The effect of additives on the biodegradation of polyhydroxyalkanoate (PHA) in marine field trials.

The persistence of conventional fossil fuel-derived plastics in marine ecosystems has raised significant environmental concerns. Biodegradable plastics are being explored as an alternative. This study investigates the biodegradation behaviour in two marine environments of melt-extruded sheets of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) bioplastic as well as blends of PHBV with a non-toxic plasticiser (triethyl citrate, TEC) and composites of PHBV with wood flour. Samples were submerged for up to 35 weeks in two subtropical marine conditions: on the sandy seabed in the sublittoral benthic zone and the sandy seabed of an open air mesocosm with pumped seawater. Rates of biodegradation, lag times and times to 95 % mass loss (T95) were determined through mass loss data and Gompertz modelling. Mechanisms of biodegradation were studied through changes in molecular weight, mechanical properties and surface features. Results reveal a rapid biodegradation rate for all PHBV samples, demonstrating a range of specific biodegradation rates relative to exposed surface area of 0.03 ± 0.01 to 0.09 ± 0.04 mg.d-1.cm-2. This rapid rate of biodegradation meant that the subtle variations in biodegradation mechanisms across different sample thicknesses and additive compositions had little effect on overall lifetimes, with the T95 for most samples being around 250-350 days, regardless of site, highlighting the robust biodegradability of PHBV in seawater. It was only the PHBV-wood flour composite that showed faster biodegradation, and that was only in the exposed ocean site. The mesocosm site was otherwise shown to be a good model for the open ocean, with very comparable biodegradation rates and changes in mechanical properties over time.

Physical and mechanical properties of ocular thin films: a systematic review and meta-analysis.

The ocular thin film presents a potential solution for addressing challenges to ocular drug delivery. In this review, we summarise the findings of a comprehensive review analysing 336 formulations from 68 studies. We investigated the physical and mechanical properties of ocular thin films, categorised into natural polymer-based, synthetic polymer-based, and combined polymer films. The results showed that the type of polymers used impacted mucoadhesion force, moisture absorption:moisture loss ratio, pH, swelling index, and elongation percentage. Significant relationships were found between these properties within each subgroup. The results also highlighted the influence of plasticisers on elongation percentage, mucoadhesion force, swelling index, and moisture absorption:moisture loss ratio. These findings have implications for designing and optimising ocular drug formulations and selecting appropriate plasticisers to achieve formulations with the desired properties.

Plasticiser leaching from polyvinyl chloride microplastics and the implications for environmental risk assessment.

Microplastics in aquatic environments is a growing concern, particularly due to the leaching of chemical additives such as plasticisers. To develop comprehensive environmental risk assessments (ERAs) of high-concern polymers and plasticisers, an understanding of their leachability is required. This work investigated diethylhexyl phthalate (DEHP) and bisphenol A (BPA) leaching from polyvinyl chloride (PVC) microplastics (average diameter = 191 µm) under simulated marine conditions. Leaching behaviours were quantified using gel permeation chromatography (GPC) and thermal gravimetric analysis (TGA), and the polymer's physiochemical properties analysed using differential scanning calorimetry (DSC), Fourier Transform-Infrared Spectroscopy (FT-IR) and optical microscopy. Experimental data were fitted to a diffusion and boundary layer model, which found that BPA leaching was temperature-dependent (diffusion-limited), whereas DEHP leaching was controlled by surface rinsing. Model predictions also highlighted the importance of microplastic size on leaching dynamics. These data contribute towards greater accuracy in ERAs of microplastics, with implications for water quality and waste management, including decommissioning of plastic infrastructure.

Safety assessment of the substance poly(2-hydroxypropanoic acid), n-octyl/n-decyl esters, for use in food contact materials.

