Exploration and performance evaluation of microwave-induced plasma with different discharge gases for ambient desorption/ionization mass spectrometry.

RATIONALE: Microwave-induced plasma (MIP) with different discharge gases of argon or helium provides significant plasma-based ambient desorption/ionization sources, which have potential applicability in direct analysis of complex samples without any sample pre-treatment. In this study, experiments were conducted to better understand microwave-induced plasma desorption/ionization (MIPDI) sources and the corresponding ionization mechanisms. METHODS: Emission spectra of microwave-induced argon (MIP-Ar) and helium (MIP-He) plasmas were obtained from the plasma tail flame of a MIP source. Compounds including L-phenylalanine, L-serine, L-valine, urea, 4-acetaminophen, gallic acid and L-ascorbic acid were analyzed using both sources. Polyethylene glycol 400 (PEG400) oligomers were detected by MIP-Ar and MIP-He mass spectrometry at different microwave powers. Mass spectra of higher molecular weight PEGs (including PEG800, PEG1000 and PEG2000) were also acquired using both sources. RESULTS: In the emission spectra, N2 , H-I and O-I species were observed by MIP-Ar/He. In addition, SiO2 , Na-I, Si-I and Si-II species were generated by MIP-He. In the mass spectra of compounds, [M+H]+ , [2M+H]+ , [M+O+H]+ , [M+2O-H]+ and fragment ions were observed. In the mass spectra of PEG400 obtained by MIP-Ar/He at different microwave powers, higher molecular weight oligomers could only be observed with higher microwave power. PEGs with molecular weights as high as 1000 Da were also successfully analyzed by MIPDI. CONCLUSIONS: According to the different natures of the samples, either MIP-Ar or MIP-He can be chosen as a working ion source for mass spectrometry. The MIPDI source is potentially applicable to the analysis of compounds with high molecular weights, especially polymers with high degree of polymerization (such as PEG2000), which is a challenging issue for the traditional ambient ionization sources. Copyright © 2017 John Wiley & Sons, Ltd.

Air activation of charcoal monoliths for capacitive energy storage.

Charcoal monoliths derived from waste wood were activated with air for the application of electrochemical capacitor electrodes and an insight was given into the activation mechanism. The mild air activation is effective and pollution-free compared to the common chemical activation using KOH etc. for the preparation of crack-free carbon monoliths. The activation process was controlled by altering the activation temperature and time, and their effects on the nanostructure of charcoal monoliths were studied. As the activation temperature or time increased, air eroded the defective surface of charcoal layer-by-layer, with the oxygen atoms being introduced by chemisorption and oxidation reactions and removed by dehydration and decomposition reactions. Meanwhile, micro-pores were produced. The electrode activated at 300 °C for 1 h, with a specific surface area of 567 m2 g-1 and a high micro-porosity of 86%, exhibited a specific capacitance of 203 F g-1 and 35.5 F cm-3. Moreover, it presented a higher total capacitance of 3.6 F cm-2 than most reported pellet electrodes. These findings give a reasonable picture of the air activation process and are instructive to prepare activated carbon monoliths under an oxidizing environment.

Synergetic effect of laser and micro-fabricated glow discharge plasma in a new ion source for ambient mass spectrometry.

A new ambient ionization technique named laser ablation micro-fabricated glow discharge plasma (LA-MFGDP) was developed for mass spectrometry in this study. This technique used low energy laser for sample ablation and ionized sample aerosol with MFGDP in sequence. The combination of laser ablation and MFGDP exhibited a synergetic effect that significantly improved the performance of MFGDP. Experimental results showed that MFGDP dominated the ionization process while laser played the role of desorption in LA-MFGDP. [M+H]+ and M+ proved that proton transfer reactions and charge transfer reactions were involved in the ionization process, respectively, indicating that the ionization character was the same as MFGDP. LA-MFGDP could analyze less volatile samples that were unable to be detected by MFGDP because laser significantly improved the ionization capability of MFGDP. Strong ion signals were obtained by LA-MFGDP with low sample consumption. The limits of detection (LODs) of LA-MFGDP was as low as three orders of magnitude than that of MFGDP, which demonstrated that LA-MFGDP possessed an outstanding advantage in detecting trace substances. LA-MFGDP was successfully applied to detect pharmaceutical tablets without any pretreatment. Benefited from the excellent performance, LA-MFGDP offers great potential in broadening the application of ambient mass spectrometry.

