Poly[(R)-3-hydroxy butyrate] Melt Processing: Strategy for Prevention of Degradation Reactions

Poly[(R)-3-hydroxy butyrate] (PHB) as well as all the components of the poly[(R)-3-hydroxy alkanoate]s (PHAs) family tend to degrade during processing at temperatures above their melting point via a hydrolytic mechanism induced by moisture attack and a concerted reaction mechanism induced by temperature. Therefore, the PHAs stabilization in the molten state is particularly important for production of biodegradable ecocompatible plastic items of commercial value. In order to refrain the indicated negative degradation effects, PHB was melt processed in a torque rheometer in the presence of a polymeric carbodiimide agent. Processed specimens were characterized by using FTIR, GPC, DSC, TGA and tensile properties. GPC analysis showed that the increase of the additive content in the formulation resulted in an increase of PHB molecular weight. However, decreasing in PHB thermal stability, glass transition temperature and mechanical properties, was observed with the increase of the additive amount. This behaviour most likely arises from the formation of new chemical structures promoted by the presence of the additive aimed at preventing the onset of hydrolitic processes.     

Biosynthesis of poly-(R)-3-hydroxyalkanoate: An emulsion polymerization

Poly-(R)-3-hydroxyalkanoates (PHAs) are bacterial storage polyesters, which are accumulated by a wide variety of microorganisms as a reserve of carbon and energy. Currently, these biopolymers are receiving much attention because of their potential application as biodegradable and biocompatible plastics. The polymer appears as submicron intracellular granules. The biosynthesis of these granules has been studied extensively but many observations remain inexplicable. This paper draws an analogy between the process of emulsion polymerization and that of granule formation. This analogy may explain many of the unknown features of granule formation and may also lead to useful applications of granules as latex products.     

Synthesis of a block copolymer of poly(3-hydroxybutyrate) and poly(ethylene glycol) and its application to biodegradable polymer blends

A block copolymer {P[(R,S)-HB-b-EG]} of atactic poly[(R,S)-3-hydroxybutyrate] {P[(R,S)-HB]} and poly(ethylene glycol) (PEG) was prepared by the ring-opening polymerization of -butyrolactone in the presence of a macroinitiator (PEG/ZnEt₂/H₂O) which had been produced by the reaction of ,-dihydroxy PEG ( _n=3000) with ZnEt₂/H₂O (1/0.6) catalyst. The block copolymer ( _n=10,500, _w/ _n=1.2) was an A-B-A triblock copolymer comprising atactic P[(R,S)-HB] (A) and PEG (B) segments. The miscibility, physical properties, and biodegradability of binary blends of microbial poly[(R)-3-hydroxybutyrate] {P[(R)-HB]} with the block copolymer P[(R,S)-HB-b-EG] has been studied. The glass-transition temperature (T _g) data showed that the P[(R)-HB]/P[(R,S)-HB-b-EG] blend was miscible in the amorphous state. The P[(R)-HB] film became flexible and tough by means of blending with P[(R,S)-HB-b-EG] block copolymer. The enzymatic degradation of blend films was carried out at 37°C and pH 7.4 in a 0.1M phosphate solution of an extracellular PHB depolymerase fromAlcaligenes faecalis. The enzymatic degradation took place solely on the surface of the blend films.     

Degradation of Poly(3-hydroxybutyrate) and Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) by Some Soil Aspergillus spp.

Systematic screening of 45 soil fungi for degradation polyhydroxyalkanoic acids (PHAs) has led to the selection of 6 potent Aspergillus isolates belonging to A. flavus, A. oryzae, A. parasiticus, and A. racemosus. Degradation of PHAs as determined by tube assay method revealed that these Aspergillus spp. were more efficient in degrading poly(3-hydroxybutyrate) [P(3HB)] compared to copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid (P3HB-co-16% 3HV). Moreover, the extent of degradation in mineral base medium was much better than those in complex organic medium. For all the Aspergillus spp. tested, maximum degradation was recorded at a temperature of 37°C with significant inhibition of growth. The optimum pH range for degradation was 6.5–7.0 with degradation being maximum at pH 6.8. The extent of polymer degradation increased with increase in substrate concentration, the optimum concentration for most of the cultures being 0.4% and 0.2% (w/v) for P(3HB) and P(3HB-co-16%3HV) respectively. Supplementation of the degradation medium with additional carbon sources exerted significant inhibitory effect on both P(3HB) and P(3HB-co-16%3HV) degradation.     

