Liquid Ionization Research Articles

Nanometallurgy in solution: organometallic synthesis of intermetallic Pd-Ga colloids and their activity in semi-hydrogenation catalysis.

Nanoparticles (NPs) of Pd1--xGax (x = 0.67, 0.5, 0.33), stabilized in non-aqueous colloidal solution, were obtained via an organometallic approach under mild conditions using [Pd2(dvds)3] and GaCp* as all-hydrocarbon ligated metal-precursor compounds (dvds = 1,1,3,3-tetramethyl-1,3-divinyl-disiloxane; Cp* = η5-C5Me5; Me = CH3). The reaction of the two precursors involves the formation of a library of molecular clusters [PdnGamCp*y(dvds)z], as shown by liquid injection field desorption ionization mass spectrometry (LIFDI-MS). Full characterization of the catalytic system (HR-TEM, EDX, DLS, PXRD, XPS, NMR, IR, Raman) confirmed the formation of ultra-small, spherical NPs with narrow size distributions ranging from 1.2 ± 0.2 nm to 2.1 ± 0.4 nm (depending on the Pd : Ga ratio). The catalytic performance of the Pd1--xGax NPs in the semi-hydrogenation of terminal and internal alkynes and the influence of the gallium content on product selectivity were investigated. The highest activities (65%) and selectivities (81%) are achieved using colloids with a "stoichiometric" Pd/Ga ratio of 1 : 1 at 0 °C and 2.0 bar H2 pressure. While lower Ga ratios lead to an increase in activity, higher Ga contents increase the olefin selectivity but are detrimental to the activity.

Development of a handheld liquid extraction pen for on-site mass spectrometric analysis of daily goods.

We present a handheld liquid extraction pen (LEP) combined with a self-sustaining electrospray ionization platform for ambient mass spectrometry within a laboratory-independent workspace. The LEP enables direct sampling from various surfaces and textures, independent of sample shape without precise sample positioning or dedicated sample preparation. The combination of liquid extraction of analytes through the pen and electrospray ionization (ESI) opens a broad field of applications. Qualitative and semi-quantitative analysis is presented for pesticides, plasticizers and drugs which were analyzed from representative consumer goods, such as fruits, toys and pills. Food authentication via metabolomic fingerprinting and multivariate statistics is demonstrated for the analysis of fish fillets and coffee. The LEP source uses a rechargeable battery to power a compressor. Ambient air is used for solvent nebulization in ESI. Through a pressure pump with integrated solvent reservoir, a solvent flow through the LEP and ESI source is generated. Measurement times of more than three hours are possible. The ion source is adaptable to any kind of mass spectrometer equipped with an atmospheric pressure interface. Measurements were performed on orbital trapping instruments and on a miniature mass spectrometer. Coupled to the miniaturized mass spectrometer, the completely portable LEP-MS instrument has dimensions of 48.4 × 27.0 × 18.0 cm (l × w × h).

Stability and decay of surface electrostatic charges in liquids

Abstract Understanding the mechanism of the stability and decay of surface electrostatic charges in different liquid environments is critical for the reliability of devices based on electrostatic functions or preventing the damage from electrostatic charge accumulation. In this work, the influences of surface electrostatic charges in polar and protic (Ethanol and Water), polar and aprotic (Tetrahydrofuran and Chloroform), and non-polar and aprotic (Benzene and Hexane) liquids have been investigated. Results prove that ionization in liquid or polarity of the liquid molecules can determine the electrostatic charges neutralization, and adding small amount of matter (1% Vol) that can ionize in non-polar and aprotic liquids can avoid the electrostatic charges accumulation. Moreover, air-bubble-structured electret is designed to improve the water-against ability for surface electrostatic charges.

