Novel unexpected functions of PHA granules.

Polyhydroxyalkanoates (PHA), polyesters accumulated by numerous prokaryotes in the form of intracellular granules, have been for decades considered being predominantly storage molecules. However, numerous recent discoveries revealed and emphasized their complex biological role for microbial cells. Most of all, it was repeatedly reported and confirmed that the presence of PHA granules in prokaryotic cells enhances stress resistance and robustness of microbes against various environmental stress factors such as high or low temperature, freezing, oxidative, and osmotic pressure. It seems that protective mechanisms of PHA granules are associated with their extraordinary architecture and biophysical properties as well as with the complex and deeply interconnected nature of PHA metabolism. Therefore, this review aims at describing novel and unexpected properties of PHA granules with respect to their contribution to stress tolerance of various prokaryotes including common mesophilic heterotrophic bacteria, but also extremophiles or photo-autotrophic cyanobacteria. KEY POINTS: • PHA granules present in bacterial cells reveal unique properties and functions. • PHA enhances stress robustness of bacterial cells.

Two-piece zirconia versus titanium implants after 80 months: Clinical outcomes from a prospective randomized pilot trial.

OBJECTIVES: To prospectively evaluate, as part of an ongoing randomized pilot trial, the clinical outcomes of two-piece zirconia implants in comparison with titanium implants 80 months after delivery of all-ceramic (lithium disilicate) single-tooth restorations. MATERIAL AND METHODS: The original sample included 31 (16 zirconia and 15 titanium) implants in 22 healthy patients. In addition to evaluating implant survival and success, a number of clinical or radiographic parameters were statistically analyzed: plaque index (PI), bleeding on probing (BOP), pink esthetic score (PES), and marginal bone loss (MBL). Both implant groups were compared using a Mann-Whitney U test. RESULTS: Three implants (2 zirconia and 1 titanium) had been lost, so that 28 implants (14 zirconia and 14 titanium) in 21 patients could be evaluated after a mean of 80.9 (SD: 5.5) months. All surviving implants had remained stable, in the absence of any fixture or abutment fractures and without any chipping, fracture, or debonding of crowns. The zirconia implants were associated with PI values of 11.07% (SD: 8.11) and the titanium implants with 15.20% (SD: 15.58), the respective figures for the other parameters being 16.43% (SD: 6.16) or 12.60% (SD: 7.66) for BOP; 11.11 (SD: 1.27) or 11.56 (SD: 1.01) for PES; and 1.38 mm (SD: 0.81) or 1.17 mm (SD: 0.73) for MBL. CONCLUSIONS: No significant differences were found between the clinical outcomes of two-piece zirconia and titanium implants based on the aforementioned parameters after 80 months of clinical service. Our results should be interpreted with the limited sample size in mind.

What keeps polyhydroxyalkanoates in bacterial cells amorphous? A derivation from stress exposure experiments.

Polyhydroxyalkanoates (PHA) are storage polymers accumulated by numerous prokaryotes in form of intracellular granules. Native PHA granules are formed by amorphous polymer which reveals considerably higher elasticity and flexibility as compared to crystalline pure PHA polymers. The fact that bacteria store PHA in amorphous state has great biological consequences. It is not clear which mechanisms protect amorphous polymer in native granules from transition into thermodynamically favorable crystalline state. Here, we demonstrate that exposition of bacterial cells to particular stressors induces granules aggregation, which is the first but not sufficient condition for PHA crystallization. Crystallization of the polymer occurs only when the stressed bacterial cells are subsequently dried. The fact that both granules aggregation and cell drying must occur to induce crystallization of PHA indicates that both previously suggested hypotheses about mechanisms of stabilization of amorphous state of native PHA are valid and, in fact, both effects participate synergistically. It seems that the amorphous state of the polymer is stabilized kinetically by the low rate of crystallization in limited volume in small PHA granules and, moreover, water present in PHA granules seems to function as plasticizer protecting the polymer from crystallization, as confirmed experimentally for the first time by the present work.

Accuracy assessment of 3D-printed tooth replicas.