Synthesis of Short-chain-length/Medium-chain-length Polyhydroxyalkanoate (PHA) Copolymers in Peroxisome of the Transgenic Arabidopsis Thaliana Harboring the PHA Synthase Gene from Pseudomonas sp. 61-3

In this paper, the photosynthetic production of short-chain-length/medium-chain-length polyhydroxyalkanoate (PHA) copolymers is reported. The wild-type and highly active doubly mutated PHA synthase 1 (S325T/Q481K, abbreviated ST/QK) genes from Pseudomonas sp. 61-3 were introduced into Arabidopsis thaliana. Peroxisome targeting signal 1 (PTS1) was used to target PHA synthases into the peroxisome to synthesize PHA from the intermediates of the β-oxidation pathway. The transgenic Arabidopsis produced PHA copolymers consisting of 40–57 mol% 3-hydroxybutyrate, 21–49 mol% 3-hydroxyvalerate, 8–18 mol% 3-hydroxyhexanoate, and 2–8 mol% 3-hydroxyoctanoate. The maximum PHA contents were 220μ g/g cell dry weight (cdw) in leaves, and 36μ g/g cdw in stems, respectively. The expression of the ST/QK mutated PHA synthase in leaves gene did not lead to significant difference in PHA content and monomer composition of PHAs, compared to the wild-type PHA synthase gene, suggesting that the supply of monomers may be a rate-determining step of PHA biosynthesis in the peroxisome. However, in stems, there were significant differences dependent on whether the wild-type or ST/QK mutated PHA synthase was expressed. These results suggest that tissue-specific monomer availability is important in determining the final mol% composition of PHA copolymers produced by the peroxisome in plants.     

Polyurethanes Based on Atactic Poly[(R,S)-3-hydroxybutyrate]: Preliminary Degradation Studies in Simulated Body Fluids

The aliphatic polyurethanes based on atactic poly[(R,S)-3-hydroxybutyrate] (a-PHB) and commercial oligomerols: poly(ε-caprolactone)diol and polyoxytetramethylenediol were investigated. a-PHB was obtained by anionic ring-opening polymerization of (R,S)-β-butyrolactone. The 4,4′-methylenedicyclohexyl diisocyanate and 1,4-butanediol were used as contributors of hard segments. The aim of the study was to determine the influence of synthetic, atactic a-PHB in soft segments of polyurethanes on their degradability in simulated body fluids (SBF) and Ringer solution. The incubation of polymer samples in both degradative solutions was carried out for 36 weeks. It was concluded that the presence of a-PHB in polyurethane structure accelerated their degradation in SBF and in Ringer solution and, protected the calcification process.     

Purification of Aspergillus fumigatus (Pdf1) Poly(β-hydroxybutyrate) (PHB) Depolymerase Using a New, Single-Step Substrate Affinity Chromatography Method: Characterization of the PHB Depolymerase Exhibiting Novel Self-Aggregation Behavior

The extracellular poly(-hydroxybutyrate) (PHB) depolymerase of Aspergillus fumigatus Pdf1 was purified by a new, simple, one-step affinity chromatography method using the substrate PHB. The purified enzyme was glycosylated, with the molecular mass of 40 KD, and exhibited a novel self-aggregation behavior by means of hydrophobic interaction that was resolved by Triton X-100 (TX-100) pretreatment of enzyme and also TX-100 incorporation in the native gel. The apparent K _m value of purified enzyme for PHB was 119 g/mL and 3-hydroxybutyrate was detected as the main endproduct of PHB hydrolysis. The depolymerase was insensitive to phenylmethyl sulfonyl fluoride (PMSF), sodium azide, ethylenediaminetetraacetic acid (EDTA), and para-chloromercuric benzoic acid (PCMB), but was inactivated by dithioerythritol (DTT) and showed specificity for short chain-length poly(-hydroxyalkanoates) (PHAs) such as PHB, poly(hydroxyvalerate) (PHV), and copolymers of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV). Medium-chain-length PHA failed to get hydrolyzed. The enzyme, however, exhibited strong cross reactivity with the Comamonas sp. PHB depolymerase antibodies, but not with PHV depolymerase antibodies of Pseudomonas lemoignei. Southern hybridization and dot blot analysis of A. fumigatus Pdf1 genomic DNA with alkaline phosphatase labeled probes of P. lemoignei PHB and PHV depolymerase genes revealed no homology, although the enzyme hydrolyzed both PHB and PHV.     