Rapid identification and desorption mechanisms of nitrogen-based explosives by ambient micro-fabricated glow discharge plasma desorption/ionization (MFGDP) mass spectrometry.

A novel technique of micro-fabricated glow discharge plasma desorption/ionization mass spectrometry was investigated for the first time in negative ion mode in this study. Negative ion micro-fabricated glow discharge plasma desorption/ionization mass spectrometry (NI-MFGDP-MS) was successfully applied to identify trace explosives in open air. Six explosives and explosives-related compounds were directly analyzed in seconds with this ion source. The ions of [M-H]- were predominant for 2-methyl-1,3,5-trinitrobenzene (trinitrotoluene, TNT) and 2,4,6-trinitrophenol (picric acid), and [M+NO3]- were dominant ions for 1,3,5-trinitro-perhydro-1,3,5-triazine (cyclonite, RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (octogen, HMX), 1,2,3-trinitroxypropane (nitroglycerin, NG), and pentaerythritol tetranitrate (PETN). The limits of detection (LOD) were from 87.5pgmm-2 to 0.4 fg mm-2 and the relative standard deviation (RSD) ranged between 5.8% and 16.8% for the explosives involved in this study. The reliability of NI-MFGDP-MS was characterized by the analysis of a picric acid-RDX-PETN mixture and a mixture of RDX-pond water. NI-MFGDP-MS and ESI-MS were compared with these explosives and along with collision induced dissociation (CID) experiments. The results showed that electron capture, proton abstraction reaction, nucleophilic attack, ion-molecule attachment, decomposition and anion attachment took place during the NI-MFGDP-MS measurement. These findings provide a guideline and a supplement to the chemical libraries for rapid and accurate detection of explosives. The method shows great potential for fast, in situ, on-line and high throughput detection of explosives in the field of antiterrorism.

Effects of h-BN addition on microstructures and mechanical properties of ß-CaSiO3 bioceramics.

The main purpose of this study consists in investigating the effects of h-BN addition on the sinterability of ß-CaSiO3 (ß-CS) bioceramics. ß-CS bioceramics with different contents of h-BN were prepared at the sintering temperature ranging from 800°C to 1100°C. The results showed that h-BN can be successfully used as sintering additive by being oxidized to form low melting point B2O3 related glassy phase and enhanced the flexural strength by the formation of rod-like ß-CS grains. ß-CS bioceramics with 1wt% h-BN sintered at 1000°C revealed flexural strength and fracture toughness of 182.2MPa and 2.4MPam(1/2) respectively, which were much higher than that of pure ß-CS bioceramics (30.2MPa, 0.53MPam(1/2)) fabricated in the same processing condition.

Effects of silica sol on the microstructure and mechanical properties of CaSiO3 bioceramics.

CaSiO3 ceramics were fabricated with silica sol addition by pressureless sintering. The effects of silica sol on phase composition, microstructure and mechanical properties of CaSiO3 ceramics were investigated. The silica sol additive was found to be effective in speeding up pore elimination, improving the grain growth, decreasing the sintering temperature and shortening the sintering time. When the amount of SiO2 was 5wt%, a flexural strength of 186.2MPa was achieved with an open porosity of 3.9%. The main crystal phase was ß-CaSiO3 below sintering temperature of 1150°C.

The improved mechanical properties of ß-CaSiO3 bioceramics with Si3N4 addition.

The motivation of this study is to investigate the effect of Si3N4 addition on the sinterability of ß-CaSiO3 ceramics. ß-CaSiO3 ceramics with different content of Si3N4 were prepared at the sintering temperature ranging from 1000°C to 1150°C. The results showed that Si3N4 can be successfully used as sintering additive by being oxidized to form SiO2. The ß-CaSiO3 ceramics with 3wt% Si3N4 sintered at 1100°C revealed flexural strength, hardness and fracture toughness of 157.2MPa, 4.4GPa and 2.3MPam(1/2) respectively, which was much higher than that of pure ß-CaSiO3 ceramics (41.1MPa, 1.0GPa, 1.1MPam(1/2)). XRD analysis and SEM observation indicated that the main phase maintained to be ß-phase after sintering.