Marta Martínez-Sanz

Optimization of the dispersion of unmodified bacterial cellulose nanowhiskers into polylactide via melt compounding to significantly enhance barrier and mechanical properties.

In the present study, property-enhanced polylactide (PLA) nanocomposites containing bacterial cellulose nanowhiskers (BCNW) were prepared by melt compounding. With the aim of improving the nanocrystals dispersion in the final melt processed nanocomposites, these were preincorporated either into PLA nanostructured fibers by electrospinning or into an ethylene vinyl-alcohol copolymer (EVOH) by solution precipitation. An optimized dispersion of the nanofiller in the nanocomposites produced by applying these preincorporation methods, when compared to the direct melt mixing of the freeze-dried nanowhiskers with the polymeric matrix, was confirmed by morphological studies. Enhanced dispersion of BCNW was critical for enhancing the barrier and mechanical properties of the nanocomposites. Thus, for concentrations around the percolation threshold, that is, 2-3 wt % BCNW, nanocomposites produced by the electrospinning preincorporation method showed increased elastic modulus and tensile strength, preserving the ductility of the pure PLA. Moreover, in the optimized nanocomposites the water permeability of PLA was reduced by 43% and the oxygen barrier also decreased to a significant extent. This paper provides a successful route to solve the long-standing issue related to the dispersion of highly polar unmodified cellulose nanowhiskers into PLA via the industrially meaningful melt compounding processing.

Characterization of polyhydroxyalkanoates synthesized from microbial mixed cultures and of their nanobiocomposites with bacterial cellulose nanowhiskers.

The present work reports on the production and characterization of polyhydroxyalkanoates (PHAs) with different valerate contents, which were synthesized from microbial mixed cultures, and the subsequent development of nanocomposites incorporating bacterial cellulose nanowhiskers (BCNW) via solution casting processing. The characterization of the pure biopolyesters showed that the properties of PHAs may be strongly modified by varying the valerate ratio in the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) copolymer, as expected. Increasing the valerate content was seen to greatly decrease the melting temperature and enthalpy of the material, as well as its rigidity and stiffness, resulting in a more ductile behaviour. Additionally, the higher valerate PHA displayed higher permeability to water and oxygen and higher moisture sensitivity. Subsequently, BCNW were incorporated into both PHA grades, achieving a high level of dispersion for a 1 wt.-% loading, whereas some agglomeration took place for 3 wt.-% BCNW. As evidenced by DSC analyses, BCNW presented a nucleating effect on the PHA matrices. BCNW also increased the thermal stability of the polymeric matrices when properly dispersed due to strong matrix-filler interactions. Barrier properties were seen to depend on relative humidity and improved at low nanofiller loadings and low relative humidity.

Evidence for differential interaction mechanism of plant cell wall matrix polysaccharides in hierarchically-structured bacterial cellulose

The interaction mechanism of two plant cell wall polysaccharides, arabinoxylan and xyloglucan, with cellulose has been investigated by means of bacterial cellulose fermentation to mimic the cell wall biosynthesis process. The combination of small angle scattering techniques with XRD and SEM has enabled the identification of different structural features comprising hierarchically-assembled bacterial cellulose, i.e. cellulose microfibrils and ribbons. The SANS results have been described by a core–shell formalism, which accounts for the presence of regions with different solvent accessibility and supports the existence of microfibril sub-structure within the ribbons. Additionally, SAXS and XRD results suggest that the microfibril packing and crystalline structure are not affected by arabinoxylan, while xyloglucan interferes with the crystallization and assembly processes, resulting in less crystalline Iβ-rich microfibrils. This specific interaction mechanism is therefore crucial for the cellulose microfibril cross-linking effect of xyloglucan in plant cell walls. It is proposed that the distinct interaction mechanisms identified have their origin in the differential structural role of arabinoxylan and xyloglucan in plant cell walls.