Anaerobic microbial degradation of poly (3-hydroxyalkanoates) with various terminal electron acceptors

The microbial degradation of poly (3-hydroxyalkanoates) (PHAs) under anaerobic conditions with various terminal electron acceptors was examined. Nitrate-reducing consortia were established using activated sludge, and PHAs were shown to be biodegradable under these conditions. A positive correlation between carbon dioxide production and nitrate reduction was demonstrated. Nitrous oxide accumulated as the main N-containing product of nitrate reduction. The amount of PHAs in activated sludge cultures decreased approximately 20% within 40 days of incubation. Attempts were made to establish iron- and sulfate-reducing consortia from spring water, yet it could not be demonstrated that the mixed cultures were capable of degrading PHAs. Pure cultures of iron- and sulfate-reducing bacteria could not utilize PHAs as sole carbon sources. Methanogenic environments sampled included pond sediment and rumen fluid. PHAs were fermented to methane and carbon dioxide after 10 weeks by a sediment consortium, with 43 to 57% of the substrate carbon transformed to methane. Although it could not be demonstrated that PHAs were biodegraded by a rumen fluid consortium, a facultative anaerobic bacterium, identified as aStaphylococcus sp., that could grow on PHAs was isolated from rumen fluid.     

High-Efficiency Production of Bioplastics from Biodegradable Organic Solids

Microbial polyhydroxyalkanoates (PHAs) have been extensively studied as environmentally friendly biodegradable thermoplastics. The major obstacle to wide acceptance of PHAs is their high price, mainly attributed to the costs of raw materials and polymer recovery. A large amount of organic solids are discarded from food production and consumption and may be used as carbonaceous raw materials for production of PHAs. A novel technology was investigated at bench-top scale to produce PHAs from food scraps. The harvested cell mass had a high PHA content (72.6% of dry cell mass), the same as obtained from pure glucose and organic acids. The organic solid was first digested in an acidogenic reactor in which about 60% solid was converted to fermentative products, including short-chain fatty acids. The four major acids were acetic, propionic, butyric, and lactic acids at concentrations of 6, 2, 27, and 33 g/L, respectively. The acids were transported through a membrane barrier via molecular diffusion to an airlift bioreactor, where the acids were utilized by an enriched culture of Ralstonia eutropha for PHA synthesis. Purification of fermentative acids was not performed in this molecular diffusion–based integration of acidogenesis and polymerization. By using a dialysis membrane as the barrier, the dry cell mass concentration and PHA content reached 22.7 g/L and 72.6%, respectively. The PHA was a copolymer of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with 2.8 mole % of hydroxyvalerate.     

Topographical imaging as a means of monitoring biodegradation of poly(hydroxyalkanoate) films

Poly(hydroxyalkanoates) (PHAs) are a class of bacterially-derived polymers that are naturally biodegradable through the action of extracellular depolymerase enzymes secreted by a number of different bacteria and fungi. In this paper we describe the development of topographical imaging protocols (by both scanning electron microscopy; SEM, and confocal microscopy; CM) as a means of monitoring the biodegradation of solution cast films of poly(3-hydroxybutanoate-co-3-hydroxyhexanoate) (P3HB/3HHx) and medium-chain-length (mcl-) PHA. Pseudomonas lemoignei and Comamonas P37C were used as sources for PHA depolymerase enzymes as these bacteria are known to degrade at least one of the polymers in question. SEM revealed the bacterial colonization of the film surfaces while CM permitted the comparative assessment of the roughness of the film surfaces upon exposure to the two bacterial strains. By dividing the total surface area of the film (A′) by the total area of the scan (A) it was possible to monitor biodegradation by observing differences in the topography of the film surface. Prior to inoculation, P3HB/3HHx films had an A′/A ratio of 1.06. A 24-h incubation with P. lemoignei increased the A′/A ratio to 1.47 while a 48- and 120-h incubation with Comamonas resulted in A′/A ratios of 1.16 and 1.33, respectively. These increases in the A′/A ratios over time demonstrated an increase in the irregularity of the film surface, indicative of PHA polymer breakdown. Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture.     

