Expanding Lipidome Coverage Using LC-MS/MS Data-Dependent Acquisition with Automated Exclusion List Generation

Untargeted omics analyses aim to comprehensively characterize biomolecules within a biological system. Changes in the presence or quantity of these biomolecules can indicate important biological perturbations, such as those caused by disease. With current technological advancements, the entire genome can now be sequenced; however, in the burgeoning fields of lipidomics, only a subset of lipids can be identified. The recent emergence of high resolution tandem mass spectrometry (HR-MS/MS), in combination with ultra-high performance liquid chromatography, has resulted in an increased coverage of the lipidome. Nevertheless, identifications from MS/MS are generally limited by the number of precursors that can be selected for fragmentation during chromatographic elution. Therefore, we developed the software IE-Omics to automate iterative exclusion (IE), where selected precursors using data-dependent topN analyses are excluded in sequential injections. In each sequential injection, unique precursors are fragmented until HR-MS/MS spectra of all ions above a user-defined intensity threshold are acquired. IE-Omics was applied to lipidomic analyses in Red Cross plasma and substantia nigra tissue. Coverage of the lipidome was drastically improved using IE. When applying IE-Omics to Red Cross plasma and substantia nigra lipid extracts in positive ion mode, 69% and 40% more molecular identifications were obtained, respectively. In addition, applying IE-Omics to a lipidomics workflow increased the coverage of trace species, including odd-chained and short-chained diacylglycerides and oxidized lipid species. By increasing the coverage of the lipidome, applying IE to a lipidomics workflow increases the probability of finding biomarkers and provides additional information for determining etiology of disease.

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Assessment of Reproducibility of Laser Electrospray Mass Spectrometry using Electrospray Deposition of Analyte

A nonresonant, femtosecond (fs) laser is employed to desorb samples of Victoria blue deposited on stainless steel or indium tin oxide (ITO) slides using either electrospray deposition (ESD) or dried droplet deposition. The use of ESD resulted in uniform films of Victoria blue whereas the dried droplet method resulted in the formation of a ring pattern of the dye. Laser electrospray mass spectrometry (LEMS) measurements of the ESD-prepared films on either substrate were similar and revealed lower average relative standard deviations for measurements within-film (20.9%) and between-films (8.7%) in comparison to dried droplet (75.5% and 40.2%, respectively). The mass spectral response for ESD samples on both substrates was linear (R²?>?0.99), enabling quantitative measurements over the selected range of 7.0?×?10^?11 to 2.8?×?10^?9 mol, as opposed to the dried droplet samples where quantitation was not possible (R²?=?0.56). The limit of detection was measured to be 210 fmol.

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Contribution of the surface dipole moment and the contact potential-induced disjoining pressure to the stress balance at a three-phase contact

The contact between three insulators results in a set up of contact potentials related to the adsorbed dipole moment at each surface. The produced electric field applies force (disjoining pressure) on each interface. This disjoining pressure is a long-ranged force (1/distance²) which is proportional to the difference between the dielectric permittivities of the phases on the two sides of the interface and, for small angles, to the square of the contact angle. The contact potential leads to a logarithmic perturbation of the profile of the three-phase contact zone.     

A New Approach to Increasing the Resolution of a Mass Spectrometer with Wedge-Shaped Reflectors

The paper describes the investigation of the ion-optical properties of a laser TOF mass spectrometer including two successively positioned wedge-shaped ion mirrors. Some specific properties of the configuration of ion trajectories near their reflection in the second ion reflector are found. The dependence of aberrations on ion energy acquired toothed shape for the resolution of the analyzer higher than 3000–5000. The approximation of the dependence gave a 15^th degree polynomial. The calculation of polynomial coefficients showed a great contribution to the duration of ion packets for aberrations of higher order. The discovered features allowed us to suggest a way of the local correction of nearby trajectories in the total ion flux. By correcting the local motion of individual groups of ions, we could reduce temporary aberration to 1–1.6 ns, depending on ion energy. For the time of ion flight ~35 μs, such duration limits the resolution of the analyzer by a value not less than 10000. The real length of ion drift path was about 30 cm. The total overall sizes of the ionoptical system were ~24 × 19 × 5 cm.     

