Medium Chain Length Poly Research Articles

Optimizing a Fed-Batch High-Density Fermentation Process for Medium Chain-Length Poly(3-Hydroxyalkanoates) in Escherichia coli.

Production of medium chain-length poly(3-hydroxyalkanoates) [PHA] polymers with tightly defined compositions is an important area of research to expand the application and improve the properties of these promising biobased and biodegradable materials. PHA polymers with homopolymeric or defined compositions exhibit attractive material properties such as increased flexibility and elasticity relative to poly(3-hydroxybutyrate) [PHB]; however, these polymers are difficult to biosynthesize in native PHA-producing organisms, and there is a paucity of research toward developing high-density cultivation methods while retaining compositional control. In this study, we developed and optimized a fed-batch fermentation process in a stirred tank reactor, beginning with the biosynthesis of poly(3-hydroxydecanoate) [PHD] from decanoic acid by β-oxidation deficient recombinant Escherichia coli LSBJ using glucose as a co-substrate solely for growth. Bacteria were cultured in two stages, a biomass accumulation stage (37°C, pH 7.0) with glucose as the primary carbon source and a PHA biosynthesis stage (30°C, pH 8.0) with co-feeding of glucose and a fatty acid. Through iterative optimizations of semi-defined media composition and glucose feed rate, 6.0 g of decanoic acid was converted to PHD with an 87.5% molar yield (4.54 g L–1). Stepwise increases in the amount of decanoic acid fed during the fermentation correlated with an increase in PHD, resulting in a final decanoic acid feed of 25 g converted to PHD at a yield of 89.4% (20.1 g L–1, 0.42 g L–1 h–1), at which point foaming became uncontrollable. Hexanoic acid, octanoic acid, 10-undecenoic acid, and 10-bromodecanoic acid were all individually supplemented at 20 g each and successfully polymerized with yields ranging from 66.8 to 99.0% (9.24 to 18.2 g L–1). Using this bioreactor strategy, co-fatty acid feeds of octanoic acid/decanoic acid and octanoic acid/10-azidodecanoic acid (8:2 mol ratio each) resulted in the production of their respective copolymers at nearly the same ratio and at high yield, demonstrating that these methods can be used to control PHA copolymer composition.

Antioxidant Network Based on Sulfonated Polyhydroxyalkanoate and Tannic Acid Derivative.

A novel generation of gels based on medium chain length poly(3-hydroxyalkanoate)s, mcl-PHAs, were developed by using ionic interactions. First, water soluble mcl-PHAs containing sulfonate groups were obtained by thiol-ene reaction in the presence of sodium-3-mercapto-1-ethanesulfonate. Anionic PHAs were physically crosslinked by divalent inorganic cations Ca2+, Ba2+, Mg2+ or by ammonium derivatives of gallic acid GA-N(CH3)3+ or tannic acid TA-N(CH3)3+. The ammonium derivatives were designed through the chemical modification of gallic acid GA or tannic acid TA with glycidyl trimethyl ammonium chloride (GTMA). The results clearly demonstrated that the formation of the networks depends on the nature of the cations. A low viscoelastic network having an elastic around 40 Pa is formed in the presence of Ca2+. Although the gel formation is not possible in the presence of GA-N(CH3)3+, the mechanical properties increased in the presence of TA-N(CH3)3+ with an elastic modulus G’ around 4200 Pa. The PHOSO3−/TA-N(CH3)3+ gels having antioxidant activity, due to the presence of tannic acid, remained stable for at least 5 months. Thus, the stability of these novel networks based on PHA encourage their use in the development of active biomaterials.

Production of a novel medium chain length poly(3-hydroxyalkanoate) using unprocessed biodiesel waste and its evaluation as a tissue engineering scaffold.

SummaryThis study demonstrated the utilization of unprocessed biodiesel waste as a carbon feedstock for Pseudomonas mendocina CH50, for the production of PHAs. A PHA yield of 39.5% CDM was obtained using 5% (v/v) biodiesel waste substrate. Chemical analysis confirmed that the polymer produced was poly(3‐hydroxyhexanoate‐co‐3‐hydroxyoctanoate‐co‐3‐hydroxydecanoate‐co‐3‐hydroxydodecanoate) or P(3HHx‐3HO‐3HD‐3HDD). P(3HHx‐3HO‐3HD‐3HDD) was further characterized and evaluated for its use as a tissue engineering scaffold (TES). This study demonstrated that P(3HHx‐3HO‐3HD‐3HDD) was biocompatible with the C2C12 (myoblast) cell line. In fact, the % cell proliferation of C2C12 on the P(3HHx‐3HO‐3HD‐3HDD) scaffold was 72% higher than the standard tissue culture plastic confirming that this novel PHA was indeed a promising new material for soft tissue engineering.