Separation and identification of diacylglycerols containing branched chain fatty acids by liquid chromatography-mass spectrometry

A combination of two chromatographic and two enzymatic methods was used for the analysis of molecular species of lipids from Gram-positive bacteria of the genus Kocuria. Gram-positive bacteria contain a majority of branched fatty acids (FAs), especially iso- and/or anteiso-FAs. Two strains K. rhizophila were cultivated at three different temperatures (20, 28, and 37°C) and the majority phospholipid, i.e., the mixture of molecular species of phosphatidylglycerols (PGs) was separated by means of hydrophilic interaction liquid chromatography (HILIC). After enzymatic hydrolysis of PGs by phospholipase C and derivatization of the free OH group, the sn-1,2-diacyl-3-acetyl triacylglycerols (AcTAGs) were separated by reversed phase HPLC. Molecular species such as i-15:0/i-15:0/2:0, ai-15:0/ai-15:0/2:0, and 15:0/15:0/2:0 (straight chains) were identified by liquid chromatography-positive electrospray ionization mass spectrometry. The tandem mass spectra of both standards and natural compounds containing iso, anteiso and straight chain FAs with the same carbons were identical. Therefore, for identification of the ratio of two regioisomers, i.e. i-15:0/ai-15:0/2:0 vs. ai-15:0/i-15:0/2:0, they were cleavage by pancreatic lipase. The mixture of free fatty acids (FFAs) and 2-monoacylglycerols (2-MAGs) was obtained. After their separation by TLC and esterification and/or transesterification, the fatty acid methyl esters were quantified by GC-MS and thus the ratio of regioisomers was determined.It has been shown that the ratio of PG (containing as majority i-15: 0 / i-15: 0, i-15: 0 / ai-15: 0 and / or ai-15: 0 / i-15: 0 and ai-15: 0 / ai-15: 0 molecular species) significantly affected the membrane flow of bacterial cells cultured at different temperatures.

Flowing cryogenic liquid target for terahertz wave generation

Terahertz wave emission from liquids excited by intense laser pulses not only reflects the details in laser–matter interaction but also offers bright terahertz wave sources. Flowing liquid targets possess the advantage of providing a fresh area for each laser pulse. To demonstrate a debris-free target under laser excitation, we investigate the use of liquid nitrogen as a target. By creating a flowing liquid nitrogen line in an ambient environment, we successfully observe broadband terahertz wave emission under short pulse excitation. Our cryogenic line is able to sustain the excitation of a high-repetition-rate (1 kHz) laser. The terahertz peak field emitted from liquid nitrogen is comparable to that from liquid water, yet a broader bandwidth is observed. This demonstration prompts opportunities in choosing potential materials for studying terahertz wave generation processes and in understanding laser-induced ionization of different liquids.

Microalgal metabolites as anti-cancer/anti-oxidant agents reduce cytotoxicity of elevated silver nanoparticle levels against non-cancerous vero cells

Heavy metal pollution has become a major concern globally as it contaminates eco-system, water networks and as finely suspended particles in air. In this study, the effects of elevated silver nanoparticle (AgNPs) levels as a model system of heavy metals, in the presence of microalgal crude extracts (MCEs) at different ratios, were evaluated against the non-cancerous Vero cells, and the cancerous MCF-7 and 4T1 cells. The MCEs were developed from water (W) and ethanol (ETH) as green solvents. The AgNPs-MCEs-W at the 4:1 and 5:1 ratios (v/v) after 48 and 72 h treatment, respectively, showed the IC50 values of 83.17–95.49 and 70.79–91.20 μg/ml on Vero cells, 13.18–28.18 and 12.58–25.7 μg/ml on MCF-7; and 16.21–33.88 and 14.79–26.91 μg/ml on 4T1 cells. In comparison, the AgNPs-MCEs-ETH formulation achieved the IC50 values of 56.23–89.12 and 63.09–91.2 μg/ml on Vero cells, 10.47–19.95 and 13.48–26.61 μg/ml on MCF-7; 14.12–50.11 and 15.13–58.88 μg/ml on 4T1 cells, respectively. After 48 and 72 h treatment, the AgNPs-MCE-CHL at the 4:1 and 5:1 ratios exhibited the IC50 of 51.28–75.85 and 48.97–69.18 μg/ml on Vero cells, and higher cytotoxicity at 10.47–16.98 and 6.19–14.45 μg/ml against MCF-7 cells, and 15.84–31.62 and 12.58–24.54 μg/ml on 4T1 cells, respectively. The AgNPs-MCEs-W and ETH resulted in low apoptotic events in the Vero cells after 24 h, but very high early and late apoptotic events in the cancerous cells. The Liquid Chromatography-Mass Spectrometry-Electrospray Ionization (LC-MS-ESI) metabolite profiling of the MCEs exhibited 64 metabolites in negative ion and 56 metabolites in positive ion mode, belonging to different classes. The microalgal metabolites, principally the anti-oxidative components, could have reduced the toxicity of the AgNPs against Vero cells, whilst retaining the cytotoxicity against the cancerous cells.

