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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Resource availability governs polyhydroxyalkanoate (PHA) accumulation and diversity of methanotrophic enrichments from wetlands

Aquatic environments account for half of global CH 4 emissions, with freshwater wetlands being the most significant contributors. These CH 4 fluxes can be partially offset by aerobic CH 4 oxidation driven by methanotrophs. Additionally, some methanotrophs can convert CH 4 into polyhydroxyalkanoate (PHA), an energy storage molecule as well as a promising bioplastic polymer. In this study, we investigate how PHA-accumulating methanotrophic communities enriched from wetlands were shaped by varying resource availability (i.e., C and N concentrations) at a fixed C/N ratio. Cell yields, PHA accumulation, and community composition were evaluated in high (20% CH 4 and 10 mM NH 4 + ) and low resource (0.2% CH 4 and 0.1 mM NH 4 + ) conditions simulating engineered and environmental settings, respectively. High resource availability decreased C-based cell yields, while N-based cell yields remained stable, suggesting nutrient exchange patterns differed between methanotrophic communities at different resource concentrations. PHA accumulation was only observed in high resource enrichments, producing approximately 12.6% ± 2.4% (m/m) PHA, while PHA in low resource enrichments remained below detection. High resource enrichments were dominated by Methylocystis methanotrophs, while low resource enrichments remained significantly more diverse and contained only a minor population of methanotrophs. This study demonstrates that resource concentration shapes PHA-accumulating methanotrophic communities. Together, this provides useful information to leverage such communities in engineering settings as well as to begin understanding their role in the environment.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1997

Suppressed PHA Activation of T Lymphocytes in Simulated Microgravity Is Restored by Direct Activation of Protein Kinase C with Phorbol Ester

Various aspects of spaceflight, including microgravity, cosmic radiation, and physiological stress, may perturb immune function. We sought to understand the impact of microgravity alone on the cellular mechanisms critical to immunity. We utilized clinostatic RWV bioreactors that simulate aspects of microgravity to analyze the response of human PBMC to polyclonal activation. PHA responsiveness in the RWV was almost completely diminished. IL-2 and IFN-gamma secretion was reduced whereas IL- 1 beta and IL-6 secretion was increased, suggesting that monocytes may not be as adversely affected by simulated microgravity as T cells. Activation marker expression (CD25, CD69, CD71) was significantly reduced in RWV cultures. Furthermore, addition of exogenous IL-2 to these cultures did not restore proliferation. Reduced cell-cell and cell-substratum interactions may play a role in the loss of PHA responsiveness. However, PHA activation in Teflon culture bags that limit cell-substratum interactions did not suppress PHA activation. Furthermore, increasing cell density and, therefore, cell-cell interactions in the RWV cultures did not help restore PHA activation. However, placing PBMC within small collagen beads did partially restore PHA responsiveness. Activation of both PBMC and purified T cells with PMA and ionomycin was unaffected by RWV culture, indicating that signaling mechanisms downstream of PKC activation and calcium flux are not sensitive to simulated microgravity. Furthermore, submitogenic doses of PMA alone but not ionomycin alone restored PHA responsiveness of PBMC in RWV culture. Thus, our data indicate that during polyclonal activation the signaling pathways upstream of PKC activation are sensitive to simulated microgravity.

Cooper, David↗
NASA NTRS1998

Suppressed PHA activation of T lymphocytes in simulated microgravity is restored by direct activation of protein kinase C

Utilizing clinostatic rotating wall vessel (RWV) bioreactors that simulate aspects of microgravity, we found phytohemagglutinin (PHA) responsiveness to be almost completely diminished. Activation marker expression was significantly reduced in RWV cultures. Furthermore, cytokine secretion profiles suggested that monocytes are not as adversely affected by simulated microgravity as T cells. Reduced cell-cell and cell-substratum interactions may play a role in the loss of PHA responsiveness because placing peripheral blood mononuclear cells (PBMC) within small collagen beads did partially restore PHA responsiveness. However, activation of purified T cells with cross-linked CD2/CD28 and CD3/CD28 antibody pairs was completely suppressed in the RWV, suggesting a defect in signal transduction. Activation of purified T cells with PMA and ionomycin was unaffected by RWV culture. Furthermore, sub-mitogenic doses of PMA alone but not ionomycin alone restored PHA responsiveness of PBMC in RWV culture. Thus our data indicate that during polyclonal activation the signaling pathways upstream of PKC activation are sensitive to simulated microgravity.