Improved processability of electrospun poly[(R)-3-hydroxybutyric acid] through blending with medium-chain length poly(3-hydroxyalkanoates) produced by Pseudomonas putida from oleic acid

Polyhydroxyalkanoates are bacterial biopolyesters having good biocompatibility and biodegradability. Poly[(R)-3-hydroxybutyric acid] is the least expensive/costly and most easily available member of this family. However, poly[(R)-3-hydroxybutyric acid] is very brittle because of its high crystallinity. Its poor processability poses limitations on its application. Blending of this material with another amorphous flexible polymer has been a common practice. In this research, we have improved the properties of poly[(R)-3-hydroxybutyric acid] through blending with a palm oil-based medium-chain length polyhydroxyalkanoate. Solution blending was carried out at four different ratios to produce electrospun fibres. As expected, the addition of medium-chain length polyhydroxyalkanoate has reduced the brittleness of poly[(R)-3-hydroxybutyric acid], through reducing the crystallinity. In addition, it has enabled the reduction of the diameter of the electrospun fibres and shifted it from micrometre towards nanometres, which can improve its porosity and permeability to make it a potential material in biomedical applications.

Reactive mcl‐PHA: A Sustainable Alternative for Innovative Hybrid Materials

AbstractThe ability to incorporate medium chain length poly(hydroxyalkanoate) (mcl‐PHA) in the styrene miniemulsion polymerization process was investigated. As a result, novel poly(hydroxyalkanoate)‐co‐poly(stryrene) (PHA‐co‐PS) copolymers were synthesized in the form of stable organic–organic hybrid latexes. Evidence of chemical grafting of mcl‐PHA and cross‐linking of the PHA grafts was obtained using NMR, differential scanning calorimetry (DSC), gel extraction, and rheological analysis. A high degree of mcl‐PHA grafting was achieved by maintaining proper miniemulsion polymerization conditions throughout the course of the polymerization. The incorporation of PHA grafts was a function of the level of PHA in the formulations as well as the reaction conditions, as evidenced by solvent extraction and rheological analysis. DSC showed shifts in the Tg of PS towards higher temperatures, indicating chemical interaction of PS‐PHA. magnified image

Biosynthesis and characterization of polyhydroxyalkanoates by Pseudomonas guezennei from alkanoates and glucose

The biosynthesis of medium chain length poly(3-hydroxyalkanoates) mcl PHAs by Pseudomonas guezennei using glucose, sodium octanoate, and 10-undecenoic acid as sole or mixed carbon sources was investigated. Chemical composition of polyesters was analyzed by GCMS and NMR. The copolyester produced by P. guezennei from glucose mainly consisted of 3-hydroxyoctanoate and 3-hydroxydecanoate, and the presence of 3-hydroxydodec-5-enoate was demonstrated. Using sodium octanoate as the sole nutrient, the microorganism produced a poly(3-hydroxyoctanoate) (PHO) polymer containing up to 94mol% 3-hydroxyoctanoate. Biosynthesis of poly[(3-hydroxyoctanoate)-co-(3-hydroxyundecenoate)] (PHOU) copolymers bearing terminal reactive double bonds on its side chains with unsaturation degree ranging from 8.8% to 78.2% was obtained by tuning the ratio of sodium octanoate/10-undecenoic acid in the medium. Thermal analysis indicated semi-crystalline polymers with melting temperatures (Tm) ranging from 46 to 55°C, fusion enthalpy (ΔH) comprised between 3 and 35J/g and glass transition temperature (Tg) from −36 to −44°C, except for the highly amorphous 78.2% unsaturated PHOU with a low Tg (−50°C). Molecular weights determined by GPC ranged from 119000 and 530000g/mol.The biosynthesis of natural polyesters with controlled ratio of vinyl-terminated side chains is of great interest for further chemical modifications.

A micellization study of medium chain length poly(3-hydroxyalkanoate)-based amphiphilic diblock copolymers

In this article, we report the first micellization study of amphiphilic copolymers composed of bacterial medium chain length poly(3-hydroxyalkanoates) (mcl-PHAs). A series of diblock copolymers based on fixed poly(ethylene glycol) (PEG) block (5000gmol−1) and a varying poly(3-hydroxyoctanoate-co-3-hydroxyhexanoate) (PHOHHx) segment (1500–7700gmol−1) have been synthesized using “click” chemistry. These copolymers self-assembled to form micelles in aqueous media. The influence of PHOHHx block molar mass on the hydrodynamic size and on the critical micelle concentration (CMC) has been studied using dynamic light scattering and fluorescence spectroscopy, respectively. With increasing PHOHHx length, narrowly distributed micelles with diameters ranging from 44 to 90nm were obtained, with extremely low CMC (up to 0.85mg/L). Cryogenic transmission electron microscopy (Cryo-TEM) showed that micelles took on a spherical shape and exhibited narrow polydispersity. Finally, the colloidal stability of the micelles against physiological NaCl concentration has been demonstrated, suggesting they are promising candidates for drug delivery applications.