The EFSA Panel on Food Contact Materials, Enzymes and Processing Aids (CEP) assessed the safety of poly(2-hydroxypropanoic acid), n-octyl/n-decyl esters (OLA8), which is intended to be used as a plasticiser into polylactic acid (PLA) in contact with non-fatty foods. OLA8 is intended to be used at up to 5% and 15% w/w with or without starch, respectively (or with other additives with similar function). The migration for 10 days at 40°C from the film without starch was 0.16 mg/kg in 10% ethanol and 0.01 mg/kg in 3% acetic acid, while from the film with the starch it was well above 0.05 mg/kg food in all simulants. Some of the testing conditions were inconsistently reported. The substance did not induce gene mutations in bacterial cells and did not induce structural chromosomal aberrations or polyploidy in mammalian cells, thus, does not raise concern for genotoxicity. Instead of providing a 90-day oral toxicity study, a hydrolysis study in ■■■■■ was submitted to read-across from the authorised starting substances, ■■■■■ and the ■■■■■. However, the data provided did not allow to perform the read-across, thus no appropriate toxicological data were provided to support migration above 0.05 mg/kg food (including for contact with 10% ethanol and use in combination with starch). The Panel concluded that OLA8 does not raise a safety concern for the consumer if it is used as an additive at up to 15% w/w in the manufacture of PLA articles that do not contain starch (and other additives with similar function), that are intended to be in contact for 10 days at 40°C with foods simulated by 3% acetic acid and from which the migration does not exceed 0.05 mg/kg food.

Development, testing, parameterisation, and calibration of a human PBK model for the plasticiser, di (2-ethylhexyl) adipate (DEHA) using in silico, in vitro and human biomonitoring data.

Introduction: A physiologically based biokinetic model for di (2-ethylhexyl) adipate (DEHA) based on a refined model for di-(2-propylheptyl) phthalate (DPHP) was developed to interpret the metabolism and biokinetics of DEHA following a single oral dosage of 50 mg to two male and two female volunteers. Methods: The model was parameterized using in vitro and in silico methods such as, measured intrinsic hepatic clearance scaled from in vitro to in vivo and algorithmically predicted parameters such as plasma unbound fraction and tissue:blood partition coefficients (PCs). Calibration of the DEHA model was achieved using concentrations of specific downstream metabolites of DEHA excreted in urine. The total fractions of ingested DEHA eliminated as specific metabolites were estimated and were sufficient for interpreting the human biomonitoring data. Results: The specific metabolites of DEHA, mono-2-ethyl-5-hydroxyhexyl adipate (5OH-MEHA), mono-2-ethyl-5-oxohexyl adipate (5oxo-MEHA), mono-5-carboxy-2-ethylpentyl adipate (5cx-MEPA) only accounted for ∼0.45% of the ingested DEHA. Importantly, the measurements of adipic acid, a non-specific metabolite of DEHA, proved to be important in model calibration. Discussion: The very prominent trends in the urinary excretion of the metabolites, 5cx-MEPA and 5OH-MEHA allowed the important absorption mechanisms of DEHA to be modelled. The model should be useful for the study of exposure to DEHA of the general human population.

Co-occurrence of macroplastics, microplastics, and legacy and emerging plasticisers in UK soils.

Despite a theoretical link between plastic and plasticiser occurrence in the terrestrial environment, there are few empirical studies of the relationship between these contaminants in soils. We carried out a field study to assess the co-occurrence of plastic waste, and legacy and emerging plasticisers in UK soils (n = 19) from various land uses (woodlands, urban roadsides, urban parklands, landfill-associated). Surface plastics and soil microplastics were quantified and characterised using ATR-FTIR and µ-FTIR. Eight legacy (phthalate) and three emerging (adipate, citrate, trimellitate) plasticisers were quantified using GC-MS. Surface plastics were found at higher prevalence at landfill-associated and urban roadside sites, with levels significantly (2 orders of magnitude) greater than in woodlands. Microplastics were detected in landfill-associated (mean 12.3 particles g-1 dw), urban roadside (17.3 particles g-1 dw) and urban parkland (15.7 particles g-1 dw) soils, but not in woodland soils. The most commonly detected polymers were polyethene, polypropene and polystyrene. Mean ∑plasticiser concentration in urban roadside soils (3111 ng g-1 dw) was significantly higher than in woodlands (134 ng g-1 dw). No significant difference was found between landfill-associated (318 ng g-1 dw) and urban parkland (193 ng g-1 dw) soils and woodlands. Di-n-butyl phthalate (94.7% detection frequency) and the emerging plasticiser trioctyl trimellitate (89.5%) were the most commonly detected plasticisers, with diethylhexyl phthalate (493 ng g-1 dw) and di-iso-decyl phthalate (96.7 ng g-1 dw) present at the highest concentrations. ∑plasticiser concentrations were significantly correlated with surface plastic (R2 = 0.23), but not with soil microplastic concentrations. Whilst plastic litter seems a fundamental source of plasticisers in soils, mechanisms such as airborne transport from source areas may be as important. Based on the data from this study, phthalates remain the dominant plasticisers in soils, but emerging plasticisers are already widespread, as reflected by their presence in all land uses studied.

