Kirsi S. Mikkonen

Biocomposites of Nanofibrillated Cellulose, Polypyrrole, and Silver Nanoparticles with Electroconductive and Antimicrobial Properties

In this work, flexible and free-standing composite films of nanofibrillated cellulose/polypyrrole (NFC/PPy) and NFC/PPy-silver nanoparticles (NFC/PPy-Ag) have been synthesized for the first time via in situ one-step chemical polymerization and applied in potential biomedical applications. Incorporation of NFC into PPy significantly improved its film formation ability resulting in composite materials with good mechanical and electrical properties. It is shown that the NFC/PPy-Ag composite films have strong inhibition effect against the growth of Gram-positive bacteria, e.g., Staphylococcus aureus. The electrical conductivity and strong antimicrobial activity makes it possible to use the silver composites in various applications aimed at biomedical treatments and diagnostics. Additionally, we report here the structural and morphological characterization of the composite materials with Fourier-transform infrared spectroscopy, atomic force microscopy, and scanning and transmission electron microscopy techniques.

Carboxymethylation of alkali extracted xylan for preparation of bio-based packaging films

This study describes the synthesis of carboxymethylxylan (CMX) and investigates its suitability as a film for packaging applications. High-purity polymeric xylan was extracted from commercial bleached birch kraft pulp and converted to CMX with three different degrees of substitution (DSs). The water vapor sorption, mechanical, and barrier properties of the films prepared from CMX were tested. Increasing DS of CMX films resulted in an increase in elongation at break and a decrease in tensile strength and Youngs modulus. The DS also affected the barrier properties of the films. CMX films with higher DS showed improved (reduced) oxygen permeability (OP), and the water vapor permeability (WVP) increased with DS. It was demonstrated that the carboxymethylation of xylan recovered from industrial side-streams and its conversion to packaging films could be a viable option to valorize xylan.

Films from Glyoxal-Crosslinked Spruce Galactoglucomannans Plasticized with Sorbitol

Films were prepared from a renewable and biodegradable forest biorefinery product, spruce O-acetyl-galactoglucomannans (GGMs), crosslinked with glyoxal. For the first time, cohesive and self-standing films were obtained from GGM without the addition of polyol plasticizer. In addition, glyoxal-crosslinked films were prepared using sorbitol at 10, 20, 30, and 40% (wt.-% of GGM). Glyoxal clearly strengthened the GGM matrix, as detected by tensile testing and dynamic mechanical analysis. The elongation at break of films slightly increased, and Youngs modulus decreased with increasing sorbitol content. Interestingly, the tensile strength of films was constant with the increased plasticizer content. The effect of sorbitol on water sorption and water vapor permeability (WVP) depended on relative humidity (RH). At low RH, the addition of sorbitol significantly decreased the WVP of films. The glyoxal-crosslinked GGM films containing 20% sorbitol exhibited the lowest oxygen permeability (OP) and WVP of the studied films and showed satisfactory mechanical performance.

Enzymatic oxidation as a potential new route to produce polysaccharide aerogels

Specific enzymatic oxidation of terminal galactosyl-containing polysaccharides (guar galactomannan (GM), and tamarind seed galactoxyloglucan (XG)) was used to prepare hydrogels. The hydrogels were lyophilized to form novel types of polysaccharide aerogels: biobased and biodegradable, lightweight, and stiff materials. The compressive moduli of the aerogels were greatly dependent on the oxidation, polysaccharide type, freezing method, and ambient moisture. Ice crystal templated, oriented aerogels from oxidized XG (XG-OX) showed the highest compressive modulus, 359 kPa, when determined parallel to the freezing and drying direction (i.e., the vertical direction). The water vapor sorption of freeze-dried GM and XG was not significantly affected by oxidation, even though the oxidized GM (GM-OX) and XG-OX aerogels were no longer water-soluble. GM-OX and XG-OX aerogels absorbed liquid water 40 and 20 times their initial weight, respectively. Focused ion beam scanning electron microscopy showed that the inner structure of oriented aerogels from GM-OX consisted of a honeycomb architecture with a pore diameter of some tens of micrometers. On the other hand, corresponding aerogels from XG-OX seemed to contain longer capillaries oriented in the freezing direction. This observation was supported by imaging the XG-OX aerogels using high-resolution synchrotron X-ray microtomography. The enzymatic hydro- and aerogel preparation method is considered a green way to obtain novel, functional products from polysaccharides.

Specific enzymatic tailoring of wheat arabinoxylan reveals the role of substitution on xylan film properties.

To increase understanding of the applicability of agro biomass by-products as biodegradable film formers, the effect of wheat arabinoxylan (WAX) fine structure on film properties was studied by applying specific enzyme modifications. WAX was selectively modified to mimic the natural variations of different arabinoxylans, particularly the degree of mono and disubstitution of α-L-arabinofuranosyl (Araf) units in β-D-xylopyranosyl (Xylp) backbone residues. The resulting modified WAX samples had similar arabinose-to-xylose (Ara/Xyl) ratios, but they differed in the number of unsubstituted Xylp units. The substitution of WAX was found to affect, in particular, tensile strength, crystallinity, and oxygen permeability properties of the films, as statistically significant decreases in tensile strength and oxygen permeability took place after WAX de-branching. An increase in the number of unsubstituted Xylp units decreased the temperature of relaxation of small-scale molecular motions of WAX (β-relaxation) and increased the degree of crystallinity of the films.