Application of Activated Charcoal in the Downstream Processing of Bacterial Olefinic Poly(3-hydroxyalkanoates)

Medium chain length poly(hydroxyalkanoates) (mcl-PHAs) are bacterial thermoplastic elastomers with a large potential in medical applications. The present study provides a novel process to isolate and purify poly([R]-3-hydroxy-omega-undecenoate-co-3-hydroxy-omega-nonenoate-co-3-hydroxy-omega-heptenoate) (PHUE) and poly([R]-3-hydroxy-omega-undecenoate-co-3-hydroxy-omega-nonenoate-co-3-hydroxyoctanoate-co-3-hydroxy-omega-heptenoate-co-3-hydroxyhexanoate) (PHOUE) from Pseudomonas putida species. Three different types of activated charcoal were compared with regard to their capability to selectively remove impurities. The product 'Charcoal activated, powder, pure' from Merck was found to be most suitable. Using ethyl acetate as solvent, the polyesters were extracted from freeze-dried biomass at room temperature and simultaneously purified by addition of activated charcoal at the beginning of the extraction. The period of extraction was one hour and the ratio solvent to biomass was 15:1 (vol/wt). After extraction, the solids were separated by pressure filtration through a metallic lace tissue. The filtrate was again passed through the previously accumulated filter cake, followed by a second filtration through a 0.45 microm membrane to remove finest coal particles. The resulting filtrate was concentrated, thus yielding polyesters whose quality and yield depended on the quantity of activated charcoal applied. For highly pure PHUE and PHOUE with low endotoxin levels, the optimum ratio of activated charcoal to solvent for extraction (V/V) was found to be 0.5 for PHUE and 0.25 for PHOUE. The yields with regard to the raw polymers amounted to 55 wt% for PHUE and 75 wt% for PHOUE, which are acceptable for polymers that can be used for medical applications.

Microbial medium chainlength poly[(R)-3-hydroxyalkanoate] shows liquid crystal behaviour

Medium chainlength (mcl) polyhydroxyalkanoates (PHAs) are a class of polymers receiving attention because of their potential as renewable, biodegradable and high tech properties. Unlike most short chain PHAs, mcl-PHAs are low crystallinity and elastomeric in character. In this paper we wish to point out that in their broad properties mcl-PHAs might be classified as thermotropic liquid crystals with dynamic conformational disorder and long range orientational order. As the characterization of mcl-PHAs progresses, their similarities to liquid crystalline elastomers are noteworthy. Wunderlich coined the acronym CONDIS from the words “conformational disorder” to categorize this type of liquid crystal. Thermal analysis reveals a T g of −40 to −45 °C with several T m peaks. The chemistry of the elastomer from 13C NMR confirms the poly(3-hydroxynonanoate), PHN, composition of the starting material along with two other samples containing double bonds: PHNU-18 and PHNU-31 where the numeral stands for the percent of double bonds.

Controlled Synthesis of Well Defined Poly(3‐hydroxyalkanoate)s‐based Amphiphilic Diblock Copolymers Using Click Chemistry

AbstractA modular synthesis of short chain length and medium chain length poly(3‐hydroxyalkanoate)s‐b‐poly(ethylene glycol) (PHAs‐b‐PEG) diblock copolymers is described. First, length‐controlled oligomers of hydrophobic poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBHV), poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBHHx), and poly(3‐hydroxyoctanoate‐co‐hydroxyhexanoate) (PHOHHx) containing a carboxylic acid end group were obtained by thermal treatment, with molar masses ranging from 3 800 to 15 000 g · mol−1. After quantitative functionalization with propargylamine, ligation with azide‐terminated poly(ethylene glycol) of 5 000 g · mol−1 was accomplished using the copper (I) catalyzed azide alkyne cycloaddition (CuAAC). Well‐defined diblock copolymers were obtained up to 93% yield, with molar masses ranging from 9 900 to 23 100 g · mol−1. All products were fully characterized using 1H NMR, COSY, SEC, TGA, and DSC. magnified image

Synthesis and characterization of poly(3-hydroxyalkanoates) from Brassica carinata oil with high content of erucic acid and from very long chain fatty acids

