Polyhydroxyalkanoate Composition Research Articles

Novel differential scanning calorimetry (DSC) application to select polyhydroxyalkanoate (PHA) producers correlating 3-hydroxyhexanoate (3-HHx) monomer with melting enthalpy.

Polyhydroxyalkanoate (PHA) is an environmental alternative to petroleum-based plastics because of its biodegradability. The polymer properties of PHA have been improved by the incorporation of different monomers. Traditionally, the monomer composition of PHA has been analyzed using gas chromatography (GC) and nuclear magnetic resonance (NMR), providing accurate monomer composition. However, sequential analysis of the thermal properties of PHA using differential scanning calorimetry (DSC) remains necessary, providing crucial insights into its thermal characteristics. To shorten the monomer composition and thermal property analysis, we directly applied DSC to the analysis of the obtained PHA film and observed a high correlation (r2 = 0.98) between melting enthalpy and the 3-hydroxyhexanoate (3-HHx) mole fraction in the polymer. A higher 3-HHx fraction resulted in a lower melting enthalpy as 3-HHx provided the polymer with higher flexibility. Based on this, we selected the poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(3HB-co-3HHx)) producing strain from Cupriavidus strains that newly screened and transformed with vectors containing P(3HB-co-3HHx) biosynthetic genes, achieving an average error rate below 1.8% between GC and DSC results. Cupriavidus sp. BK2 showed a high 3-HHx mole fraction, up to 10.38mol%, with Tm(℃) = 171.5 and ΔH of Tm (J/g) = 48.0, simultaneously detected via DSC. This study is an example of the expansion of DSC for PHA analysis from polymer science to microbial engineering.

Biodegradable polymer casting films for drug delivery and cell culture

In this work, for the first time, films were obtained based on biodegradable polyhydroxyalkanoates (PHAs) - a copolymer of 3-hydroxybutyrate-co-3-hydroxyvalerate P(3HB-co-3HV) and a copolymer of 3-hydroxybutyrate-co-4-hydroxybutyrate P(3HB-co-4HB), containing drugs of different chemical structure and action - antibiotics (ceftazidime, doripenem), antiseptic (chlorhexidine) and tissue regeneration stimulator (Actovegin) for drug delivery and cell culture. Using SEM, AFM and measuring the contact angles of water wetting, it is shown how PHAs composition and loading of films of P(3HB-co-3HV) and P(3HB-co-4HB) with drugs affect the porosity, roughness indicators and adhesive properties of the surface. The constructed films are a depot form of drug, the release of which in vitro is realized for a long time, without burst releases, corresponds to Korsmeyer-Peppas and Higuchi models with diffusion character. Films loaded with antibiotics have pronounced antibacterial activity and suppress the development of pathogens S. aureus and E. coli, without a pronounced negative effect on the adhesion and proliferation of epidermal cells. In the cultures of human keratinocytes HaCaT it was shown that the presence of actovegin, as well as ceftazidime in the films, exhibits a stimulating effect, increasing their number. The results demonstrate the suitability of the depot-films for cellular technologies and are promising for the reconstruction of tissues complicated by infection.

Exploring the Future of Polyhydroxyalkanoate Composites with Organic Fillers: A Review of Challenges and Opportunities.

Biopolymers from renewable materials are promising alternatives to the traditional petroleum-based plastics used today, although they face limitations in terms of performance and processability. Natural fillers have been identified as a strategic route to create sustainable composites, and natural fillers in the form of waste by-products have received particular attention. Consequently, the primary focus of this article is to offer a broad overview of recent breakthroughs in environmentally friendly Polhydroxyalkanoate (PHA) polymers and their composites. PHAs are aliphatic polyesters obtained by bacterial fermentation of sugars and fatty acids and are considered to play a key role in addressing sustainability challenges to replace traditional plastics in various industrial sectors. Moreover, the article examines the potential of biodegradable polymers and polymer composites, with a specific emphasis on natural composite materials, current trends, and future market prospects. Increased environmental concerns are driving discussions on the importance of integrating biodegradable materials with natural fillers in our daily use, emphasizing the need for clear frameworks and economic incentives to support the use of these materials. Finally, it highlights the indispensable need for ongoing research and development efforts to address environmental challenges in the polymer sector, reflecting a growing interest in sustainable materials across all industries.

