Two methods for the separation of monounsaturated octadecenoic acid isomers

The identification and quantification of complex mixtures of cis and trans octadecenoic (18:1) fatty acid isomers presents a major challenge for conventional one-dimensional GC/FID analysis of their methyl esters. We have compared the use of two methods to achieve optimized separations of positional and geometrical octadecenoic fatty acid isomers—comprehensive two-dimensional gas chromatography (GC × GC), and silver ion high performance liquid chromatography interfaced to atmospheric pressure photoionization (APPI) mass spectrometry. Nine isomers of octadecenoic acid methyl ester were well separated on a single silver ion column with a mobile phase of 0.018% acetonitrile and 0.18% isopropanol in hexane. Reproducible retention times were obtained with relative standard deviations of around 1% over 5 injections. The extra selectivity and reproducibility afforded by APPI-MS, together with the wide separation of cis and trans isomers by silver ion chromatography, resulted in a promising method for measurement of octadecenoic acid FAME. The GC × GC separation was performed using various column combinations, and optimal separation was obtained by coupling an ionic liquid column (Supelco SLB-IL100 [1,9-di(3-vinyl-imidazolium) nonane bis(trifluoromethyl) sulfonyl imidate]) in the first dimension with a SGE BPX50 (50% phenyl polysilphenylene-siloxane) in the second dimension. These methods have been applied to the analysis of octadecenoic acid in milk and beef fat.     

Asymmetrical hippocampal connectivity in mesial temporal lobe epilepsy: evidence from resting state fMRI

Background

Recent studies have shown that the human right-hemispheric auditory cortex is particularly sensitive to reduction in sound quality, with an increase in distortion resulting in an amplification of the auditory N1m response measured in the magnetoencephalography (MEG). Here, we examined whether this sensitivity is specific to the processing of acoustic properties of speech or whether it can be observed also in the processing of sounds with a simple spectral structure. We degraded speech stimuli (vowel /a/), complex non-speech stimuli (a composite of five sinusoidals), and sinusoidal tones by decreasing the amplitude resolution of the signal waveform. The amplitude resolution was impoverished by reducing the number of bits to represent the signal samples. Auditory evoked magnetic fields (AEFs) were measured in the left and right hemisphere of sixteen healthy subjects.

Results

We found that the AEF amplitudes increased significantly with stimulus distortion for all stimulus types, which indicates that the right-hemispheric N1m sensitivity is not related exclusively to degradation of acoustic properties of speech. In addition, the P1m and P2m responses were amplified with increasing distortion similarly in both hemispheres. The AEF latencies were not systematically affected by the distortion.

Conclusions

We propose that the increased activity of AEFs reflects cortical processing of acoustic properties common to both speech and non-speech stimuli. More specifically, the enhancement is most likely caused by spectral changes brought about by the decrease of amplitude resolution, in particular the introduction of periodic, signal-dependent distortion to the original sound. Converging evidence suggests that the observed AEF amplification could reflect cortical sensitivity to periodic sounds.     

Commensurability effects in magnetic properties of superconducting Nb thin films with periodic submicrometric pores

Pinning properties in 100 nm thick continuous and porous superconducting Nb films are examined by ac susceptibility and dc magnetization measurements. The Nb film was deposited on a smooth Si substrate, while the porous film, Nb_P, was deposited on an anodized Al oxide substrate. Pores or “antidots” 40 nm in diameter, 100 nm apart, form a triangular array. The porous film presents commensurate or matching field effects for applied magnetic fields where the magnetic flux threading each unit cell is an integer number of the flux quantum, where ac shielding capability and dc diamagnetic magnetization show an abrupt increase. The response to ac fields as a function of temperature and dc field provided a way to determine that Nb_P sample has higher pinning than the continuous one, and that T_C suppression due to fluxoid quantization is not relevant for the investigated temperature range.     

Hydrolytic resistance of Na2O---B2O3---SiO2 gels prepared by sol-gel process

Alkoxide derived gels were prepared in the system Na₂O---B₂O₃---SiO₂. The gel compositions were situated in the liquid-liquid immiscibility area of the phase equilibrium diagram.

Hydrolytic resistance tests were performed on the gels heat-treated at temperatures ranging between 120 to 850 °C. The Na₂O, B₂O₃ and SiO₂ extracted from the attack gels were analyzed. The experimental results indicate that the amount of B₂O₃ has a significant influence on the chemical durability of the heat-treated gels. At temperatures of 850 °C the greater the B₂O₃ mol% the greater are the amounts of Na₂O and B₂O₃ extracted. Different behaviour was observed for gels heat-treated at 600 °C where the amounts of B₂O₃ and Na₂O extracted slightly increases as the B₂O₃ mol% increases. Small amounts of extracted SiO₂ were always observed.

These results are complemented with other measurements so that an explanation of the controlling mechanism is given.     