Direct Liquid Extraction and Ionization Techniques for Understanding Multimolecular Environment in Biological Systems

Direct Liquid Extraction and Ionization Techniques for Understanding Multimolecular Environment in Biological Systems

Root membrane lipids as potential biomarkers to discriminate silage-corn genotypes cultivated on podzolic soils in boreal climate.

Root membrane lipids are important biomolecules determining plant's ability to adapt to different growing environmental or climatic conditions. Herein, we demonstrate the potential use of root membrane lipids as biomarkers to discriminate silage-corn genotypes based on herbicide and insect/pest resistance genetic traits when cultivated on podzolic soils under short growing and moderately warm summer season in boreal climate. Lipids in root membranes of field grown silage-corn genotypes were previously quantified at crop maturity by ultra-high-performance liquid chromatography-hydrophilic interaction chromatography-heated electrospray ionization mass spectrometry. The lipid identified and quantified in silage-corn roots were phospholipids, glycolipids and sphingolipids. Following hierarchical cluster analysis, three groups of membrane lipids were observed to be very effective in segregating the five silage-corn genotypes. The first group consisted of hexosylceramide (HexCer), phosphatidylcholine (PC) and phosphatidylinositol (PI). The second group consisted of lysophosphatidic acid (LPA16:0) and lysophosphatidylcholine (LPC16:0), while the third group consisted of 37 molecular species from observed lipids (phospholipids, glycolipids, sphingolipids). Partial least squares-discriminant analysis (PLS-DA) based on 37 membrane lipid species, as well as principal component analysis using the variables important in projection derived from the PLS-DA segregated the five silage-corn genotypes into three groups according to their pesticide/herbicide resistant traits. This study is second to none using root lipidomics in discriminating different silage-corn genotypes based on their herbicide and insect/pest resistance genetic traits for cultivation in boreal climates. The segregated genotypes possess three different genetic traits for herbicide and insect/pest resistance including VT Double Pro (VT2P), VT Triple Pro Roundup Ready (VT3P/RR) and Roundup Ready-2 corn (RR2). These findings demonstrate that root membrane lipids could serve as appropriate chemical biosignatures to identify silage-corn genotypes based on herbicide and insect/pest resistance genetic traits suitable for cultivation in boreal climates.

Measurements of argon-scintillation and -electroluminescence properties for low mass WIMP dark matter search

It has been demonstrated that the liquid argon scintillation detector is an excellent particle detector for use in various physics experiments, particularly those seeking evidence of WIMPs dark matter. The detector observes primary scintillation signal (S1) and/or secondary electroluminescence signal (S2). It is crucial that the properties of the detector are understood comprehensively so that such projects reduce systematic uncertainty and improve sensitivity. This work covers the recent measurements, taken using the liquid argon test facility at Waseda University, of the liquid argon scintillation and ionization responses for nuclear and electronic recoils. Additionally, a basic study of the gaseous argon luminescence signal, which involves the S2 signal, is presented herein. The luminescence process of the S2 signal, based on this measurement, is then discussed along with a suggested new mechanism called neutral Bremsstrahlung.

