TEMPO-mediated oxidation on galactomannan: Gal/Man ratio and chain flexibility dependence.

Guar (GG) and locust bean (LBG) galactomannans (GMs) oxidation at C-6 was performed with catalyst TEMPO, in which the reaction progress was monitored by consume of NaOH solution. The products were characterized by spectroscopic analysis, infrared, and (1)H-nuclear magnetic resonance, confirming the presence of aldehydes groups as intermediate of reaction to carboxylic acid. From high performance anion exchange chromatography with pulsed amperometric detection Man/Gal molar ratio was determined and demonstrated a preference to oxidize Man during the reaction on both GMs, following a first order kinetics of oxidation. The comparative macromolecular behavior of native and oxidized GMs was obtained through the analysis by high performance size exclusion chromatography, and the persistence length (Lp) was 6nm and 4nm to native LBG and GG, respectively. A more accessible OH-6 at mannose residue in LBG could be related with a two times faster reaction than GG. The selective oxidation with catalyst TEMPO proved to be efficient to increase the flexibility of the GMs during oxidation. Short reaction time and ß-elimination process were mainly observed to LBG, probably due to a more favorable oxidation access to the polysaccharide main chain.

Physicochemical and in vitro biocompatibility of films combining reconstituted bacterial cellulose with arabinogalactan and xyloglucan.

Reconstituted cellulose films were generated using residual bacterial cellulose membranes mechanically defibrillated (RBC fibrils) recycled following wound dressing production via a dry-cast process. Arabinogalactan (AG) extracted from Pereskia aculeata leaves and/or a xyloglucan (GHXG) from Guibourtia hymenifolia seeds were incorporating into the RBC at various compositions, and new films were created using the same process. Biocomposite properties were evaluated by scanning electron microscopy, contact angle (CA), and X-ray diffraction measurements. The attachment and proliferation of murine L929 fibroblasts on RBC and RBC/Hydrocolloids (HD) were also evaluated. RBC films with 20-30% GHXG replacement improved film stability and the inclusion of HD increased microfiber aggregation and reduced porous regions. Changes in the hydrophilic characteristics were also observed and owing to the adhesion effect the inclusion of HD on RBC led to a statistically significant effect of the mechanical properties of films. The RBC/AG films supported L929 adhesion similar to that observed for commercial bacterial cellulose, indicating their potential use for biomedical applications.

Nanometric organisation in blends of gellan/xyloglucan hydrogels.

Mixtures of gellan gum (GL) and a xyloglucan (XGJ) extracted from Hymenaea courbaril seeds were prepared in a solution of 0.15 mol L(-1) NaCl. Rheology measurements revealed that 2.4 g L(-1) pure GL formed a brittle hydrogel, and GL-XGJ blends showed improved pseudoplastic character with higher XGJ contents. SAXS analyses showed that the Rg dimensions ranged from 1.3 to 4.9 nm, with larger values occurring as the amount of XGJ increased, and diffusion tests indicated that better diffusion of methylene blue dye was obtained in the network with a higher XGJ content. AFM topographic images of the films deposited onto mica revealed fewer heterogeneous surfaces with increased XGJ contents. The water contact angle revealed more hydrophobic character on all of the films, and the wettability decreased with increasing amounts of XGJ. Therefore, the demonstrated benefit of using XGJ blends is the production of a soft material with improved interface properties.

Property evaluations of dry-cast reconstituted bacterial cellulose/tamarind xyloglucan biocomposites.

We describe the mechanical defibrillation of bacterial cellulose (BC) followed by the dry-cast generation of reconstituted BC films (RBC). Xyloglucan (XGT), extracted from tamarind seeds, was incorporated into the defibrillated cellulose at various compositions, and new films were created using the same process. Microscopy and contact angle analyses of films revealed an increase in the microfibre adhesion, a reduced polydispersity in the diameters of the microfibrils and increased hydrophobic behaviour as a function of %XGT. X-ray diffraction analysis revealed changes to the crystallographic planes of the RBC and the biocomposite films with preferential orientation along the (110) plane. Compared with BC, RBC/XGT biocomposite with 10% XGT exhibited improvement in its thermal properties and in Young's modulus. These results indicated a reorganisation of the microfibres with mechanical treatment, which when combined with hydrocolloids, can create cellulose-based materials that could be applied as scaffolding for tissue engineering and drug release.

AFM characterization of spin coated carboxylated polystyrene nanospheres/xyloglucan layers on mica and silicon.

