Ion current surface for a double focusing mass spectrometer of reversed geometry

Ion currents obtained for fragmentations in a mass spectrometer of reversed geometry have been represented as three-dimensional surfaces, which are termed ‘ion current surfaces’. In addition to ion current, useful dimensions of the ion current surfaces are a parameter ln(|ρ|) where ρ = (V₀/V)(E/E₀) and a parameter ln(|m*|) where m* = (V₀/V)m_B. Each ion reaction occurring in the source and flight path gives rise to a pattern of peaks and ridges on the surface. If the major features of the surface corresponding to each ion reaction are projected onto the zero ion current plane, they are disposed in a characteristic trapezoidal pattern. All simple and linked modes of scanning correspond to cross-sections of the surfaces, and representing the scanning modes in this light facilitates the identification of ‘cross-talk’.     

The Synthesis and Liquid Crystal Properties of Some 2,5-Disubstituted Pyridines

The synthesis is reported of fifteen three-ring 2,5-disubstituted pyridines and two pyridine-N-oxides where the pyridine rings carry a variety of alkyl, aryl, cyclohexyl, cyclohexylethyl and fluorinated-aryl substituents. The mesomorphic transition temperatures for these compounds have been measured; all the compounds show enantiotropic phases. The different substituent effects are discussed and comparisons are made with previous work on analogous systems where the hetero-function is replaced by C-F.     

Universal scaling of the elliptic flow data at RHIC

Recent PHOBOS measurements of the excitation function for the pseudo-rapidity dependence of the elliptic flow in Au + Au collisions at RHIC have posed a significant theoretical challenge. Here we show that these differential measurements, as well as the RHIC measurements on transverse momentum satisfy a universal scaling relation predicted by the Buda-Lund model, based on exact solutions of perfect fluid hydrodynamics. We also show that the recently found transverse kinetic energy scaling of the elliptic flow is a special case of this universal scaling.     

Increase of Redox Potential during the Evolution of Enzymes Degrading Recalcitrant Lignin

To investigate how ligninolytic peroxidases acquired the uniquely high redox potential they show today, their ancestors were resurrected and characterized. Unfortunately, the transient Compounds I (CI) and II (CII) from peroxide activation of the enzyme resting state (RS) are unstable. Therefore, the reduction potentials (E°′) of the three redox couples (CI/RS, CI/CII and CII/RS) were estimated (for the first time in a ligninolytic peroxidase) from equilibrium concentrations analyzed by stopped-flow UV/Vis spectroscopy. Interestingly, the E°′ of rate-limiting CII reduction to RS increased 70 mV from the common peroxidase ancestor to extant lignin peroxidase (LiP), and the same boost was observed for CI/RS and CI/CII, albeit with higher E°′ values. A straightforward correlation was found between the E°′ value and the progressive displacement of the proximal histidine Hϵ1 chemical shift in the NMR spectra, due to the higher paramagnetic effect of the heme Fe³⁺. More interestingly, the E°′ and NMR data also correlated with the evolutionary time, revealing that ancestral peroxidases increased their reduction potential in the evolution to LiP thanks to molecular rearrangements in their heme pocket during the last 400 million years.     

H2‐Fueled ATP Synthesis on an Electrode: Mimicking Cellular Respiration

ATP, the molecule used by living organisms to supply energy to many different metabolic processes, is synthesized mostly by the ATPase synthase using a proton or sodium gradient generated across a lipid membrane. We present evidence that a modified electrode surface integrating a NiFeSe hydrogenase and a F₁F₀‐ATPase in a lipid membrane can couple the electrochemical oxidation of H₂ to the synthesis of ATP. This electrode‐assisted conversion of H₂ gas into ATP could serve to generate this biochemical fuel locally when required in biomedical devices or enzymatic synthesis of valuable products.     

Selective synthesis of 4-thiomethyl-1,3-dioxolan-2-ones under microwave irradiation using an environmentally benign KF/Al2O3/PEG-400 system

Research on Chemical Intermediates - We describe a simple and rapid method for selective synthesis of 4-thiomethyl-1,3-dioxolan-2-ones promoted by KF/Al2O3 using PEG-400 as solvent under microwave...     

Electrochemical Detection Using an Engraved Microchip – Capillary Electrophoresis Platform

The present study describes a simple strategy to integrate electrochemical detection with an assembled microchip‐capillary electrophoresis platform. The electrochemical cell was integrated with a microfluidic device consisting of five plastic squares interconnected with fused silica capillaries, forming a four‐way injection cross between the separation channel and three side‐arms (each of 15 mm in length) acting as buffer/sample reservoirs. The performance of the system was evaluated using electrodes made with either carbon ink, carbon nanotubes, or gold and under different experimental conditions of pH, capillary length, and injection time. Using this system it was possible to separate the neurotransmitters dopamine and cathecol and to quantify phenol from a real sample using a linear calibration curve with a calculated LOD of 0.7 µM. A similar concept was applied to determine glucose, by including a pre‐reactor filled with beads modified with glucose oxidase (GOx). The latter system was used to determine glucose in a commercial sample, with a recovery of 95.2 %. Overall, the presented approach represents a simple, inexpensive, and versatile approach to integrate electrochemical detection with CE separations without requiring access to microfabrication facilities.     

Behaviour of a non-local equation modelling linear friction welding

A non-local parabolic equation modelling linear friction weldingis studied. The equation applies on the half line and containsa non-linearity of the form . For f(u) = e^u, global existence and convergence to a steadystate are proved. Numerical calculations are also carried outfor this case and for f(u) = (– u)^1/a.     

Phase equilibrium measurements of ternary systems formed by linoleic and linolenic acids in carbon dioxide/ethanol mixtures

This work reports phase equilibrium measurements for the ternary systems linoleic (acid + CO₂ + ethanol) and (linolenic acid + CO₂ + ethanol). The fatty acids present in the ternary systems were selected based on composition of banana peel oil extracted by supercritical CO₂ at 20 MPa and 313 K. The motivation of this research relies on the fact that these unsaturated fatty acids are recognized to play an important role in lowering blood pressure and serum cholesterol and because they are present in high concentrations in banana peel extract. Besides that, equilibrium data of these compounds are scarce in literature. The phase equilibrium experiments were performed using a high-pressure variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 19 MPa. For both systems, only vapour–liquid phase transitions were visually recorded for all data measured.