Degradation Pathway Proposal, Structure Elucidation, and In Silico Toxicity Prediction of Dapagliflozin Propane Diol Hydrolytic Degradation Products

Dapagliflozin (DAP) is therapeutic agent for diabetes mellitus type II patients with insufficient glycemic control by exercise and diet. Stability-indicating LC–MS method was developed and validated on C8 column and method was able to separate DAP and three major hydrolytic degradation products. Structure elucidation of three major identified hydrolytic degradation products (DPs) and establishment of degradation pathway were executed with the combine application of liquid chromatography-positive mode electrospray ionization tandem mass spectrometry and high-resolution mass spectrometry. Further ProTox-II was used to predict in silico toxicity for each DPs and compared with DAP.

Study of oxygenation and hydrogenation of tris(8-hydroxyquinoline) aluminum generated by electrode deposition using liquid extraction surface analysis nanoelectrospray ionization mass spectrometry

N-oxygenated and N-hydrogenated molecules of 8-hydroxyquinoline with a wide range of N values, generated by the deposition of Al, ITO, and MgAg electrodes on 10 nm thick tris(8-hydroxyquinoline) aluminum (Alq3) molecular films are analyzed by liquid extraction surface analysis combined with nanoelectrospray ionization mass spectrometry (LESA nano-ESI-MS) for the first time. Based on the relative ion intensities of oxygenated and hydrogenated molecules, Al deposition causes greater chemical reduction of Alq3 than ITO and MgAg deposition. Additionally, the relative ion intensities of 1-, 2-, and 3-oxygenated molecules decrease stepwise, so that oxidation of the 8-hydroxyquinoline molecules is thought to proceed stochastically.

Potentilla alba Extracts Affect the Viability and Proliferation of Non-Cancerous and Cancerous Colon Human Epithelial Cells.

The aim of this study was to determine the anti-tumor activity of extracts isolated from Potentilla alba L. on human colon cancer cells of the HT-29 line and on non-cancer colon epithelial cells of the CCD 841 CoTr line. The research methods we used to determine the cytotoxic and proliferative properties were 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and neutral red (NR) assays, the ability to produce nitric oxide, the Griess method, and the biochemical properties like 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing antioxidant power (FRAP) methods indicating reduction activity of tested samples. In order to obtain a phytochemical profile of the different extracts an analytical method based on liquid chromatography-photodiode array detection-electrospray ionization ion-trap time-of-flight mass spectrometry (LC-PDA-ESI-MS/TOF) was applied. Finally, the effects of the extracts on the morphology and cell counts were assessed by May–Grünwald–Giemsa staining. After a comprehensive analysis of all the experiments, the extracts were found to demonstrate cytotoxic properties, they stimulated the division of non-cancer cells, and they were able to scavenge free radicals. In the NR method, the cell viability dropped to approximately 80% compared to the control. In the MTT assay, tumor cell proliferation decreased to 9.5% compared to the control. Therefore, we concluded that this plant has medical potential.

Liquid Sampling-Atmospheric Pressure Glow Discharge Ionization as a Technique for the Characterization of Salt-Containing Organic Samples.

Typical ionization techniques used for mass spectrometry (MS) analysis face challenges when trying to analyze organic species in a high-salt environment. Here, we present results using a recently developed ionization source, liquid sampling-atmospheric pressure glow discharge (LS-APGD), for marine-relevant salt-containing organic samples. Using two representative sample types, a triglyceride mixture and dissolved organic matter, this method is compared to traditional electrospray ionization (ESI) under saline and neat conditions. LS-APGD produced equal or higher (15%+) ion intensities than those of ESI for both salt-containing and neat samples, although important differences linked with adduct formation in high-salt conditions explain the molecular species observed. For all sample types, LS-APGD observed a higher diversity of molecules under optimized settings (0.25 mm electrode spacing at 20 mA) compared to traditional ESI. Furthermore, because the LS-APGD source ionizes molecular species in a ∼1 mm3 volume plasma using a low-power source, there is the potential for this method to be applied in field studies, eliminating desalting procedures, which can be time-consuming and nonideal for low-concentration species.

