Prebiotic Formation of Peptides Through Bubbling and Arc Plasma.

The abiotic synthesis of peptides, widely regarded as one of the key chemical reactions on the prebiotic Earth, is thermodynamically constrained in solution. Herein, a simulation of the lightning phenomenon on the sea surface using bubble bursting and arc plasma under ambient conditions enables dipeptide formation of six amino acids with conversion ratios ranging from 2.6% to 25.5%. Additionally, we observed the formation of biologically active tripeptides and investigated the stereoselectivity of the dipeptide formation reaction. By utilizing a mixture of 20 amino acids in the reaction, 102 possible dipeptides were generated. These results establish experimental constructions to mimic achievable prebiotic conditions and provide a credible pathway for endogenous biopolymer synthesis on prebiotic Earth.

Long term online desalting analysis of MS/LC-MS using thermal assisted recrystallization ionization.

Mass spectrometric analysis of non-volatile salts containing samples remains challenging due to salt-induced ion suppression and contamination. This challenge is even more pronounced for a liquid chromatography-mass spectrometry analysis, where the accumulation of salts in the transmission system poses an ongoing problem. In this study, a novel thermal assisted recrystallization ionization mass spectrometry (TARI-MS) device was developed to achieve efficient on-line desalting and prolonged analysis of saline samples. The core component of this device was a heated plate positioned between the electrospray unit and the MS inlet. The desalting mechanism was demonstrated as the spontaneous separation of target molecules from salts during the "crystallization" process. After optimization, the angle between the nebulizer and the heated plate was 45°; the distance between the front end of the heated plate and the MS inlet was 2 mm; the distance between the front edge of the heated plate and the center of the sample spray projected onto the heating plate was 3 mm; the distance between the emitter of nebulizer and the heated plate was 3 mm. TARI-MS realized direct analysis of eight drugs dissolved in eight commonly used non-volatile salts solutions (up to 0.5 mol/L). The high sensitivity, repeatability, linearity, accuracy, and intra- and inter-day precision of TARI-MS confirm its reliability as a robust tool for the analysis of saline samples. Furthermore, TARI-MS allowed continuous analysis of salty eluates of LC for up to nearly 1 h without maintenance and verified the feasibility of LC-MS analysis through detecting a five-drug mixture and a crude aripiprazole product. Finally, six impurities in the crude aripiprazole product were successfully detected by LC-TARI-MS. The established method holds promise for applications across academic and pharmaceutical domains.

Ortho C-H Bond Activations in an Atmospheric Microwave Plasma Ion Source.

C-H bond ortho-substitution reaction has always been a significant and challenging topic in organic chemistry. We proposed a synthesis method based on microwave plasma torches. High-resolution mass spectrometry was used to monitor rapid reaction products. 2-Alkylbenzimidazole can be formed through the reaction of phenylnitrenium ion and nitriles on a millisecond scale. This reaction can achieve the one-step formation of benzimidazoles from benzene ring single-substituted compounds without the addition of external oxidants or catalysts. A similar C-H bond activation reaction can be accomplished with ketones. Meanwhile, the microwave plasma reactor was modified, and the resulting 2-methylbenzimidazole was successfully collected, indicating the device has good application potential in organic reactions such as C-H bond activation reaction.

Nonderivatized Method for the Detection of Perfluoroalkane Sulfonyl Fluorides by Liquid Chromatography-Microwave Plasma Torch Ionization Mass Spectrometry.

Per- and polyfluoroalkyl substances (PFAS) have caused widespread environmental concern in recent years. Among them, the levels of perfluoroalkane sulfonyl fluorides (PFASFs) in the environment have rarely been reported due to the lack of sensitive analytical methods. Herein, a novel liquid chromatography-microwave plasma torch ionization-mass spectrometry (LC-MPTI-MS) technique was designed for the direct analysis of PFASFs in the environment. The collaborative action of reactive oxygen species (such as hydroxyl radicals) and the elevated temperature within the ambient MPTI environment results in the replacement of the fluorine atom in sulfonyl fluoride by oxygen, leading to the detection of perfluoroalkanesulfonic acid (PFSA) ions by MS. Concurrently, LC was employed to separate other PFSAs that are present in the environment. Three PFASFs exhibited good linearity within the range of 1-500 µg/L with R2 > 0.994. The limit of detections (LODs) and the limit of quantifications (LOQs) were measured at 39.32-87.87 and 131.07-292.90 ng/L, respectively. The method was utilized for the direct detection of spiked perfluorooctane sulfonyl fluoride (PFOSF) in wastewater with recoveries of 77.16 to 124.81%. Our approach circumvents the laborious process of chemical derivatization and is anticipated to serve as a robust tool for determining the levels and behaviors of PFASFs in the environment.

