Common Modeling Strategies Research Articles

The study of fingerprint characteristics of the emanations from human arm skin using the original sampling system by SPME-GC/MS

An efficient and noninvasive method consisting of an original sampling device, solid phase microextraction (SPME) and gas chromatography–mass spectrometry (GC–MS) was developed to analyze volatile organic emanations from the skin of human arms. The emanations were sampled by SPME connected with the active sampling device for 30 min and transferred into GC–MS immediately for the consequent analysis. The sampling projects for 15 candidates were scheduled in both winter and spring with the same optimized conditions. Thirty-five compounds were finally identified according to various degrees of certainty. Different emission behaviors specified with principal component analysis (PCA) and similar fingerprint characteristics were observed clearly by comparisons of chromatograms of different seasons. Top ten emanations contributing to characteristics in different seasons were attempted to be described using comparisons based on common model strategy. The large amounts of experimental data were all handled by the corresponding chemometrics strategies with the homemade chromatographic data processing system. The results suggest that the analysis based on fingerprint characteristics of human skin emanations could provide useful and important clues to reveal biomarkers among the mixture of human skin emanations.

Heavy-atom skeleton quantization and proton tunneling in "intermediate-barrier" hydrogen bonds.

Quantum effects on proton transfer through barriers of several kcal/mol in hydrogen bonds are investigated theoretically in malonaldehyde. Such "intermediate-barrier" proton transfer processes play a key role in the catalytic activity of some enzymes. Tunneling is shown to be significant in this reaction even at room temperature. More importantly, the quantum nature of the heavy molecular frame atoms is found to substantially enhance proton tunneling. These findings have far-reaching implications for common modeling strategies of proton transfer in complex systems such as biomolecules.