• Biomass extraction using non-chlorinated solvents for biocompatibility improvement of polyhydroxyalkanoates

      Jiang, Guozhan; Johnston, Brian; Townrow, David E; Radecka, Iza; Koller, Martin; Chaber, Pawel; Adamus, Grazyna; Kowalczuk, Marek (MDPI, 2018-07-03)
      An economically viable method to extract polyhydroxyalkanoates (PHAs) from cells is desirable for this biodegradable polymer of potential biomedical applications. In this work, two non-chlorinated solvents, cyclohexanone and -butyrolactone, were examined for extracting PHA produced by the bacterial strain Cupriavidus necator H16 cultivated on vegetable oil as a sole carbon source. The PHA produced was determined as a poly(3-hydroxybutyrate) (PHB) homopolyester. The extraction kinetics of the two solvents was determined using gel permeation chromatography (GPC). When cyclohexanone was used as the extraction solvent at 120 C in 3 min, 95% of the PHB was recovered from the cells with a similar purity to that extracted using chloroform. With a decrease in temperature, the recovery yield decreased. At the same temperatures, the recovery yield of -butyrolactone was significantly lower. The effect of the two solvents on the quality of the extracted PHB was also examined using GPC and elemental analysis. The molar mass and dispersity of the obtained polymer were similar to that extracted using chloroform, while the nitrogen content of the PHB extracted using the two new solvents was slightly higher. In a nutshell, cyclohexanone in particular was identified as an expedient candidate to efficiently drive novel, sustainable PHA extraction processes.
    • Branched polyurethanes based on synthetic polyhydroxybutyrate with tunable structure and properties

      Brzeska, Joanna; Elert, Anna; Morawska, Magda; Sikorska, Wanda; Rutkowska, Maria; Kowalczuk, Marek (MDPI, 2018-07-26)
      Branched, aliphatic polyurethanes (PURs) were synthesized and compared to linear analogues. The influence of polycaprolactonetriol and synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) in soft segments on structure, thermal and sorptive properties of PURs was determined. Using FTIR and Raman spectroscopies it was found that increasing the R,S-PHB amount in the structure of branched PURs reduced a tendency of urethane groups to hydrogen bonding. Melting enthalpies (on DSC thermograms) of both soft and hard segments of linear PURs were higher than branched PURs, suggesting that linear PURs were more crystalline. Oil sorption by samples of linear and branched PURs, containing only polycaprolactone chains in soft segments, was higher than in the case of samples with R,S-PHB in their structure. Branched PUR without R,S-PHB absorbed the highest amount of oil. Introducing R,S-PHB into the PUR structure increased water sorption. Thus, by operating the number of branching and the amount of poly([R,S]-3-hydroxybutyrate) in soft segments thermal and sorptive properties of aliphatic PURs could be controlled.
    • Fabrication and in-vivo study of micro-colloidal zanthoxylum acanthopodium-loaded bacterial cellulose as a burn wound dressing

      Pasaribu, Khatarina Meldawati; Gea, Saharman; Ilyas, Syafruddin; Tamrin, Tamrin; Sarumaha, Appealwan Altruistis; Sembiring, Ardiansyah; Radecka, Izabela (MDPI, 2020-06-27)
      Bacterial cellulose (BC) is a biopolymer commonly used for wound dressing due to its high biocompatible properties either in-vitro or in-vivo. The three-dimensional fiber structure of BC becomes an advantage because it provides a template for the impregnation of materials in order to improve BC’s properties as a wound dressing, since BC has not displayed any bioactivity properties. In this study, micro-colloidal Zanthoxylum acanthopodium (MZA) fruit was loaded into BC fibers via an in-situ method. Z. acanthopodium is known to have anti-inflammatory, antioxidant and antimicrobial activities that can support BC to accelerate the wound healing process. The FTIR, XRD and SEM analysis results showed that the loading process of MZA and the composite fabrication were successfully carried out. The TGA test also showed that the presence of MZA in BC fibers decreased Tmax composite from BC, from 357.8 to 334.5 °C for BC-MZA3. Other aspects, i.e., water content, porosity, hemocompatibility and histology studies, also showed that the composite could potentially be used as a wound dressing.
    • Forensic engineering of advanced polymeric materials—part V: Prediction studies of aliphatic–aromatic copolyester and polylactide commercial blends in view of potential applications as compostable cosmetic packages

      Sikorska, Wanda; Rydz, Joanna; Wolna-Stypka, Katarzyna; Musioł, Marta; Adamus, Grażyna; Kwiecień, Iwona; Janeczek, Henryk; Duale, Khadar; Kowalczuk, Marek (MDPI, 2017-06-29)
      The main aim of the present study was to determine the behavior of the specimens from Ecovio, in the form of dumbbell-shaped samples and films, during degradation in selected cosmetic ingredients such as water and paraffin. The (bio)degradation test of the prototype cosmetic package (sachet) made from a PBAT (poly[(1,4-butylene adipate)-co-(1,4-butylene terephthalate)]) and PLA (polylactide) blend was investigated under industrial composting conditions, and compared with the sample behavior during incubation in cosmetic media at 70 °C. During the degradation tests, the changes of the samples were evaluated using optical microscopy, 1H NMR (proton nuclear magnetic resonance) and GPC (gel permeation chromatography) techniques. The structures of the degradation products were investigated using ESI-MSn (mass spectrometry with electrospray ionization on positive and negative ions) analysis. The thermal properties of selected materials were determined by DSC (differential scanning calorimetry) and TGA (thermogravimetric analysis) analysis. It was concluded that the PBAT and PLA blend studied had a good stability during aging in cosmetic media, and could be recommended for long-shelf-life compostable packaging of cosmetics, especially with oily ingredients.
    • Mass spectrometry reveals molecular structure of polyhydroxyalkanoates attained by bioconversion of oxidized polypropylene waste fragments

