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Effects of interaural decoherence about level of responsiveness to be able to interaural level variations across frequency.
The proportion of heifers estrual by the first timepoint was greater (P less then 0.0001) with Approach 72 (76 %; 302/395) compared to Approach 66 (61 %; 242/399). The proportion of heifers pregnant as a result of AI differed (P = 0.0005) by semen type (59 % [240/404] for conventional compared with 48 % [187/390] for sex-sorted) but was not affected by approach or approach × semen type. In summary, pregnancy per AI of heifers receiving sex-sorted or conventional semen following the 14-d CIDR®-PG protocol did not differ when STAI was delayed 6 h. The proportion of estrual heifers prior to the first timepoint, however, was greater with later STAI.Supramolecular solvents (dubbed SUPRAS) are gaining momentum as extractants of compounds of interest from complex matrixes such as foodstuff and biological and environmental samples. However, their powerful extraction mechanism, based on multiligand ability for solute binding, fails when applied to very polar compounds, hindering their applicability to the extraction of highly polar metabolites. In this work, we introduce the synthesis, characterization, and application of a new kind of SUPRAS formed by heptafluorobutyric acid (HFBA). The polar hydrophobicity of this perfluorinated acid results in a SUPRAS, which coacervates at acidic pHs, that shows a great capability to extract amino acids and oligopeptides (recoveries in the range 81-105%) with nonpolar alkyl, cyclic or aromatic side chain substituents (with log D > -3.62). To further demonstrate the potential of this novel SUPRAS, an analytical methodology for the determination of opiorphin in real saliva samples was developed and fully validated. The HFBA-based SUPRAS was synthetized in situ from 950 µL of stabilized saliva, by the addition of 150 µL of HFBA and 400 µL of HCl 37% (v/v). The resulting SUPRAS was directly injected into a LC-MS/MS system for further quantification. Quantitative recoveries in the range of 87-110% were obtained with relative standard deviations below 20%. The HFBA-based SUPRAS is, therefore, capable of efficiently extracting opiorphin from saliva samples and shows a high potential for the determination of several amino acids and oligopeptides from biological samples.A simple and effective analytical method to determine six contaminants, including five benzophenones (BP, BP-1, BP-3, BP-8, and BP-12) and bisphenol A (BPA) in infant formulas was developed in this study. For this, a sequential experimental design was used to optimize the extraction and cleanup method using low temperature partition (LTP) combined with dispersive solid phase extraction (dSPE). The effect of primary secondary amine (PSA), sodium chloride (NaCl), graphitized carbon black (GCB), octadecyl (C18), strong anion exchanger (SAX), water, acetonitrile (ACN) and, ultrasound (US) time were evaluated using a sequential design of experiments including a Plackett-Burman, a central composite rotatable design, and the Derringer and Suich's tool. find more The method was validated, and it showed a limit of quantification varying from 0.06 to 2 mg.kg-1, good precision ( less then 20% RSD), and recovery (52-106%). The method proposed was applied to twenty-five samples of commercial infant formulas.Concurrent measurement of tyrosine, tryptophan and their metabolites, and other co-factors could help to diagnose and better understand a wide range of metabolic and neurological disorders. The two metabolic pathways are closely related to each other through co-factors, regulator molecules and enzymes. By using high performance liquid chromatography coupled to electrospray ionization triple quadrupole mass spectrometry, we present a robust, selective and comprehensive method to determine 30 molecules within 20 min using a Waters Atlantis dC18. The method was validated according to the guideline of European Medicines Agency on bioanalytical method validation. Analytical performance met all the EMA requirements and the assay covered the relevant clinical concentrations. Linear correlation coefficients were all >0.998. Intra-day and inter-day accuracy were between 80-119% and 81-117%, precision 1-19% respectively. The method was applied to measure TYR, TRP and their metabolites, and other neurologically important molecules in human serum and CSF samples. The assay can facilitate the diagnosis and is suitable for determination of reference values in clinical laboratories.Capillary electrophoresis coupled to mass spectrometry is a power tool in untargeted metabolomics studies to analyze charged and polar compounds. However, identification is a challenge due to the variability of migration times and the lack of MS/MS spectra in CE-TOF-MS, the type of instruments most frequently employed. We present here a CE-MS search platform incorporated in CEU Mass Mediator to annotate metabolites with a confidence level L2. For its the development we analyzed 226 compounds using two fragmentor voltages 100 and 200 V. The information obtained, such as relative migration times (RMT) and in-source fragments, were incorporated into the platform. In addition, we validated the CE-MS search functionality using different types of biological samples such as plasma samples (human, rat, and rabbit), mouse macrophages, and human urine. The RMT tolerance percentage for the search of metabolites has been determined, establishing 5% for all compounds, except for the compounds migrating in the electro-osmotic flow, for which the tolerance should be of 10%. It has also been demonstrated the robustness of the in-source fragmentation, which makes possible the annotation of compounds by means of their fragmentation pattern. As an example, 3-methylhistidine and 1-methilhistidine, whose RMT are very close, have been annotated. Studies of the fragmentation mechanisms of acyl-L-carnitines have shown that in-source fragmentation follows the general fragmentation rules and is a suitable alternative to MS/MS.An online solid-phase extraction (SPE)-coupled liquid chromatography-mass spectrometry (LC-MS) method was established for the determination of 10 nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) in water. Water samples were mixed with methanol to generate 40% methanol solutions (v/v), and filtered by 0.45 μm membrane. The filtration with polytetrafluoroethylene(PTFE) membrane got higher recovery rates than nylon membrane, especially for 4-ring and 5-ring nitro-PAHs. 2.5 mL solution was directly injected into online SPE flow path to allow for online purification and enrichment of target analytes in the SPE column. The nitro-PAHs eluted from the SPE column were automatically transferred to the analytical flow path by a well-designed valve-switching system. With the optimization of LC and MS condition, ten nitro-PAH isomers was separated and detected from each other by LC-MS/MS with negative atmospheric pressure chemical ionization (APCI). It was firstly found that nitro-PAHs could produce strong [M-H]- precursor ions in the primary MS besides [M+e]- and [M+15]-.
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