Microstructured Gel Polymer Electrolyte and an Interdigital Electrode-Based Iontronic Barometric Pressure Sensor with High Resolution over a Broad Range.

We present a novel iontronic barometric pressure sensor based on a gel polymer electrolyte and interdigital electrodes with a much simpler structure than that of existing devices. By introducing high-density microstructures on the gel polymer electrolyte and one side electrode arrangement configuration, the developed sensor offers high performances with an ultrahigh resolution of 10 Pa, an ultrawide barometric pressure-response range from -92 to 7 kPa, a fast response time of ∼15 ms, and excellent long-term stability. The single pressure sensor is able to detect positive and negative barometric pressures without needing any additional means and can operate as a barometric altimeter with a resolution of about one-floor height. The performances of the sensors significantly surpass those of existing barometric pressure sensors. This work provides a new strategy for making high-performance barometric pressure sensors that are highly sought for commercial applications such as altitude detection, negative pressure ambulance, and consumer electronics.

Rapid analysis of pharmaceutical and personal care products by soft microwave-based plasma ionization-linear ion trap mass spectrometer (SMPI-LTQ) in natural water.

In this study, a soft microwave plasma torch (SMPT) combined with a mass spectrometer (MS) was used for the first time as an analytical method to detect and analyze various pharmaceutical and personal care products (PPCPs) in aquatic environments without the need for sample pretreatment. For this purpose, ambient SMPT was used to generate plasma for ionizing the analyte molecules. Accordingly, nine PPCPs were identified by the SMPT-MS, and their identification was verified by collision-induced dissociation (CID). The technique's performance was verified with known PPCP samples, and the limits of detection (LOD) and quantification (LOQ) obtained over a linear range of 50-1 µg/L were 1.56 to 2.81 and 2.07 to 3.62 µg/L, respectively, with the standard addition recovery rate falling between 87.14 and 115.16%. These results show that the method has excellent sensitivity and selectivity, suggesting that SMPT can rapidly and directly detect PPCPs in environmental water, making it a promising method for rapid water quality inspection.

Catalyst-Free Oxidation Reactions in a Microwave Plasma Torch-Based Ion/Molecular Reactor: An Approach for Predicting the Atmospheric Oxidation of Pollutants.

The atmospheric oxidation of chemicals has produced many new unpredicted pollutants. A microwave plasma torch-based ion/molecular reactor (MPTIR) interfacing an online mass spectrometer has been developed for creating and monitoring rapid oxidation reactions. Oxygen in the air is activated by the plasma into highly reactive oxygen radicals, thereby achieving oxidation of thioethers, alcohols, and various environmental pollutants on a millisecond scale without the addition of external oxidants or catalysts (6 orders of magnitude faster than bulk). The direct and real-time oxidation products of polycyclic aromatic hydrocarbons and p-phenylenediamines from the MPTIR match those of the long-term multistep environmental oxidative process. Meanwhile, two unreported environmental compounds were identified with an MPTIR and measured in the actual water samples, which demonstrates the considerable significance of the proposed device for both predicting the environmental pollutants (non-target screening) and studying the mechanism of atmospheric oxidative processes.

Heat-Assisted Dual Neutral Spray Ionization for High-Performance Online Desalting in Mass Spectrometric Analysis.

In mass spectrometry (MS), nonvolatile salts contaminate the transmission system and cause ion suppression, hampering MS analysis. When MS is combined with liquid chromatography (LC) that uses a salty mobile phase, the problems become more intractable due to long analysis time. Here, a novel heat-assisted dual neutral spray ionization (HADSI) method was developed, which projected sample solution spray and solvent spray onto a heated plate to achieve online desalting and high ionization. The experimental parameters of HADSI were optimized, which indicated that the plate temperature was crucial for ionization and desalination. Eight drug compounds dissolved in various commonly used buffers were directly analyzed using HADSI-MS, even though the concentration of PBS buffer reached 500 mmol/L. The established method showed considerable sensitivity in the positive ion mode with the limits of detection at the level of nmol/L, and good linearity (R2 > 0.99) was achieved for all the analyzed compounds. The repeatability and intra- and interday precisions of the method were evaluated, demonstrating the feasibility and reliability of the analysis of salty samples by HADSI-MS. Further, the method was demonstrated to tolerate the long-time analysis of high-salt LC eluates and the device was easy to maintain. Finally, a crude roxithromycin product was separated by LC and then analyzed by HADSI-MS, and seven unknown impurities and nine known impurities were successfully detected. Our results indicated that HADSI-MS may have potential applications in academic and industrial fields.

Multidimensional identification of disaccharide isomers based on non-covalent complexes and tandem mass spectrometry.