AIM: The production of individual tooth replicas has two applications in dental practice: tooth autotransplantations and dental root analogue implants. These applications require a particularly high degree of precision. The purpose of this study was to establish and evaluate a method for fabricating individual 3D-printed tooth replicas. MATERIALS AND METHODS: 10 patients requiring extraction of a wisdom tooth and a preoperative cone beam computed tomography (CBCT) scan were included; exclusion criteria were intraoperative fragmentation or fracture of the tooth. 3D Slicer 4.6.2 was used for tooth segmentation and model generation based on CBCT data. The tooth replicas were manufactured by selective laser melting (SLM). The extracted teeth and 3D-printed replicas were scanned and tested for surface deviations in CloudCompare 2.8.1. RESULTS: The mean absolute surface deviation between the 3D-printed teeth and the corresponding extracted teeth ranged from 0.13 to 0.25 mm, with standard deviations of 0.10 to 0.21 mm; 95% of the measured surface points deviated less than 0.474 mm; the surface area was reduced by -6.0% and the volume by -3.4%. The root mean square was 0.238 mm and the mean maximum absolute surface deviation was 0.927 mm. The SLM technique showed a high precision with a mean absolute deviation of 0.045 mm and a standard deviation of 0.04 mm. CONCLUSION: 3D-printed tooth replicas with a very high accuracy could be produced based on CBCT data. The described method is suitable for manufacturing tooth replicas for use in tooth autotransplantations or for fabricating root analogue implants.

Evaluation of smartphone-based testing to generate exploratory outcome measures in a phase 1 Parkinson's disease clinical trial.

BACKGROUND: Ubiquitous digital technologies such as smartphone sensors promise to fundamentally change biomedical research and treatment monitoring in neurological diseases such as PD, creating a new domain of digital biomarkers. OBJECTIVES: The present study assessed the feasibility, reliability, and validity of smartphone-based digital biomarkers of PD in a clinical trial setting. METHODS: During a 6-month, phase 1b clinical trial with 44 Parkinson participants, and an independent, 45-day study in 35 age-matched healthy controls, participants completed six daily motor active tests (sustained phonation, rest tremor, postural tremor, finger-tapping, balance, and gait), then carried the smartphone during the day (passive monitoring), enabling assessment of, for example, time spent walking and sit-to-stand transitions by gyroscopic and accelerometer data. RESULTS: Adherence was acceptable: Patients completed active testing on average 3.5 of 7 times/week. Sensor-based features showed moderate-to-excellent test-retest reliability (average intraclass correlation coefficient = 0.84). All active and passive features significantly differentiated PD from controls with P < 0.005. All active test features except sustained phonation were significantly related to corresponding International Parkinson and Movement Disorder Society-Sponsored UPRDS clinical severity ratings. On passive monitoring, time spent walking had a significant (P = 0.005) relationship with average postural instability and gait disturbance scores. Of note, for all smartphone active and passive features except postural tremor, the monitoring procedure detected abnormalities even in those Parkinson participants scored as having no signs in the corresponding International Parkinson and Movement Disorder Society-Sponsored UPRDS items at the site visit. CONCLUSIONS: These findings demonstrate the feasibility of smartphone-based digital biomarkers and indicate that smartphone-sensor technologies provide reliable, valid, clinically meaningful, and highly sensitive phenotypic data in Parkinson's disease. © 2018 The Authors. Movement Disorders published by Wiley Periodicals, Inc. on behalf of International Parkinson and Movement Disorder Society.

Light scattering on PHA granules protects bacterial cells against the harmful effects of UV radiation.

Numerous prokaryotes accumulate polyhydroxyalkanoates (PHA) in the form of intracellular granules. The primary function of PHA is the storage of carbon and energy. Nevertheless, there are numerous reports that the presence of PHA granules in microbial cells enhances their stress resistance and fitness when exposed to various stress factors. In this work, we studied the protective mechanism of PHA granules against UV irradiation employing Cupriavidus necator as a model bacterial strain. The PHA-accumulating wild type strain showed substantially higher UV radiation resistance than the PHA non-accumulating mutant. Furthermore, the differences in UV-Vis radiation interactions with both cell types were studied using various spectroscopic approaches (turbidimetry, absorption spectroscopy, and nephelometry). Our results clearly demonstrate that intracellular PHA granules efficiently scatter UV radiation, which provides a substantial UV-protective effect for bacterial cells and, moreover, decreases the intracellular level of reactive oxygen species in UV-challenged cells. The protective properties of the PHA granules are enhanced by the fact that granules specifically bind to DNA, which in turn provides shield-like protection of DNA as the most UV-sensitive molecule. To conclude, the UV-protective action of PHA granules adds considerable value to their primary storage function, which can be beneficial in numerous environments.