NASA Discipline Cell Biology↗
DOE OSTI2025

Innovative Polyhydroxyalkanoates (PHA) Production with Microbial Electrochemical Technology (MET)

The project “Innovative Polyhydroxyalkanoates (PHA) Production with Microbial Electrochemical Technology (MET)” addressed food waste disposal challenges by successfully converting food waste to bioplastics (known as PHAs). The novel process created by our team of researchers from universities, national labs, and industry substantially enhanced overall carbon conversion efficiency of food waste processing (> 50%), while reducing disposal costs (> 25%). The project showed economic viability potential at community scale through pilot-scale demonstration at a relevant scale (50 L reactor volume) with more than 100 hours of PHA production using realistic conditions. The project goal was to valorize food waste by shunting traditional anaerobic digestion processing and creating a value-added PHA processing route that improves the economics and sustainability of local, community-scale, wet organic waste treatment. First, the food waste undergoes microbial-based, dark fermentation to break down the food to small carbon chains known as volatile fatty acids (VFAs). Instead of microorganisms converting the VFAs into methane using normal anaerobic digestion processing, our innovative process inhibits methane production. This preserves the produced VFAs for extraction and use by a novel Haloferax mediterranei (HM) archaea, which effectively converts the VFAs to bioplastics. The project added microbial electrochemical cells (MEC) to the dark fermentation process to enhance the VFAs produced and optimize the type of bioplastics formed.

36 MATERIALS SCIENCE↗
NASA NTRS2004

Analysis of CRRES PHA Data for Low-Energy-Deposition Events

This effort analyzed the low-energy deposition Pulse Height Analyzer (PHA) data from the Combined Release and Radiation Effects Satellite (CRRES). The high-energy deposition data had been previously analyzed and shown to be in agreement with spallation reactions predicted by the Clemson University Proton Interactions in Devices (CUPID) simulation model and existing environmental and orbit positioning models (AP-8 with USAF B-L coordinates). The scope of this project was to develop and improve the CUPID model by increasing its range to lower incident particle energies, and to expand the modeling to include contributions from elastic interactions. Before making changes, it was necessary to identify experimental data suitable for benchmarking the codes; then, the models to the CRRES PHA data could be applied. It was also planned to test the model against available low-energy proton or neutron SEU data obtained with mono-energetic beams.

McNulty, P. J.↗
DOE OSTI2026

Bioelectrocatalytic conversion of CO₂ to PHA bioplastics using engineered methylotrophs

The sustainable generation of biodegradable plastics represents an opportunity to capture atmospheric CO 2 while reducing plastic waste accumulation in the environment. This study implements an integrated platform for bioelectrocatalytic CO 2 conversion to medium-chain-length polyhydroxyalkanoates (mcl-PHAs). Immobilizing cobalt phthalocyanine electrocatalysts on a covalent-organic framework in a gas recirculation electrolyzer enabled CO 2 -to-methanol conversion with a carbon conversion efficiency of 98%. Integration of polymer biosynthesis pathways enabled Methylotuvimicrobium alcaliphilum 20Z R to produce ~20% mcl-PHA of the dry cell weight with a CO 2 -to-bioproducts carbon conversion efficiency of 50%. This cell line was adapted to high sodium bicarbonate media, eliminating costly intermediate separation steps while improving economic potential. Transcriptomic analysis revealed sulfate transporters and peptidoglycan biosynthesis as key pathways involved in sodium bicarbonate halotolerance. Altogether, this research presents a foundation for integrating divergent chemical and biological processes into a transformative electrobiomanufacturing platform, addressing the need for alternative pipelines for generating valuable plastics and chemicals.