Glycans are the most abundant organic polymers in nature. They are essential to living organisms and regulate a wide range of biological functions. However, mass spectrometry-based identification of glycan isomers remains challenging due to the complexity of their structures including their complex compositions, linkages, and anomeric configurations. In this study, two novel complex ions, the mononuclear copper-bound dimeric ions [(Cu2+)(A)(L-His)-H]+ and the mononuclear copper-bound quaternary ions [(Cu2+)(A)(L-Ser)3-H]+ (where A denotes a disaccharide, and L-Ser/His denotes l-serine/histidine), were designed for the collision-induced dissociation-based identification and relative quantification of 14 disaccharide isomers. When the unique fragmentation patterns of the above two types of complex ions were mapped into a three-dimensional vector, all the isomers were completely distinguished. Of note, the established method is able to identify mixtures of linkage isomers only using tandem mass spectrometry based on linkage-specific fragment ions of histidine-based complex ions. Finally, the method was successfully applied to the identification and relative quantification of two disaccharide isomers (lactose and sucrose) in dairy beverages. In conclusion, the established method is sensitive to subtle structural differences in disaccharide isomers and has the potential to be used for the differentiation of various glycans.

A Novel Integrated APCI and MPT Ionization Technique as Online Sensor for Trace Pesticides Detection.

The misuse of pesticides poses a tremendous threat to human health. Excessive pesticide residues have been shown to cause many diseases. Many sensor detection methods have been developed, but most of them suffer from problems such as slow detection speed or narrow detection range. So, the development of rapid, direct and sensitive means of detecting trace amounts of pesticide residues is always necessary. A novel online sensor technique was developed for direct analysis of pesticides in complex matrices with no sample pretreatment. The portable sensor ion source consists of an MPT (microwave plasma torch) with desolventizing capability and an APCI (atmosphere pressure chemical ionization), which provides abundant precursor ions and a strong electric field. The performance which improves the ionization efficiency and suppresses the background signal was verified by using pesticide standard solution and pesticide pear juice solution measurements with an Orbitrap mass spectrometer. The limit of detection (LOD) and the limit of quantization (LOQ) of the method were measured by pear juice solutions that were obtained in the ranges of 0.034-0.79 µg/L and 0.14-1 µg/L. Quantitative curves were obtained ranging from 0.5 to 100 µg/L that showed excellent semi-quantitative ability with correlation coefficients of 0.985-0.997. The recoveries (%) of atrazine, imidacloprid, dimethoate, profenofos, chlorpyrifos, and dichlorvos were 96.6%, 112.7%, 88.1%, 85.5%, 89.2%, and 101.9% with the RSDs ranging from 5.89-14.87%, respectively. The results show that the method has excellent sensitivity and quantification capability for rapid and direct detection of trace pesticide.

Arc-Induced Nitrate Reagent Ion for Analysis of Trace Explosives on Surfaces Using Atmospheric Pressure Arc Desorption/Ionization Mass Spectrometry.

This study presents the rapid surface detection of explosives by employing atmospheric pressure arc desorption/ionization mass spectrometry (APADI-MS) using point-to-plane arc discharge. In APADI, neutral explosives readily bind to the gas-phase nitrate ion, NO3-, induced by arc discharge to form anionic adducts [M+NO3]-. This avoids the need for inorganic anionic additives such as NO3-, NO2-, Cl-, acetate, and trifluoroacetate for unique explosive ionization pathways and simplifies mass spectra. The analytical performance of APADI was thoroughly evaluated for the rapid detection of 10 explosives at levels in the range of 800 fg-1 µg. Arc-induced nitrogen oxide anions promoted the formation of characteristic adducts, such as [M+NO3]-, and improved the instrument response for all the explosives tested. APADI showed considerable sensitivity in the negative ion mode with limits of detection in the low picogram range, particularly when explosives were analyzed on a copper or aluminum foil substrate. APADI coupled with an Orbitrap mass spectrometer displayed a good linear response for the studied explosives. The linearity and intraday and interday precisions were evaluated, demonstrating the feasibility and robustness of APADI-MS for the detection of trace explosives on solid surfaces. The mechanisms of APADI for explosive ionization and desorption were examined and verified by performing density functional theory calculations.

Dual ambient plasma source ionization mass spectrometry for the rapid detection of trace sterols in urban water: Rapid detection of trace sterols in urban water.

A direct analytical method based on dual ambient plasma ion source tandem mass spectrometry was used for the simultaneous determination of four sterols in the environment. This technology has very high sensitivity and the method detects the four sterols in methanol-water (1:3) solutions with limits of detection (LOD) and limits of quantification (LOQ) ranging from 1.2 ng/L to 6.9 ng/L and 7.6 ng/L to 10.0 ng/L, respectively. The method was also used to test water quality at three locations within the city and successfully detected all four sterols at very low concentrations. The dual plasma source tandem mass spectrometry technique is extremely simple, rapid, sensitive and highly efficient compared to other traditional methods, providing a useful screening tool for sterols in water.