Stretching single polysaccharide molecules using AFM: A potential method for the investigation of the intermolecular uronate distribution of alginate?

Illustrative examples of the way in which the molecular force-extension behaviour of polysaccharides is governed by the nature of the linkage between their constituent pyranose rings are presented for a series of standard homopolymers. These results agree with previously proposed general hypotheses regarding the possibility of generating force-induced conformational transitions, and with the predictions of a model in which the inter-conversion of pyranose conformers is assumed to be an equilibrium process on the timescale of the molecular stretching. Subsequently, we investigate the potential of the technique in the characterisation of co-polymeric polysaccharides in which the nature of the glycan linkages is different between the two distinct residue types. Specifically, we explore the possibility that the ratio of mannuronic acid (M) to guluronic acid (G) in alginate chains will be reflected in their single molecule stretching behaviour, owing to their contrasting equatorial and axial linkages. Furthermore, as the technique described interrogates the sample one polymer at a time we outline the promise of, and the obstacles to, obtaining a new level of characterisation using this methodology where differences observed in the single molecule stretching curves obtained from single alginate samples reflectsomething of the real intermolecular distribution of the M / G ratio

Development of gelatin-alginate hydrogels for burn wound treatment

Hydrogels are interesting as wound dressing for burn wounds to maintain a moist environment. Especially gelatin and alginate based wound dressings show strong potential. Both polymers are modified by introducing photocrosslinkable functionalities and combined to hydrogel films (gel-MA/alg-MA). In one protocol gel-MA films are incubated in alg-MA solutions and crosslinked afterward into double networks. Another protocol involves blending both and subsequent photocrosslinking. The introduction of alginate into the gelatin matrix results in phase separation with polysaccharide microdomains in a protein matrix. Addition of alg(-MA) to gel-MA leads to an increased swelling compared to 100% gelatin and similar to the commercial Aquacel Ag dressing. In vitro tests show better cell adhesion for films which have a lower alginate content and also have superior mechanical properties. The hydrogel dressings exhibit good biocompatibility with adaptable cell attachment properties. An adequate gelatin-alginate ratio should allow application of the materials as wound dressings for several days without tissue ingrowth

Interplay between Structure and Dynamics in Chitosan Films Investigated with Solid-State NMR, Dynamic Mechanical Analysis, and X-ray Diffraction

Modern solid-state NMR techniques, combined with X-ray diffraction, revealed the molecular origin of the difference in mechanical properties of self-associated chitosan films. Films cast from acidic aqueous solutions were compared before and after neutralization, and the role of the counterion (acetate vs Cl⁻) was investigated. There is a competition between local structure and long-range order. Hydrogen bonding gives good mechanical strength to neutralized films, which lack long-range organization. The long-range structure is better defined in films cast from acidic solutions in which strong electrostatic interactions cause rotational distortion around the chitosan chains. Plasticization by acetate counterions enhances long-range molecular organization and film flexibility. In contrast, Cl⁻ counterions act as a defect and impair the long-range organization by immobilizing hydration water. Molecular motion and proton exchange are restricted, resulting in brittle films despite the high moisture content

Carbohydrate hydrogels with stabilized phage particles for bacterial biosensing: bacterium diffusion studies

Bacteriophage particles have been reported as potentially useful in the development of diagnosis tools for pathogenic bacteria as they specifically recognize and lyse bacterial isolates thus confirming the presence of viable cells. One of the most representative microorganisms associated with health care services is the bacterium Pseudomonas aeruginosa, which alone is responsible for nearly 15 % of all nosocomial infections. In this context, structural and functional stabilization of phage particles within biopolymeric hydrogels, aiming at producing cheap (chromogenic) bacterial biosensing devices, has been the goal of a previous research effort. For this, a detailed knowledge of the bacterial diffusion profile into the hydrogel core, where the phage particles lie, is of utmost importance. In the present research effort, the bacterial diffusion process into the biopolymeric hydrogel core was mathematically described and the theoretical simulations duly compared with experimental results, allowing determination of the effective diffusion coefficients of P. aeruginosa in the agar and calcium alginate hydrogels tested.Financial support to Victor M. Balcao, via an Invited Research Scientist fellowship (FAPESP Ref. No. 2011/51077-8) by Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP, Sao Paulo, Brazil), is hereby gratefully acknowledged

Structural Regime Identification in Ionotropic Alginate Gels: Influence of the Cation Nature and Alginate Structure

International audienceThe morphologies of several ionotropic alginate hydrogels and aerogels were investigated by SAXS according to the nature of the divalent metal cation (Mn2+, Co2+, Zn2+, Cu2+) and the guluronic fraction of the alginate. All alginate hydrogel and aerogel samples show isotropic small-angle X-ray scattering. Gelation results from cooperative associations of cations and chain segments and yields different nanostructures, that is, nanofibrillar morphology or multiple junction morphology, according to cation type and eventually mannuronic/guluronic ratio. Therefore, Mn and Cu gels present the same morphology whatever the guluronic ratio, whereas Co and Zn gels yield different nanostructures. In the size range investigated by SAXS (similar to 10-200 angstrom), the structure of aerogels obtained by CO2 supercritical drying is found to be inherited from the morphology of the parent hydrogel whatever the initial structural regime