Biodegradable and Biocompatible Polyhydroxy-alkanoates (PHA): Auspicious Microbial Macromolecules for Pharmaceutical and Therapeutic Applications.

Polyhydroxyalkanoates (PHA) are bio-based microbial biopolyesters; their stiffness, elasticity, crystallinity and degradability are tunable by the monomeric composition, selection of microbial production strain, substrates, process parameters during production, and post-synthetic processing; they display biological alternatives for diverse technomers of petrochemical origin. This, together with the fact that their monomeric and oligomeric in vivo degradation products do not exert any toxic or elsewhere negative effect to living cells or tissue of humans or animals, makes them highly stimulating for various applications in the medical field. This article provides an overview of PHA application in the therapeutic, surgical and tissue engineering area, and reviews strategies to produce PHA at purity levels high enough to be used in vivo. Tested applications of differently composed PHA and advanced follow-up products as carrier materials for controlled in vivo release of anti-cancer drugs or antibiotics, as scaffolds for tissue engineering, as guidance conduits for nerve repair or as enhanced sutures, implants or meshes are discussed from both a biotechnological and a material-scientific perspective. The article also describes the use of traditional processing techniques for production of PHA-based medical devices, such as melt-spinning, melt extrusion, or solvent evaporation, and emerging processing techniques like 3D-printing, computer-aided wet-spinning, laser perforation, and electrospinning.

First-in-human assessment of PRX002, an anti-α-synuclein monoclonal antibody, in healthy volunteers.

BACKGROUND: α-Synuclein is a major component of pathologic inclusions that characterize Parkinson's disease. PRX002 is an antibody that targets α-synuclein, and its murine parent antibody 9E4 has been shown in preclinical studies to reduce α-synuclein pathology and to protect against cognitive and motor deteriorations and progressive neurodegeneration in human α-synuclein transgenic mice. METHODS: This first-in-human, randomized, double-blind, placebo-controlled, phase 1 study assessed the impact of PRX002 administered to 40 healthy participants in 5 ascending-dose cohorts (n = 8/cohort) in which participants were randomly assigned to receive a single intravenous infusion of study drug (0.3, 1, 3, 10, or 30 mg/kg; n = 6/cohort) or placebo (n = 2/cohort). RESULTS: PRX002 demonstrated favorable safety, tolerability, and pharmacokinetic profiles at all doses tested, with no immunogenicity. No serious adverse events, discontinuations as a result of adverse events, or dose-limiting toxicities were reported. Serum PRX002 exposure was dose proportional; the average terminal half-life across all doses was 18.2 days. A significant dose-dependent reduction in free serum α-synuclein (unbound to PRX002) was apparent within 1 hour after PRX002 administration, whereas total α-synuclein (free plus bound) increased dose-dependently, presumably because of the expected change in kinetics following antibody binding. CONCLUSIONS: This study demonstrates that serum α-synuclein can be safely modulated in a dose-dependent manner after single intravenous infusions of an anti-α-synuclein antibody. These findings support continued development of PRX002, including further characterization of its safety, tolerability, pharmacokinetics, and pharmacodynamic effects in the central nervous system in patients with Parkinson's disease. © 2016 The Authors. Movement Disorders published by Wiley Periodicals, Inc. on behalf of International Parkinson and Movement Disorder Society.

Footprint area analysis of binary imaged Cupriavidus necator cells to study PHB production at balanced, transient, and limited growth conditions in a cascade process.

