Comprehensive Biodegradation Analysis of Chemically Modified Poly(3-hydroxybutyrate) Materials with Different Crystal Structures.

This work presents a comprehensive analysis of the biodegradation of polyhydroxybutyrate (PHB) and chemically modified PHB with different chemical and crystal structures in a soil environment. A polymer modification reaction was performed during preparation of the chemically modified PHB films, utilizing 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexane as a free-radical initiator and maleic anhydride. Films of neat PHB and chemically modified PHB were prepared by extrusion and thermocompression. The biological agent employed was natural mixed microflora in the form of garden soil. The course and extent of biodegradation of the films was investigated by applying various techniques, as follows: a respirometry test to determine the production of carbon dioxide through microbial degradation; scanning electron microscopy (SEM); optical microscopy; fluorescence microscopy; differential scanning calorimetry (DSC); and X-ray diffraction (XRD). Next-generation sequencing was carried out to study the microbial community involved in biodegradation of the films. Findings from the respirometry test indicated that biodegradation of the extruded and chemically modified PHB followed a multistage (2-3) course, which varied according to the spatial distribution of amorphous and crystalline regions and their spherulitic morphology. SEM and polarized optical microscopy (POM) confirmed that the rate of biodegradation depended on the availability of the amorphous phase in the interspherulitic region and the width of the interlamellar region in the first stage, while dependence on the size of spherulites and thickness of spherulitic lamellae was evident in the second stage. X-ray diffraction revealed that orthorhombic α-form crystals with helical chain conformation degraded concurrently with ß-form crystals with planar zigzag conformation. The nucleation of PHB crystals after 90 days of biodegradation was identified by DSC and POM, a phenomenon which impeded biodegradation. Fluorescence microscopy evidenced that the crystal structure of PHB affected the physiological behavior of soil microorganisms in contact with the surfaces of the films.

Selected Simple Natural Antimicrobial Terpenoids as Additives to Control Biodegradation of Polyhydroxy Butyrate.

In this experimental research, different types of essential oils (EOs) were blended with polyhydroxybutyrate (PHB) to study the influence of these additives on PHB degradation. The blends were developed by incorporating three terpenoids at two concentrations (1 and 3%). The mineralization rate obtained from CO2 released from each sample was the factor that defined biodegradation. Furthermore, scanning electron microscope (SEM), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA) were used in this research. The biodegradation percentages of PHB blended with 3% of eucalyptol, limonene, and thymol after 226 days were reached 66.4%, 73.3%, and 76.9%, respectively, while the rate for pure PHB was 100% after 198 days, and SEM images proved these results. Mechanical analysis of the samples showed that eucalyptol had the highest resistance level, even before the burial test. The other additives showed excellent mechanical properties although they had less mechanical strength than pure PHB after extrusion. The samples' mechanical properties improved due to their crystallinity and decreased glass transition temperature (Tg). DSC results showed that blending terpenoids caused a reduction in Tg, which is evident in the DMA results, and a negligible reduction in melting point (Tm).

The Effect of Application of Chicken Gelatin on Reducing the Weight Loss of Beef Sirloin after Thawing.

