Rapid Detection of Trace Organic Amines in Seawater: An Innovative Approach Using Photoelectron-Induced Chemical Ionization TOFMS with Online Derivatization and Dynamic Purging-Release Techniques.

Organic amines (OAs) have gained substantial interest in atmospheric chemistry due to their distinctive acid-base neutralization characteristics for secondary organic aerosols and new particle formation. To address the need for sensitive and online analysis of OAs, including dimethylamine (DMA), diethylamine (DEA), trimethylamine (TMA), and triethylamine (TEA), in seawater, a home-built photoelectron-induced chemical ionization TOFMS, coupled with online derivatization and dynamic purge-release apparatus, has been developed. Sodium hypochlorite is used to derivatize high-solubility DMA and DEA, substituting hydrogen atoms with chlorine atoms to obtain more volatile derivatives, [DMA-H + Cl] and [DEA-H + Cl]. Sodium carbonate is used to reduce the solubility of the OAs in solution to enhance detection sensitivity. Microbubbles generated from 250 to 300 mL/min of zero air at the gas-liquid interface efficiently transfer dissolved OAs into the gas phase. Water vapor in the purged gas is ionized by photoelectrons to form (H2O)n·H+, which ionizes OAs and their derivatives to produce characteristic ions [OAs + H]+ or [OAs-H + Cl]·H+ characteristic ion. After optimizing the experimental conditions, the limits of quantification (S/N = 10) of the four OAs including DMA, DEA, TMA, and TEA can be as low as 1.1 0.68, 0.85, and 0.49 nmol/L, respectively within a 5 min analysis time, using only 5 mL of seawater sample. This method enhances sensitivity by over 5-fold and reduces analysis time to 21.7%, respectively, compared with conventional methods. Subsequently, this method was successfully applied to quantify 15 seawater samples from 5 typical marine environments, which demonstrates its practicability and reliability for analysis of trace amines in seawater.

Emissions of Formamide and Ammonia from Foam Mats: Online Measurement Based on Dopant-Assisted Photoionization TOFMS and Assessment of Their Exposure for Children.

Formamide has been classified as a Class 1B reproductive toxicant to children by the European Union (EU) Chemicals Agency. Foam mats are a potential source of formamide and ammonia. Online dopant-assisted atmospheric pressure photoionization time-of-flight mass spectrometry (DA-APPI-TOFMS) coupled with a Teflon environmental chamber was developed to assess the exposure risk of formamide and ammonia from foam mats to children. High levels of formamide (average 3363.72 mg/m3) and ammonia (average 1586.78 mg/m3) emissions were measured from 21 foam mats with three different raw material types: ethylene-vinyl acetate (EVA: n = 7), polyethylene (PE: n = 7), and cross-linked polyethylene (XPE: n = 7). The 28 day emission testing for the selected PE mat showed that the emissions of formamide were 2 orders of magnitude higher than the EU emission limit of 20 µg/m3, and formamide may be a permanent indoor contaminant for foam mat products during their life cycle. The exposure assessment of children aged 0.5-6 years showed that the exposure dose was approximately hundreds of mg/kg-day, and the age group of 0.5-2 years was subject to much higher dermal exposures than others. Thus, this study provided key relevant information for further studies on assessing children's exposure to indoor air pollution from foam mats.

Development and Application of a Chemical Ionization Focusing Integrated Ionization Source TOFMS for Online Detection of OVOCs in the Atmosphere.

Single photon ionization (SPI) based on vacuum ultraviolet (VUV) lamps has been extensively investigated and applied due to its clean mass spectra as a soft ionization method. However, the photon energy of 10.6 eV and photon flux of 1011 photons s-1 of a commercial VUV lamp limits its range of ionizable analytes as well as its sensitivity. This work designs a chemical ionization focusing integrated (CIFI) ionization source time-of-flight mass spectrometry (TOFMS) based on a VUV lamp for the detection of volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs). The photoelectrons obtained from the VUV lamp via the photoelectric effect ionized the oxygen and water in the air to obtain the reagent ions. The ion-molecule-reaction region (IMR) is constituted by a segmented quadrupole that radially focuses the ions using a radio-frequency electric field. This significantly enhances the yield and transport efficiency of the product ions leading to a great improvement in sensitivity. As a result, a 44-fold and 1154-fold increase in the signal response for benzene and pentanal were achieved, respectively. To verify the reliability of the ionization source, the linear correspondence and repeatability of benzene and pentanal were investigated. Satisfactory dynamic linearity was obtained in the mixing ratio range of 5-50 ppbv, and the relative standard deviation (RSD) of inter-day reached 3.91% and 6.26%, respectively. Finally, the CIFI-TOFMS was applied to the determination of OVOCs, and the LOD of 12 types of OVOCs reached the pptv level, indicating that the ionization source has the potential for accurate and sensitive online monitoring of atmospheric OVOCs.

Point-of-care detection of sevoflurane anesthetics in exhaled breath using a miniature TOFMS for diagnosis of postoperative agitation symptoms in children.