Statistical distribution of cell and poly[3-(R)-hydroxybutyrate] (PHB) granule size and number of granules per cell are investigated for PHB production in a five-stage cascade (5CSTR). Electron microscopic pictures of cells from individual cascade stages (R1-R5) were converted to binary pictures to visualize footprint areas for polyhydroxyalkanoate (PHA) and non-PHA biomass. Results for each stage were correlated to the corresponding experimentally determined kinetics (specific growth rate µ and specific productivity π). Log-normal distribution describes PHA granule size dissimilarity, whereas for R1 and R4, gamma distribution best reflects the situation. R1, devoted to balanced biomass synthesis, predominately contains cells with rather small granules, whereas with increasing residence time τ, maximum and average granule sizes by trend increase, approaching an upper limit determined by the cell's geometry. Generally, an increase of intracellular PHA content and ratio of granule to cell area slow down along the cascade. Further, the number of granules per cell decreases with increasing τ. Data for µ and π obtained by binary picture analysis correlate well with the experimental results. The work describes long-term continuous PHA production under balanced, transient, and nutrient-deficient conditions, as well as their reflection on the granules size, granule number, and cell structure on the microscopic level.

Designing Hydrophobically Modified Polysaccharide Derivatives for Highly Efficient Enzyme Immobilization.

In this contribution, a hydrophobically modified polysaccharide derivative is synthesized in an eco-friendly solvent water by conjugation of benzylamine with the backbone of the biopolymer. Owing to the presence of aromatic moieties, the resulting water-soluble polysaccharide derivative self-assembles spontaneously and selectively from solution on the surface of nanometric thin films and sheets of polystyrene (PS). The synthetic polymer modified in this way bears a biocompatible nanolayer suitable for the immobilization of horseradish peroxidase (HRP), a heme-containing metalloenzyme often employed in biocatalysis and biosensors. Besides the detailed characterization of the polysaccharide derivative, a quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM) are used to investigate the binding efficiency and interaction of HRP with the tailored polysaccharide interfaces. Subsequent enzyme activity tests reveal details of the interaction of HRP with the solid support. The novel polysaccharide derivative and its use as a material for the selective modification of PS lead to a beneficial, hydrophilic environment for HRP, resulting in high enzymatic activities and a stable immobilization of the enzyme for biocatalytic and analytic purposes.

All-ceramic restoration of zirconia two-piece implants--a randomized controlled clinical trial.

OBJECTIVES: Aim of this controlled prospective randomized study was to evaluate the outcome of two-piece zirconia implants compared to titanium implants over a period of up to 24 months. MATERIAL AND METHODS: A total of 31 implants (16 zirconia/Ziterion vario Z(®) + 15 titanium/Ziterion vario T(®) ) were inserted primary stable (>30 Ncm) in the maxilla (7) and mandible (24) of 22 patients (13 male, nine female) requiring neither bone nor soft tissue augmentation. After a healing period of 6 months in the maxilla and 4 months in the mandible, ceramic abutments were luted adhesively to the zirconia implants and definitive all-ceramic restoration was performed with high-density ceramics. Radiographic bone levels, condition of the peri-implant mucosa, aesthetic outcome, implant survival and success were recorded for up to 24 months. RESULTS: Measurements of mean marginal bone levels 24 months after surgery showed a significant bone loss (P < 0.001) in both groups (Ti: 1.43 (SD ± 0.67) vs. Zir 1.48 (SD ± 1.05). One zirconia implant was lost 8 months after restoration. No further complications were recorded, giving an overall survival and success rate of 93.3% for zirconia and 100% for titanium implants after a period of up to 24 months. CONCLUSIONS: After 24 months, success rates of the two-piece ceramic implants showed no significant difference compared to control two-piece titanium implants. The bonded zirconia implant abutment connection appears to be capable with clinical application over the observed period. However, further control measurements need to confirm the presented data.

Recent advances in elementary flux modes and yield space analysis as useful tools in metabolic network studies.

A review of the use of elementary flux modes (EFMs) and their applications in metabolic engineering covered with yield space analysis (YSA) is presented. EFMs are an invaluable tool in mathematical modeling of biochemical processes. They are described from their inception in 1994, followed by various improvements of their computation in later years. YSA constitutes another precious tool for metabolic network modeling, and is presented in details along with EFMs in this article. The application of these techniques is discussed for several case studies of metabolic network modeling provided in respective original articles. The article is concluded by some case studies in which the application of EFMs and YSA turned out to be most useful, such as the analysis of intracellular polyhydroxyalkanoate (PHA) formation and consumption in Cupriavidus necator, including the constraint-based description of the steady-state flux cone of the strain's metabolic network, the profound analysis of a continuous five-stage bioreactor cascade for PHA production by C. necator using EFMs and, finally, the study of metabolic fluxes in the metabolic network of C. necator cultivated on glycerol.