Compositional Limitations in Poly–3–Hydroxyalkanoates Produced by Pseudomonas oleovorans

It is well known that Pseudomonas oleovorans can utilize sodium octanoate for both cell growth and the synthesis of polyhydroxyalkanoates (PHAs), but it can utilize sodium butyrate only for limited cell growth and not for the polyester formation when this substrate is the sole carbon source. Therefore, these two substrates were evaluated as cofeeds for the possible incorporation of 3-hydroxybutyryl groups in the resulting PHA. When sodium butyrate and sodium octanoate were fed to P. oleovorans as cosubstrates in various proportions, the resultant cell density and polymer content were proportional to the amount of sodium octanoate in the feed. The PHA extracted from cells grown in all combinations of these cosubstrates had similar unit compositions of approximately 8 mole % 3-hydroxyhexanoate, 91 mole % 3-hydroxyoctanoate and 1 mole % 3-hydroxydecanoate. 3-Hydroxybutyrate units were not detected in any of the PHAs isolated, indicating that these units could not be incorporated in the copolymer synthesized by P. oleovorans either because the cell did not synthesize that monomer or, if it did, the PHA synthase could not copolymerize it with the longer chain monomers.     

Tween 20 and Its Major Free Fatty Acids as Carbon Substrates for the Production of Polyhydroxyalkanoates in Pseudomonas aeruginosa ATCC 27853

The ability of Pseudomonas aeruginosa ATCC 27853 to grow and synthesize polyhydroxyalkanoates (PHAs) using Tween 20 as the sole carbon source was investigated. Tween 20 could support cell growth and PHA production. The polymer produced from Tween 20 was compared with those produced from its major free fatty acids components: lauric (C₁₂), myristic (C₁₄), and palmitic (C₁₆) acids. Gas-chromatographic analysis of methanolyzed samples and ¹³C-Nuclear Magnetic Resonance (NMR) showed that the PHAs obtained are composed of even carbon atoms 3-hydroxyalkanoates ranging from C₆ to C₁₄, with C₈ and C₁₀ as the predominant components. The nature of the carbon sources used had little influence on the composition, but was found to be important in determining the average molecular weight, shorter chain fatty acids yielding higher molecular weight products. Fast Atom Bombardment-Mass Spectrometry (FAB-MS) of partially pyrolyzed samples, coupled to statistical analysis, showed that these PHAs are random copolymers.     

Soil Biodegradation of PHBV/Peach Palm Particles Biocomposites

There is great interest in developing eco-friendly green biocomposites from plant-derived natural fibers and crop-derived bioplastics attributable to their renewable resource-based origin and biodegradable nature. Fully biodegradable composites, made from both biodegradable polymeric matrices and natural fibers, should be advantageous in some applications, such as one way packaging. Polyhydroxyalkanoates (PHAs) are naturally occurring biodegradable polymers produced from a wide range of microorganisms, with poly(3-hydroxybutyrate) P(3HB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) being important examples of PHAs. In this work, biocomposites of PHBV consisting of a PHBV matrix incorporating peach palm particles (PPp), [i.e., 100/0, 90/10, 80/20 and 75/25 (%w/w) PHBV/PPp] were processed by injection molding at 160 °C. The effect of PPp loading on the thermal and the mechanical properties, as well as on the morphological behavior of the PHBV/PPp biocomposites was investigated. Soil biodegradation tests were carried out by burying specimen beakers containing aged soil and kept under controlled temperature and humidity in accordance with ASTM G160-98. Degradation of the biocomposites was evaluated by visual analysis, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) following test exposures of up to 5 months. The addition of PPp reduced the maximum strength and the elongation at break of the biocomposites. On the other hand, the Young’s modulus improved with the PPp content. Micrographs of the fracture surfaces following tensile strength testing revealed a large distance between the PHBV matrix and PPp particles although a low interaction is expected. Where measured, these distances tended increase as the PPp content of the biocomposites increased. Soil biodegradation tests indicated that the biocomposites degraded faster than the neat polymer due to the presence of cavities that resulted from introduction of the PPp and that degradation increased with increasing PPp content. These voids allowed for enhanced water adsorption and greater internal access to the soil-borne degrader microorganisms.     

