Adriana Kovalcik

Characterization of the promising poly(3-hydroxybutyrate) producing halophilic bacterium Halomonas halophila

This work explores molecular, morphological as well as biotechnological features of the highly promising polyhydroxyalkanoates (PHA) producer Halomonas halophila. Unlike many other halophiles, this bacterium does not require expensive complex media components and it is capable to accumulate high intracellular poly(3-hydroxybutyrate) (PHB) fractions up to 82% of cell dry mass. Most remarkably, regulating the concentration of NaCl apart from PHB yields influences also the polymers molecular mass and polydispersity. The bacterium metabolizes various carbohydrates including sugars predominant in lignocelluloses and other inexpensive substrates. Therefore, the bacterium was employed for PHB production on hydrolysates of cheese whey, spent coffee grounds, sawdust and corn stover, which were hydrolyzed by HCl; required salinity of cultivation media was set up during neutralization by NaOH. The bacterium was capable to use all the tested hydrolysates as well as sugar beet molasses for PHB biosynthesis, indicating its potential for industrial PHB production.

Characterization of polyhydroxyalkanoates produced by Synechocystis salina from digestate supernatant

The current commercial production of polyhydroxyalkanoates (PHA) is based on heterotrophic bacteria, using organic carbon sources from crops. To avoid the competition with food and feed production, cyanobacteria, metabolising PHA from carbon dioxide can be used. This research focuses on the investigation of the thermal and rheological properties of PHA polymers accumulated by Synechocystis salina, which had been cultivated in digestate supernatant and a mineral medium. The dried bacterial cells had a polymer content of 5.5-6.6%. The relevance of the derived PHA polymers for the common melt polymer processing was correlated with their molecular mass distribution as well as with their thermal and rheological properties. The determined thermal and rheological properties showed that PHA polymers accumulated by S. salina on digestate supernatant or mineral medium are comparable with the commercial available poly(3-hydroxybutyrate). However, the results showed that PHA polymers in general require modification before melt processing to increase their stability in the molten state.

Cyanobacteria Biorefinery — Production of poly(3-hydroxybutyrate) with Synechocystis salina and utilisation of residual biomass

This study evaluates a biorefinery concept for producing poly(3-hydroxybutyrate) (PHB) with the cyanobacterial strain Synechocystis salina. Due to this reason, pigment extraction and cell disruption were investigated as pre-treatment steps for the harvested cyanobacterial biomass. The results demonstrated that at least pigment removal was necessary to obtain PHB with processable quality (weight average molecular weight: 569-988kgmol-1, melting temperature: 177-182°C), which was comparable to heterotrophically produced PHB. The removed pigments could be utilised as additional by-products (chlorophylls 0.27-1.98mgg-1 TS, carotenoids 0.21-1.51mgg-1 TS, phycocyanin 0-127mgg-1 TS), whose concentration depended on the used nutrient source. Since the residual biomass still contained proteins (242mgg-1 TS), carbohydrates (6.1mgg-1 TS) and lipids (14mgg-1 TS), it could be used as animal feed or converted to biomethane (348 mn3 t-1VS) and fertiliser. The obtained results indicate that the combination of photoautotrophic PHB production with pigment extraction and utilisation of residual biomass offer the highest potential, since it contributes to decrease the environmental footprint of the process and because biomass could be used in a cascading way and the nutrient cycle could be closed.

Residual wood polymers facilitate compounding of microfibrillated cellulose with poly(lactic acid) for 3D printer filaments

Microfibrillated cellulose (MFC) is a fascinating material with an obvious potential for composite reinforcement due to its excellent mechanics together with high specific surface area. However, in order to use this potential, commercially viable solutions to important technological challenges have to be found. Notably, the distinct hydrophilicity of MFC prevents efficient drying without loss in specific surface area, necessitating storage and processing in wet condition. This greatly hinders compounding with important technical polymers immiscible with water. Differently from cellulose, the chemistry of the major wood polymers lignin and hemicellulose is much more diverse in terms of functional groups. Specifically, the aromatic moieties present in lignin and acetyl groups in hemicellulose provide distinctly less polar surface-chemical functionality compared to hydroxyl groups which dominate the surface-chemical character of cellulose. It is shown that considerable advantages in the production of MFC-filled poly(lactic acid) filaments for three-dimensional printing can be obtained through the use of MFC containing residual lignin and hemicellulose due to their advantageous surface-chemical characteristics. Specifically, considerably reduced agglomerations of MFC in the filaments in combination with improved printability and improved toughness of printed objects are achieved. This article is part of a discussion meeting issue ‘New horizons for cellulose nanotechnology’.

