Patrizia Sadocco

Antibacterial activity of nanocomposites of silver and bacterial or vegetable cellulosic fibers.

Cellulose/Ag nanocomposites were prepared using two distinct methodologies and two cellulose substrates: vegetable and bacterial cellulose. These nanocomposites were characterized in terms of their morphology and chemical composition. Detailed studies on the antibacterial activity of these materials were carried out for Bacillus subtilis, Staphylococcus aureus and Klebsiella pneumoniae. Silver nanoparticles present in the cellulosic fibers in concentrations as low as 5.0x10(-4)wt.% make these nanocomposites effective antibacterial materials. We anticipate that the versatile use of these cellulose-based nanocomposites can bring a promising strategy to produce a wide range of interesting materials where antibacterial properties are crucial.

Antibacterial activity of optically transparent nanocomposite films based on chitosan or its derivatives and silver nanoparticles

Colloidal silver nanoparticles (NPs) were prepared using the citrate and borohydride reduction methods and were then investigated as fillers in three matrices: unmodified chitosan, water-soluble chitosan and a N-alkyl chitosan derivative. The nanocomposites were used to prepare cast thin films (9-19 μm thickness) and characterized for their optical and antimicrobial properties. The optical properties of the materials were adjusted either by varying the Ag NPs content in the films (0.5-3.9% w/w) or by using samples of Ag NPs with distinct particle size distributions. The antibacterial activity towards both Gram-positive (Staphylococcus aureus) and Gram-negative bacteria (Klebsiella pneumoniae and Escherichia coli) was investigated for the various composites. For the unmodified chitosan nanocomposites, the bactericidal effect depended on their Ag content while such an effect was always observed for water-soluble chitosan and N-alkyl chitosan based materials. This research provides a basis for the evaluation of chitosan/silver composites in applications requiring flexible films with tuned optical properties and antimicrobial activity.

Electrostatic assembly of Ag nanoparticles onto nanofibrillated cellulose for antibacterial paper products

Nanofibrillated cellulose offers new technological solutions for the development of paper products. Here, composites of nanofibrillated cellulose (NFC) and Ag nanoparticles (NP) were prepared for the first time via the electrostatic assembly of Ag NP (aqueous colloids) onto NFC. Distinct polyelectrolytes have been investigated as macromolecular linkers in order to evaluate their effects on the building-up of Ag modified NFC and also on the final properties of the NFC/Ag composite materials. The NFC/Ag nanocomposites were first investigated for their antibacterial properties towards S. aureus and K. pneumoniae microorganisms as compared to NFC modified by polyelectrolytes linkers without Ag. Subsequently, the antibacterial NFC/Ag nanocomposites were used as fillers in starch based coating formulations for Eucalyptus globulus-based paper sheets. The potential of this approach to produce antimicrobial paper products will be discussed on the basis of complementary optical, air barrier and mechanical data.

Bioinspired antimicrobial and biocompatible bacterial cellulose membranes obtained by surface functionalization with aminoalkyl groups.

There has been a great deal of interest in the use of nanostructured bacterial cellulose membranes for biomedical applications, including tissue implants, wound healing, and drug delivery. However, as bacterial cellulose does not intrinsically present antimicrobial properties, in the present study, antimicrobial bacterial cellulose membranes were obtained by chemical grafting of aminoalkyl groups onto the surface of its nanofibrillar network. This approach intends to mimic intrinsic antimicrobial properties of chitosan. Interestingly, these novel grafted bacterial cellulose membranes (BC-NH2) are simultaneously lethal against S. aureus and E. coli and nontoxic to human adipose-derived mesenchymal stem cells (ADSCs) and thus may be useful for biomedical applications. In addition to these biological properties, the bioactive nanostructured BC-NH2 membranes also present improved mechanical and thermal properties.

Small-angle X-ray scattering study of the phase structure of poly(d-(−)-3-hydroxybutyrate) and atactic poly(epichlorohydrin) blends

Abstract Isothermally crystallized and annealed blends of poly( d -(−)-3-hydroxybutyrate) (PHB) and atactic poly(epichlorohydrin) (aPECH) were examined by wide-angle X-ray diffraction and small-angle X-ray scattering (WAXD and SAXS). The lateral crystal dimensions of PHB increased with annealing treatment and with increasing aPECH component in the blends, while the long-period distances of the blends were slightly smaller than for pure PHB. The scattering observed for the blends resulted from the superposition of the scattering arising from the crystalline regions (made up by alternate stacking of lamellae and thin amorphous layers) and from the aPECH inhomogeneity present outside them. The structural information was obtained, from the SAXS curves, on the basis of Glatter and Debye-Bueche approaches. The results suggest that, during melt-crystallization of PHB, segregation of aPECH occurs within the growing spherulite with its dispersion in the interfibrillar zones that are larger than the interlamellar regions but smaller than the overall spherulite. The aPECH molecules are dispersed at the molecular level in the interfibrillar zones where they can assume a random-coil conformation. The detection of a glass transition temperature ( T g ) close to the aPECH T g value indicates low interactions at the segmental level between the two polymers. The annealing treatment produced a general perfectioning and rearrangement of the sample morphology, enhancing the crystallinity and the crystal dimensions of PHB in the pure state and in the blends, and probably favouring the trend of the aPECH molecules to assume a globular conformation.