In the operation using sevoflurane as an anesthetic, some patients, especially children, will have agitation symptoms after awakening from anesthesia. The incidence of agitation is about 20%, and current detection methods cannot predict the probability of a patient with agitation. In this paper, a magnetic field enhanced photoelectron ionization (MEPEI) miniature time-of-flight mass spectrometer (TOFMS) was developed for point-of-care detection and verification of the relationship between postoperative agitation symptoms and sevoflurane concentration in exhaled breath. The MEPEI source is water vapor resistant and can directly ionize sevoflurane via capillary sampling and obtain its characteristic ion [C4H3F6O]+ (m/z 181), and the analysis time of exhaled breath is only 60 s. Three standard curves of 0.5-80 ppmv, 80-2000 ppmv and 2000-15 000 ppmv were formulated to quantitatively detect sevoflurane in different scenarios, the coefficient of determination (R2) was higher than 0.9882 and the relative standard deviation (RSD) of signal intensity was only 1.24%. The results indicated that four of the 46 child patients had agitation symptoms. Partial least squares-discriminant analysis (PLS-DA) was performed to analyze the data, and an identification and treatment strategy was established for child patients with agitation symptoms. The new miniature MEPEI-TOFMS was also successfully used to evaluate the concentration of sevoflurane in a medical environment. The real-time monitoring of sevoflurane concentration in exhalation indicates the potential of this method for low-cost and convenient point-of-care (POC) detection and diagnosis of agitation symptoms.

On-site leakage locating of underground natural gas pipeline based on Ne tracer by miniature time-of-flight mass spectrometry.

Natural gas pipeline leakage seriously endangers people's lives and properties, and there is an urgent need for on-site, rapid, and accurate locating the leakage point of the underground natural gas pipeline. Here, we added neon gas to natural gas pipelines as a tracer gas, and used a miniature time-of-flight mass spectrometry (mini-TOFMS) to on-site detect neon gas to quickly locate the leak point of underground natural gas pipelines. The mini-TOFMS used capillary tube sampling to directly analyze the leaked neon gas without sample preparation, and the analysis time of a single sample was only 60 s, which was less than one-seventeenth that of traditional off-line gas chromatography (GC) method. The mini-TOFMS exhibited a linear response range from 69 ppmv to 3.0 × 105 ppmv with the limit of detection (LOD, S/N = 3) of 19.0 ppmv. The correlation of GC and mini-TOFMS for Ne quantitative analysis was as high as 0.98. The performance of the newly designed method with the mini-TOFMS was demonstrated by on-site locating the underground natural gas pipeline leakage point in the experimental station. And leakage point of the natural gas pipeline, especially for those pipelines with different gas pressure buried under the same road, can be found more efficiently and accurately.

Single-cell profiling reveals immune disturbances landscape and HLA-F-mediated immune tolerance at the maternal-fetal interface in preeclampsia.

Background: Preeclampsia is a pregnancy-specific disorder that always causes maternal and fetal serious adverse outcome. Disturbances in maternal immune tolerance to embryo at the maternal-fetal interface (MFI) may be associated with preeclampsia onset. Recent studies have revealed the reduced expression pattern of HLA-F at the MFI in preeclampsia, while the mechanism of it mediating maternal fetal immune tolerance has not been revealed. Methods: Single-cell RNA sequencing on placental decidua was performed to reveal the immune disturbances landscape at the MFI in preeclampsia. Human Jar cells and NK-92MI cells were employed to study the role of HLA-F in trophoblasts and lymphocyte. Results: A total of 101,250 cells were classified into 22 cell clusters. Disease-related IGFBP1+SPP1+ extracellular villus trophoblast (EVT) was identified in the preeclamptic placental decidua, accompanied by newly discovered immune cellular dysfunction such as reduced ribosomal functions of NK populations and abnormal expression of antigen-presenting molecules in most cell clusters. Certain genes that are characteristic of the intermediate stage of myeloid or EVT cell differentiation were found to have unexplored but important functions in the pathogenesis of preeclampsia; specifically, we detected enhanced cell cross-talk between IGFBP1+SPP1+ EVT2 or SPP1+M1 cells and their receptor cell populations at the MFI of PE patients compared to controls. With respect to HLA-F, mIF staining confirmed its reduced expression in PE samples compared to controls. Over-expression of HLA-F in Jar cells promoted cell proliferation, invasion, and migration while under-expression had the opposite effect. In NK-92MI cells, over-expression of HLA-F increased the secretion of immunoregulation cytokines such as CSF1 and CCL22, and promoted adaptive NKG2C+NK cell transformation. Conclusions: We revealed the immune disturbance landscape at the MFI in preeclampsia. Our findings regarding cellular heterogeneity and immune cellular dysfunction, as revealed by scRNA-seq, and the function of HLA-F in cells provide new perspectives for further investigation of their roles in the pathogenesis of preeclampsia, and then provide potential new therapeutic target.

A dopant-assisted iodide-adduct chemical ionization time-of-flight mass spectrometer based on VUV lamp photoionization for atmospheric low-molecular-weight organic acids analysis.

Formic and acetic acids are the most abundant gaseous organic acids and play the key role in the atmospheric chemistry. In iodine-adduct chemical ionization mass spectrometry (CIMS), the low utilization efficiency of methyl iodide and humidity interference are two major issues of the vacuum ultraviolet (VUV) lamp initiated CIMS for on-line gaseous formic and acetic acids analysis. In this work, we present a new CIMS based on VUV lamp, and the ion-molecular reactor is separated into photoionization and chemical ionization zones by a reducer electrode. Acetone was added to the photoionization zone, and the VUV photoionization acetone provided low-energy electrons for methyl iodide to generate I-, and the addition of acetone reduced the amount of methyl iodide by 2/3. In the chemical ionization zone, a headspace vial containing ultrapure water was added for humidity calibration, and the vial changes the sensitivity as a function of humidity from ambiguity to well linear correlation (R2 > 0.95). With humidity calibration, the CIMS can quantitatively measure formic and acetic acids in the humidity range of 0%-88% RH. In this mode, limits of detection of 10 and 50 pptv are obtained for formic and acetic acids, respectively. And the relative standard deviation (RSD) of quantitation stability for 6 days were less than 10.5%. This CIMS was successfully used to determine the formic and acetic acids in the underground parking and ambient environment of the Shandong University campus (Qingdao, China). In addition, we developed a simple model based formic acid concentration to assess vehicular emissions.