No abstract

Anthocyanins were extracted from a mixture of berries of Vaccinium angustifolium and Vaccinium myrtilloïdes at 7.7 degrees C, 26 degrees C, and 79 degrees C using ethanol alone or ethanol acidified with hydrochloric, citric, tartaric, lactic, or phosphoric acids at a solvent to solid ratio of 10. The effect of these parameters on extracted anthocyanins stability was investigated. The pH-differential and HPLC-DAD methods were used to determine anthocyanin contents. Extracted anthocyanins were purified on a C-18 solid-phase extraction cartridge and characterized by HPLC/electrospray ionization/mass spectrometry (HPLC-ESI-MS/MS). Anthocyanins were identified according to their HPLC retention times, elution order, and MS fragmentation pattern and by comparison with standards and published data. Anthocyanin extractions gave different yields depending on the type of added acid and the extraction temperature. High yields of monomeric and total anthocyanins (26.3 and 28.9 mg/g of dry matter) were obtained at 79 degrees C using phosphoric acid. Extraction using tartaric acid at 79 degrees C provided the lowest degradation index (1.05). Anthocyanins were stable and browning by polyphenol oxidase was inhibited under these conditions. Of the six common anthocyanindins, five were identified in the extracts, namely, delpinidin, cyanidin, peonidin, petunidin, and malvidin; pelargonidin was not found. In addition to well-known major anthocyanins, new anthocyanins were identified for the first time in extracts of wild blueberries from Quebec.

The pKa's of 13 heterocyclic aromatic compounds have been measured in tetrahydrofuran (THF) using 13C nmr spectroscopy. The acidifying effect of a nitrogen heteroatom is seen to be quite large (4–6 pK units versus C—H) on an adjacent C—H bond but small on a more remote hydrogen. Most of these aromatic heterocycles are sufficiently acidic, pKa < 34, to be completely deprotonated by lithium tetramethylpiperidide in THF. Benzoxazole appears to be an extremely strong carbon acid, its ring-opened isomer having a pKa of less than 15.7.

Aminosilanes hydrolyze rapidly in aqueous acidic solutions and exhibit good stability; however 1H NMR measurements indicate that γ‐MPS (γ‐methacryloxypropyltrimethoxy silane) hydrolyzes slowly and condenses rapidly under similar conditions. The rate constant of these two reactions depends upon the pH of the solution, and the rate constant of the condensation reaction also depends upon the initial γ‐MPS concentration. The hydrolysis is faster and the condensation slower at low pH's. These factors explain why an induction period is observed before the adsorption of γ‐MPS onto mica takes place and why it does not occur if the induction period is too long. Using the Lentz technique, it is also shown that the main species resulting from the condensation of a concentrated γ‐MPS solution is a cyclic trimer or tetramer, in agreement with literature results.