CO2 utilization↗
DOE OSTI2024

Overexpression of RuBisCO form I and II genes in Rhodopseudomonas palustris TIE-1 augments polyhydroxyalkanoate production heterotrophically and autotrophically

ABSTRACT With the rising demand for sustainable renewable resources, microorganisms capable of producing bioproducts such as bioplastics are attractive. While many bioproduction systems are well-studied in model organisms, investigating non-model organisms is essential to expand the field and utilize metabolically versatile strains. This investigation centers on Rhodopseudomonas palustris TIE-1, a purple non-sulfur bacterium capable of producing bioplastics. To increase bioplastic production, genes encoding the putative regulatory protein PhaR and the depolymerase PhaZ of the polyhydroxyalkanoate (PHA) biosynthesis pathway were deleted. Genes associated with pathways that might compete with PHA production, specifically those linked to glycogen production and nitrogen fixation, were deleted. Additionally, RuBisCO form I and II genes were integrated into TIE-1’s genome by a phage integration system, developed in this study. Our results show that deletion of phaR increases PHA production when TIE-1 is grown photoheterotrophically with butyrate and ammonium chloride (NH 4 Cl). Mutants unable to produce glycogen or fix nitrogen show increased PHA production under photoautotrophic growth with hydrogen and NH 4 Cl. The most significant increase in PHA production was observed when RuBisCO form I and form I & II genes were overexpressed, five times under photoheterotrophy with butyrate, two times with hydrogen and NH 4 Cl, and two times under photoelectrotrophic growth with N 2 . In summary, inserting copies of RuBisCO genes into the TIE-1 genome is a more effective strategy than deleting competing pathways to increase PHA production in TIE-1. The successful use of the phage integration system opens numerous opportunities for synthetic biology in TIE-1. IMPORTANCE Our planet has been burdened by pollution resulting from the extensive use of petroleum-derived plastics for the last few decades. Since the discovery of biodegradable plastic alternatives, concerted efforts have been made to enhance their bioproduction. The versatile microorganism Rhodopseudomonas palustris TIE-1 (TIE-1) stands out as a promising candidate for bioplastic synthesis, owing to its ability to use multiple electron sources, fix the greenhouse gas CO 2 , and use light as an energy source. Two categories of strains were meticulously designed from the TIE-1 wild-type to augment the production of polyhydroxyalkanoate (PHA), one such bioplastic produced. The first group includes mutants carrying a deletion of the phaR or phaZ genes in the PHA pathway, and those lacking potential competitive carbon and energy sinks to the PHA pathway (namely, glycogen biosynthesis and nitrogen fixation). The second group comprises TIE-1 strains that overexpress RuBisCO form I or form I & II genes inserted via a phage integration system. By studying numerous metabolic mutants and overexpression strains, we conclude that genetic modifications in the environmental microbe TIE-1 can improve PHA production. When combined with other approaches (such as reactor design, use of microbial consortia, and different feedstocks), genetic and metabolic manipulations of purple nonsulfur bacteria like TIE-1 are essential for replacing petroleum-derived plastics with biodegradable plastics like PHA.

Ranaivoarisoa, Tahina Onina↗
DOE OSTI2026

Upcycling plastic waste into polyhydroxyalkanoates with high carbon conversion via CO 2 plasma-enabled deconstruction

