1H NMR assignment of oligomeric grafts of maleic anhydride-grafted polyolefin.

The (1)H NMR assignment of oligomeric grafts of maleic anhydride (MA)-grafted polyolefin (PO), MA-g-PO hereafter, was experimentally demonstrated for the first time using NMR spectroscopy. (13)C DEPT, (1)H-(1)H DQF-COSY, and (1)H T(2)-edited spectroscopy of MA-g-PO proved that peaks of the intermediate methine protons of succinic anhydride oligomeric grafts, which are nearly tetrameric, are observed at 2.5-3.5 ppm and show broadening.

Absolute asymmetric photoreactions of aliphatic amino acids by circularly polarized synchrotron radiation: critically pH-dependent photobehavior.

The absolute asymmetric photoreaction (AAP) of racemic aliphatic amino acids, such as alanine (Ala) and leucine (Leu), by left- and right-handed circularly polarized light (l- and r-CPL) irradiation was investigated in aqueous solutions at various pHs, by using the Onuki-type polarizing undulator installed in an electron storage ring. The magnitude of the optical purity (op) generated and the enantiomer-enriching mechanism operative in the AAP were found to be entirely dependent on the ionic state (and thus pH) of the amino/carboxylic acid moieties. At pH 1, the op of Ala and Leu determined by circular dichroism (CD) spectral measurement gradually developed with CPL irradiation, according to Kagan's equation. In contrast, irradiation at pH 7 gave op's much smaller than the theoretical values predicted by Kagan's equation. However, it turned out that the photodecomposition at pH 7 produces the corresponding alpha-hydroxycarboxylic acids stereoselectively, the CD sign of which is just opposite to that of the remaining amino acid, thus affording the apparently small op. It is concluded that, irrespective of solution pH, the AAP of amino acid proceeds upon CPL irradiation. At pH 1, the photodecomposition of valine, Leu, and isoleucine occurs via a Norrish type II mechanism, which is also applicable to other amino acids possessing a gamma-hydrogen. In the case of amino acids lacking a gamma-hydrogen, such as glycine and Ala, the photodecomposition mechanism is a photodeamination/hydroxylation and a Norrish type I reaction. At pH 7, the main photoproducts were ammonia and alpha-hydroxycarboxylic acids that were produced via photodeamination.