Application of X-ray and neutron small angle scattering techniques to study the hierarchical structure of plant cell walls: A review

Plant cell walls present an extremely complex structure of hierarchically assembled cellulose microfibrils embedded in a multi-component matrix. The biosynthesis process determines the mechanism of cellulose crystallisation and assembly, as well as the interaction of cellulose with other cell wall components. Thus, a knowledge of cellulose microfibril and bundle architecture, and the structural role of matrix components, is crucial for understanding cell wall functional and technological roles. Small angle scattering techniques, combined with complementary methods, provide an efficient approach to characterise plant cell walls, covering a broad and relevant size range while minimising experimental artefacts derived from sample treatment. Given the system complexity, approaches such as component extraction and the use of plant cell wall analogues are typically employed to enable the interpretation of experimental results. This review summarises the current research status on the characterisation of the hierarchical structure of plant cell walls using small angle scattering techniques.

High-barrier coated bacterial cellulose nanowhiskers films with reduced moisture sensitivity

This study reports on the development and characterization of bacterial cellulose (BCNW) films coated with hydrophobic layers, presenting enhanced barrier properties. Pure BCNW films showed good transparency and thermal stability, high rigidity and extremely low oxygen permeability at 0%RH. The dramatic increase in oxygen permeability at 80%RH, due to the hydrophilic character of BCNW, was counteracted through coating the films with annealed PLA electrospun nanostructured fibres or hydrophobic silanes. The use of electrospinning was crucial to attain a good adhesion between the hydrophilic BCNW and the hydrophobic PLA layer. After electrospinning, the fibres were homogenised by annealing, thus obtaining a uniform and continuous coating. Coated systems showed a hydrophobic surface and protected the BCNW from moisture, thus reducing ca. 70% the water permeability and up to 97% the oxygen permeability at 80%RH. Furthermore, this novel approach was seen to protect BCNW films from moisture more efficiently than coating with hydrophobic silanes.

Hierarchical architecture of bacterial cellulose and composite plant cell wall polysaccharide hydrogels using small angle neutron scattering

Small angle neutron scattering (SANS) has been applied to characterise the structure of pure bacterial cellulose hydrogels, and composites thereof, with two plant cell wall polysaccharides (arabinoxylan and xyloglucan). Conventional published models, which assume that bacterial cellulose ribbons are solid one-phase systems, fail to adequately describe the SANS data of pure bacterial cellulose. Fitting of the neutron scattering profiles instead suggests that the sub-structure of cellulose microfibrils contained within the ribbons results in the creation of regions with distinct values of neutron scattering length density, when the hydrogels are subjected to H2O/D2O exchange. This may be represented within a core-shell formalism that considers the cellulose ribbons to comprise a core containing impermeable crystallites surrounded by a network of paracrystalline cellulose and tightly bound water, and a shell containing only paracrystalline cellulose and water. Accordingly, a fitting function comprising the sum of a power-law term to account for the large scale structure of intertwined ribbons, plus a core-shell cylinder with polydisperse radius, has been applied; it is demonstrated to simultaneously describe all SANS contrast variation data of pure and composite bacterial cellulose hydrogels. In addition, the resultant fitting parameters indicate distinct interaction mechanisms of arabinoxylan and xyloglucan with cellulose, revealing the potential of this approach to investigate the role of different plant cell wall polysaccharides on the biosynthesis process of cellulose.

Multi-scale model for the hierarchical architecture of native cellulose hydrogels

The structure of protiated and deuterated cellulose hydrogels has been investigated using a multi-technique approach combining small-angle scattering with diffraction, spectroscopy and microscopy. A model for the multi-scale structure of native cellulose hydrogels is proposed which highlights the essential role of water at different structural levels characterised by: (i) the existence of cellulose microfibrils containing an impermeable crystalline core surrounded by a partially hydrated paracrystalline shell, (ii) the creation of a strong network of cellulose microfibrils held together by hydrogen bonding to form cellulose ribbons and (iii) the differential behaviour of tightly bound water held within the ribbons compared to bulk solvent. Deuterium labelling provides an effective platform on which to further investigate the role of different plant cell wall polysaccharides in cellulose composite formation through the production of selectively deuterated cellulose composite hydrogels.