Butylamino-functionalized cellulose nanocrystal films: barrier properties and mechanical strength

Cellulose nanocrystals (CNCs), which are strong, rod-like constituents of plant cellulose, are promising materials for green packaging applications as the material is capable of forming tortuous network structures with efficient barriers against outside gases. Here, a two-step procedure based on periodate oxidation followed by reductive amination was used as a pretreatment to modify bleached birch chemical wood pulp. Individualized CNCs were obtained from three different butylamino-functionalized pulps by mechanical homogenization. The fabricated CNCs were utilized to form transparent barrier films with a vacuum filtration method. All the butylamino-functionalized CNC films showed capability to resist oxygen permeability even at high relative humidity (RH 80%), and values as low as 5.9 ± 0.2 cm3 μm per m2 per day per kPa were recorded for pure cellulose based film using tert-butylamino-functionalized CNCs. In addition a barriers against water vapor permeation and dynamic vapor sorption were determined up to relative humidities of 80 and 90%, respectively. For surface characterization of the films time-dependent contact angles and surface roughness were measured. The films had good mechanical characteristics with tensile strength of 105.7 ± 9.7 MPa, strain-to-failure of 6.4 ± 0.6% and a Youngs modulus of 5.8 ± 0.8 GPa.

Comparison of microencapsulation properties of spruce galactoglucomannans and arabic gum using a model hydrophobic core compound.

In the present study, microencapsulation and the physical properties of spruce ( Picea abies ) Omicron-acetyl-galactoglucomannans (GGM) were investigated and compared to those of arabic gum (AG). Microcapsules were obtained by freeze-drying oil-in-water emulsions containing 10 wt % capsule materials (AG, GGM, or a 1:1 mixture of GGM-AG) and 2 wt % alpha-tocopherol (a model hydrophobic core compound that oxidizes easily). Microcapsules were stored at relative humidity (RH) of 0, 33, and 66% at 25 degrees C for different time periods, and their alpha-tocopherol content was determined by HPLC. X-ray microtomography analyses showed that the freeze-dried emulsions of GGM had the highest and those of AG the lowest degree of porosity. According to X-ray diffraction patterns, both freeze-dried AG and GGM showed an amorphous nature. The storage test showed that anhydrous AG microcapsules had higher alpha-tocopherol content than GGM-containing capsules, whereas under 33 and 66% RH conditions GGM was superior in relation to the retention of alpha-tocopherol. The good protection ability of GGM was related to its ability to form thicker walls to microcapsules and better physical stability compared to AG. The glass transition temperature of AG was close to the storage temperature (25 degrees C) at RH of 66%, which explains the remarkable losses of alpha-tocopherol in the microcapsules under those conditions.

Recent Studies on Hemicellulose-Based Blends, Composites and Nanocomposites

Hemicelluloses are abundant polysaccharides, occurring in all plants as structural components. In spite of their abundance, the industrial utilization of hemicelluloses is minor in comparison with the use of starch and cellulose. Recent studies on the use of hemicelluloses as blends, composites and nanocomposites have brought up new possibilities for hemicellulose utilization, such as in biodegradable packaging materials and edible coatings.

Novel nanobiocomposite hydrogels based on sage seed gum-laponite: Physico-chemical and rheological characterization

In this study, the physico-chemical and rheo-mechanical properties of sage seed gum hydrogel, reinforced by various ratios (0-25 wt.%) of Laponite, were investigated. Particles size measurements indicated the formation of large SSG-Laponite microstructures upon nanoparticle adding, due to the interactions generated between the anionic SSG and the charged surfaces of clay platelets. Laponite affected the surface tension and density of the SSG-based systems significantly, but only influenced the ζ-potential above 20 wt.%. The dynamic rheological behavior of SSG-based nanocomposites reflected the reinforcing effect of secondary structures and percolated three-dimensional network, suggested a structural modification of the hydrogels with the Laponite loading. An improvement in texture profile analysis parameters was observed in Laponite content ≤5 wt.%, whereas for nanoparticles >5 wt.%, a significant decrease was obtained. In conclusion, Laponite improved the rheological and physico-chemical properties of SSG-based hydrogel and extended its potential as promising future bio-products for industrial applications.

Physicochemical and rheo-mechanical properties of titanium dioxide reinforced sage seed gum nanohybrid hydrogel

Sage seed gum (SSG) is a promising biopolymer candidate for utilization and substitution prevalent galactomannan gels of interest in soft biomaterial applications. Herein, physicochemical and rheo-mechanical properties of SSG matrix reinforced by various titanium dioxide (TiO2) nanoparticles loading (0-25wt%) were monitored. Particle size and density of the nanocomposite increased with raising TiO2 content, due to the creation of more compact agglomerated and aggregated microstructure. Increasing the particle size resulted in lower electrophoretic mobility of SSG-TiO2 systems upon nanoparticles addition, confirmed the adsorption of TiO2 on the SSG macromolecule. Mechanical spectra of the SSG-based nanocomposites demonstrated a more solid-like behavior by lower frequency-dependent viscoelastic moduli, suggested a structural decoration of the nanohybrid gels discussed in terms of polymer bridging effect and formation of percolated matrix-particle superstructure. Crucial textural parameters improved with increasing TiO2 until a critical level (15 wt%), after which further increments in filler resulted in a reduction of hardness, adhesiveness and apparent modulus of elasticity. Deformation of rod-like junction zones acting as physical crosslinks in the system and fracture theory were used to explain the strain-stiffening and adhesive behavior of SSG-based gels, respectively. The nanocomposite gels with tunable functional properties might be ideal candidates for biomaterial industry.