PHA from acetic acid: Manipulating microbial production of polyhydroxyalkanoates for use in steel coatings

This research sought to determine the impact of various culture parameters on the composition of polyhydroxyalkanoate (PHA), which was intended for use in steel coating. PHAs are biodegradable biopolymers that can be made by glycogen accumulating organisms (GAOs), which produce two types of monomers, 3-hydroxybutyrate (HB), and 3-hydroxyvalerate (HV). Several different culture parameters (acetate concentration, nitrogen and phosphate availability, temperature and pH) were varied and their effect on the PHA composition was measured. The results showed that the HB relative content was lower at acetate concentrations higher than 6 g/L and pH 6.5 and 7. The HV content increased from 26 % to 43 % for 18 °C and 28 °C, respectively. Nitrogen concentration did not influence PHA composition whereas 100 mg/L of phosphate induced a HV content equal to 47 %. A positive Pearson correlation between HB content and PHA yield was found in this research. This study showed how the culture conditions might be varied to change the PHA composition to serve a specific function, like replacing steel coating with biodegradable polymers.

Enhancing PHA production through metal-organic frameworks: Mechanisms involving superproton transport and bacterial metabolic pathways

The effective fermentation of organic waste for polyhydroxyalkanoate (PHA) production is crucial for waste pollution prevention and comprehensive utilization. Glycerol, a common component of organic waste and a by-product of biodiesel production, can serve as a valuable raw material for PHA synthesis. This study explored the potential of metal-organic frameworks (MOFs), specifically MOF-808, to enhance the PHA production by Cupriavidus necator (C. necator) and Bacillus cereus (B. cereus) using glycerol as the substrate. Our results demonstrated that the addition of MOF-808 significantly promoted PHA synthesis without altering the PHA composition. Notably, the proportion of PHA to cell dry weight (CDW) increased significantly (P < 0.05) in both C. necator (from 17.17% to 30.43%) and B. cereus (from 11.30% to 37.93%), with a shortened growth period observed in the latter. The enhanced superproton transport properties of MOF-808 elevated the ATP energy supply level, regulated coenzyme A metabolism, and modulated the PHA synthesis pathway in the bacterial strains. Additionally, MOF-808 improved the utilization of the PHA precursor acetyl-CoA by C. necator, and enhanced the PHA production in B. cereus by facilitating cell growth and PHA synthesis in two distinct stages. Importantly, the recovered MOF-808 structure remained stable, enabling potential recycling. This study provides compelling evidence for the enhancement of PHA production and offers valuable insights into the utilization of organic waste as a valuable resource.

Performance of production of polyhydroxyalkanoates from food waste fermentation with Rhodopseudomonas palustris

The use of waste as a carbon source can significantly reduce the cost of production of Polyhydroxyalkanoates (PHAs). In this study, an acidified hydrolysate solution derived from food waste (FW) was used as a carbon source for the synthesis of PHAs by Rhodopseudomonas palustris (R. palustris) and optimized the process parameters. The results showed that the PHAs yield reached 48.62% under optimal conditions (an incubation time of 30 days, volatile fatty acids (VFAs) in substrate concentration of 2202.21 mg⋅L−1, an initial pH of 8.0, and inoculum concentration of 15%). The fraction of VFAs affects the composition of PHAs, R. palustris first uses VFAs with an even number of carbons to synthesize poly(3-hydroxybutyrate)(3HB), and later uses VFAs with an odd number of carbons to synthesize poly-3-hydroxyvalerate (3HV). Pathways for the synthesis of PHAs by R. palustris were inferred. R. palustris is a strain with the potential to synthesize PHAs.

Resorbable Nanomatrices from Microbial Polyhydroxyalkanoates: Design Strategy and Characterization.