Plastic deconstruction into fermentable intermediates is a key step for microbial bio-upcycling into value-added products. In this study, CO 2 plasma deconstruction was used as an electrified route to convert polyethylene into oxygenated intermediates and liquid (OIL). The resulting OIL was rich in fatty acids, fatty alcohols, and hydrocarbons, making it a suitable feedstock for medium-chain-length polyhydroxyalkanoate (mcl-PHA) production by Pseudomonas putida NRRL B-14688 and Pseudomonas resinovorans NRRL B-2649. Compared with batch fermentation and monocultures, fed-batch co-cultivation markedly improved biomass formation and PHA accumulation, likely due to complementary substrate utilization, particularly hydrocarbon conversion by P. resinovorans. Using virgin polyethylene-derived OIL (Vir-OIL), the co-culture achieved 40.11% mcl-PHA content and about 18% PHA yield based on total OIL fed. More importantly, OIL produced from post-consumer single-use plastic films (PCR-OIL) was directly fermented and well supported the cell growth and PHA accumulation, achieving 38.11% PHA content and about 14.7% PHA yield. Based on emulsified OIL fractions, PHA yields for Vir-OIL and PCR-OIL were comparable (∼28%). PHA granules were extracted from PCR-OIL-grown cells with high recovery (88.25%) and purity (94.8%). Five monomers were identified in the polymer, including 3-hydroxyhexanoate (3HHx), 3-hydroxyoctanoate (3HO), 3-hydroxydecanoate (3HD), 3-hydroxydodecanoate (3HDD), and 3-hydroxytetradecanoate (3HTD), with 3HO (44.28%) and 3HD (40.60%) as the dominant units. The polymer exhibited moderate molecular weight and narrow dispersity (M n = 65.4 kDa, M w = 92.1 kDa, Đ = 1.40) and low crystallinity (T m ≈ 76.6 °C, X c ≈ 15.5%). These characteristics indicate elastomer-like behavior, making the material suitable for flexible applications such as films, coatings, adhesives, and blend modifiers. Overall, this study establishes a CO 2 plasma-assisted route for generating fermentable polyethylene-derived intermediates and demonstrates that fed-batch co-culture fermentation can effectively funnel plastic-derived carbon into mcl-PHA.

42 ENGINEERING↗
DOE OSTI2025

Quorum-driven microbial consortium for Bioplastic production from agro-waste

Microbial consortia have high relevance in natural environments. Here we present the production of polyhydroxyalkanoates (PHA) from agro-industrial residues by a synthetic interkingdom consortium formed by the saprotrophic fungus Ophiostoma piceae CECT 20146, which encodes a wide range of lignocellulolytic enzymes, and a natural PHA producer, Pseudomonas putida KT2440. Two agro-industrial residues were utilized: Brewer's Spent Grain (BSG) as a carbon/nitrogen source and biofilm scaffold and waste cooking oil (WCO) as a carbon source for PHA synthesis. Through biochemistry, microscopy, and omics analyses, it is shown that P. putida accumulates up to 40.2% of intracellular PHA when the quorum sensing molecule, farnesol (naturally produced by O. piceae) is added, thanks to the increased proliferation of P. putida cells. An interactive Shiny application has also been developed for an easy visualization and comprehension of all the transcriptomics and metabolomics data: https://jgf-bioinformatics.shinyapps.io/Visualization_app/. These results support the increased PHA production of the consortium by an induction of gene phaG, which redirects intermediaries of the fatty acid biosynthesis to PHA precursors, and the repression of the PHA depolymerase phaZ in P. putida. The trophic interaction between microorganisms seems to rely on the citric acid produced by O. piceae and the glycerol liberated from WCO, which can both be consumed by P. putida. Bioreactor scale-up experiments allowed a 3.3-fold increase in the PHA concentration in the consortium (6.7 g·L-1) without pretreatment or sterilization of the substrates, laying the groundwork for the implementation of an industrial consolidated bioprocess (CBP).

Bacteria↗
DOE OSTI2024

The phototrophic purple non‐sulfur bacteria Rhodomicrobium spp. are novel chassis for bioplastic production

