Retention behavior of conjugated and isolated n-alkadienes. Identification of n-nona- and n-decadienes by capillary gas chromatography using structure-retention correlations and mass spectrometry

The isomerization products of n-C8---C10 a,¿-alkadienes were separated on a high-efficiency squalane column (195 m × 0.25 mm I.D.) with 500,000 effective plates. Of the 102 possible n-C8---C10 dienes with isolated and conjugated double bonds, only nine groups of isomers were not separated. All isomers, except those with cumulated double bonds, were identified (23 octadienes, 33 nonadienes and 46 decadienes). The n-octadienes were identified by matching measured and published retention data. Because of the lack of standards, retention data and mass spectra of n-nona- and decadienes, and because the previously reported identification method for n-dienes up to C8 was succesful, the problem of the identification of C9---C10 n-alkadienes was solved similarly by using structure-retention correlations and combined capillary gas chromatography-mass spectrometry. Based on these results, the retention behaviour of the conjugated and isolated n-alkadienes, on squalane stationary phase, is generalized

Isolation, identification and characterisation of ballan wrasse Labrus bergylta plasma pigment

This work was supported by co-funding from Innovate U.K. (formerly Technology Strategy Board), Marine Harvest Scotland and Scottish Seafarms Ltd (project ref: 81199) as well as the University of Stirling, Impact studentship funding scheme. Mass spectrometry analysis was performed by the BSRC Mass Spectrometry Facility, University of St Andrews.This study confirmed that observations of blue-green colouration in plasma fractions of the ballan wrasse Labrus bergylta were caused by the linear tetra-pyrrole biliverdin and that the molecule was of the physiologically relevant IXα isomer. Accumulation appears driven by chromogenic association with an unknown protein moiety which precludes enzymatic reduction and would suggest active management. It was demonstrated that the pigment did not fluctuate relative to ontogeny, or indeed binary gender in the species of interest, but mobilisation and depletion in the subset of individuals undergoing sex change at the time of study supports a potential association with gender inversion processes. It is of note that although biliverdin does have some effect on external colouration, the evidence is indicative that crypsis is a supplementary function thus other factors must be considered.PostprintPeer reviewe

Optimization of selectivity by tuning column temperatures for series-coupled capillary columns in dual-oven gas chromatographic systems

A method has been developed and evaluated for optimization of the selectivity of series-coupled capillary columns in a twin-oven gas chromatographic system in the shortest possible analysis time. The temperatures of either one or both columns were varied independently (partial optimization) or simultaneously (overall optimization), in order to separate the maximum number of sample components. The method is based upon computer-aided calculation of Kováts indices of the coupled columns by means of second and third order (polynomial) functions of the temperatures of the individual columns. The applicability and limitations of the methods are discussed and illustrated with separations of a synthetic hydrocarbon mixture of 33 components

Yeast cell wall extracts from Saccharomyces cerevisiae varying in structure and composition differentially shape the innate immunity and mucosal tissue responses of the intestine of zebrafish (Danio rerio)

With the rising awareness of antimicrobial resistance, the development and use of functional feed additives (FFAs) as an alternative prophylactic approach to improve animal health and performance is increasing. Although the FFAs from yeasts are widely used in animal and human pharma applications already, the success of future candidates resides in linking their structural functional properties to their efficacy in vivo. Herein, this study aimed to characterise the biochemical and molecular properties of four proprietary yeast cell wall extracts from S. cerevisiae in relation to their potential effect on the intestinal immune responses when given orally. Dietary supplementation of the YCW fractions identified that the α-mannan content was a potent driver of mucus cell and intraepithelial lymphocyte hyperplasia within the intestinal mucosal tissue. Furthermore, the differences in α-mannan and β-1,3-glucans chain lengths of each YCW fraction affected their capacity to be recognised by different PRRs. As a result, this affected the downstream signalling and shaping of the innate cytokine milieu to elicit the preferential mobilisation of effector T-helper cell subsets namely Th17, Th1, Tr1 and FoxP3+-Tregs. Together these findings demonstrate the importance of characterising the molecular and biochemical properties of YCW fractions when assessing and concluding their immune potential. Additionally, this study offers novel perspectives in the development specific YCW fractions derived from S. cerievisae for use in precision animal feeds

Activation by SLAM Family Receptors Contributes to NK Cell Mediated "Missing-Self" Recognition.

Natural Killer (NK) cells attack normal hematopoietic cells that do not express inhibitory MHC class I (MHC-I) molecules, but the ligands that activate NK cells remain incompletely defined. Here we show that the expression of the Signaling Lymphocyte Activation Molecule (SLAM) family members CD48 and Ly9 (CD229) by MHC-I-deficient tumor cells significantly contributes to NK cell activation. When NK cells develop in the presence of T cells or B cells that lack inhibitory MHC-I but express activating CD48 and Ly9 ligands, the NK cells' ability to respond to MHC-I-deficient tumor cells is severely compromised. In this situation, NK cells express normal levels of the corresponding activation receptors 2B4 (CD244) and Ly9 but these receptors are non-functional. This provides a partial explanation for the tolerance of NK cells to MHC-I-deficient cells in vivo. Activating signaling via 2B4 is restored when MHC-I-deficient T cells are removed, indicating that interactions with MHC-I-deficient T cells dominantly, but not permanently, impair the function of the 2B4 NK cell activation receptor. These data identify an important role of SLAM family receptors for NK cell mediated "missing-self" reactivity and suggest that NK cell tolerance in MHC-I mosaic mice is in part explained by an acquired dysfunction of SLAM family receptors

The variable functional effects of the pacing site in normal and scarred ventricles

The pacing site has been shown to influence functional improvement with cardiac resynchronization therapy. We evaluated the effects of the pacing site on left ventricular (LV) function in an animal model. Equilibrium radionuclide angiography was acquired in sinus rhythm (NSR) and with ventricular pacing, from three pacing sites in seven normal and eight infarcted dogs. QRS duration, electrical activation pattern, wall motion, LV ejection fraction (EF), synchrony of ventricular contraction, and mean arterial pressure (MAP), were related to the pacing site and infarct size, during each of 120 episodes. Little changed during pacing in normals. In infarcted dogs, LV wall motion, and synchrony worsened, LVEF and MAP often fell. These changes related to altered activation patterns which were influenced by the pacing site but were not related to infarct size. Hemodynamic and functional LV changes after infarction were found to vary with the pacing site and associated conduction and synchrony

Spin Glass Ordering in Diluted Magnetic Semiconductors: a Monte Carlo Study

We study the temperature-dilution phase diagram of a site-diluted Heisenberg antiferromagnet on a fcc lattice, with and without the Dzyaloshinskii-Moriya anisotropic term, fixed to realistic microscopic parameters for $IIB_{1-x} Mn_x Te$ (IIB=Cd, Hg, Zn). We show that the dipolar Dzyaloshinskii-Moriya anisotropy induces a finite-temperature phase transition to a spin glass phase, at dilutions larger than 80%. The resulting probability distribution of the order parameter P(q) is similar to the one found in the cubic lattice Edwards-Anderson Ising model. The critical exponents undergo large finite size corrections, but tend to values similar to the ones of the Edwards-Anderson-Ising model.Comment: 4 pages plus 3 postscript figure