A microfluidic platform integrating paper adsorption-based sample clean-up and voltage-assisted liquid desorption electrospray ionization mass spectrometry for biological sample analysis

Clinical application of direct sampling electrospray ionization mass spectrometry (ESI-MS) remains limited due to problems associated with very “dirty” sample matrices. Herein we report on a microfluidic platform that allows direct mass spectrometric analysis of serum samples of microliter sizes. The platform integrates in-line paper adsorption-based sample clean-up and voltage assisted liquid desorption ESI-MS/MS (VAL DESI-MS/MS) to detect multiple targeted compounds of clinical interest. Adenosine monophosphate (AMP), adenosine diphosphate (ADP), and adenosine triphosphate (ATP) were selected as model analytes. Simultaneous quantification of these compounds in human serum samples was demonstrated. For all the three compounds, linear calibration curves were obtained in a concentration range from 0.20 to 20.0 μmol/L with r2 values ≥ 0.996. Limits of detection were 0.019, 0.015, and 0.011 μmol/L for AMP, ADP, and ATP, respectively. Recovery was found in the range from 96.5% to 103.5% at spiking concentrations of 0.25 and 2.50 μmol/L. The results indicate that the proposed microfluidic mass spectrometric platform is robust and effective. It may have a potential in clinical analysis.

Condensed Phase Membrane Introduction Mass Spectrometry with In Situ Liquid Reagent Chemical Ionization in a Liquid Electron Ionization Source (CP-MIMS-LEI/CI)

Direct mass spectrometry has grown significantly due to wide applicability, relative ease of use, and high sample throughput. However, many current direct mass spectrometry methods are largely based on ambient ionization techniques that can suffer from matrix effects and poor selectivity. A strategy that addresses these shortcomings is condensed phase membrane introduction mass spectrometry-liquid electron ionization utilizing in situ liquid reagent chemical ionization (CP-MIMS-LEI/CI). In CP-MIMS measurements, a semipermeable hollow fiber polydimethylsiloxane membrane probe is directly immersed into a complex sample. Neutral, hydrophobic analytes permeating the membrane are entrained by a continuously flowing liquid acceptor phase (nL/min) to an LEI/CI source, where the liquid is nebulized, followed by analyte vaporization and ionization. This study marks the first intentional exploitation of the liquid CP-MIMS acceptor phase as an in situ means of providing liquid chemical ionization (CI) reagents for improved analyte sensitivity and selectivity (CP-MIMS-LEI/CI). Acetonitrile and diethyl ether were used as a combination acceptor phase/CI proton transfer reagent system for the direct analysis of dialkyl phthalates. Using isotopically labeled reagents, the gas phase ionization mechanism was found to involve reagent autoprotonation, followed by proton transfer to dialkyl phthalates. A demonstration of the applicability of CP-MIMS-LEI/CI for rapid and sensitive screening of bis(2-ethylhexyl) phthalate in house dust samples is presented. The detection limit in house dust (6 mg/kg) is comparable to that obtained by conventional analyses, but without time-consuming sample workup or chromatographic separation steps.

Measurement of liquid argon scintillation and ionization response on nuclear recoils under electric fields up to 3 kV/cm

A liquid argon (LAr) scintillation detector has several features that make it attractive for use in various physics projects such as dark matter searches. One of the key quantities in these projects is the scintillation and ionization response on nuclear recoils (NR) with an energy of several tens of keV and below. The response is known to be dependent on the recoil energy and applied electric field. Although these properties have been measured in previous studies, a systematic understanding and indepth discussions that include low energy and high electric fields have not been conducted. Here, the scintillation and ionization efficiencies of NR with an energy of a few tens of keV under electric fields ranging from 0 to 3 kV/cm are measured. The calibration data are taken with a 252Cf radioactive neutron source with a small-sized double-phase time projection chamber. We employ a parametrization model to describe the response, and it allows to fully predict the efficiencies at any recoil energy and any electric field below 3 kV/cm.