Study of metabolic network of Cupriavidus necator DSM 545 growing on glycerol by applying elementary flux modes and yield space analysis.

A metabolic network consisting of 48 reactions was established to describe intracellular processes during growth and poly-3-hydroxybutyrate (PHB) production for Cupriavidus necator DSM 545. Glycerol acted as the sole carbon source during exponential, steady-state cultivation conditions. Elementary flux modes were obtained by the program Metatool and analyzed by using yield space analysis. Four sets of elementary modes were obtained, depending on whether the pair NAD/NADH or FAD/FADH2 contributes to the reaction of glycerol-3-phosphate dehydrogenase (GLY-3-P DH), and whether 6-phosphogluconate dehydrogenase (6-PG DH) is present or not. Established metabolic network and the related system of equations provide multiple solutions for the simultaneous synthesis of PHB and biomass; this number of solutions can be further increased if NAD/NADH or FAD/FADH2 were assumed to contribute in the reaction of GLY-3-P DH. As a major outcome, it was demonstrated that experimentally determined yields for biomass and PHB with respect to glycerol fit well to the values obtained in silico when the Entner-Doudoroff pathway (ED) dominates over the glycolytic pathway; this is also the case if the Embden-Meyerhof-Parnas pathway dominates over the ED.

Carbon Recycling of High Value Bioplastics: A Route to a Zero-Waste Future.

Today, 98% of all plastics are fossil-based and non-biodegradable, and globally, only 9% are recycled. Microplastic and nanoplastic pollution is just beginning to be understood. As the global demand for sustainable alternatives to conventional plastics continues to rise, biobased and biodegradable plastics have emerged as a promising solution. This review article delves into the pivotal concept of carbon recycling as a pathway towards achieving a zero-waste future through the production and utilization of high-value bioplastics. The review comprehensively explores the current state of bioplastics (biobased and/or biodegradable materials), emphasizing the importance of carbon-neutral and circular approaches in their lifecycle. Today, bioplastics are chiefly used in low-value applications, such as packaging and single-use items. This article sheds light on value-added applications, like longer-lasting components and products, and demanding properties, for which bioplastics are increasingly being deployed. Based on the waste hierarchy paradigm-reduce, reuse, recycle-different use cases and end-of-life scenarios for materials will be described, including technological options for recycling, from mechanical to chemical methods. A special emphasis on common bioplastics-TPS, PLA, PHAs-as well as a discussion of composites, is provided. While it is acknowledged that the current plastics (waste) crisis stems largely from mismanagement, it needs to be stated that a radical solution must come from the core material side, including the intrinsic properties of the polymers and their formulations. The manner in which the cascaded use of bioplastics, labeling, legislation, recycling technologies, and consumer awareness can contribute to a zero-waste future for plastics is the core topics of this article.

Archaeal production of polyhydroxyalkanoate (PHA) co- and terpolyesters from biodiesel industry-derived by-products.

The archaeon Haloferax mediterranei was selected for production of PHA co- and terpolyesters using inexpensive crude glycerol phase (CGP) from biodiesel production as carbon source. CGP was assessed by comparison with the application of pure glycerol. Applying pure glycerol, a copolyester with a molar fraction of 3-hydroxybutyrate (3HB) of 0.90 mol/mol and 3-hydroxyvalerate (3HV) of 0.10 mol/mol, was produced at a volumetric productivity of 0.12 g/Lh and an intracellular PHA content of 75.4 wt.-% in the sum of biomass protein plus PHA. Application of CGP resulted in the same polyester composition and volumetric productivity, indicating the feasibility of applying CGP as feedstock. Analysis of molar mass distribution revealed a weight average molar mass M w of 150 kDa and polydispersity P i of 2.1 for pure glycerol and 253 kDa and 2.7 for CGP, respectively; melting temperatures ranged between 130 and 140°C in both setups. Supplying γ -butyrolactone as 4-hydroxybutyrate (4HB) precursor resulted in a poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate-co-4-hydroxybutyrate] (PHBHV4HB) terpolyester containing 3HV (0.12 mol/mol) and 4HB (0.05 mol/mol) in the poly[(R)-3-hydroxybutyrate] (PHB) matrix; in addition, this process runs without sterilization of the bioreactor. The terpolyester displayed reduced melting (melting endotherms at 122 and 137°C) and glass transition temperature (2.5°C), increased molar mass (391 kDa), and a polydispersity similar to the copolyesters.

