Ultra performance liquid chromatography – mass spectrometry studies of formalin‐induced alterations of human brain lipidome

The development of ‘omics’ sciences offers new opportunities for the study of neurodegenerative diseases but increases at the same time the sample demand on brain banks that collect and store valuable human post‐mortem tissue. Our study aims to evaluate in lipidomics the potential of formalin‐fixed tissue compared with the cryopreservation method, considered as the gold standard for biochemical research. Two complementary liquid chromatography/mass spectrometry analytical platforms were used on the basis of hybrid quadrupole time‐of‐flight and triple quadrupole mass spectrometers. Untargeted fingerprinting, semitargeted profiling of specific lipid classes and targeted monitoring of lipid species were performed in formalin‐fixed and cryopreserved samples to provide detailed information at the molecular level on the formalin‐induced alterations of the brain tissue. In vitro incubations of lipid standards were also performed to further describe the degradation processes induced by formaldehyde. Phospholipid compounds were found to be extensively hydrolysed, whilst the sphingolipid ones were preserved. N‐methylation and N‐formylation of amine‐containing phospholipids have also been evidenced. These findings show that the potential detrimental effect of formalin on the analytes of interest must be taken into account when analysing formalin‐fixed samples. Copyright © 2014 John Wiley & Sons, Ltd.     

Pd@SnO2 and SnO2@Pd Core@Shell Nanocomposite Sensors

Pd@SnO₂ and SnO₂@Pd core@shell nanocomposites are prepared via a microemulsion approach. Both nanocomposites exhibit high‐surface, porous matrices of SnO₂ shells (>150 m² g^?1) with very small SnO₂ crystallites (<10 nm) and palladium (Pd) nanoparticles (<10 nm) that are uniformly distributed in the porous SnO₂ matrix. Although similar by first sight, Pd@SnO₂ and SnO₂@Pd are significantly different in view of their structure with Pd inside or outside the SnO₂ shell and in view of their sensor performance. As SMOX‐based sensors (SMOX: semiconducting metal oxide), both nanocomposites show a very good sensor performance for the detection of CO and H₂. Especially, the Pd@SnO₂ core@shell nanocomposite is unique and shows a fast response time (τ₉₀ < 30 s) and a very good response at low temperature (<250 °C), especially under humid‐air conditions. Extraordinarily high sensor signals are observed when exposing the Pd@SnO₂ nanocomposite to CO in humid air. Under these conditions, even commercial sensors (Figaro TGS 2442, Applied Sensor MLC, E2V MICS 5521) are outperformed.     

Preservation theorems in linear continuous logic

Linear continuous logic is the fragment of continuous logic obtained by restricting connectives to addition and scalar multiplications. Most results in the full continuous logic have a counterpart in this fragment. In particular a linear form of the compactness theorem holds. We prove this variant and use it to deduce some basic preservation theorems.     

Mitigation of signal suppression caused by the use of trifluoroacetic acid in liquid chromatography mobile phases during liquid chromatography/mass spectrometry analysis via post‐column addition of ammonium hydroxide

A method has been developed to reduce the mass spectrometric ion signal suppression associated with the use of TFA as an additive in LC mobile phases. Through post‐column infusion of diluted NH₄OH solution to LC eluents, the ammonium ion introduced causes the neutral analyte‐TFA ion pair to dissociate which consequently releases the protonated analyte as free ions into the gas phase (through regular electrospray ionization mechanisms). An ion signal improvement from 1.2 to 20 times for a variety of compounds had been achieved through the application of this method. The molar ratios of NH₄OH:TFA which result in a reduction of signal suppression were determined to be between 0.5:1 and 50:1. In addition, it was shown that this NH₄OH infusion method could reduce the level of doubly‐charged species and the product ions formed via in‐source collision. The use of diluted NH₄OH solution is favorable since it is compatible with mass spectrometry analysis, and it is applicable in both positive and negative‐ion generation mode. Copyright © 2012 John Wiley & Sons, Ltd.