Freezing is one of the oldest and most-often-used traditional methods to prolong the shelf life of meat. However, the negative phenomenon of this process is the weight loss of water that occurs after the meat is thawed. Together with the water that escapes from the meat during thawing, there are large weight losses in this valuable raw material. Another negative aspect is that mineral and extractive substances, vitamins, etc. also leave the meat, resulting in irreversible nutritional losses of nutrients in the meat, which are subsequently missing for use by the consumer of the meat. The main goal of this work is to reduce these losses by using gelatin coatings. Gelatin was prepared from chicken paws according to a patented biotechnological procedure, which uses the very gentle principle of obtaining gelatin with the usage of enzymes. This unique method is friendly to the environment and innocuous for the product itself. At the same time, it ensures that the required principles achieve a circular economy with the use of the so far very-little-used slaughter byproducts, which in most parts of the world end up in uneconomic disposal by burning or landfilling without using this unique potential source of nutrients. Gelatin coatings on the surface of the beef steak were created by immersing the meat in a solution based on gelatin of different composition. A coating containing 3%, 5% or 8% gelatin with 10% or 20% glycerol (by weight of gelatin) and 1% glutaraldehyde crosslinker (by weight of gelatin) has proved to be effective. The amount of glutaraldehyde added to the coating is guaranteed not to exceed the permitted EU/U.S. legislative limits. In addition to weight loss, meat pH, color and texture were also measured. Freezing was done in two ways; some samples were frozen at a normal freezing temperature of -18 °C and the other part of the experiment at deep (shock) freezing at -80 °C. Defrosting took place in two ways, in the refrigerator and in the microwave oven, in order to use the common defrosting methods used in gastronomy. A positive effect of this coating on weight loss was observed for each group of samples. The most pronounced effect of coating was found for the least gentle method of freezing (-18 °C) and thawing (microwave), with the average weight loss of the coated samples differing by more than 2% from that of the uncoated sample. No negative effect of the coating was observed for other meat properties tested, such as pH, Warner-Bratzler Shear Force (WBSF) or color. Gelatin-based coating has a positive effect on reducing the weight loss of meat after thawing. Chicken gelatin prepared by a biotechnological process has a new application in improving the quality of meat due to the retention of water and nutrients in frozen and subsequently thawed beef, which can contribute to the better quality of the subsequently gastronomically prepared dish, while maintaining the weight and nutritional quality. This also results in economic savings in the preparation of highly-valued parts of beef.

Characterization and biodegradation of ternary blends of lignosulfonate/synthetic zeolite/polyvinylpyrrolidone for agricultural chemistry.

This study investigates novel ternary polymer blends based on polyvinylpyrrolidone (PVP) as the matrix in combination with lignosulfonate and synthetic zeolite. The blends were prepared by the casting method, and their properties were analysed by various techniques, i.e. FTIR analysis, differential scanning calorimetry and thermogravimetric analysis, including tests for water solubility and uptake, and determination of adhesion and hardness. The biodegradation of the blends in soil was also evaluated, and an experiment was conducted on plant growth (Sinapis alba). Optical microscopy showed that particles of the synthetic zeolite were relatively evenly distributed in the polymer matrix, forming random networks therein. The FTIR spectra for the blends proved that hydrogen bonding interactions had occurred between the PVP/synthetic zeolite and PVP/lignosulfonate. DSC analysis confirmed the good miscibility of the PVP and lignosulfonate. TGA results indicated that the thermal stability of the PVP was maintained. Lignosulfonate had the effect of reducing the adhesion of the blends. However, it was revealed that effect depends greatly on the presence of zeolite and the concentration of lignosulfonate. The obtained results showed that the optimal composition of the blend is 2.5 wt% of zeolite and 5 wt% of lignosulfonate into the PVP. Its water solubility and uptake was satisfactory from the perspective of handling and further utilization. A respirometric biodegradation test confirmed that the ternary blend was environmentally friendly, in addition to which a germination experiment evidenced that the lignosulfonate and synthetic zeolite promoted the root growth and development of S. alba. From these findings it was concluded that the novel ternary polymer blend was applicable as either as seed carriers (in the form of seed tapes) or as a biocompatible coating to protect seeds.

Tribo-Mechanical Properties of the Antimicrobial Low-Density Polyethylene (LDPE) Nanocomposite with Hybrid ZnO-Vermiculite-Chlorhexidine Nanofillers.