Self-assembled nano-arrays have a potential application as solid-phase diagnostics in many biomedical devices. The easiness of its production is directly connected to manufacture cost reduction. In this work, we present self-assembled structures starting from spin coated thin films of carboxylated polystyrene (PSC) and xyloglucan (XG) mixtures on both mica and silicon substrates. AFM images showed PSC nanospheres on top of a homogeneous layer of XG, for both substrates. The average nanosphere diameter fluctuated for a constant speed and it was likely to be independent of the component proportions on the mixture within a range of 30-50% (v/v) PSC. It was also observed that the largest diameters were found at the center of the sample and the smallest at the border. The detected nanospheres were also more numerous at the border. This behavior presents a similarity to spin coated colloidal dispersions. We observed that the average nanosphere diameter on mica substrates was bigger than the nanosphere diameters obtained on top of silicon substrates, under the same conditions. This result seems to be possibly connected to different mixture-surface interactions.

Electrospinning of commercial guar-gum: Effects of purification and filtration.

Guar gums of two different commercial sources were successfully electrospun on both mica and copper tape at several concentrations starting from 1% (w/w). The electrospun fibers formed with the raw materials were not uniform and presented aggregates and beads within the fibers. Two different purification procedures and a filtration sequence with different pore size membranes were applied to enhance galactomannan solution homogeneity and solubility. The consequence was improved fiber morphology. We observed that the precipitation step, within the purification procedure, produced changes in the molar mass distribution and yielded different fiber diameter. Furthermore, spherical aggregates between fibers and within them disappeared after the sequential filtration. The resulting electrospun fiber diameter decreased with membrane pore diameter reduction. We conclude that the filtration process is responsible for molecular disentanglement, as well as disaggregation, which leads to improved electrospun galactomannan fiber morphology.

Galactomannan thin films as supports for the immobilization of Concanavalin A and/or dengue viruses.

The immobilization of the glucose/mannose-binding lectin from Concanavalia ensiformis seeds (ConA) onto a monolayer made of a galactomannan extracted from Leucaena leucocephala seeds (GML), which was adsorbed onto - amino-terminated surfaces, was investigated by means of ellipsometry and atomic force microscopy. The mean thickness of GML monolayer, which polysaccharide consists of linear 1→4-linked ß-D-mannopyranosil units partially substituted at C-6 by α-D-galactopyranosyl units, amounted to (1.5±0.2) nm. ConA molecules adsorbed onto GML surfaces forming (2.0±0.5) nm thick layers. However, in the presence of mannose the adsorption failed, indicating that ConA binding sites were blocked by mannose and were no longer available for mannose units present in the GML backbone. The GML film was also used as support for the adsorption of three serotypes of dengue virus particles (DENV-1, DENV-2 and DENV-3), where DENV-2 formed the thickest film (4±2) nm. The adsorbed layer of DENV-2 onto ConA-covered GML surfaces presented mean thickness values similar to that determined for DENV-2 onto bare GML surfaces. The addition of free mannose units prevented DENV-2 adsorption onto ConA-covered GML films by ~50%, suggesting competition between virus and mannose for ConA binding sites. This finding suggests that if ConA is also adsorbed to GML surface and its binding site is blocked by free mannose, virus particles are able to recognized GML mannose unities substituted by galactose. Interactions between polysaccharides thin films, proteins, and viruses are of great relevance since they can provide basis for the development of biotechnological devices. These results indicate that GML is a potential polysaccharide for biomaterials development, as those could involve interactions between ConA in immune system and viruses.

Dewetting pattern and stability of thin xyloglucan films adsorbed on silicon and mica.

Thin polysaccharide films prepared with xyloglucan (XG), a neutral polysaccharide extracted from the seeds of Guibourtia hymenifolia were prepared by spin-coating and drop deposition under pH3, pH5 and pH12, on silicon and mica substrates. Atomic force microscopy (AFM) images show flat nanoporous matrices with additional grain-like structures on both mica and silicon for pH 3 and pH 5. However, X-ray photoelectron spectroscopy (XPS) and Auger spectra of these adsorbed biopolymers prepared under alkaline condition (pH 12) reveal that Na(+) ions from the solution interact with the mica substrate surface and with XG forming chemical bonds. Both XPS and Auger results suggest XG depolymerisation during adsorption, caused by an alkaline ss-base catalyzed degradation mechanism, which is consistent with the more basic character of the mica surface under these conditions. Thus, the polysaccharide diffusion is inhibited during dewetting due to the surface bonding. On the other hand, the interaction of Na(+) in solution with the silicon surface is weaker, favoring its interaction with the polysaccharide, conserving the overall polymer structure of XG and allowing the biopolymer to slip and diffuse during dewetting, forming the final branched fractal structure.