Abstract Petroleum‐based plastics levy significant environmental and economic costs that can be alleviated with sustainably sourced, biodegradable, and bio‐based polymers such as polyhydroxyalkanoates (PHAs). However, industrial‐scale production of PHAs faces barriers stemming from insufficient product yields and high costs. To address these challenges, we must look beyond the current suite of microbes for PHA production and investigate non‐model organisms with versatile metabolisms. In that vein, we assessed PHA production by the photosynthetic purple non‐sulfur bacteria (PNSB) Rhodomicrobium vannielii and Rhodomicrobium udaipurense. We show that both species accumulate PHA across photo‐heterotrophic, photo‐hydrogenotrophic, photo‐ferrotrophic, and photo‐electrotrophic growth conditions, with either ammonium chloride (NH 4 Cl) or dinitrogen gas (N 2 ) as nitrogen sources. Our data indicate that nitrogen source plays a significant role in dictating PHA synthesis, with N 2 fixation promoting PHA production during photoheterotrophy and photoelectrotrophy but inhibiting production during photohydrogenotrophy and photoferrotrophy. We observed the highest PHA titres (up to 44.08 mg/L, or 43.61% cell dry weight) when cells were grown photoheterotrophically on sodium butyrate with N 2 , while production was at its lowest during photoelectrotrophy (as low as 0.04 mg/L, or 0.16% cell dry weight). We also find that photohydrogenotrophically grown cells supplemented with NH 4 Cl exhibit the highest electron yields – up to 58.89% – while photoheterotrophy demonstrated the lowest (0.27%–1.39%). Finally, we highlight superior electron conversion and PHA production compared to a related PNSB, Rhodopseudomonas palustris TIE‐1. This study illustrates the value of studying non‐model organisms like Rhodomicrobium for sustainable PHA production and indicates future directions for exploring PNSB metabolisms.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Polyhydroxyalkanoates in emerging recycling technologies for a circular materials economy

Circular polymer systems, specifically polyesters operating through chemical and biological technologies, are approaching a critical moment of industrial adoption and scale-up feasibility. At the same time, polyhydroxyalkanoate (PHA) production, scale-up, and resulting material development is converging toward commodity applications. The current PHA end-of-life philosophy, however, focalizes leveraging inherent biodegradability to circumvent plastic waste accumulation. If indeed a substantial replacement of incumbent single-use plastics with PHA alternatives is to be met in commercial manufacture, we emphasize the importance of linking PHA development with feasible polymer recycling technologies. In other words, a PHA materials economy is significantly more carbon- and cost-favorable when efficient mechanical (reprocessing), chemical (deconstruction, depolymerization), or biological (enzymatic) recycling is prioritized over biodegradation or composting. In this perspective, we discuss strategies for PHA recyclable-by-design principles, guidable by developing machine learning tools, as well as material compatibility with closed-loop recycling technologies. Additionally, we posit compelling life-cycle assessment incentives for adopting polymer reclamation over competing pathways. Ultimately, we hope this narrative further inspires the alignment between PHA design with growing calls for a circular material economy.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Challenges, progress, and future perspectives for cyanobacterial polyhydroxyalkanoate production

Polyhydroxyalkanoates (PHA) are a promising bio-based alternative to traditional plastics derived from petroleum. Cyanobacteria are photosynthetic organisms that produce PHA from CO 2 and sunlight, which can potentially reduce production costs and environmental footprint in comparison to heterotrophic bacteria cultures because (1) they utilize inorganic carbon sources for growth and (2) they do not require intensive aeration for oxygenation. Moreover, supplementing precursors such as propionate, acetate, valerate, etc., can be used to obtain various copolymers with plastic customizable properties in comparison to the classical homopolymers, such as polyhydroxybutyrate, PHB. This critical review covers the latest advances in PHA production, including recent discoveries in the metabolism interplay between PHA and glycogen production, and new insights into cultivation strategies that enhance PHA accumulation, and purification processes. This review also addresses the challenges and suggests potential solutions for a viable industrial PHAs production process.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Bioconversion of Agave Bagasse Lignin to Medium-Chain-Length Polyhydroxyalkanoates by Pseudomonas putida

Inadequate disposal of Agave tequilana bagasse (ATB) brings environmental and economic issues to tequila producing regions. Recent works have proposed technologies for valorization of the polysaccharide’s fractions of ATB. However, lignin bioconversion has not been investigated due to its recalcitrant nature. In this work, a systematic pretreatment is proposed to release the lignocellulosic fractions and produce medium-chain-length polyhydroxyalkanoates (PHA) from the lignin fraction of ATB. Nuclear magnetic resonance (NMR) analyses revealed that ATB lignin contained 63% of β-O-4 interunit linkages, making this lignin more suitable for pretreatment and biodegradation compared to other lignins. Exploratory experiments revealed that two-stage fermentation is suitable for PHA production from ATB lignin using wild type and engineered Pseudomonas putida strains. PHA increased from 0.09 to 0.39 g/L compared to single batch fermentation. Further improvement to 0.76 g/L was possible by using a central composite design to optimize the inoculum, substrate, and nitrogen concentrations. Finally, PHA depolymerase gene phaZ was knocked out from P. putida and tested at optimal conditions, enabling a PHA titer of 0.97 g/L. Analyses by NMR and GC-MS confirmed lignin derivatives consumption and decrease of β-O-4 linkages. This study lays the foundations to enable agave lignin bioprocessing and opens new avenues for ATB biorefineries.