From a series of biodegradable natural polymers of polyhydroxyalkanoates (PHAs)-poly-3-hydroxybutyrate (P(3HB) and copolymers containing, in addition to 3HB monomers, monomers of 3-hydroxyvalerate (3HV), 3-hydroxyhexanoate (3HHx), and 4-hydroxybutyrate (4HB), with different ratios of monomers poured-solvent casting films and nanomembranes with oriented and non-oriented ultrathin fibers were obtained by electrostatic molding. With the use of SEM, AFM, and measurement of contact angles and energy characteristics, the surface properties and mechanical and biological properties of the polymer products were studied depending on the method of production and the composition of PHAs. It has been shown in cultures of mouse fibroblasts of the NIH 3T3 line and diploid human embryonic cells of the M22 line that elastic films and nanomembranes composed of P(3HB-co-4HB) copolymers have high biocompatibility and provide adhesion, proliferation and preservation of the high physiological activity of cells for up to 7 days. Polymer films, namely oriented and non-oriented nanomembranes coated with type 1 collagen, are positively evaluated as experimental wound dressings in experiments on laboratory animals with model and surgical skin lesions. The results of planimetric measurements of the dynamics of wound healing and analysis of histological sections showed the regeneration of model skin defects in groups of animals using experimental wound dressings from P(3HB-co-4HB) of all types, but most actively when using non-oriented nanomembranes obtained by electrospinning. The study highlights the importance of nonwoven nanomembranes obtained by electrospinning from degradable low-crystalline copolymers P(3HB-co-4HB) in the effectiveness of the skin wound healing process.

From Organic Wastes and Hydrocarbons Pollutants to Polyhydroxyalkanoates: Bioconversion by Terrestrial and Marine Bacteria

The use of fossil-based plastics has become unsustainable because of the polluting production processes, difficulties for waste management sectors, and high environmental impact. Polyhydroxyalkanoates (PHA) are bio-based biodegradable polymers derived from renewable resources and synthesized by bacteria as intracellular energy and carbon storage materials under nutrients or oxygen limitation and through the optimization of cultivation conditions with both pure and mixed culture systems. The PHA properties are affected by the same principles of oil-derived polyolefins, with a broad range of compositions, due to the incorporation of different monomers into the polymer matrix. As a consequence, the properties of such materials are represented by a broad range depending on tunable PHA composition. Producing waste-derived PHA is technically feasible with mixed microbial cultures (MMC), since no sterilization is required; this technology may represent a solution for waste treatment and valorization, and it has recently been developed at the pilot scale level with different process configurations where aerobic microorganisms are usually subjected to a dynamic feeding regime for their selection and to a high organic load for the intracellular accumulation of PHA. In this review, we report on studies on terrestrial and marine bacteria PHA-producers. The available knowledge on PHA production from the use of different kinds of organic wastes, and otherwise, petroleum-polluted natural matrices coupling bioremediation treatment has been explored. The advancements in these areas have been significant; they generally concern the terrestrial environment, where pilot and industrial processes are already established. Recently, marine bacteria have also offered interesting perspectives due to their advantageous effects on production practices, which they can relieve several constraints. Studies on the use of hydrocarbons as carbon sources offer evidence for the feasibility of the bioconversion of fossil-derived plastics into bioplastics.

Biosynthesis of Polyhydroxyalkanoate Terpolymer from Methanol via the Reverse β-Oxidation Pathway in the Presence of Lanthanide.

Methylorubrum extorquens AM1 is the attractive platform for the production of value-added products from methanol. We previously demonstrated that M. extorquens equipped with PHA synthase with broad substrate specificity synthesized polyhydroxyalkanoates (PHAs) composed of (R)-3-hydroxybutyrate and small fraction of (R)-3-hydroxyvalerate (3HV) and (R)-3-hydroxyhexanoate (3HHx) units on methanol. This study further engineered M. extorquens for biosynthesis of PHAs with higher 3HV and 3HHx composition focusing on the EMC pathway involved in C1 assimilation. The introduction of ethylmalonyl-CoA decarboxylase, catalyzing a backward reaction in the EMC pathway, aiming to increase intracellular propionyl/butyryl-CoA precursors did not affect PHA composition. Reverse β-oxidation pathway and subsequent (R)-specific hydration of 2-enoyl-CoA were then enhanced by heterologous expression of four genes derived from Ralstonia eutropha for the conversion of propionyl/butyryl-CoAs to the corresponding (R)-3-hydroxyacyl-CoA monomers. The resulting strains produced PHAs with higher 3HV and 3HHx compositions, while the methylotrophic growth was severely impaired. This growth impairment was interestingly restored by the addition of La3+ without a negative impact on PHA biosynthesis, suggesting the activation of the EMC pathway by La3+. The engineered M. extorquens synthesized PHA terpolymer composed of 5.4 mol% 3HV and 0.9% of 3HHx with 41% content from methanol as a sole carbon source in the presence of La3+.

