Determination of the uronic acid composition of seaweed dietary fibre by HPLC

A high-performance liquid chromatographic (HPLC) method is described for determination of the ratio of beta-d-mannuronic acid to alpha-l-guluronic acid (M/G ratio) in dietary fibre of edible seaweeds. Total dietary fibre (TDF) content was determined gravimetrically. The TDF fraction was hydrolysed with 12 m and 1 m H(2)SO(4), then neutralized with AG 4 x 4 resin. The uronic acids were separated in a Tracer Extrasil SAX 5 micro m column (25 cm x 4 mm) at 35 degrees C, with 2 mm KH(2)PO(4) containing 5% methanol as mobile phase at a fl ow rate of 1.5 mL/min. The detection wavelength was UV 210 nm. The chromatographic identifications of beta-d-mannuronic acid and alpha-l-guluronic acid were confirmed by liquid chromatography-mass spectrometry (LC-MS). The method precision was 1.4% for beta-d-mannuronic acid and 3.5% for alpha-l-guluronic acid. The method was used to determine M/G ratio in canned seaweeds (Saccorhiza polyschides and Himanthalia elongata) and in dried seaweeds (H. elongata, Laminaria ochroleuca, Undaria pinnatifida, Palmaria sp. and Porphyra sp.).     

Surface tension and density of mixtures of 1,3-dioxolane+alkanols at 298.15 K: analysis under the extended Langmuir model

Surface tensions (sigma) for [1,3-dioxolane+methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and 1-pentanol] and excess molar volumes (v(E)) for [1,3-dioxolane+methanol, ethanol, 1-propanol, 2-propanol, and 2-butanol] at the temperature 298.15 K and normal atmospheric pressure have been determined as a function of mole fractions. The magnitude of these experimental quantities is discussed in terms of the nature and type of intermolecular interactions in binary mixtures. In order to analyze the surface tension behavior, the extended Langmuir (EL) model was used and the results obtained for the systems containing 1,3-dioxolane were compared with those of other formerly published series: [1,4-dioxane+alkanes] and [1,4-dioxane+alcohols].     

Chemoselective hydrogenation catalysts: Pt on mesostructured CeO2 nanoparticles embedded within ultrathin layers of SiO2 binder

Pt on mesostructured CeO(2) nanoparticles embedded within ultrathin layers of highly structured SiO(2) binder shows highest activity reported with 80% selectivity for the chemoselective hydrogenation of crotonaldehyde. Characterization by transmission electron microscopy (TEM), CO adsorption, and X-ray photoelectron spectroscopy (XPS) show the presence of small Pt metal particles, preferentially located on CeO(2) (70%) together with the formation of Pt-CeO(2-x) sites at the interface between Pt and CeO(2) (4 nm) nanoparticles. These sites are able to polarize the carbonyl group and facilitate the selective hydrogenation of this with respect to the double bond.     

Asymmetric Diels–Alder cycloadditions of d-erythrose 1,3-butadienes to achiral t-butyl 2H-azirine 3-carboxylate

Two d-erythrose 1,3-butadienes were reacted with electrophilic achiral t-butyl 2H-azirine 3-carboxylate giving cycloadducts with good yields and moderate selectivity. The isomers could be separated to give the major (R)-isomers at C-2 in approximately 50% yield in both cases. Alternatively LACASA-DA methodology was applied to one of the reactions leading to homochiral (R)- and (S)-products by changing the chiral nature of an extra chiral BINOL inductor used.     

Optically active imidazole N-oxides derived from l-prolinamine1

Starting with (S)-1-benzylprolinamine and α-hydroxyimino ketones, enantiomerically pure bisheterocyclic imidazole N-oxides bearing the (S)-configured N-benzyl(pyrrolidin-2-yl)methyl residue were prepared. These N-oxides reacted with 2,2,4,4-tetramethylcyclobutane-1,3-dithione to give the corresponding optically active imidazole-2-thione derivatives via a sulfur transfer reaction. Reduction of the N-oxides with Raney-nickel led to deoxygenation, whereas catalytic hydrogenation (Pd/C) in ethanol occurred with simultaneous deoxygenation and debenzylation, leading to optically active 1-(pyrrolidin-2-yl)methyl-1H-imidazoles. Alkylation of the prepared imidazole N-oxides and their respective imidazoles with butyl and hexyl bromide and subsequent anion exchange gave optically active N-alkoxy- and N-alkylimidazolium tetrafluoroborates, respectively, with the properties of ‘room temperature ionic liquids’.     

Cinchona based squaramide catalysed enantioselective Michael addition of α-nitrophosphonates to aryl acrylates: enantioselective synthesis of quaternary α-aminophosphonates

Several cinchona based squaramide catalysts were applied to the asymmetric Michael addition of α-nitroethylphosphonates to acrylic acid aryl esters, resulting in high yields and enantioselectivities. The absolute configuration of one of the quaternary α-nitrophosphonate adducts was deduced from its experimental and calculated CD spectra. The adducts were reduced to their cyclic aminophosphonates by catalytic hydrogenation.     

Electrophilic trifluoromethylation by copper-catalyzed addition of CF3-transfer reagents to alkenes and alkynes

Regio- and stereoselective Cu-catalyzed addition of the above hypervalent iodine reagent to alkynes and alkenes was achieved. In the presence of CuI, the reaction is suitable to perform trifluoromethyl-benzoyloxylation and trifluoromethyl-halogenation of alkenes and alkynes. Electron-donating substituents accelerate the process, and alkenes react faster than alkynes emphasizing the electrophilic character of the addition reaction.     

Synthesis of the O-linked hexasaccharide containing β-D-Galf-(1→2)-β-D-Galf in Trypanosoma cruzi mucins

The hexasaccharide β-D-Galp-(1→2)-[β-D-Galp-(1→3)]-β-D-Galp-(1→6)-[β-D-Galf(1→2)-β-D-Galf(1→4)]-D-GlcNAc (1) is the largest carbohydrate structure released as alditol by reductive β-elimination from mucins of some strains of T. cruzi. The terminal β-D-Galp units are sites of sialylation by trans-sialidase which transfers sialic acid from the host to the parasite. Hexasaccharide 1 was synthesized by a [3 + 3]-convergent strategy based on a nitrile assisted glycosylation, using the trichloroacetimidate method. The β-D-Galf-(1→2)-β-D-Galf-D-GlcNAc synthon was sequentially constructed from the reducing end to the non-reducing end employing benzyl α-D-galactofuranoside as starting material for the internal Galf unit. The choice of this novel precursor, obtained in one-reaction step from galactose, allowed the introduction of an orthogonal and participating levulinoyl group at O-2. Thus, the diastereoselective construction of the Galf-β(1→4)-GlcNAc linkage by the trichloroacetimidate method of glycosylation was achieved. The (1)H NMR spectrum of alditol 2 was identical to the product released by β-elimination from the parasite mucin.     

Layer-block dendrimers with alternating thienylenevinylene and phenylenevinylene units

A series of new hybrid, layer-block π-conjugated dendrons and dendrimers with alternating thienylenevinylene and phenylenevinylene units has been prepared by means of an orthogonal and convergent-growth methodology that made use of the Horner-Wadsworth-Emmons (HWE) reaction. The placement of the thiophene and benzene rings can be accurately controlled to afford a large variety of dendritic structures, although access to compounds of high generation proved difficult. The optical properties of the synthesized dendrimers were determined by UV/vis and fluorescence spectroscopy, and the influence of the generation and nature of the core on the behavior of these materials was evaluated.