will reduce the light collection ability and even cannot receive any echo. From this point of view, we propose a scanning LiDAR overlap factor calculation method based on the tridimensional ray-tracing method, which can be applied to scanning LiDAR with any special laser intensity distribution, any type of telescope (reflector, refractor, or mixed), and any shape obstruction (i.e., the reflector of a coaxial optical system). A case study for our LiDAR with a scanning mirror is carried out, and a MATLAB program is written to analyze the laser emission and reception process. Sensitivity analysis is carried out as a function of scanning mirror rotation speed and detector position, and the results guide how to optimize the overlap factor for our LiDAR. The results of this research will have a guiding significance in scanning LiDAR design and assembly.

The online combination of capillary electrophoresis (CE) with mass spectrometry (MS) has long been desired for the capability of direct and simultaneous separation and detection with high efficiency, accuracy, and throughput. In this work, a novel CE-MS interface was developed, using dielectric barrier discharge ionization (DBDI). The interface employed a spray tip with a coaxial three-layer structure, into which the CE sample solution, the sheath liquid, and the nebulizing gas were introduced. The spray tip was put between the DBDI outlet and the MS inlet, thus the CE sample solution could be blended with the sheath liquid, then nebulized. The nebulized sample could be ionized by DBDI, and finally analyzed by MS. The key parameters of the interface were optimized. Then, proof-of-concept experiments separating and detecting the mixture of metronidazole and acetaminophen solutions were conducted. The results showed high separation efficiency, low time consumption, high reproducibility, and convenience in operation. In addition, the interface exhibited a high tolerance of non-volatile salts and surfactants, which would be widely used in CE analyses. All of these results demonstrated that the newly developed CE-DBDI-MS interface could be successfully used in CE-MS studies, and could be further utilized in multiple areas involving efficient separation and detection.

The trace H 2 S in range of 0-20ppm has been measured by means of off-axis integrated cavity output spectroscopy (OA-ICOS) technology combined with tunable diode laser absorption spectroscopy (TDLAS) technology. The instrument uses off-axis alignment geometry to eliminate the problem of mode matching between laser and optical resonant cavity, in absenting the piezoelectric transducer. Combined with the high sensitivity of the TDLAS technology, sensitivity of the instrument is improved. The repeatability of instrument in H 2 S measurement achieves to 0.303ppm (3σ), linearity less than ±1% F.S., which meet the requirement of trace H 2 S measurement in petrochemical or natural gas industry.

Diode laser absorption spectroscopy (DLAS) has become an important analytical technique for highly sensitive and specific gas concentration measurements as it is reliable, fast and accurate. In this work a diode laser sensor has been developed to monitor ammonia at sub-ppm in 1510-nm region. The system was designed to control the de-nitrification process with selective catalytic reduction (SCR) abatement system. To ensure that NOx is reacted completely and to avoid secondary pollution resulted from ammonia slip, it is essential to monitor emissions of ammonia for controlling the amount of NH 3 injection. NH 3 concentration is demanded not to exceed 5ppm, preferably 2-3ppm. In order to provide enough sensitivity, the sensor uses DLAS with wavelength modulation as AC detection of absorption line derivatives, at frequencies where the laser noise is reduced, coupled with coherent electronic detection techniques. Experiment results demonstrate that the sensor with the second-harmonic detection shows in-situ, continuous measurements with low detection limit (60 ppb), fast response (