Polyhydroxyalkanoates from industrial cheese whey: Production and characterization of polymers with differing hydroxyvalerate content

The composition of polyhydroxyalkanoate (PHA) monomers affects the properties and final applications of PHA polymers. This study focused on the feasibility of producing tailored PHA differing in hydroxyvalerate (HV) content, through manipulation of the acidogenic fermented stream composition, and on the characterization of PHA properties to determine the best composition for melt processing. Cheese whey was used as a feedstock, and changes in the organic loading rate during acidogenic fermentation led to the production of a fermented stream with an HV precursor content of 9–33 wt%. In the PHA production assays, a PHA content of 50 ± 11 wt%. (VSS basis) and yield of 0.76 ± 0.14 gCODPHA.gCODFP-1 were obtained. Fermented stream supplementation with HV precursors during the PHA accumulation assays indicated the feasibility of producing tailored PHA with differing HV content without a need for the selection of new cultures. The thermal properties of PHA were found to be controlled by the HV content, and PHA with approximately 30 wt% HV had the lowest melting temperature. These results demonstrated the robustness of the process at pilot scale, thus supporting full-scale applications in tailored PHA production.

Production of a newly discovered PHA family member with an isobutyrate-fed enrichment culture

Using microbial enrichment cultures for the production of waste-derived polyhydroxyalkanoates (PHAs) is a promising technology to recover secondary resources. Volatile fatty acids (VFAs) form the preferred substrate for PHA production. Isobutyrate is a VFA appearing in multiple waste valorization routes, such as anaerobic fermentation, chain elongation, and microbial electrosynthesis, but has never been assessed individually on its PHA production potential. This research investigates isobutyrate as sole carbon source for a microbial enrichment culture in comparison to its structural isomer butyrate. The results reveal that the enrichment of isobutyrate has a very distinct character regarding microbial community development, PHA productivity, and even PHA composition. Although butyrate is a superior substrate in almost every aspect, this research shows that isobutyrate-rich waste streams have a noteworthy PHA-producing potential. The main finding is that the dominant microorganism, a Comamonas sp., is linked to the production of a unique PHA family member, poly(3-hydroxyisobutyrate) (PHiB), up to 37% of the cell dry weight. This is the first scientific report identifying microbial PHiB production, demonstrating that mixed microbial communities can be a powerful tool for discovery of new metabolic pathways and new types of polymers.Key points• PHiB production is a successful storage strategy in an isobutyrate-fed SBR• Isomers isobutyrate and butyrate reveal a very distinct PHA production behavior• Enrichments can be a tool for discovery of new metabolic pathways and polymersGraphical abstract

Properties of Degradable Polyhydroxyalkanoates (PHAs) Synthesized by a New Strain, Cupriavidus necator IBP/SFU-1, from Various Carbon Sources.

The bacterial strain isolated from soil was identified as Cupriavidus necator IBP/SFU-1 and investigated as a PHA producer. The strain was found to be able to grow and synthesize PHAs under autotrophic conditions and showed a broad organotrophic potential towards different carbon sources: sugars, glycerol, fatty acids, and plant oils. The highest cell concentrations (7–8 g/L) and PHA contents were produced from oleic acid (78%), fructose, glucose, and palm oil (over 80%). The type of the carbon source influenced the PHA chemical composition and properties: when grown on oleic acid, the strain synthesized the P(3HB-co-3HV) copolymer; on plant oils, the P(3HB-co-3HV-co-3HHx) terpolymer, and on the other substrates, the P(3HB) homopolymer. The type of the carbon source influenced molecular-weight properties of PHAs: P(3HB) synthesized under autotrophic growth conditions, from CO2, had the highest number-average (290 ± 15 kDa) and weight-average (850 ± 25 kDa) molecular weights and the lowest polydispersity (2.9 ± 0.2); polymers synthesized from organic carbon sources showed increased polydispersity and reduced molecular weight. The carbon source was not found to affect the degree of crystallinity and thermal properties of the PHAs. The type of the carbon source determined not only PHA composition and molecular weight but also surface microstructure and porosity of the polymer films. The new strain can be recommended as a promising P(3HB) producer from palm oil, oleic acid, and sugars (fructose and glucose) and as a producer of P(3HB-co-3HV) from oleic acid and P(3HB-co-3HV-co-3HHx) from palm oil.