Refinement and calibration of a human PBPK model for the plasticiser, Di-(2-propylheptyl) phthalate (DPHP) using in silico, in vitro and human biomonitoring data.

An existing physiologically based pharmacokinetic model for Di-(2-propylheptyl) phthalate (DPHP) was refined to improve the simulations of the venous blood concentrations of the primary monoester metabolite, mono-(2-propylheptyl) phthalate (MPHP). This was considered a significant deficiency that should be addressed because the primary metabolite of other high molecular weight phthalates has been associated with toxicity. The various processes that influence the concentration of DPHP and MPHP in blood were re-evaluated and modified. A few simplifications of the existing model were made, including the removal of enterohepatic recirculation (EHR) of MPHP. However, the primary development was describing the partial binding of MPHP to plasma proteins following uptake of DPHP and metabolism in the gut affording better simulation of the trends observed in the biological monitoring data. Secondly, the relationship between blood concentrations and the urinary excretion of secondary metabolites was explored further because the availability of two data streams provides a better understanding of the kinetics than reliance on just one. Most human studies are conducted with few volunteers and generally with the absence of blood metabolite measurements which would likely imply an incomplete understanding of the kinetics. This has important implications for the "read across" approach proposed as part of the development of New Approach Methods for the replacement of animals in chemical safety assessments. This is where the endpoint of a target chemical is predicted by using data for the same endpoint from another more "data rich" source chemical. Validation of a model parameterized entirely with in vitro and in silico derived parameters and calibrated against several data streams would constitute a data rich source chemical and afford more confidence for future evaluations of other similar chemicals using the read-across approach.

Understanding plasticiser leaching from polystyrene microplastics.

Plastic pollution in our oceans is of growing concern particularly due to the presence of toxic additives, such as plasticisers. Therefore, this work aims to develop a comprehensive understanding of the leaching properties of plasticisers from microplastics. This work investigates the leaching of phthalate acid ester (dioctyl terephthalate (DEHT) and diethylhexyl phthalate (DEHP)) and diphenol (bisphenol A (BPA) and bisphenol S (BPS)) plasticisers from polystyrene (PS) microplastics (mean diameter = 136 µm to 1.4 mm) under controlled aqueous conditions (temperature, agitation, pH and salinity). The leaching behaviours of plasticised polymers were quantified using gel permeation chromatography, high performance liquid chromatography and thermal gravimetric analysis, and the particle's plasticisation characterised using differential scanning calorimetry. Leaching rates of phthalate acid ester and diphenol plasticisers were modelled using a diffusion and boundary layer model, whereby these behaviours varied depending on their plasticisation efficiency of PS, the size of the microplastic particle and the surrounding abiotic conditions. Leaching behaviours of DEHT and DEHP were strongly influenced by the microplastic-surface water boundary layer properties, thus wave action (i.e., water agitation) increased the leaching rate of these plasticiser up to 66 % over 21-days, whereas BPA and BPS plasticisers displayed temperature- and size-dependent leaching and were limited by molecular diffusion throughout the bulk polymer (i.e., the microplastic). This information will improve predictions of plasticiser concentration (both that remain in the plastic and released into the surrounding water) at specific time points during the lifetime of a plastic, ultimately ensuring greater accuracy in the assessment of toxicity responses and environmental water quality.

Equilibrium distribution of diethyl phthalate plasticiser in cellulose acetate-based materials: Modelling and parameter estimation of temperature and composition effects.