Utilization of Broken Rice for the Production of Poly(3-hydroxybutyrate)

The feasibility of utilizing non edible rice (broken rice) for production of fine materials such as poly(3-hydroxybutyrate) (PHB) was considered as one of the alternative ways of keeping the environment clean for sustainable development. Thus, production of PHB from broken rice by simultaneous saccharification and fermentation (SSF) was investigated. During the SSF process, the rice (15% w/v) material was hydrolyzed to glucose, which was utilized by Cupriavidus necator for growth and production of PHB. The PHB content reached 38% at 58 h fermentation. The PHB had weight average molar mass (Mw) and polydipersity index of 3.82 × 10⁵ (g/mol) and 4.15, respectively. Differential calorimetric scan of the PHB showed a melting temperature (Tm) of 176 °C. Given that the PHB was a homopolymer (which consisted of (R)-3-hydroxybutyric acid monomers), it was thought that broken rice could be a raw material for production of both PHB and (R)-3-hydroxybutyric acid. This SSF process would not only help in the utilization of broken rice or non edible rice, but would also serve as a model for utilization of other raw materials that contain starch for production of PHB.     

Enzymatic Degradation and Aminolysis of Microbial Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Single Crystals

Solution-grown single crystals of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] were hydrolyzed by polyhydroxybutyrate (PHB) depolymerase from Ralstonia pickettii T1. Enzymatic degradation proceeded from the edges of lamellar crystals, yielding serrated contour and small crystal fragments. Gel permeation chromatography analysis revealed that the molecular weights of the crystals decreased during enzymatic degradation, suggesting that the enzymatic hydrolysis of chain-folding regions at the crystal surfaces occurred in addition to the enzymatic degradation at crystal laterals or edges. After P(3HB-co-4HB) single crystals were aminolysed in 20% aqueous methylamine solution to remove the folded-chain regions and enzymatic degradation by lipase from Rhizopus oryzae to remove 4HB components at crystal surfaces of single crystal aminolyzed, it was found that a small amount (up to ca. 2 mol%) of 4HB component can be incorporated into the P(3HB) mother crystal lattice irrespective of the 4HB content.     

Degradation of poly(3-hydroxybutyrate), PHB,by bacteria and purification of a novel PHB depolymerase fromComamonas sp.

Bacteria capable of growing on poly(3-hydroxybutyrate), PHB, as the sole source of carbon and energy were isolated from various soils, lake water, activated sludge, and air. Although all bacteria utilized a wide variety of monomeric substrates for growth, most of the strains were restricted to degrade PHB and copolymers of 3-hydroxybutyrate and 3-hydroxyvalerate, P(3HB-co-3HV). Five strains were also able to decompose a homopolymer of 3-hydroxyvalerate, PHV. Poly(3-hydroxyoctanoate), PHO, was not degraded by any of the isolates. One strain, which was identified asComamonas sp., was selected, and the extracellular depolymerase of this strain was purified from the medium by ammonium sulfate precipitation and by chromatography on DEAE-Sephacel and Butyl-Sepharose 4B. The purified PHB depolymerase was not a glycoprotein. The relative molecular masses of the native enzyme and of the subunits were 45,000 or 44,000, respectively. The purified enzyme hydrolyzed PHB, P(3HB-co-3HV), and—at a very low rate—also PHV. Polyhydroxyalkanoates, PHA, with six or more carbon atoms per monomer or characteristic substrates for lipases were not hydrolyzed. In contrast to the PHB depolymerases ofPseudomonas lemoignei andAlcaligenes faecalis T₁, which are sensitive toward phenylmethylsulfonyl fluoride (PMSF) and which hydrolyze PHB mainly to the dimeric and trimeric esters of 3-hydroxybutyrate, the depolymerase ofComamonas sp. was insensitive toward PMSF and hydrolyzed PHB to monomeric 3-hydroxybutyrate indicating a different mechanism of PHB hydrolysis. Furthermore, the pH optimum of the reaction catalyzed by the depolymerase ofComamonas sp. was in the alkaline range at 9.4.     

Laboratory Measurement of Dry Deposition of Ozone onto Northern Chinese Soil Samples

We used laboratory experiments to investigate surface resistance (R _c) to dry deposition of ozone (O₃) on different types of soil samples collected from the arid deserts and the Loess Plateau of northern China. Furthermore, we measured the factors that affected R _c, which depends on the physical and chemical interaction between trace constituents and the deposition surface, and evaluated deposition velocity (V _d). There was little influence of geometric surface area, soil weight, or O₃ concentration on V _d of O₃. The effect of relative humidity (RH) (i.e. moisture content of the soil) on O₃ uptake was in agreement with results reported in the literature: a distinct RH dependence of V _d and little uptake under water-saturated conditions were observed. R _c values for all the soil samples examined were in the range 0.21–3.3 s mm⁻¹ and were exponentially related to the surface area of the particles and the organic carbon content of each soil sample at RH of both <10 and 60%.     