Regulating the monomer of polyhydroxyalkanoate from mixed microbial culture: with particular emphasis on substrate composition: A review

Polyhydroxyalkanoate (PHA), produced by mixed microbial cultures (MMCs), is a biodegradable biopolyester that alleviates the global plastic crisis in the nearest future. Even PHA has become a research hotspot, reviews on PHA composition determining thermodynamic and processing properties of PHA products are rare. The primary focus of the evaluation relies on the factors affecting the PHA monomer composition of MMC-PHA production. Besides, since the volatile fatty acids (VFAs) composition of the substrates strongly influences the PHA monomer composition, regulating the ratio of even-carbon to odd-carbon VFAs, PHA, vary properties could be obtained predictably. So oriented acid production process, the first stage process in three-stage MMC-PHA production that can regulate the VFAs composition, is also comprehensively introduced to help understand PHA monomer regulation.

Effect of the solid retention time in the obtention of polyhydroxyalkanoates

<ns3:p><ns3:bold>Background:</ns3:bold><ns3:bold> </ns3:bold>The effect of solid retention time (SRT) over cheese whey substrates in a fermentation process drives changes in the composition of polyhydroxyalkanoates (PHAs) obtained. Volatile fatty acids produced in the first step of an anaerobic sequencing batch reactor were used as substrates to produce PHA using mixed microbial cultures under aerobic dynamic feeding conditions.</ns3:p><ns3:p> <ns3:bold>Methods: </ns3:bold>Analytical methods were used for the standard analysis of parameters of interest including measuring the amount of ammonium and phosphate, chemical oxygen demand, among others.</ns3:p><ns3:p> <ns3:bold>Results</ns3:bold>: The SRT increasing from 4 to 6 and 10 days produced changes in the distribution of volatile fatty acids produced. The polyhydroxybutyrate-hydroxyvalerate copolymers formed in the accumulation stage gave the following results: 58:42, 68:32 and 81:19 (%), referred to SRTs of 10, 6 and 4 days, respectively. The maximum PHA accumulation obtained at 10 days of SRT was 52% of the dry cell weight within 7 h, reaching a PHA productivity of 0.62 g L<ns3:sup>−1</ns3:sup> h<ns3:sup>−1</ns3:sup> and a storage yield of 0.37.</ns3:p><ns3:p> <ns3:bold>Conclusion:</ns3:bold><ns3:bold> </ns3:bold>The SRT variation impact on the distribution of volatile fatty acids in the acidogenic reactor and consequently on the PHA production and composition formed in the accumulation stage.</ns3:p>

A review on the potential of polyhydroxyalkanoates production from oil-based substrates

Polyhydroxyalkanoate (PHA) is a type of polyesters produced in the form of accumulated intracellular granules by many microorganisms. It is viewed as an environmentally friendly bioproduct due to its biodegradability and biocompatibility. The production of the PHA using oil substrates such as waste oil and plant oil, has gained considerable attention due to the high product yield and lower substrate cost. Nevertheless, the PHA fermentation using oil substrate is complicated due to the heterogenous fatty acid composition, varied bio-accessibility and possible inhibitory effect on the bacterial culture. This review presents the current state-of-the-art of PHA production from oil-based substrates. This paper firstly discusses the technical details, such as the choice of bacteria strain and fermentation conditions, characteristic of the oil substrate as well as the PHA composition and application. Finally, the paper discusses the challenges and prospects for up-scaling towards a cleaner and effective bioprocess. From the literature review, depending on the cell culture and the type of PHA produced, the oil platform can have a PHA yield of 0.2–0.8 g PHA/g oil substrate, with PHA content mostly from 40 to 90% of the cell dry weight. There is an on-going search for more effective oil-utilising PHA producers and lower cost substrate for effective PHA production. The final application of the PHA polymer influences the treatment needed during downstream processing and its economic performance. PHA with different compositions exhibits varied decomposition behaviour under different conditions, requiring further insight towards its management towards a sustainable circular economy.

