Versatility of tandem mass spectrometry for focused analysis of oxylipids

Liquid chromatography‐tandem mass spectrometry (LC‐MS/MS) in the multiple reaction monitoring (MRM) scan mode has been the primary MS method applied for the target identification of specific and minor oxylipids in complex matrices, such as eicosanoids and docosanoids, which are potent lipid mediators derived from polyunsaturated fatty acid oxygenation. However, the high specificity of MRM can limit the detection of species with m/z MRM transitions not covered by the method. In addition to MRM, tandem‐quadrupole mass analyzers enable other experiments to be conducted, by fragmenting ions via collision‐induced dissociation process (CID). This paper presents the potential of tandem mass spectrometry for the focused analysis of oxylipids. We have successfully developed an LC‐MS/MS method for the identification of precursor ions of m/z 115, a diagnostic product ion of 5‐hydroxy‐ and 5‐epoxy‐fatty acids. As a proof of concept, the developed method was used to discover several oxylipids oxidized at C5 derived from arachidonic acid (C20 : 4) oxygenation in a hypothalamus rat extract that were not identified using the target MRM methodology. The proposed focused MS/MS‐based approach in a tandem mass analyzer has proven to be a powerful strategy to accelerate the identification of oxylipids with structural similarities and assist the field of lipidomic research. Copyright © 2015 John Wiley & Sons, Ltd.     

Cosmology from <Emphasis Type="Italic">f</Emphasis>(<Emphasis Type="Italic">R</Emphasis>,<Emphasis Type="Italic">T</Emphasis>) Theory in a Variant Speed of Light Scenario

In this work I present a generalization of f(R, T) gravity, by allowing the speed of light to vary. Cosmological solutions are presented for matter and radiation-dominated universes, the former allowing the universe expansion to accelerate while the latter contemplating a possible alternative to inflationary scenario. Remarkably, standard gravity is always retrieved for a special case of f(R, T).     

Multilevel hybrid split-step implicit tau-leap

In biochemically reactive systems with small copy numbers of one or more reactant molecules, the dynamics is dominated by stochastic effects. To approximate those systems, discrete state-space and stochastic simulation approaches have been shown to be more relevant than continuous state-space and deterministic ones. In systems characterized by having simultaneously fast and slow timescales, existing discrete space-state stochastic path simulation methods, such as the stochastic simulation algorithm (SSA) and the explicit tau-leap (explicit-TL) method, can be very slow. Implicit approximations have been developed to improve numerical stability and provide efficient simulation algorithms for those systems. Here, we propose an efficient Multilevel Monte Carlo (MLMC) method in the spirit of the work by Anderson and Higham (SIAM Multiscal Model. Simul. 10(1), 2012). This method uses split-step implicit tau-leap (SSI-TL) at levels where the explicit-TL method is not applicable due to numerical stability issues. We present numerical examples that illustrate the performance of the proposed method.     

A study of CO<Subscript>2</Subscript> capture by high initial strength Portland cement pastes at early curing stages by new non-conventional thermogravimetry and non-conventional differential thermal analysis

Although the literature presents intensive studies based on monitoring cement hydration in adiabatic and semi-adiabatic environments, such as non-conventional differential thermal analysis (NCDTA) systems, studies of cement hydration in controlled climatic chambers are very rare. Using three W/C ratios (0.5, 0.6 and 0.7) and three relative humidity conditions (60, 80 and 100%) at 25 °C, the authors analyzed in real time the evolution of cement hydration reaction during the first 24 h in an environmental-controlled chamber. The main objective of this paper is to present two new developed systems of NCDTA (NNCDTA) and non-conventional TG and to show, using high-strength sulfate-resistant Portland cement pastes in a controlled chamber as application examples, how the developed systems measure on real time the thermal effects and the mass changes that occur during hydration and carbonation reactions. The captured CO₂ mass can be quantified as it occurs by carbonation curves. The results are in agreement with the mechanical and structural properties of the used pastes and with their TG/DTG data, after being processed by different operational conditions. Carbonation for 24 h alters significantly the cement hydrated paste composition, resulting in final poor mechanical resistance properties. However, carbonation for 1 h, in specific conditions, enhances them when compared to a non-carbonated reference paste, due to a final higher content of silica and alumina hydrated phases and to a lower mass ratio between that of their combined water and their total mass as well.     