Morphology of <Emphasis Type="Italic">Penicillium funiculosum</Emphasis> During Biodegradation of Poly (β-hydroxybutyrate-co-β-hydroxyvalerate) [PHBV] with Poly (ε-Caprolactone) [PCL] Blends

Blends of poly (β-hydroxybutyrate-co-β-hydroxyvalerate) with poly (ε-caprolactone) were produced using melt mixing and solvent casting techniques. The biodegradation of blends was tested based in the ASTM G21-90 using Penicillium funiculosum fungal specie. The CO₂ production during biodegradation was measured and fitted using the Gompertz model. Biodegradation of blends varies according to the mixing technique and the proportion of bacterial polymers in the blends. Although lag phase was larger, solvent-casted blends were easier to degrade due to their porous surface and relative lower crystallinity. P. funiculosum morphology during biodegradation appeared to be related to carbon availability i.e. larger and more complex conidiophores, more phialides per conidiophore and the presence of double-phialides, were found in blends with higher PHAs proportion. P. funiculosum morphology was independent to the blending technique used. Hence, morphology of P. funiculosum could be useful as a reference for carbon bioavailability of the blends.     

The Effect of Interaction Between White-rot Fungi and Indigenous Microorganisms on Degradation of Polycyclic Aromatic Hydrocarbons in Soil

White-rot fungi applied for soil bioremediation have to compete with indigenous soil microorganisms. The effect of competition on both indigenous soil microflora and white-rot fungi was evaluated with regard to degradation of polycyclic aromatic hydrocarbons (PAH) with different persistence in soil. Sterile and non-sterile soil was artificially contaminated with ¹⁴C-labeled PAH consisting of three (anthracene), four (pyrene, benz[a]anthracene) and five fused aromatic rings (benzo[a]pyrene, dibenz[a,h]anthracene). The two fungi tested,Dichomitus squalens and Pleurotus ostreatus, produced similar amounts of ligninolytic enzymes in soil, but PAH mineralization by P. ostreatus was significantly higher. Compared to the indigenous soil microflora, P.ostreatus mineralized 5-ring PAH to a larger extent, while the indigenous microflora was superior in mineralizing 3-ring and 4-ring PAH. In coculture the special capabilities of both soil microflora and P. ostreatus were partly restricted due to antagonistic interactions, but essentially preserved. Thus, soil inoculation with P. ostreatus significantly increased the mineralization of high-molecular-weight PAH, and at the same time reduced the mineralization of anthracene and pyrene. Regarding the mineralization of low-molecular-weight PAH, the stimulation of indigenous soil microorganisms by straw amendment was more efficient than application of white-rot fungi.     

Bacterial Poly(Hydroxyalkanoate) Polymer Production from the Biodiesel Co-product Stream

A co-product stream from soy-based biodiesel production (CSBP) containing glycerol, fatty acid soaps, and residual fatty acid methyl esters (FAME) was utilized as a fermentation feedstock for the bacterial synthesis of poly(3-hydroxybutyrate) (PHB) and medium-chain-length poly(hydroxyalkanoate) (mcl-PHA) polymers. Pseudomonas oleovorans NRRL B-14682 and P. corrugata 388 grew and synthesized PHB and mcl-PHA, respectively, when cultivated in up to 5% (w/v) CSBP. In shake flask culture, P. oleovorans grew to 1.3 ± 0.1 g/L (PHA cellular productivity = 13–27% of the bacterial cell dry weight; CDW) regardless of the initial CSBP concentration, whereas P. corrugata reached maximum cell yields of 2.1 g/L at 1% CSBP, which tapered off to 1.7 g/L as the CSBP media concentration was increased to 5% (maximum PHA cellular productivity = 42% of the CDW at 3% CSBP). While P. oleovorans synthesized PHB from CSBP, P. corrugata produced mcl-PHA consisting primarily of 3-hydroxyoctanoic acid (C_8:0; 39 ± 2 mol%), 3-hydroxydecanoic acid (C_10:0; 26 ± 2 mol%) and 3-hydroxytetradecadienoic acid (C_14:2; 15 ± 1 mol%). The molar mass (M_n) of the PHB polymer decreased by 53% as the initial CSBP culture concentration was increased from 1% to 5% (w/v). In contrast, the M_n of the mcl-PHA polymer produced by P. corrugata remained constant over the range of CSBP concentrations used.