Identification of regions affecting enzyme activity, substrate binding, dimer stabilization and polyhydroxyalkanoate (PHA) granule morphology in the PHA synthase of Aquitalea sp. USM4

Polyhydroxyalkanoates (PHAs) are biopolyesters synthesized by microorganisms as intracellular energy reservoirs under stressful environmental conditions. PHA synthase (PhaC) is the key enzyme responsible for PHA biosynthesis, but the importance of its N- and C-terminal ends still remains elusive. Six plasmid constructs expressing truncation variants of Aquitalea sp. USM4 PhaC (PhaC1As) were generated and heterologously expressed in Cupriavidus necator PHB−4. Removal of the first six residues at the N-terminus enabled the modulation of PHA composition without altering the PHA content in cells. Meanwhile, deletion of 13 amino acids from the C-terminus greatly affected the catalytic activity of PhaC1As, retaining only 1.1–7.4% of the total activity. Truncation(s) at the N- and/or C-terminus of PhaC1As gradually diminished the incorporation of comonomer units, and revealed that the N-terminal region is essential for PhaC1As dimerization whereas the C-terminal region is required for stabilization. Notably, transmission electron microscopy analysis showed that PhaC modification affected the morphology of intracellular PHA granules, which until now is only known to be regulated by phasins. This study provided substantial evidence and highlighted the significance of both the N- and C-termini of PhaC1As in regulating intracellular granule morphology, activity, substrate specificity, dimerization and stability of the synthase.

Changes in Mechanical Properties of Polyhydroxyalkanoate with Double Silanized Cellulose Nanocrystals Using Different Organosiloxanes

Polyhydroxyalkanoate (PHA) is a biodegradable plastic with great potential for tackling plastic waste and marine pollution issues, but its commercial applications have been limited due to its poor processability. In this study, surface-modified cellulose nanocrystals were used to improve the mechanical properties of PHA composites produced via a melt-extrusion process. Double silanization was conducted to obtain hydrophobically treated CNC-based fillers, using tetraethyl orthosilicate (TEOS) and methyltrimethoxysilane (MTMS). The morphology, particle size distributions, and surface characteristics of the silanized CNCs and their compatibility with a PHA polymer matrix differed by the organosiloxane treatment and drying method. It was confirmed that the double silanized CNCs had hydrophobic surface characteristics and narrow particle size distributions, and thereby showed excellent dispersibility in a PHA matrix. Adding hydrophobically treated CNCs to form a PHA composite, the elongation at break of the PHA composites was improved up to 301%, with little reduction of Young’s modulus, compared to pure PHA. Seemingly, the double silanized CNCs added played a similar role to a nucleation agent in the PHA composite. It is expected that such high ductility can improve the mechanical properties of PHA composites, making them more suitable for commercial applications.

Laser Processing of Polymer Films Fabricated from PHAs Differing in Their Monomer Composition.

The study reports results of using a CO2-laser in continuous wave (3 W; 2 m/s) and quasi-pulsed (13.5 W; 1 m/s) modes to treat films prepared by solvent casting technique from four types of polyhydroxyalkanoates (PHAs), namely poly-3-hydroxybutyrate and three copolymers of 3-hydroxybutyrate: with 4-hydroxybutyrate, 3-hydroxyvalerate, and 3-hydroxyhexanoate (each second monomer constituting about 30 mol.%). The PHAs differed in their thermal and molecular weight properties and degree of crystallinity. Pristine films differed in porosity, hydrophilicity, and roughness parameters. The two modes of laser treatment altered these parameters and biocompatibility in diverse ways. Films of P(3HB) had water contact angle and surface energy of 92° and 30.8 mN/m, respectively, and average roughness of 144 nm. The water contact angle of copolymer films decreased to 80–56° and surface energy and roughness increased to 41–57 mN/m and 172–290 nm, respectively. Treatment in either mode resulted in different modifications of the films, depending on their composition and irradiation mode. Laser-treated P(3HB) films exhibited a decrease in water contact angle, which was more considerable after the treatment in the quasi-pulsed mode. Roughness parameters were changed by the treatment in both modes. Continuous wave line-by-line irradiation caused formation of sintered grooves on the film surface, which exhibited some change in water contact angle (76–80°) and reduced roughness parameters (to 40–45 mN/m) for most films. Treatment in the quasi-pulsed raster mode resulted in the formation of pits with no pronounced sintered regions on the film surface, a more considerably decreased water contact angle (to 67–76°), and increased roughness of most specimens. Colorimetric assay for assessing cell metabolic activity (MTT) in NIH 3T3 mouse fibroblast culture showed that the number of fibroblasts on the films treated in the continuous wave mode was somewhat lower; treatment in quasi-pulsed radiation mode caused an increase in the number of viable cells by a factor of 1.26 to 1.76, depending on PHA composition. This is an important result, offering an opportunity of targeted surface modification of PHA products aimed at preventing or facilitating cell attachment.