Understanding the transport and fate of semi-volatile organic compounds (SVOCs) such as phthalates in indoor environments is fundamental for quantifying levels of human exposure and preventing adverse health effects. In this context, the partition coefficient of phthalates between indoor built materials and/or consumer goods and the surrounding atmosphere represents a key parameter for determining concentration distributions. Partition coefficients are also of fundamental importance for describing degradation phenomena associated with plasticiser loss from polymeric materials. However, this key parameter has only been determined for a limited number of systems and environmental conditions. Here, we assess the partitioning behaviour of the diethyl phthalate (DEP) plasticiser in cellulose acetate (CA)-based materials for the first time, determining the effects of temperature and plasticiser composition on equilibrium distributions at temperatures between 20 and 80 °C and using CA samples with DEP contents ranging from 6 to 22 wt%. Additionally, we propose a model to describe and quantify the effect of temperature and plasticiser composition, with model parameters being estimated using non-linear regression and measurements from 130 distinct experiments. Finally, we assess the suitability of our developed model to simulate the migration of DEP from CA-based materials.

Bisphenol S Impairs Oestradiol Secretion during In Vitro Basal Folliculogenesis in a Mono-Ovulatory Species Model.

Bisphenol S (BPS) affects terminal folliculogenesis by impairing steroidogenesis in granulosa cells from different species. Nevertheless, limited data are available on its effects during basal folliculogenesis. In this study, we evaluate in vitro the effects of a long-term BPS exposure on a model of basal follicular development in a mono-ovulatory species. We cultured ovine preantral follicles (180−240 µm, n = 168) with BPS (0.1 µM (possible human exposure dose) or 10 µM (high dose)) and monitored antrum appearance and follicular survival and growth for 15 days. We measured hormonal secretions (oestradiol (at day 13 [D13]), progesterone and anti-Müllerian hormone [D15]) and expression of key follicular development and redox status genes (D15) in medium and whole follicles, respectively. BPS (0.1 µM) decreased oestradiol secretion compared with the control (−48.8%, p < 0.001), without significantly impairing antrum appearance, follicular survival and growth, anti-Müllerian hormone and progesterone secretion and target gene expression. Thus, BPS could also impair oestradiol secretion during basal folliculogenesis as it is the case during terminal folliculogenesis. It questions the use of BPS as a safe BPA substitute in the human environment. More studies are required to elucidate mechanisms of action of BPS and its effects throughout basal follicular development.

Melting Point Depression of Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymers in Supercritical Carbon Dioxide in the Presence of Menthol as a Solid Co-Plasticiser.

The melting behaviour of the triblock polymers, Pluronic F38, F68, F77, F108, and F127, was investigated in pressurised CO2 and in the presence of menthol. The melting points of the polymers combined with 0, 10, 25, and 50 wt% of menthol were studied at atmospheric pressure and compared with those at 10 and 20 MPa in supercritical carbon dioxide (scCO2). The highest melting point depressions of 16.8 ± 0.5 °C and 29.0 ± 0.3 °C were observed at 10 and 20 MPa, respectively. The melting point of triblock polymers in pressurised CO2 was found to be dependent on molecular weight, poly(propylene oxide) (PPO) content, and menthol percentage. The melting point of most of the polymers studied in this work can be reduced to room temperature, which can be pivotal to the formulation development of thermolabile substances using these polymers.

Viscoelastic and Properties of Amphiphilic Chitin in Plasticised Polylactic Acid/Starch Biocomposite.