Antibacterial Activity of Nanocomposites of Copper and Cellulose

The design of cheap and safe antibacterial materials for widespread use has been a challenge in materials science. The use of copper nanostructures combined with abundant biopolymers such as cellulose offers a potential approach to achieve such materials though this has been less investigated as compared to other composites. Here, nanocomposites comprising copper nanofillers in cellulose matrices have been prepared by in situ and ex situ methods. Two cellulose matrices (vegetable and bacterial) were investigated together with morphological distinct copper particulates (nanoparticles and nanowires). A study on the antibacterial activity of these nanocomposites was carried out for Staphylococcus aureus and Klebsiella pneumoniae, as pathogen microorganisms. The results showed that the chemical nature and morphology of the nanofillers have great effect on the antibacterial activity, with an increase in the antibacterial activity with increasing copper content in the composites. The cellulosic matrices also show an effect on the antibacterial efficiency of the nanocomposites, with vegetal cellulose fibers acting as the most effective substrate. Regarding the results obtained, we anticipate the development of new approaches to prepare cellulose/copper based nanocomposites thereby producing a wide range of interesting antibacterial materials with potential use in diverse applications such as packaging or paper coatings.

Influence of the morphology and of the supermolecular structure on the enzymatic degradation of bacterial poly(3-hydroxybutyrate)

Abstract Films of poly(3-hydroxybutyrate) (PHB) were crystallized from the melt by different thermal treatments and submitted to enzymatic degradation by using a PHB depolymerase purified from Aureobacterium saperdae culture. The morphology and the supermolecular structure of PHB films were investigated to explain differences in the kinetics of enzymatic degradation. Differential scanning calorimetry, optical microscopy, wide-angle X-ray diffraction and small-angle X-ray scattering were employed to characterize the PHB films. A decreasing of enzymatic degradation rate was observed with the increasing of crystallinity and crystal dimension of the PHB films. PHB samples showing the same degree of crystallinity and similar value of lamellar thickness were prepared using different isothermal crystallization and annealing temperatures. The differences in the enzymatic degradation rate of these films were explained in terms of morphological parameters.

Fluorescent Bioactive Corrole Grafted-Chitosan Films.

Transparent corrole grafted-chitosan films were prepared by chemical modification of chitosan with a corrole macrocycle, namely, 5,10,15-tris(pentafluorophenyl)corrole (TPFC), followed by solvent casting. The obtained films were characterized in terms of absorption spectra (UV-vis), FLIM (fluorescence lifetime imaging microscopy), structure (FTIR, XPS), thermal stability (TGA), thermomechanical properties (DMA), and antibacterial activity. The results showed that the chemical grafting of chitosan with corrole units did not affect its film-forming ability and that the grafting yield increased with the reaction time. The obtained transparent films presented fluorescence which increases with the amount of grafted corrole units. Additionally, all films showed bacteriostatic effect against S. aureus, as well as good thermomechanical properties and thermal stability. Considering these features, promising applications may be envisaged for these corrole-chitosan films, such as biosensors, bioimaging agents, and bioactive optical devices.

Antibacterial activity and biodegradability assessment of chemically grafted nanofibrillated cellulose

Nanofibrillated cellulose (NFC) and their derivatives were prepared using three chemical surface modification strategies. All grafting was characterized by FTIR and contact angle measurements in order to evaluate the efficiency of grafting. Antibacterial activities of neat and grafted samples were investigated against two kinds of bacteria (i.e. Gram+ (Staphylococcus aureus) and Gram- (Klebsiella pneumoniae)). All the grafted samples displayed promising results with at least bacteriostatic effect or bactericidal properties. They also strongly enhanced the photo-catalytic antimicrobial effect of TiO2. This study proves that it is better to use grafted NFC either alone or for functionalization with TiO2 if anti-bacterial properties are desired. The cellulose backbone is known to be easily biodegradable in different biodegradation conditions and environments. The chemical surface modifications applied on NFC in the present work did not negatively influence this valuable property of cellulose but help for monitoring this property, which could be very useful for paper, packaging and composites.

Characterization of a poly(3-hydroxybutyrate) depolymerase fromaureobacterium saperdae: Active site and kinetics of hydrolysis studies

An extracellular poly(3-hydroxybutyrate) (PHB) depolymerase was purified fromAureobacterium saperdae cultural medium by using hydrophobic interaction chromatography. The isolated enzyme was composed of a single polypeptide chain with a molecular mass of 42.7 kDa as determined by SDS-PAGE and by native gel filtration on TSK-HW-55S. The enzyme was not a glycoprotein. Its optimum activity occurred at pH 8.0 and it showed a broad pH stability, ranging from pH 3 to pH 11.N-Bromosuccinamide and 2-hydroxy-5-nitrobenzyl bromide completely inactivated the enzyme, suggesting the involvement of tryptophan residues at the active site of the protein. The enzyme was very sensitive to diisopropyl fluorophosphate and diazo-dl-norleucine methyl ester, showing the importance of serine and carboxyl groups. The modification of cysteine residues byp-hydroxy mercuricbenzoate did not cause a loss of activity, whereas dithiothreitol rapidly inactivated the enzyme, revealing the presence of disulfide bonds.A saperdae depolymerase acted on the surface layer of PHB films and the degradation proceeded by surface erosion releasing monomers and dimers of 3-hydroxybutric acid. The degradation of PHB films byA. saperdae depolymerase was partially inhibited in the presence of excess amounts of enzyme. This phenomenon, already observed by Mukaiet al. with poly(hydroxyalkanoates) depolymerases fromAlcaligenes faecalis, Pseudomonas pickettii, andComamonas testosteroni, was analyzed according to the kinetic model proposed by these authors. The experimental data evidenced a general agreement with the kinetic model, although higher initial degradation rates were found withA. saperdae depolymerase.