We report two methods that have allowed the attachment of glucose, mannose and lactose to one or both of the cyclopentadienyl rings of ferrocene. The resulting ferrocene-carbohydrate conjugates were synthesised by the reaction of thioglycosides with ferrocenemethanol and 1,1'-ferrocenedimethanol in acidic media. A second method based on the regiospecific copper(I)-catalysed cycloaddition of propargyl glycoside, azidomethyl and bis(azidomethyl)ferrocene as well as azidoethyl glycoside and ethynylferrocene was also used and led to the synthesis of 1,2,3-triazole-containing glycoconjugates. The electrochemical behaviour of the synthesised glycoconjugates was investigated. In addition, their binding interactions with beta-cyclodextrin were studied by means of NMR spectroscopy, isothermal titration calorimetry, and cyclic and differential pulse voltammetric experiments. These techniques allowed the determination of the thermodynamic parameters of the complexes, the stability constants for the complexes formed with both the neutral and the oxidised states of the ferrocenyl glycoconjugates, the mode of inclusion and the diffusion coefficients for both the glycoconjugates and the complexes.
The composition of tender leaves from five species of the family Cruciferae (Alliaria petiolata, Cardaria draba, Cakile maritima, Capsella bursa‐pastoris and Sisymbrium irio)from different locations of the southeast of Spain (Almeria) was investigated. The proximate composition, mineral elements (Na, K, Ca, Mg, P, Fe, Cu, Zn and Mn), fatty acids, vitamin C, carotenoids and oxalic acid contents were determined. The available carbohydrate contents ranged from 1.4% ‐ 8.2%. Vitamin C contents were high, specially in Alliaria petiolata (261 mg/100 g). Carotenoid content was relatively high in Alliaria petiolata (13.3 mg). Mineral elements were present at higher concentrations than is common for other green leafy vegetables. Fiber amounts were also remarkable (1.96–5.38 g/100 g). The ω3 series of fatty acids were predominant in the three species (Capsella bursa‐pastoris 54.02%). Oxalic acid values and ratios of oxalic acid/Ca were moderate, being higher in C. maritima. We believe that these species of crucifers could be used for dietary purposes, due to the amount and diversity of nutrients they contain.
A convenient method for the synthesis of b-d-gluco-, b-d-galacto-, 2-acetamido-2-deoxy-b-d-gluco-and ad-mannopyranosylamine clusters based on cyclomaltoheptaose (b-cyclodextrin) is presented. The synthesis involves: 1) the one-pot synthesis of the acetylated chloroacetyl N-glycoside derivatives of d-glucose, d-galactose, 2-acetamido-2-deoxy-d-glucose and d-mannose from the corresponding glycosyl azides, 2) conversion of the chloroacetyl N-glycosides into their isothiouronium derivatives, then 3) attachment of the Nglycosides onto heptakis(6-deoxy-6-iodo) and heptakis(6-chloroacetamido-6-deoxy) b-cyclodextrin by means of nucleophilic displacement with caesium carbonate in dimethylformamide, and 4) de-O-acetylation of b-cyclodextrin derivatives. The chloroacetyl N-glycoside derivatives were easily prepared by mild reduction of the azide function by one of two methods: a) by the Staudinger reaction, with nBu 3 P, and b) with 1,3-propanedithiol, as reducing reagents.
The inclusion behavior and concanavalin A binding properties of hepta-antennated and newly synthesized tetradeca-antennated C-6-branched mannopyranosyl and glucopyrannosyl cyclomaltoheptaose (beta-cyclodextrin) derivatives have been evaluated by isothermal titration microcalorimetry and enzyme-linked lectin assay (ELLA), respectively. The synthesis of three first-order dendrimers based on a beta-cyclodextrin core containing 14 1-thio-beta-D-glucose, 1-thio-beta-mannose, and 1-thio-beta-rhamnose residues was performed following a convergent approach and involving (1) preparation of a thiolated bis-branched glycoside building block and (2) attachment of the building block onto heptakis(6-deoxy-6-iodo)-beta-cyclodextrin. Calorimetric titrations performed at 25 degrees C in buffered aqueous solution (pH 7.4) gave the affinity constants and the thermodynamic parameters for the inclusion complex formation of these beta-cyclodextrin derivatives with guests sodium 8-anilino-1-naphthalensulfonate (ANS) and 2-naphthalenesulfonate. The host capability of the persubstituted beta-cyclodextrins decreased with respect to the native beta-CD when sodium 2-naphthalenesulfonate was used as a guest and improved when ANS was used as a guest molecule. Heptavalent mannoclusters based on beta-CD cores enhance the lectin binding affinity due to the cluster effect; however, the increase of the valency from 7 to 14 ligands did not contribute to the improvement of the concanavalin A binding affinity. In addition, the synthesized hyperbranched mannoCDs lost completely the capability as a host molecules.
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