The enhancement of the PLA thermomechanical properties is significant due to its suitability as a replacement for primary synthetic polymer use in diverse industrial production. The amphiphilic chitin was used as a compatibilizer in PLA/starch biocomposite. The properties of plasticised polylactic acid blended with starch, and amphiphilic chitin was studied for enhanced thermomechanical and viscoelastic properties. Chitin was modified using acetylated substitution reaction and blended with plasticised PLA/starch biocomposite. The biocomposite was prepared with combined compression and melt extrusion techniques. The biocomposite's thermomechanical, thermal, mechanical, and morphological properties were studied using dynamic mechanical analysis, TGA-DSC, tensile test, and scanning electron microscopy. The storage and loss modulus were significantly enhanced with increased amphiphilic chitin content. Similarly, the single peak of tan delta showed good miscibility of the polymeric blend. Additionally, the modulus increases with frequency change from 1 Hz to 10 Hz. The thermal stability of the biocomposite was observed to be lower than the neat PLA. The tensile properties of the biocomposite increased significantly more than the neat PLA, with P4S4C having the highest tensile strength and modulus of 87 MPa and 7600 MPa. The SEM images show good miscibility with no significant void in the fractured surface. The viscoelastic properties of PLA were enhanced considerably with plasticizer and amphiphilic chitin with improved biodegradability. The properties of the biocomposite can be adapted for various industrial applications.

PAEs Derivatives' Design for Insulation: Integrated In-Silico Methods, Functional Assessment and Environmentally Friendly Molecular Modification.

As a common substance in production and life, phthalic acid esters (PAEs), the main component of plastics, have brought more and more serious problems to the environment. This study normalized the insulation, toxicity, and bioconcentration data of 13 PAEs to eliminate the dimensional coefficients of each index, and then used the comprehensive index method to calculate the comprehensive effect value of PAEs with three properties. The comprehensive effect value was used as the data source to construct the 3D-QSAR model of PAE molecular comprehensive effect. The DAP was selected as the target molecule, the distribution of each force field in the three-dimensional equipotential map was analyzed, and 30 molecular modification schemes were created. The constructed single-effect models of insulation, toxicity, and bioconcentration of PAEs and the scoring function module of DS software were used to evaluate the stability and environmental friendliness of PAE derivative molecules. Four PAE derivatives were screened for increased comprehensive effects, enhanced insulation, and reduced toxicity and bioconcentration. By calculating the binding energy of the target molecule and the derivative molecule with the degrading enzyme under different applied electric fields, it was found that the binding energy of DAP-1-NO2-2-CH2C6H5 decreases more than DAP does when there is an applied electric field, indicating that the degradation ability of degrading enzymes on PAE derivative molecules is reduced, which indirectly proves that the insulation is enhanced. The innovation of this paper lies in the insulation, toxicity, and bioenrichment data of PAEs being processed by mathematical method for the first time, and PAEs with high insulation, low toxicity, and low bioconcentration were designed by building a comprehensive model.

Development, Testing, Parameterisation and Calibration of a Human PBPK Model for the Plasticiser, Di-(2-propylheptyl) Phthalate (DPHP) Using in Silico, in vitro and Human Biomonitoring Data.

A physiologically based pharmacokinetic model for Di-(2-propylheptyl) phthalate (DPHP) was developed to interpret the biokinetics in humans after single oral doses. The model was parameterized with in vitro and in silico derived parameters and uncertainty and sensitivity analysis was used during the model development process to assess structure, biological plausibility and behaviour prior to simulation and analysis of human biological monitoring data. To provide possible explanations for some of the counter-intuitive behaviour of the biological monitoring data the model included a simple lymphatic uptake process for DPHP and enterohepatic recirculation (EHR) for DPHP and the mono ester metabolite mono-(2-propylheptyl) phthalate (MPHP). The model was used to simultaneously simulate the concentration-time profiles of blood DPHP, MPHP and the urinary excretion of two metabolites, mono-(2-propyl-6-hydroxyheptyl) phthalate (OH-MPHP) and mono-(2-propyl-6-carboxyhexyl) phthalate (cx-MPHP). The availability of blood and urine measurements permitted a more robust qualitative and quantitative investigation of the importance of EHR and lymphatic uptake. Satisfactory prediction of blood DPHP and urinary metabolites was obtained whereas blood MPHP was less satisfactory. However, the delayed peak of DPHP concentration relative to MPHP in blood and second order metabolites in urine could be explained as a result of three processes: 1) DPHP entering the systemic circulation from the lymph, 2) rapid and very high protein binding and 3) the efficiency of the liver in removing DPHP absorbed via the hepatic route. The use of sensitivity analysis is considered important in the evaluation of uncertainty around in vitro and in silico derived parameters. By quantifying their impact on model output sufficient confidence in the use of a model should be afforded. This approach could expand the use of PBPK models since parameterization with in silico techniques allows for rapid model development. This in turn could assist in reducing the use of animals in toxicological evaluations by enhancing the utility of "read across" techniques.