Waste as feedstock for polyhydroxyalkanoate production from activated sludge: Implications of aerobic dynamic feeding and acidogenic fermentation

Polyhydroxyalkanoates (PHA) are the ideal substitute for petroleum-derived non-biodegradable plastics. However, the cost of polymer production restricts the large-scale implementation. Waste feedstocks are a perfect carbon source to balance the cost and waste disposal and minimization. The suitability of activated sludge as inoculum for PHA production from potential waste feedstocks was analyzed for an affordable production strategy through waste management in a three-step methodology. The methodology involves a combined acidogenic fermentation and aerobic dynamic feeding strategy to improve PHA accumulation. Firstly, the specificity of waste feedstock for storage response was increased through volatile fatty acid (VFAs) production by tuning the process elements during acidogenic fermentation depending on the type of substrate. Secondly, activated sludge enriched through aerobic dynamic feeding strategy for improved storage response weeds out non-accumulators through various approaches. Finally, PHA accumulation bulks the enriched mix culture with PHA through different routes to enable economic downstream processing. The acidogenic fermentation critically impacts PHA composition and property along with operating conditions during the process. These studies point towards the feasibility of integrating PHA production by three-step methodology to the existing waste treatment facility and its future scope. Further investigations to improve the efficiency of the process and polymer properties can lead to cheaper polymer production more comprehensive market application.

Properties of degradable polyhydroxyalkanoates with different monomer compositions

PurposeTo synthesize and investigate polyhydroxyalkanoates (PHAs) with different monomer composition and percentages and polymer films prepared from them. ResultsVarious PHAs: homopolymer poly-3-hydroxybutyrate P(3HB) and 2-, 3-, and 4-component copolymers comprising various combinations of 3-hydroxybutyrate (3HB), 3-hydroxyvalerate (3HV), 4-hydroxybutyrate (4HB), and 3-hydroxyhexanoate (3HHx) monomers were synthesized under specialized conditions. Relationships were found between the monomer composition of PHAs and their molecular-weight and thermal properties and degree of crystallinity. All copolymers had decreased weight average molecular weights, Mw (to 390–600 kDa), and increased values of polydispersity (3.2–4.6) compared to the P(3HB). PHA copolymers showed different thermal behavior: an insignificant decrease in Tmelt and the presence of the second peak in the melting region and changes in parameters of crystallization and glass transition. At the same time, they retained thermostability, and the difference between Tmelt and Tdegr was at least 100–120 °C. Incorporation of 4HB, 3HV, and 3HHx monomer units into the 3-hydroxybutyrate chain caused changes in the amorphous to crystalline ratio and decreased the degree of crystallinity (Cx) to 20–40%. According to the degree to which the monomers reduced crystallinity, they were ranked as follows: 4HB – 3HHx – 3HV. A unique set of films was produced; their surface properties and physical/mechanical properties were studied as dependent on PHA composition; monomers other than 3-hydroxybutyrate were found to enhance hydrophilicity, surface development, and elasticity of polymer films. ConclusionAn innovative set of PHA copolymers was synthesized and solution-cast films were prepared from them; the copolymers and films were investigated as dependent on polymer chemical composition. Results obtained in the present study contribute to the solution of a critical issue of producing degradable polymer materials.