On the extraction of cellulose nanowhiskers from food by-products and their comparative reinforcing effect on a polyhydroxybutyrate-co-valerate polymer

Abstract The present work reports on the characterization of cellulose nanowhiskers (CNW) extracted from three different food by-products, i.e., wheat straw (WSCNW), Brewer’s spent grains (BGCNW) and olive pomace (OPCNW), by using an optimized hydrolysis method similar to that developed to extract bacterial cellulose nanowhiskers (BCNW). WSCNW and BGCNW were seen to present optimal properties, with aspect ratio, crystallinity and thermal stability values comparable to those of BCNW. Additionally, the optimized hydrolysis treatment led to extraction yields higher than those previously reported for food by-products. The CNW were subsequently incorporated into a commercial polyhydroxybutyrate-co-valerate polymer (PHBV) by solution casting, and the produced nanocomposites were characterized. Although the addition of BGCNW and WSCNW was advantageous in terms of mechanical performance in comparison with OPCNW, no significant enhancement of the pure PHBV mechanical properties was reported because of the low nanofiller loadings used and the inherent difficulty of achieving a high degree of dispersion by the casting method. Interestingly, BGCNW and WSCNW presented reduced moisture sensitivity as compared with BCNW, leading to greater barrier performance and resulting in oxygen permeability reductions up to 26xa0% with WSCNW and 44xa0% with BGCNW.

Cellulose-pectin composite hydrogels: intermolecular interactions and material properties depend on order of assembly

Plant cell walls have a unique combination of strength and flexibility however, further investigations are required to understand how those properties arise from the assembly of the relevant biopolymers. Recent studies indicate that Ca2+-pectates can act as load-bearing components in cell walls. To investigate this proposed role of pectins, bioinspired wall models were synthesised based on bacterial cellulose containing pectin-calcium gels by varying the order of assembly of cellulose/pectin networks, pectin degree of methylesterification and calcium concentration. Hydrogels in which pectin-calcium assembly occurred prior to cellulose synthesis showed evidence for direct cellulose/pectin interactions from small-angle scattering (SAXS and SANS), had the densest networks and the lowest normal stress. The strength of the pectin-calcium gel affected cellulose structure, crystallinity and material properties. The results highlight the importance of the order of assembly on the properties of cellulose composite networks and support the role of pectin in the mechanics of cell walls.

Dispersing Bacterial Cellulose Nanowhiskers in Polylactides via Electrohydrodynamic Processing

In the present study, hybrid electrospun polylactide (PLA) fibers reinforced with highly dispersed crystalline bacterial cellulose nanowhiskers (BCNW) in solution concentrations up to 15xa0wt% were developed and characterized. The overall aim was to encapsulate dispersed BCNW in fibers to be later re-dispersed in virgin PLA by melt compounding. Initially, the suitability of three different solvents [1,1,1,3,3,3-hexafluoro-2-propanol (HFP), acetone–chloroform and chloroform/polyethylene glycol (PEG)] for fiber production was evaluated and solutions containing 5xa0wt% BCNW were used to generate electrospun hybrid PLA fibers. These fibers presented a homogeneous morphology, as assessed by scanning electron microscopy, and transmission electron microscopy images demonstrated that BCNW were well distributed along the fibers. Differential scanning calorimetry analyses showed that the incorporation of PEG into the fibers resulted in a Tg drop due to a plasticization effect and decreased thermal stability as a result of low interactions between the matrix and the BCNW. Subsequently, fibers were produced from the selected solutions (HFP and acetone–chloroform) containing up to 15xa0wt% BCNW. As a result of the great increase in the viscosity of the solutions, lower solids contents were required, leading to a better dispersion and incorporation degree of BCNW within the fibers. HFP was found to be a more suitable solvent, since higher incorporation levels were estimated by X-ray diffraction and improved matrix–filler interactions were suggested by a slight increase in the Tg of the fibers.