Impacts of brewing time, brewing temperature and brands on the leaching of phthalates and bisphenol A in dry tea.

Although tea is often considered a healthy drink, there is the possibility for it to contain bisphenol A and phthalates. This project was designed to quantitate the amount of these compounds when tea was prepared in a variety of conditions, and with a variety of different brands and flavours. BPA and phthalates were extracted using solid phase extraction and quantitated using gas chromatography - mass spectrometry. The leaching concentration of di-n-butyl phthalate, a major phthalate in dry tea samples, increased with respect to both brewing time and temperature at rates of 5.9 ng/g/min and 2.3 ng/g/°C, respectively. Loose leaf green teas showed lower concentrations of contaminants than bagged teas. The highest concentrations found of all compounds were for benzylbutyl phthalate in both Brand2 English breakfast and Brand2 green teas with concentrations of 244 ± 76 ng/g and 197 ± 9 ng/g, respectively. Di-n-butyl phthalate, benzylbutyl phthalate and bis-2-ethylhexyl phthalate were all present in concentrations of 50 ng/g or more in 3 or more samples.

Water sorption and diffusion in cellulose acetate: The effect of plasticisers.

The conservation of cellulose acetate plastics in museum collections presents a significant challenge, due to the material's instability. Several studies have led to an understanding of the role of relative humidity (RH) and temperature in the decay process. It is well established that a major decay mechanism in cellulose acetate museum objects is the loss of plasticiser, and that the main decay mechanism of the polymer chain involves hydrolysis reactions. This leads to the loss of sidechain groups and the breakdown of the main polymer backbone. However, interactions between these decay mechanisms, specifically the way in which the loss of plasticiser can modify the interaction between cellulose acetate and water, has not yet been investigated. This research addresses the role of RH, studying the sorption and diffusion of water in cellulose acetate and how this interaction can be affected by plasticiser concentration using Dynamic Vapour Sorption (DVS).

Plastics and the microbiome: impacts and solutions.

Global plastic production has increased exponentially since manufacturing commenced in the 1950's, including polymer types infused with diverse additives and fillers. While the negative impacts of plastics are widely reported, particularly on marine vertebrates, impacts on microbial life remain poorly understood. Plastics impact microbiomes directly, exerting toxic effects, providing supplemental carbon sources and acting as rafts for microbial colonisation and dispersal. Indirect consequences include increased environmental shading, altered compositions of host communities and disruption of host organism or community health, hormone balances and immune responses. The isolation and application of plastic-degrading microbes are of substantial interest yet little evidence supports the microbial biodegradation of most high molecular weight synthetic polymers. Over 400 microbial species have been presumptively identified as capable of plastic degradation, but evidence for the degradation of highly prevalent polymers including polypropylene, nylon, polystyrene and polyvinyl chloride must be treated with caution; most studies fail to differentiate losses caused by the leaching or degradation of polymer monomers, additives or fillers. Even where polymer degradation is demonstrated, such as for polyethylene terephthalate, the ability of microorganisms to degrade more highly crystalline forms of the polymer used in commercial plastics appears limited. Microbiomes frequently work in conjunction with abiotic factors such as heat and light to impact the structural integrity of polymers and accessibility to enzymatic attack. Consequently, there remains much scope for extremophile microbiomes to be explored as a source of plastic-degrading enzymes and microorganisms. We propose a best-practice workflow for isolating and reporting plastic-degrading taxa from diverse environmental microbiomes, which should include multiple lines of evidence supporting changes in polymer structure, mass loss, and detection of presumed degradation products, along with confirmation of microbial strains and enzymes (and their associated genes) responsible for high molecular weight plastic polymer degradation. Such approaches are necessary for enzymatic degraders of high molecular weight plastic polymers to be differentiated from organisms only capable of degrading the more labile carbon within predominantly amorphous plastics, plastic monomers, additives or fillers.