Interfacial Capacitance of Graphene Oxide Films Electrodes: Fundamental Studies on Electrolytes Interface Aiming (Bio)Sensing Applications

The understanding of bidimensional materials dynamics and its electrolyte interface equilibrium, such as graphene oxide (GO), is critical for the development of a capacitive biosensing platform. The interfacial capacitance (C_i) of graphene-based materials may be tuned by experimental conditions such as pH optimization and cation size playing key roles at the enhancement of their capacitive properties allowing their application as novel capacitive biosensors. Here we reported a systematic study of C_i of multilayer GO films in different aqueous electrolytes employing electrochemical impedance spectroscopy for the application in a capacitive detection system. We demonstrated that the presence of ionizable oxygen-containing functional groups within multilayer GO film favors the interactions and the accumulation of cations in the structure of the electrodes enhancing the GO C_i in aqueous solutions, where at pH 7.0 (the best condition) the C_i was 340 μF mg⁻¹ at −0.01 V vs Ag/AgCl. We also established that the hydrated cation radius affects the mobility and interaction with GO functional groups and it plays a critical role in the Ci, as demonstrated in the presence of different cations Na⁺=640 μF mg⁻¹, Li⁺=575 μF mg⁻¹ and TMA⁺=477 μF mg⁻¹. As a proof-of-concept, the capacitive behaviour of GO was explored as biosensing platform for standard streptavidin-biotin systems. For this system, the C_i varied linearly with the log of the concentration of the targeting analyte in the range from 10 pg mL⁻¹ to 100 ng mL⁻¹, showing the promising applicability of capacitive GO based sensors for label-free biosensing.     

The production of high polymer to surfactant microlatexes

Starved‐feed microemulsion polymerization of styrene was investigated. The influence of the type (SDS or Dowfax 2A1) and concentration of anionic surfactant on the final particle size of latex made by the polymerization of microemulsions of styrene was studied. In addition, the influence of 1‐pentanol and acrylic acid as cosurfactants was examined. Latexes with 20% solids content and polymer to surfactant ratio of 22 were produced, with a particle diameter of 42 nm and very low polydispersity indexes. Smaller particles are produced using SDS than Dowfax 2A1 for the same weight fraction of surfactant; however, similar particle sizes were obtained with the same molar concentrations of SDS and Dowfax 2A1. Further shot additions of monomer increased solids level as high as 40% and polymer to surfactant ratios greater than 40, with particles remaining monodisperse with average diameter smaller than 60 nm. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 48–54, 2010     

Monitoring electrochemical reactions in situ using steady-state free precession C NMR spectroscopy

All attempts to use in situ¹³C NMR in spectroelectrochemical studies, using static cells and unlabeled substrates, have failed due to the very long average time (several hours). In this paper, we demonstrated that steady-state free precession (SSFP) pulse sequence can enhance signal to noise ratio and reduces the average time of ¹³C NMR signals by more than one order of magnitude. The results showed that each ¹³C NMR spectrum during the electrochemical reduction of 9-chloroanthracene, in a static cell, can be acquired in eleven minutes. This short averaging time allowed the analysis of the reaction every 30 min during 3 h. The phase and truncation anomalies present in SSFP spectra were minimized using Traff apodization function and Krylov basis diagonalization method (KBDM).     

Chemical degradation processes of highly stable red phosphorescent organic light emitting diodes

We investigate the chemical degradation processes of highly stable red organic light emitting diodes (OLEDs) based on the triplet emitter tris(1-phenylisoquinoline)iridium(III) by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF-MS). The analysis of LDI-TOF spectra, collected on OLEDs driven at different current densities, shows a direct correlation between the lifetime of the devices and the formation of the three different reaction products: a BPhen dimer, an adduct of BPhen dimer with cesium, and the complex [BAlq₂ + Al(Me-q)₂]⁺ as well. Additionally it was possible to identify another degradation product, whose chemical structure is related to the α-NPD molecule as well to the fluorine of the used p-dopant. This product is only observable in devices aged at very high current densities.     

Chemical Composition and Antioxidant Activity of Essential Oils from Leaves of Two Specimens of Eugenia florida DC.

Eugenia florida DC. belongs to the Myrtaceae family, which is present in almost all of Brazil. This species is popularly known as pitanga-preta or guamirim and is used in folk medicine to treat gastrointestinal problems. In this study, two specimens of Eugenia florida (Efl) were collected in different areas of the same region. Specimen A (EflA) was collected in an area of secondary forest (capoeira), while specimen B (EflB) was collected in a floodplain area. The essential oils (EOs) were extracted from both specimens of Eugenia florida by means of hydrodistillation. Gas chromatography coupled to mass spectrometry (GC/MS) was used to identify the volatile compounds present, and the antioxidant capacity of the EOs was determined by antioxidant capacity (AC-DPPH) and the Trolox equivalent antioxidant (TEAC) assay. For E. florida, limonene (11.98%), spathulenol (10.94%) and α-pinene (5.21%) were identified as the main compounds of the EO extracted from sample A, while sample B comprised selina-3,11-dien-6α-ol (12.03%), eremoligenol (11.0%) and γ-elemene (10.70%). This difference in chemical composition impacted the antioxidant activity of the EOs between the studied samples, especially in sample B of E. florida. This study is the first to report on the antioxidant activity of Eugenia florida DC. essential oils.