PHA↗
DOE OSTI2026

Closing the loop on plastics: Biological and hybrid routes for converting plastic waste to polyhydroxyalkanoates

Polyhydroxyalkanoate (PHA) production from plastic-derived substrates offers a promising route to mitigate plastic pollution while reducing dependence on conventional PHA feedstocks. Plastic waste represents an abundant carbon source for microbial fermentation, but efficient conversion remains limited by incomplete deconstruction, inhibitory intermediates, low carbon recovery, and challenges in process integration. Plastic-derived streams contain diverse compounds, including fatty acids, hydrocarbons, fatty alcohols, aldehydes, esters, and aromatic compounds generated during depolymerization. These intermediates can be metabolized by selected microorganisms, particularly Pseudomonas species with versatile fatty-acid and hydrocarbon pathways, as well as Cupriavidus necator and mixed microbial cultures. Unlike reviews that address plastic upcycling or PHA biosynthesis separately, this review focuses on the deconstruction–fermentation interface that governs plastic-to-PHA conversion. It consolidates current progress in plastic deconstruction, substrate conditioning, microbial metabolism, fermentation control, polymer recovery, and techno-economic and life-cycle considerations. Here, by emphasizing substrate composition, biological compatibility, plastic‑carbon recovery, and final polymer quality, the review identifies priorities for scalable and environmentally sustainable PHA production from plastic-derived substrates.

42 ENGINEERING↗
DOE OSTI2024

Final Technical Report

The Department of Energy is interested in technologies that support the sustainable production of fuels, chemicals, and other bioproducts from plant biomass, to offset the nation’s reliance on fossil resources. The plant cell wall of energy crops provides the largest reservoir of raw materials for bioproducts. However, the widespread use of plant cell walls is hampered by their complexity and resistance to breakdown. To improve the productivity and cost-effectiveness of using energy crops to generate bioproducts, the fundamental problem of deconstructing plant cell walls must be addressed. This project developed and evaluated an innovative genetic modification technology to produce strategically designed enzymes that specifically accumulate in the plant cell wall. The resulting enzyme-engineered energy crops are expected to grow normally under natural conditions but break down more quickly and easily under high temperature during the production of biobased products. As such, this plant cell wall targeting enzyme engineering effort will reduce the cost of plant cell wall deconstruction and ultimately improve the economics of bioproducts. The overall objective of this project is to develop and evaluate the in-planta enzyme engineering technology to reduce lignocellulose deconstruction cost. The concept was first validated using tobacco plant, a model plant system that is typically used in lab testing for initial concept validation. Then the enzyme optimization was validated using switchgrass, the energy crop to be used to produce bioproducts. There are three specific objectives in this Phase I project: (1) validate the enzyme optimization concept using tobacco plant, a model plant system. (2) validate the enzyme optimization concept using switchgrass. (3) techno-economic analysis (TEA) for further scale-up application. By the end of this project, in-planta enzyme engineering was validated in both tobacco and switchgrass plants, with improved enzyme activity and saccharification efficiency. The in-planta enzyme engineering in Tabacco didn’t have a significant impact on plant growth and development. Transgenic tobacco plants with in-planta cellulose degrading enzymes showed higher biomass digestibility than wild type. Gene construction and transformation in switchgrass was much longer than expected, which delayed the research progress. Besides, in-planta engineering of lignin degrading enzyme is more challenging than cellulose degrading enzyme, in terms of expression detection. Expression of lignin degrading enzyme and cellulose degrading enzyme improved biomass yield and saccharification efficiency of switchgrass, respectively. It is promising to express both genes in switchgrass for optimized overall performance. According to the results of TEA, switchgrass biomass production cost is mainly attributed to by fertility and harvesting. Biomass production profit can increase up to 10-fold depending on biomass price. The PHA production profit is also sensitive to the biomass price. The proposed technology could potentially reduce the biomass deconstruction cost from 33% to 9% of PHA revenue, making the biomass-based PHA competitive to petroleum-based polymers even in case of relatively high biomass price of biomass. Therefore, cultivation of the genetically engineered self-deconstruction switchgrass for Polyhydroxyalkanoate (PHA) production could benefit switchgrass grower and PHA producer with attractive profits for both sectors. This new enzyme optimization approach will be beneficial for bioindustries that use energy crops as feedstocks. It will improve the economic viability of converting energy crops to renewable products that support a sustainable society and helps address the Nation’s long-term strategic needs for renewable products and reduction of reliance on fossil resources.