Epoxidised sesame oil as a biobased coupling agent and plasticiser in polylactic acid/thermoplastic yam starch blends.

This work aims to improve the physicochemical properties of polylactic acid (PLA) and thermoplastic yam starch (TPS) blends using epoxidised sesame oil (ESO). We used epoxidised sesame oil from two Colombian Caribbean crops: Dioscorea rotundata and Sesamum indicum, with an oil substitution of 58.4 %. Films were obtained through extrusion and compression moulding processes. Moisture content, solubility, contact angle, and mechanical, barrier, and structural properties were determined using optical and scanning electron microscopy, infrared Fourier transform spectroscopy. Thermal analyses were also performed using thermogravimetry and differential scanning calorimetry techniques. The results suggest that the PLA and TPS interactions can be improved with the addition of ESO as coupling agent, enhancing the interfacial adhesion between the polymers, and favouring the smoothness of the film surface. Furthermore, the ESO addition led to increased thermal stability while restricting molecular mobility, indicating a coupling agent effect. In conclusion, the use of epoxidised oil for preparing films based on high PLA content and TPS allows obtaining enhanced interfacial adhesion. Considering the above, the developed materials have potential application in semi-rigid food packaging.

The Interplay between Drug and Sorbitol Contents Determines the Mechanical and Swelling Properties of Potential Rice Starch Films for Buccal Drug Delivery.

Rice starch is a promising biomaterial for thin film development in buccal drug delivery, but the plasticisation and antiplasticisation phenomena from both plasticisers and drugs on the performance of rice starch films are not well understood. This study aims to elucidate the competing effects of sorbitol (plasticiser) and drug (antiplasticiser) on the physicochemical characteristics of rice starch films containing low paracetamol content. Rice starch films were prepared with different sorbitol (10, 20 and 30% w/w) and paracetamol contents (0, 1 and 2% w/w) using the film casting method and were characterised especially for drug release, swelling and mechanical properties. Sorbitol showed a typical plasticising effect on the control rice starch films by increasing film flexibility and by reducing swelling behaviour. The presence of drugs, however, modified both the mechanical and swelling properties by exerting an antiplasticisation effect. This antiplasticisation action was found to be significant at a low sorbitol level or a high drug content. FTIR investigations supported the antiplasticisation action of paracetamol through the disturbance of sorbitol-starch interactions. Despite this difference, an immediate drug release was generally obtained. This study highlights the interplay between plasticiser and drug in influencing the mechanical and swelling characteristics of rice starch films at varying concentrations.

Biodegradation of Poly(Lactic Acid) Biocomposites under Controlled Composting Conditions and Freshwater Biotope.

The influence of additives such as natural-based plasticiser acetyl tributyl citrate (ATBC), CaCO3 and lignin-coated cellulose nanocrystals (L-CNC) on the biodegradation of polylactic acid (PLA) biocomposites was studied by monitoring microbial metabolic activity through respirometry. Ternary biocomposites and control samples were processed by a twin-screw extruder equipped with a flat film die. Commonly available compost was used for the determination of the ultimate aerobic biodegradability of PLA biocomposites under controlled composting conditions (ISO 14855-1). In addition, the hydro-degradability of prepared films in a freshwater biotope was analysed. To determine the efficiency of hydro-degradation, qualitative analyses (SEM, DSC, TGA and FTIR) were conducted. The results showed obvious differences in the degradation rate of PLA biocomposites. The application of ATBC at 10 wt.% loading increased the biodegradation rate of PLA. The addition of 10 wt.% of CaCO3 into the plasticised PLA matrix ensured an even higher degradation rate at aerobic thermophilic composting conditions. In such samples (PLA/ATBC/CaCO3), 94% biodegradation in 60 days was observed. In contrast, neat PLA exposed to the same conditions achieved only 16% biodegradation. Slightly inhibited microorganism activity was also observed for ternary PLA biocomposites containing L-CNC (1 wt.% loading). The results of qualitative analyses of degradation in a freshwater biotope confirmed increased biodegradation potential of ternary biocomposites containing both CaCO3 and ATBC. Significant differences in the chemical and structural compositions of PLA biocomposites were found in the evaluated period of three months.