Experimental and Theoretical Studies on the Bismuth‐Triflate‐Catalysed Cycloisomerisation of 1,6,10‐Trienes and Aryl Polyenes

Cycloisomerisation of polyenes such as diethyl geranylprenylmalonate [(E)‐ 1 a ], diethyl geranylphenylmalonate [(E)‐ 2 a ] and diethyl cinnamylgeranylmalonate [(E,E)‐ 3 a ] catalysed by bismuth triflate was studied from experimental and theoretical viewpoints. Several intermediates were isolated and characterised, and calculated transition‐state structures are proposed for the three reactions. The diastereoselectivity observed during the reaction of (E)‐ or (Z)‐ 2 a in favour of the formation of trans‐fused bicyclic products is discussed in detail. The nature of the active catalytic species derived from bismuth triflate was also investigated, and the formation of a hybrid Lewis acid/Brønsted acid catalyst with water molecules is proposed, supported by experimental and theoretical data.     

Effect of residual lignin and heteropolysaccharides in nanofibrillar cellulose and nanopaper from wood fibers

Unbleached (UN), oxygen-delignified and fully-bleached (FB) birch fibers with a residual lignin content of ca. 3, 2 and <1 %, respectively, were used to produce nanofibrillated cellulose (NFC) and nanopaper by using an overpressure device. The tensile index, elongation and elastic modulus of nanopaper were compared and the effect of residual cell wall components accessed. Under similar manufacturing conditions, UN NFC produced nanopaper with a density of 0.99 g/cm³, higher than that from FB NFC (0.7 g/cm³). This translated in much lower air permeability in the case of UN nanopaper (1 and 11 mL/min for UN and FB samples, respectively). Fundamentally, these observations are ascribed to the finer fibrils produced during microfluidization of UN fibers compared to those from lower yield counterparts (AFM roughness of 8 and 17 nm and surface areas of 124 and 98 m²/g for NFC from UN and FB fibers, respectively). As a result, values of stress at break and energy absorption of nanopaper from high yield fibers are distinctively higher than those from fully bleached NFC. Interactions of water with the surface and bulk material were affected by the chemical composition and structure of the nanofibrils. While UN nanopaper presented higher water contact angles their sorption capacity (and rate of water absorption) was much higher than those measured for nanopaper from FB NFC. These and other observations provided in this contribution are proposed to be related to the mechanoradical scavenging capacity of lignin in high shear microfluidization and the presence of residual heteropolysaccharides.     

Relative basicities toward metal triflates Lewis acids by electrospray mass spectrometry

The relative Lewis basicity of a series of phosphoryl compounds toward cations M(n+)(OTf)(n-1) derived from triflate salts, M(OTf)(n), is ranked using electrospray mass spectrometry according to competitive adduct formation.     

New identification of proanthocyanidins in cinnamon (<Emphasis Type="Italic">Cinnamomum zeylanicum</Emphasis> L.) using MALDI-TOF/TOF mass spectrometry

The inner bark of Ceylon cinnamon (Cinnamomum zeylanicum L.) is commonly used as a spice and has also been widely employed in the treatment and prevention of disease. The positive health effects associated with the consumption of cinnamon could in part be due to its phenolic composition; proanthocyanidins (PA) are the major polyphenolic component in commercial cinnamon. We present a thorough study of the PA profile of cinnamon obtained using matrix-assisted laser desorption/ionization tandem time-of-flight (MALDI-TOF/TOF) mass spectrometry. In addition to the advantages of MALDI-TOF as a sensitive technique for the analysis of high-molecular-weight compounds, the tandem arrangement allows the identification of the compounds through their fragmentation patterns from MS/MS experiments. This is the first time that this technique has been used to analyze polymeric PA. The results show that cinnamon PA are more complex than was previously thought. We show here for the first time that they contain (epi)gallocatechin and (epi)catechingallate units. As gallates (galloyl moieties) and the pyrogallol group in gallocatechins have been related to the biological activity of grape and tea polyphenols, the presence of these substructures may explain some of the properties of cinnamon extracts. MALDI-TOF/TOF reveals that cinnamon bark PA include combinations of (epi)catechin, (epi)catechingallate, (epi)gallocatechin, and (epi)afzelechin, which results in a highly heterogeneous mixture of procyanidins, prodelphinidins, and propelargonidins.     

Analysis of acrylamide in food products by in-line preconcentration capillary zone electrophoresis

Two in-line preconcentration capillary zone electrophoresis (CZE) methods (field amplified sample injection (FASI) and stacking with sample matrix removal (LVSS)) have been evaluated for the analysis of acrylamide (AA) in foodstuffs. To allow the determination of AA by CZE, it was derivatized using 2-mercaptobenzoic acid. For FASI, the optimum conditions were water at pH > or = 10 adjusted with NH3 as sample solvent, 35 s hydrodynamic injection (0.5 psi) of a water plug, 35 s of electrokinetic injection (-10 kV) of the sample, and 6s hydrodynamic injection (0.5 psi) of another water plug to prevent AA removal by EOF. In stacking with sample matrix removal, the reversal time was found to be around 3.3 min. A 40 mM phosphate buffer (pH 8.5) was used as carrier electrolyte for CZE separation in both cases. For both FASI and LVSS methods, linear calibration curves over the range studied (10-1000 microg L(-1) and 25-1000 microg L(-1), respectively), limit of detection (LOD) on standards (1 microg L(-1) for FASI and 7 microg L(-1) for LVSS), limit of detection on samples (3 ng g(-1) for FASI and 20 ng g(-1) for LVSS) and both run-to-run (up to 14% for concentration and 0.8% for time values) and day-to-day precisions (up to 16% and 5% for concentration and time values, respectively) were established. Due to the lower detection limits obtained with the FASI-CZE this method was applied to the analysis of AA in different foodstuffs such as biscuits, cereals, crisp bread, snacks and coffee, and the results were compared with those obtained by LC-MS/MS.     

Tributylphosphine, excellent organocatalyst for conjugate additions of non-nucleophilic N-containing compounds

Conjugate additions of non-nucleophilic N-containing compounds such as amides, thioamides, sulfonamides, and electron-poor anilines with different Michael acceptors can be promoted through the use of tributylphosphine. The range of useful pK_a's of nucleophiles has been established (pK_a<25) and new insights into the mechanism proposed.