      Johnston, Brian; Radecka, Iza; Chiellini, Emo; Barsi, David; Ilieva, Vassilka Ivanova; Sikorska, Wanda; Musioł, Marta; Zięba, Magdalena; Chaber, Paweł; Marek, Adam A; et al. (MDPI AG, 2019-09-27)
      This study investigated the molecular structure of the polyhydroxyalkanoate (PHA) produced via a microbiological shake flask experiment utilizing oxidized polypropylene (PP) waste as an additional carbon source. The bacterial strain Cupriavidus necator H16 was selected as it is non-pathogenic, genetically stable, robust, and one of the best known producers of PHA. Making use of PHA oligomers, formed by controlled moderate-temperature degradation induced by carboxylate moieties, by examination of both the parent and fragmentation ions, the ESI-MS/MS analysis revealed the 3-hydroxybutyrate and randomly distributed 3-hydroxyvalerate as well as 3-hydroxyhexanoate repeat units. Thus, the bioconversion of PP solid waste to a value-added product such as PHA tert-polymer was demonstrated.
    • Recent advances and applications of bacterial cellulose in biomedicine

      Swingler, Sam; Gupta, Abhishek; Gibson, Hazel; Kowalczuk, Marek; Heaselgrave, Wayne; Radecka, Iza (MDPI AG, 2021-01-28)
      Bacterial cellulose (BC) is an extracellular polymer produced by Komagateibacter xylinus, which has been shown to possess a multitude of properties, which makes it innately useful as a next-generation biopolymer. The structure of BC is comprised of glucose monomer units polymerised by cellulose synthase in β-1-4 glucan chains which form uniaxially orientated BC fibril bundles which measure 3–8 nm in diameter. BC is chemically identical to vegetal cellulose. However, when BC is compared with other natural or synthetic analogues, it shows a much higher performance in biomedical applications, potable treatment, nano-filters and functional applications. The main reason for this superiority is due to the high level of chemical purity, nano-fibrillar matrix and crystallinity. Upon using BC as a carrier or scaffold with other materials, unique and novel characteristics can be observed, which are all relatable to the features of BC. These properties, which include high tensile strength, high water holding capabilities and microfibrillar matrices, coupled with the overall physicochemical assets of bacterial cellulose makes it an ideal candidate for further scientific research into biopolymer development. This review thoroughly explores several areas in which BC is being investigated, ranging from biomedical applications to electronic applications, with a focus on the use as a next-generation wound dressing. The purpose of this review is to consolidate and discuss the most recent advancements in the applications of bacterial cellulose, primarily in biomedicine, but also in biotechnology.
    • The microbial production of polyhydroxyalkanoates from waste polystyrene fragments attained using oxidative degradation

      Johnston, Brian; Radecka, Iza; Hill, David; Chiellini, Emo; Ilieva, Vassilka Ivanova; Sikorska, Wanda; Musioł , Marta; Zięba, Magdalena; Marek, Adam A.; Keddie, Daniel; et al. (MDPI, 2018-08-29)
      Excessive levels of plastic waste in our oceans and landfills indicate that there is an abundance of potential carbon sources with huge economic value being neglected. These waste plastics, through biological fermentation, could offer alternatives to traditional petrol-based plastics. Polyhydroxyalkanoates (PHAs) are a group of plastics produced by some strains of bacteria that could be part of a new generation of polyester materials that are biodegradable, biocompatible, and, most importantly, non-toxic if discarded. This study introduces the use of prodegraded high impact and general polystyrene (PS0). Polystyrene is commonly used in disposable cutlery, CD cases, trays, and packaging. Despite these applications, some forms of polystyrene PS remain financially and environmentally expensive to send to landfills. The prodegraded PS0 waste plastics used were broken down at varied high temperatures while exposed to ozone. These variables produced PS flakes (PS1–3) and a powder (PS4) with individual acid numbers. Consequently, after fermentation, different PHAs and amounts of biomass were produced. The bacterial strain, Cupriavidus necator H16, was selected for this study due to its well-documented genetic profile, stability, robustness, and ability to produce PHAs at relatively low temperatures. The accumulation of PHAs varied from 39% for prodegraded PS0 in nitrogen rich media to 48% (w/w) of dry biomass with the treated PS. The polymers extracted from biomass were analyzed using nuclear magnetic resonance (NMR) and electrospray ionization tandem mass spectrometry (ESI-MS/MS) to assess their molecular structure and properties. In conclusion, the PS0–3 specimens were shown to be the most promising carbon sources for PHA biosynthesis; with 3-hydroxybutyrate and up to 12 mol % of 3-hydroxyvalerate and 3-hydroxyhexanoate co-monomeric units generated.