The relative influence of derivatization and normalization procedures on the compound-specific stable isotope analysis of nitrogen in amino acids.

RATIONALE: Within the last decade, applications of compound-specific stable isotope analysis of nitrogen (δ15 N values) in amino acids (CSIA-AA) have developed rapidly, particularly within organismal ecology. Unlike with bulk stable isotope analysis (BSIA), the reproducibility of δ15 N-AA measurements has not been critically assessed. Two primary concerns include the diversity of techniques available for the derivatization of amino acids prior to analysis by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) and the myriad of standardization practices and quality assurance procedures used across studies. METHODS: We examined the relative effect of three normalization procedures, (1) internal reference calibration, (2) compound-specific calibration, and (3) scale-normalization, on the accuracy and precision of δ15 N-AA measurements by GC/C/IRMS and the comparability of δ15 N-AA measurements by two derivatization techniques, methoxycarbonylation-esterification and acetylation-esterification, across a range of organisms. RESULTS: The overall accuracy and precision of δ15 N-AA measurements were improved following both compound-specific calibration and scale-normalization, as was the comparability of δ15 N-AA measurements of individual amino acids between derivatization techniques across organisms. The mean difference of scale-normalized δ15 N-AA values across all organisms between the two derivatization techniques was 0.19‰, much less than the typical analytical error associated with δ15 N-AA measurements (±1‰). CONCLUSIONS: Adoption of standardized calibration procedures will be important to establishing reproducibility in δ15 N-AA measurements, particularly across derivatization techniques. It is both technically practical and desirable for users of CSIA-AA to adopt practices in quality control and assessment similar to those outlined for BSIA, including the compound-specific calibration of δ15 N-AA values, followed by scale-normalization. Copyright © 2017 John Wiley & Sons, Ltd.

Wine flavor: chemistry in a glass.

Although hundreds of chemical compounds have been identified in grapes and wines, only a few compounds actually contribute to sensory perception of wine flavor. This critical review focuses on volatile compounds that contribute to wine aroma and provides an overview of recent developments in analytical techniques for volatiles analysis, including methods used to identify the compounds that make the greatest contributions to the overall aroma. Knowledge of volatile composition alone is not enough to completely understand the overall wine aroma, however, due to complex interactions of odorants with each other and with other nonvolatile matrix components. These interactions and their impact on aroma volatility are the focus of much current research and are also reviewed here. Finally, the sequencing of the grapevine and yeast genomes in the past approximately 10 years provides the opportunity for exciting multidisciplinary studies aimed at understanding the influences of multiple genetic and environmental factors on grape and wine flavor biochemistry and metabolism (147 references).

Oxidation of cysteine and glutathione by soluble polymeric MnO2.

The kinetics of reduction of soluble polymeric MnO2 by cysteine and glutathione has been studied in the pH range of 4.0-9.0. The concentration of thiols was varied between 1 and 2 mM, while the MnO2 concentration was varied between 2 and 12 microM. In this pH range, the reaction products were identified as Mn(II) and the corresponding disulfides (cystine and glutathione disulfide). Cysteic or cysteine sulfonic acid was formed only when pH < 2. Experimental data indicate that the rate law over the pH range of 4-9 is first-order in both MnO2 and thiol concentration. Eyring plots for both thiols reacting with MnO2 indicate that the reaction is associative (deltaS(double dagger) approximately -160 J mol(-1) K(-1)) and proceeds via an inner-sphere redox process. The reaction proceeds via the formation of two different inner-sphere complexes [triple bond]Mn(IV)SR- and [triple bond]Mn(IV)SR and their further reaction to products. Both surface species are linked to each other via acid-base equilibria, and the rate constant decreases as pH increases. The presence of two ligand surface species is determined using surface complexation modeling. A reaction mechanism in agreement with the experimental results is proposed.