42 ENGINEERING↗
DOE OSTI2024

Challenges, Progress, and Future Perspectives for Cyanobacterial Polyhydroxybutyrate Production

Polyhydroxyalkanoates (PHA) are a promising bio-based alternative to traditional plastics derived from petroleum. Cyanobacteria are photosynthetic organisms that produce PHA from CO 2 and sunlight, which can potentially reduce production costs and environmental footprint in comparison to heterotrophic bacteria cultures because (1) they utilize inorganic carbon sources for growth and (2) they do not require intensive aeration for oxygenation. Moreover, supplementing precursors such as propionate, acetate, valerate, etc., can be used to obtain various copolymers with plastic customizable properties in comparison to the classical homopolymers, such as polyhydroxybutyrate, PHB. This critical review covers the latest advances in PHA production, including recent discoveries in the metabolism interplay between PHA and glycogen production, and new insights into cultivation strategies that enhance PHA accumulation, and purification processes. This review also addresses the challenges and suggests potential solutions for a viable industrial PHAs production process.

60 APPLIED LIFE SCIENCES↗
NASA NTRS2011

Fire-Retardant Polymeric Additives

Polyhydroxyamide (PHA) and polymethoxyamide (PMeOA) are fire-retardant (FR) thermoplastic polymers and have been found to be useful as an additive for imparting fire retardant properties to other compatible, thermoplastic polymers (including some elastomers). Examples of compatible flammable polymers include nylons, polyesters, and acrylics. Unlike most prior additives, PHA and PMeOA do not appreciably degrade the mechanical properties of the matrix polymer; indeed, in some cases, mechanical properties are enhanced. Also, unlike some prior additives, PHA and PMeOA do not decompose into large amounts of corrosive or toxic compounds during combustion and can be processed at elevated temperatures. PMeOA derivative formulations were synthesized and used as an FR additive in the fabrication of polyamide (PA) and polystyrene (PS) composites with notable reduction (>30 percent for PS) in peak heat release rates compared to the neat polymer as measured by a Cone Calorimeter (ASTM E1354). Synergistic effects were noted with nanosilica composites. These nanosilica composites had more than 50-percent reduction in peak heat release rates. In a typical application, a flammable thermoplastic, thermoplastic blend, or elastomer that one seeks to render flame-retardant is first dry-mixed with PHA or PMeOA or derivative thereof. The proportion of PHA or PMeOA or derivative in the mixture is typically chosen to lie between 1 and 20 weight percent. The dry blend can then be melt-extruded. The extruded polymer blend can further be extruded and/or molded into fibers, pipes, or any other of a variety of objects that may be required to be fire-retardant. The physical and chemical mechanisms which impart flame retardancy of the additive include inhibiting free-radical oxidation in the vapor phase, preventing vaporization of fuel (the polymer), and cooling through the formation of chemical bonds in either the vapor or the condensed phase. Under thermal stress, the cyclic hydroxyl/ methoxy component forms polybenzoxazole (PBO) in a reaction that absorbs heat from its surroundings. PBO under thermal stress cross-links, forming a protective char layer, which thermally insulates the polymer. Thus, the formation of the char layer further assists to extinguish the fire by preventing vaporization of the polymeric fuel.

Williams, Martha K.↗