Hyaluronan hydrogels modified by glycinated Kraft lignin: Morphology, swelling, viscoelastic properties and biocompatibility

Effects of the addition of water soluble glycinated Kraft lignin (WS/KL) on the mechanical stability and biocompatibility of hyaluronan (NaHy) hydrogels were evaluated in this work. Water soluble lignin was obtained by the modification of Kraft lignin via a Mannich reaction. It was found that WS/KL is highly compatible with hyaluronan due to its improved water solubility, which favours its use in designing new advanced composite hydrogels. The effects of the concentration of WS/KL on morphological, swelling and creep/recovery behaviours of hyaluronan hydrogels were investigated. It was detected that the creep resistance and creep recovery of NaHy hydrogels was improved by the incorporation of up to 3% (w/w) of WS/KL. In contrast, the swelling capacity of hydrogels was decreased. The cytotoxicity tests proved that glycinated KL lignin limits the viability of cells only slightly, and the final hyaluronan/lignin hydrogels were non-toxic materials.

Physicomechanical Properties and Utilization of Hydrogels Prepared by Physical and Physicochemical Crosslinking

Research concerning physical hydrogels, their morphological characteristics, swelling ability, and related mechanical properties is of increasing significance over last fifteen years due to their controllable degradability and desirable biocompatibility. Additionally, it is very important that physical crosslinking methods such as freeze-thaw cycling, heat treatment, ionic interactions, hydrophobic interactions, hydrogen bonding interactions, self-assembly stereocomplexation as well as other non-covalent interactions do not require use of chemical crosslinking agents which may induce allergic or toxic side effects. Physical crosslinked hydrogels have found their applications so far in pharmaceutical and medical areas. The engineering applications of physical hydrogels are still limited due to low mechanical toughness and short-term stability. This review explores mainly used physical crosslinking methods with examples of polymers crosslinkable with physical junctions. Special focus is given to methods improving mechanical rigidity of physical hydrogels based on anionic polysaccharides and poly(vinyl alcohol).

Effects of thermal annealing as polymer processing step on poly(lactic acid)

ABSTRACT Thermal annealing as an additional polymer processing step or post-treatment processing step enables the structural changes of amorphous parts into crystalline parts. This paper investigates the feasibility of thermal annealing at 100°C up to 90 min used as an additional processing step to modify the crystalline structure and the thermo-mechanical stability of poly(lactic acid) (PLA). Moreover, the crystallization ability of PLA has been amended by the addition of 3 wt% of wood flour and kaolin. The values of the degree of crystallinity and lamellar thickness determined by wide-angle-X-ray scattering showed that the thermal annealing of PLA samples modified with nucleating agents was an efficient processing step to increase the final crystallinity of PLA. Moreover, altered crystalline structure helped to improve the thermomechanical stability of PLA.

Copolymer of natural fibre reinforced polyester urethane: effect on physico-chemical properties through modification to interfacial adhesion

Abstract This work is dedicated to polyester urethane (PEU)-based biocomposites, with special focus placed on techniques for compatibilisation to heighten interfacial adhesion between the PEU matrix and flax fibres. Tests were conducted on the effects of modification so as to increase interfacial adhesion between the flax fibres and the polyester matrix. These tests involved a commercial silane-based compatibilising additive, two experimentally synthesised agents, oleic acid (OA) and di-tert-butyl peroxide (DTBP). Furthermore, the flax fibres underwent acid or alkali treatment. The biocomposites were characterised by gel permeation chromatography, infrared spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). Mechanical properties were investigated through tensile testing. Biocomposites with a commercial silane-based additive and synthesised agent, based on maleic-anhydride, were assessed as the best solution. Nevertheless, all modifications, excluding alkali treatment of fibres, significantly increased the performance of the material.