Immediate provisional restoration of single-piece zirconia implants: a prospective case series - results after 24 months of clinical function.

OBJECTIVE: Aim of this prospective case series was to evaluate the outcome of immediately provisionalized single-piece zirconia implants. MATERIAL AND METHODS: A total of 20 zirconia implants were inserted in single-tooth gaps in the maxilla (11) and mandible (9) of 20 patients. Implants were restored with all-ceramic CAD/CAM provisionals without occlusal contacts immediately after placement. Permanent all-ceramic restoration was performed 4 months after surgery. Plaque index (PI), bleeding on probing (BOP), Periotest(®) (PV), pink aesthetic score (PES), mean radiographic marginal bone levels (MBL), implant survival and success were evaluated up to 24 months. RESULTS: Assessment of PI at baseline and follow-ups after 6, 12, 18 and 24 months revealed 27% (±5.3), 24% (±6), 23% (±6.1), 23% (±5.3) and 22% (±6.4), respectively. Evaluation of BOP revealed 25% (±5.6), 21% (±6), 21% (±7.2), 18% (±5.9) and 15% (±5.5), respectively. Implants presented stable at follow-ups (PV). PES improved, but not statistically significant from 8.13 (±1.5) at baseline to 10 (±2) 24 months after implantation. Measurements of MBL showed a significant bone loss of 1.01 mm within the first year after placement (P < 0.001) and 1.29 mm 24 months post-implant insertion, not reaching further statistically significant levels (P > 0.05). One implant was lost 4 months after placement, resulting in a survival and success rate of 95%. CONCLUSION: Clinical and radiographic parameters demonstrated a 95% integration of immediately loaded zirconia single-piece implants. A long-term randomized-controlled clinical trial was initiated to confirm evidence of this protocol.

Extraction of short-chain-length poly-[(R)-hydroxyalkanoates] (scl-PHA) by the "anti-solvent" acetone under elevated temperature and pressure.

A novel method was developed for extraction of short-chain-length poly(hydroxyalkanoates) (scl-PHA) from microbial biomass by the well-known "scl-PHA anti-solvent" acetone at elevated temperature and pressure in a closed system combining components for extraction, filtration, and product work-up. Recovery of scl-PHA using this new approach was compared with established methods using chloroform at ambient pressure. The new method performs similar regarding product purity (98.4 vs. 97.7%) and extraction yield (96.8% by both methods), and is by far faster than established chloroform extraction (20 min vs. 12 h). Separation of the polymer from acetone is simply achieved by cooling down the acetone solution of scl-PHA, thus allows for a nearly quantitative recovery of the solvent that conveniently can be reused. Characterization of scl-PHA extracted by both methods does not reveal any significant difference in terms of molar mass and thermo analytical parameters.

Mathematical modelling and process optimization of a continuous 5-stage bioreactor cascade for production of poly[-(R)-3-hydroxybutyrate] by Cupriavidus necator.