All-oxide superconductor/ferroic hybrids

This short review focuses on interface interactions in hybrid heterostructures which combine high-temperature superconductors, ferromagnets and ferroelectrics. We specifically examine two different phenomena. One of them is electric-field effects at superconductor/ferroelectric interfaces, which allow a nonvolatile, reconfigurable nanoscale modulation of superconductivity. The second phenomenon is the proximity effect at superconductor/ferromagnet interfaces. We focus in particular on the penetration of superconducting correlations into half-metal ferromagnets. For both phenomena, an overview is given on materials’ issues, fabrication techniques, physical mechanisms and related devices.     

A cytochrome c variant resistant to heme degradation by hydrogen peroxide

BACKGROUND: Cytochrome c has peroxidase-like activity and can catalyze the oxidation of a variety of organic substrates, including aromatic, organosulfur and lipid compounds. Like peroxidases, cytochrome c is inactivated by hydrogen peroxide. During this inactivation the heme prosthetic group is destroyed. RESULTS: Variants of the iso-1-cytochrome c were constructed by site-directed mutagenesis and were found to be more stable in the presence of hydrogen peroxide than the wild type. No heme destruction was detected in a triple variant (Tyr67-->Phe/Asn52-->Ile/Cys102-->Thr) with the catalytic hydrogen peroxide concentration of 1 mM, even following the loss of catalytic activity, whereas both double variants Tyr67-->Phe/Cys102-->Thr and Asn52-->Ile/Cys102-->Thr showed a greater rate of peroxide-induced heme destruction than observed with the wild-type protein. CONCLUSIONS: Heme destruction and catalytic inactivation are two independent processes. An internal water molecule (Wat166) is shown to be important in the heme destruction process. The absence of a protein radical in the resistant variant suggests that the protein radical is necessary in the heme destruction process, but presumably is not involved in the reactions leading up to the protein inactivation.     

Optical behaviour of pH detectors based on sol-gel technology

Acidity is an outstanding parameter that affect the correct preservation of most part of materials engaged in artworks and heritage objects. In spite of the new generation of advanced analytical devices, the conservation/heritage management sector claims for some kind of simple, robust and low-cost device to monitor environmental acidity wherever necessary. The purpose of this paper is to offer a suitable alternative for the estimation of environmental acidity by means of detectors to be used without electrodes, solutions, pH meters, wires or batteries.Doped sol-gel thin coatings have been used as transductors for producing pH detectors. The coatings consist of a partially densified polysiloxane network and an organic dye sensitive to pH changes. The siloxane network behaves as a host for immobilisation of the dye molecules, in such a way that chemical-optical properties of the dye are preserved as far as possible. The transductors were applied on common glass substrates by dipping. Further heat-treatment allows the coating partial densification.The optical response of the detectors was analysed by VIS absorption spectroscopy, since a change of colour took place when the detectors were submitted to different pH buffered solutions. With the aim to investigate their optical behaviour as a function of pH, several experimental measurements were undertaken: absorption intensity; maximum spectral wavelength; colour coordinates; colour purity percentages. Time response and memory effect were also studied. The detector operation conditions for monitoring environmental acidity both indoor and outdoor are discussed.     

Can A Denaturant Stabilize DNA? Pyridine Reverses DNA Denaturation in Acidic pH

The stability of DNA is highly dependent on the properties of the surrounding solvent, such as ionic strength, pH, and the presence of denaturants and osmolytes. Addition of pyridine is known to unfold DNA by replacing π–π stacking interactions between bases, stabilizing conformations in which the nucleotides are solvent exposed. We show here experimental and theoretical evidences that pyridine can change its role and in fact stabilize the DNA under acidic conditions. NMR spectroscopy and MD simulations demonstrate that the reversal in the denaturing role of pyridine is specific, and is related to its character as pseudo groove binder. The present study sheds light on the nature of DNA stability and on the relationship between DNA and solvent, with clear biotechnological implications.     

Synthetic and natural silica‐aluminates as inorganic acidic catalysts in ring opening polymerization of cyclosiloxanes

Ring opening polymerization (ROP) of hexamethylcyclotrisiloxane (D₃) and octamethylcyclotetrasiloxane (D₄) was promoted by acid‐treated synthetic and natural silica‐aluminates. Silica‐alumina (1:3 Si/Al molar ratio) was obtained using a simple and economic route from precipitation of aluminum sulfate solutions. The material was treated in an acidic medium to improve the content of acid sites and successfully tested as inorganic acidic catalyst for ROP of D₃ or D₄ cyclosiloxanes. Natural bentonite was treated and used in a similar manner. Once the ROP reaction completed, the catalyst was easily removed and it was found that the recovered synthetic silica‐alumina was active in a second ROP reaction. The effect of the concentration and type of catalyst in respect to the molecular weight and polydispersity of polydimethylsiloxanes was analyzed: increasing the amount of silica‐alumina in ROP of D₄ from 0.05 to 0.1 g decreased the average molecular weight (M_n = 13–1.8 kDa) associated with an increase in the polydispersity (2.95 vs. 1.81). Analogous results were found with bentonite. These values suggest that an increase in the catalyst concentration led to a lower M_n, with a more homogeneous molecular chain dimension. Copyright © 2012 John Wiley & Sons, Ltd.