Alkylation of phenol with olefins in the presence of catalysts based on mesoporous aromatic frameworks

Mesoporous polyaromatic frameworks (PAFs) based on tetraphenylmethane were obtained and modified with sulfonic acid groups. The compounds were characterized by solid-state ¹³C NMR and IR spectroscopy, low-temperature nitrogen adsorption-desorption, and transmission electron microscopy. The acidities of the PAF-1-SO₃H and PAF-2-SO₃H samples determined by titration were 3.99 mmol g^–1 and 0.91 mmol g^–1, respectively. The catalytic activity of PAF-SO₃H for alkylation of phenol with linear terminal olefins was investigated. The reaction products were isomeric monoalkylphenols (C-alkylates), and alkyl phenyl ethers (O-alkylates).     

Preconcentration and separation of <Superscript>99</Superscript>Tc in groundwater by using TEVA resin

An effort has been made to optimize the counting time for low-level measurement of naturally occurring radioactive material (NORM) by considering the standard deviation between the activity values of different photopeaks and counting error. It is observed that at lower counting time, relative standard deviation (RSD) varies randomly, but attains a gradual trend with increasing time and also comes closure to the counting error. Therefore minimum counting time for low-level NORM measurement of ²³⁸U and ²³²Th would be the time required to stabilize the RSD values.     

Polyethylenimine and tris(2-aminoethyl)amine modified p(GA–EGMA) microbeads for sorption of uranium ions: equilibrium,kinetic and thermodynamic studies

Poly(glycidyl methacrylate-ethyleneglycol dimethacrylate), p(GA–EGMA), microbeads were prepared through suspension polymerization. It was decorated with polyethylene imine (PEIM) and tris(2-aminoethyl)amine (TAEA) ligands to decorate with polyamine groups. These microbeads were used for sorption of uranium ions from aqueous solution. The maximum sorption of uranium ions on the PEIM and TAEA modified microbeads was observed at pH 6.0. The maximum sorption capacity of acid hydrolyzed p(GA–EGMA)–OH, p(GA–EGMA)–PEIM and p(GA–EGMA)–TAEA microbeads was found to be 7.21, 87.8 and 64.3 mg g^?1. The sorption process conforms to the pseudo-second order kinetic model and the Langmuir and Temkin isotherm models well.     

Measurement of <Superscript>3</Superscript>H,gross <Emphasis Type="Italic">α/β</Emphasis> and <Superscript>222</Superscript>Rn in drinking water using the new Quantulus GCT 6220

Since the introduction of the European Council Directive 2013/51 Euratom in October 2013, the analysis of drinking water has increasingly become the focus of many laboratories in Europe. The activity of tritium, radon and the gross α/β-activity is determined routinely. In order to cope with the increased sample numbers and to reach the necessary detection limits, sensitive measuring devices are required. This work was done with the new Quantulus GCT 6220 to test the sensitivity of this system for drinking water analysis. The results indicate that this instrument is very well suited for this type of analysis and counting times are typically below the required counting times of established systems.     

Structural requirement of C11b chirality of tetrabenazine analogs as VMAT2 imaging ligands: synthesis and in vivo evaluation

We studied on the structural requirement of C11b chirality of tetrabenazine (TBZ) analogs as vesicular monoamine transporter 2 (VMAT2) ligands. TBZ analogs (2, 6a, 6b) and ¹⁸F-radiolabeled [¹⁸F]6a and [¹⁸F]6b with eliminated C11b chirality were synthesized and characterized. Competition studies demonstrated that 2, 6a and 6b displayed much lower in vivo VMAT2 bindings than TBZ. MicroPET imaging studies of [¹⁸F]6a and [¹⁸F]6b showed negligible accumulation in VMAT2-enriched regions as compared with the known VMAT2 ligand ¹⁸F-FP-(+)-DTBZ. These results suggest that C11b chirality of TBZ analogs is essential for in vivo VMAT2 binding bioactivity.     

Detection efficiency calculations using Geant4 for a broad-energy germanium gamma spectrometer

In assistance of radionuclide measurements at Canada’s Comprehensive Nuclear-Test-Ban Treaty (CTBT) laboratory, a Geant4 Monte Carlo application has been developed in simulating a broad-energy germanium detector and calculating detection efficiencies. The detector model was optimized in a reliable and non-biased manner through simultaneous tuning on gap distance and detector dimension, and was validated over various realistic measurement scenarios. All work is based on a series of experiments which covers the typical energy range of gamma radiation in environmental analysis, and considers the variety of the CTBT sample type, dimension and distance-to-detector. In all cases, the predicted efficiencies are consistent with the empirical ones within 5%, with a typical deviation of 3% in majority.