A multistage system for poly(hydroxyalkanoate) (PHA) production consisting of five continuous stirred tank reactors in series (5-CSTR) with Cupriavidus necator DSM 545 as production strain was modelled using formal kinetic relations. Partially growth-associated production of PHA under nitrogen limited growth was chosen as modelling strategy, thus the Luedeking-Piret's model of partial growth-associated product synthesis was applied as working hypothesis. Specific growth rate relations adjusted for double substrate (C and N source) limited growth according to Megee et al. and Mankad-Bungay relation were tested. The first stage of the reactor cascade was modelled according to the principle of nutrient balanced continuous biomass production system, the second one as two substrate controlled process, while the three subsequent reactors were adjusted to produce PHB under continuous C source fed and nitrogen deficiency. Simulated results of production obtained by the applied mathematical models and computational optimization indicate that PHB productivity of the whole system could be significantly increased (from experimentally achieved 2.14 g L(-1) h(-1) to simulated 9.95 g L(-1) h(-1)) if certain experimental conditions would have been applied (overall dilution rate, C and N source feed concentration). Additionally, supplemental feeding strategy for switching from batch to continuous mode of cultivation was proposed to avoid substrate inhibition.

Microbial PolyHydroxyAlkanoate (PHA) Biopolymers-Intrinsically Natural.

Global pollution from fossil plastics is one of the top environmental threats of our time. At their end-of-life phase, fossil plastics, through recycling, incineration, and disposal result in microplastic formation, elevated atmospheric CO2 levels, and the pollution of terrestrial and aquatic environments. Current regional, national, and global regulations are centered around banning plastic production and use and/or increasing recycling while ignoring efforts to rapidly replace fossil plastics through the use of alternatives, including those that occur in nature. In particular, this review demonstrates how microbial polyhydroxyalkanoates (PHAs), a class of intrinsically natural polymers, can successfully remedy the fossil and persistent plastic dilemma. PHAs are bio-based, biosynthesized, biocompatible, and biodegradable, and thus, domestically and industrially compostable. Therefore, they are an ideal replacement for the fossil plastics pollution dilemma, providing us with the benefits of fossil plastics and meeting all the requirements of a truly circular economy. PHA biopolyesters are natural and green materials in all stages of their life cycle. This review elaborates how the production, consumption, and end-of-life profile of PHAs are embedded in the current and topical, 12 Principles of Green Chemistry, which constitute the basis for sustainable product manufacturing. The time is right for a paradigm shift in plastic manufacturing, use, and disposal. Humankind needs alternatives to fossil plastics, which, as recalcitrant xenobiotics, contribute to the increasing deterioration of our planet. Natural PHA biopolyesters represent that paradigm shift.

What Are "Bioplastics"? Defining Renewability, Biosynthesis, Biodegradability, and Biocompatibility.

Today, plastic materials are mostly made from fossil resources, and they are characterized by their long lifetime and pronounced persistence in the open environment. These attributes of plastics are one cause of the ubiquitous pollution we see in our environment. When plastics end up in the environment, most of this pollution can be attributed to a lack of infrastructure for appropriately collecting and recycling plastic waste, mainly due to mismanagement. Because of the huge production volumes of plastics, their merits of being cheap to produce and process and their recalcitrance have turned into a huge disadvantage, since plastic waste has become the end point of our linear economic usage model, and massive amounts have started to accumulate in the environment, leading to microplastics pollution and other detrimental effects. A possible solution to this is offered by "bioplastics", which are materials that are either (partly) biobased and/or degradable under defined conditions. With the rise of bioplastics in the marketplace, several standards and test protocols have been developed to assess, certify, and advertise their properties in this respect. This article summarizes and critically discusses different views on bioplastics, mainly related to the properties of biodegradability and biobased carbon content; this shall allow us to find a common ground for clearly addressing and categorizing bioplastic materials, which could become an essential building block in a circular economy. Today, bioplastics account for only 1-2% of all plastics, while technically, they could replace up to 90% of all fossil-based plastics, particularly in short-lived goods and packaging, the single most important area of use for conventional plastics. Their replacement potential not only applies to thermoplastics but also to thermosets and elastomers. Bioplastics can be recycled through different means, and they can be made from renewable sources, with (bio)degradability being an option for the mismanaged fraction and special applications with an intended end of life in nature (such as in seed coatings and bite protection for trees). Bioplastics can be used in composites and differ in their properties, similarly to conventional plastics. Clear definitions for "biobased" and "biodegradable" are needed to allow stakeholders of (bio)plastics to make fact-based decisions regarding material selection, application, and end-of-life options; the same level of clarity is needed for terms like "renewable carbon" and "bio-attributed" carbon, definitions of which are summarized and discussed in this paper.