Development of a Dark Matter Detector that Uses Liquid He and Field Ionization

We describe a new detector capable of directly measuring dark matter particles with masses as low as 1 MeV/c 2. The detector is based on the quantum evaporation of helium atoms from the surface of liquid helium and their detection using field ionization. When a dark matter particle collides with an atom in liquid helium, the deposited energy results in the evaporation of helium atoms from the liquid surface. A dense array of sharp, positively charged metal tips, known as the field ionization detector array, creates a strong electric field that ionizes the helium atoms and accelerates them into a calorimeter, which detects the impact. We studied field ionization from single tips and investigated the dependence of the ionization rate on the applied voltage. We discuss the results of these single tip field ionization experiments, as well as upcoming experiments, which will focus on studying the temperature dependence of field ionization of gaseous helium at low temperatures.

Studies on liquid argon S1 and S2 properties for low mass WIMP search experiments

Liquid argon is known as an excellent target material for WIMP dark matter direct search experiment. Relatively small atomic mass (A=40) gives high nuclear recoil energy for WIMP-Ar nuclear scattering, thus it potentially has high sensitivity for low mass WIMP (<10 GeV/c2) . There are two crucial R&D topics for the liquid argon detector to explore such low mass WIMP signal, namely, deep understanding the liquid argon scintillation and ionization process for low energy deposition (<10 keV), and increasing the signal light yield by improving the argon scintillation light collection efficiency. In this paper, we report recent results from Waseda university liquid argon test facility.

Low-Energy Physics Reach of Xenon Detectors for Nuclear-Recoil-Based Dark Matter and Neutrino Experiments.

Dual-phase xenon detectors lead the search for keV-scale nuclear recoil signals expected from the scattering of weakly interacting massive particle (WIMP) dark matter, and can potentially be used to study the coherent nuclear scattering of MeV-scale neutrinos. New capabilities of such experiments can be enabled by extending their nuclear recoil searches down to the lowest measurable energy. The response of the liquid xenon target medium to nuclear recoils, however, is not well characterized below a few keV, leading to large uncertainties in projected sensitivities. In this work, we report a new measurement of ionization signals from nuclear recoils in liquid xenon down to the lowest energy reported to date. At 0.3keV, we find that the average recoil produces approximately one ionization electron; this is the first measurement of nuclear recoil signals at the single-ionization-electron level, approaching the physical limit of liquid xenon ionization detectors. We discuss the implications of these measurements on the physics reach of xenon detectors for nuclear-recoil-based WIMP dark matter searches and the detection of coherent elastic neutrino-nucleus scattering.

Exploring the Phytochemical Landscape of the Early-Diverging Flowering Plant Amborella trichopoda Baill.

Although the evolutionary significance of the early-diverging flowering plant Amborella (Amborella trichopoda Baill.) is widely recognized, its metabolic landscape, particularly specialized metabolites, is currently underexplored. In this work, we analyzed the metabolomes of Amborella tissues using liquid chromatography high-resolution electrospray ionization mass spectrometry (LC-HR-ESI-MS). By matching the mass spectra of Amborella metabolites with those of authentic phytochemical standards in the publicly accessible libraries, 63, 39, and 21 compounds were tentatively identified in leaves, stems, and roots, respectively. Free amino acids, organic acids, simple sugars, cofactors, as well as abundant glycosylated and/or methylated phenolic specialized metabolites were observed in Amborella leaves. Diverse metabolites were also detected in stems and roots, including those that were not identified in leaves. To understand the biosynthesis of specialized metabolites with glycosyl and methyl modifications, families of small molecule UDP-dependent glycosyltransferases (UGTs) and O-methyltransferases (OMTs) were identified in the Amborella genome and the InterPro database based on conserved functional domains. Of the 17 phylogenetic groups of plant UGTs (A–Q) defined to date, Amborella UGTs are absent from groups B, N, and P, but they are highly abundant in group L. Among the 25 Amborella OMTs, 7 cluster with caffeoyl-coenzyme A (CCoA) OMTs involved in lignin and phenolic metabolism, whereas 18 form a clade with plant OMTs that methylate hydroxycinnamic acids, flavonoids, or alkaloids. Overall, this first report of metabolomes and candidate metabolic genes in Amborella provides a starting point to a better understanding of specialized metabolites and biosynthetic enzymes in this basal lineage of flowering plants.