RESUMO
In this work pentose sugar (D-xylose, D-ribose and D-arabinose) gas phase dehydration reaction was investigated by means of mass spectrometric techniques and theoretical calculations. The ionic species derived from the dehydration reaction of protonated D-ribose and D-arabinose were structurally characterized by their fragmentation patterns and the relative dehydration energies measured by energy resolved CAD mass spectra. The results were compared with those recently obtained for D-xylose in the same mass spectrometric experimental conditions. Dehydration of C1-OH protonated sugars was theoretically investigated at the CCSD(T)/cc-pVTZ//M11/6-311++G(2d,2p) level of theory. Protonated pentoses are not stable and promptly lose a water molecule giving rise to the dehydrated ions at m/z 133. D-xylose, D-ribose and D-arabinose dehydration follows a common reaction pathway with ionic intermediates and transition states characterized by similar structures. Slightly different dehydration energies were experimentally measured and the relative trend was theoretically confirmed. The overall dehydration activation energy follows the order arabinoseâ¯<â¯riboseâ¯<â¯xylose. Gas-phase pentose sugar dehydration leads to the formation of protonated 2-furaldehyde as final product. Based on the experimental and theoretical evidence a new mechanistic hypothesis starting from C1-OH protonation was proposed.
Assuntos
Arabinose/química , Pentoses/química , Ribose/química , Açúcares/química , Xilose/química , Desidratação , Espectrometria de MassasRESUMO
This study was performed to assess the effectiveness of ultrasonography in the diagnosis of wrist ganglia and in their differentiation from other lesions. Sonographic examination of 73 patients with palpable masses was performed; their healthy hands and those of 25 healthy volunteers constituted the reference standard. Ganglia appeared sonographically as anechoic oval, round, or lobulated cystic structures. Ultrasound proved an accurate tool in their diagnosis, with the general advantages of easy, quick, and inexpensive application.