Materials made from low-density polyethylene (LDPE) in the form of packages or catheters are currently commonly applied medical devices. Antimicrobial LDPE nanocomposite materials with two types of nanofillers, zinc oxide/vermiculite (ZnO/V) and zinc oxide/vermiculite_chlorhexidine (ZnO/V_CH), were prepared by a melt-compounded procedure to enrich their controllable antimicrobial, microstructural, topographical and tribo-mechanical properties. X-ray diffraction (XRD) analysis and Fourier transform infrared spectroscopy (FTIR) revealed that the ZnO/V and ZnO/V_CH nanofillers and LDPE interacted well with each other. The influence of the nanofiller concentrations on the LDPE nanocomposite surface changes was studied through scanning electron microscopy (SEM), and the surface topology and roughness were studied using atomic force microscopy (AFM). The effect of the ZnO/V nanofiller on the increase in indentation hardness (HIT) was evaluated by AFM measurements and the Vickers microhardness (HV), which showed that as the concentration of the ZnO/V nanofiller increased, these values decreased. The ZnO/V and ZnO/V_CH nanofillers, regardless of the concentration in the LDPE matrix, slightly increased the average values of the friction coefficient (COF). The abrasion depths of the wear indicated that the LDPE_ZnO/V nanocomposite plates exhibited better wear resistance than LDPE_ZnO/V_CH. Higher HV and HIT microhardness values were measured for both nanofillers than the natural LDPE nanocomposite plate. Very positive antimicrobial activity against S. aureus and P. aeruginosa after 72 h was found for both nanofiller types.

Characterisation of Polyamide (PA)12 Nanocomposites with Montmorillonite (MMT) Filler Clay Used for the Incremental Forming of Sheets.

In this paper, the preparation and characterisation of polymer materials suitable for single point incremental forming (SPIF) technology were performed. Three different kinds of mixtures were selected: a mixture of neat polyamide 12 (PA12), a nanocomposite with PA12 matrix and 1% clay (Cloisite 93A), and a nanocomposite with PA12 matrix and 3% clay (Cloisite 93A). Materials were produced using a melt intercalation method followed by compression moulding. According to the needs of SPIF technology, morphological and mechanical properties were investigated in the obtained mixtures. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to characterize morphological properties. It was determined that the most desired obtained exfoliated structure of clay in the polymer matrix was achieved. Static tensile testing and dynamic mechanical analysis as well as the determination of glass transition temperature and crystallinity of all analysed materials were used to obtain mechanical and thermal properties of the mixtures. The results obtained for each mixture were compared with respect to the content of clay. The content of clay (Cloisite 93A) showed a strong influence on the properties of the obtained materials. The presence of clay (Cloisite 93A) affected the increase of tensile strength and Young's modulus, while its influence on the attained elongation was not unique.

Kinetics and mechanism of the biodegradation of PLA/clay nanocomposites during thermophilic phase of composting process.

The degradation mechanism and kinetics of polylactic acid (PLA) nanocomposite films, containing various commercially available native or organo-modified montmorillonites (MMT) prepared by melt blending, were studied under composting conditions in thermophilic phase of process and during abiotic hydrolysis and compared to the pure polymer. Described first order kinetic models were applied on the data from individual experiments by using non-linear regression procedures to calculate parameters characterizing aerobic composting and abiotic hydrolysis, such as carbon mineralization, hydrolysis rate constants and the length of lag phase. The study showed that the addition of nanoclay enhanced the biodegradation of PLA nanocomposites under composting conditions, when compared with pure PLA, particularly by shortening the lag phase at the beginning of the process. Whereas the lag phase of pure PLA was observed within 27days, the onset of CO2 evolution for PLA with native MMT was detected after just 20days, and from 13 to 16days for PLA with organo-modified MMT. Similarly, the hydrolysis rate constants determined tended to be higher for PLA with organo-modified MMT, particularly for the sample PLA-10A with fastest degradation, in comparison with pure PLA. The acceleration of chain scission in PLA with nanoclays was confirmed by determining the resultant rate constants for the hydrolytical chain scission. The critical molecular weight for the hydrolysis of PLA was observed to be higher than the critical molecular weight for onset of PLA mineralization, suggesting that PLA chains must be further shortened so as to be assimilated by microorganisms. In conclusion, MMT fillers do not represent an obstacle to acceptance of the investigated materials in composting facilities.