Pseudomonas aeruginosa produced medium chain length poly(3-hydroxyalkanoates) (mcl-PHAs) when grown on substrates containing very long chain fatty acids (VLCFA, C > 20). Looking for low cost carbon sources, we tested Brassica carinata oil (erucic acid content 35–48%) as an intact triglyceride containing VLCFA. Oleic (C 18:1), erucic (C 22:1), and nervonic (C 24:1) acids were also employed for mcl-PHA production as model substrates. The polymers obtained were analyzed by GC of methanolyzed samples, GPC, 1H and 13C NMR, ESI MS of partially pyrolyzed samples, and DSC. The repeating units of such polymers were saturated and unsaturated, with a higher content of the latter in the case of the PHA obtained from B. carinata oil. Statistical analysis of the ion intensity in the ESI mass spectra showed that the PHAs from pure fatty acids are random copolymers, while the PHA from B. carinata oil is either a pure polymer or a mixture of polymers. Weight-average molecular weight varied from ca. 56,000 g/mol for the PHA from B. carinata oil and oleic acid, to about 120,000 g/mol for those from erucic and nervonic acids. The PHAs from erucic and nervonic acids were partially crystalline, with rubbery characteristics and a melting point ( T m) of 50 °C, while the PHAs from oleic acid and from B. carinata oil afforded totally amorphous materials, with glass transition temperatures ( T g) of −52 °C and −47 °C, respectively.

Isolation and Purification of Medium Chain Length Poly(3-hydroxyalkanoates) (mcl-PHA) for Medical Applications Using Nonchlorinated Solvents

A novel process was developed to isolate poly([R]-3-hydroxyoctanoate-co-3-hydroxyhexanoate) (PHO) and poly([R]-3-hydroxy-ω-undecenoate-co-3-hydroxy-ω-nonenoate-co-3-hydroxy-ω-heptenoate) (PHUE) from Pseudomonas putida species. Methyl tert-butyl ether (MTBE), ethyl acetate, acetone, and methylene chloride efficiently extracted PHO from freeze-dried biomass. The ratio of solvent to biomass was 15:1 (vol/wt). The nonchlorinated solvents required 18 h of extraction to achieve methylene chloride's yield of 15 wt % within 60 min. In the case of PHUE, the yield was 15-17 wt % after 60 min of extraction at room temperature, independently of the solvent used. MTBE performed best in life cycle assessment (LCA) if contamination of the environment is avoided. Filtration of the extract containing 8 wt % of raw polyhydroxyalkanoate (PHA) through activated charcoal revealed colorless polymers with less than one endotoxin unit/g. The ratio (v/v) of the solution to activated charcoal was 2:1. The loss (impurities and polymers) amounted up to 50 wt %.

Role of carboxyl pendant groups of medium chain length poly(3‐hydroxyalkanoate)s in biomedical temporary applications

AbstractThe poly(3‐hydroxyoctanoate) (PHO) is a biodegradable polyester containing hydrophobic side chains. One way to obtain more hydrophilic polyester consisted in the introduction of polar groups in the side chains. Carboxyl groups (PHO75COOH25) were introduced by chemical modifications. The role of carboxyl groups was investigated in the first part as potential support for cell seeding by studying the cell adhesion and proliferation, and in the second part as potential drug carrier by comparing the abilities of PHO and PHO75COOH25 to form degradable particles. Measurements of human bladder RT112 cells adhesion were done with or without collagen IV. Adhesive RT112 cells were counted by a colorimetric MTT test. The results showed that the COOH pendant groups of PHO75COOH25 films promoted cell adhesion after 4 h of incubation. The proliferation of cells is not improved after 4 days of incubation because of a reorganization of macromolecular chains and reorientation of COOH groups. This surface restructuration when the film was in contact with water was showed by contact angle measurements. We showed that the presence of COOH groups modified the hydrophobic/hydrophilic balance and enhanced the formation of particles. Stable lyophilisable particles were then obtained with diblock copolymer P(HO75COOH25‐b‐CL); the caprolactone block (CL) was necessary to improve particles stability. The results showed that the release of doxorubicin from the particles is enhanced in presence of hydrophilic and degradable block (PHO75COOH25). It was possible to obtain a degradable functional polyester based on PHO with carboxyl pendant groups to improve degradation rate by simple hydrolysis required for drug delivery systems. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Biosynthesis of medium chain length poly(3-hydroxyalkanoates) (mcl PHAs) from cosmetic co-products by Pseudomonas raguenesii sp. nov., isolated from Tetiaroa, French Polynesia

A new bacterium, designated as strain TE9 was isolated from a microbial mat in French Polynesia and was studied for its ability to synthesize medium chain length poly-β-hydroxyalkanoates (mcl PHAs) during cultivation on cosmetics co-products. The composition of PHAs was analysed by coupled gas chromatography mass spectroscopy (GC/MS), nuclear magnetic resonance (NMR) and Fourier Transform InfraRed (FTIR) spectroscopy. PHAs were composed of C6–C14 3-hydroxyacids monomers, with a predominance of 3-hydroxyoctanoate (3HO), 3-hydroxydecanoate (3HD) and 3-hydroxydodecanoate (3HDD). Differential scanning calorimetry (DSC) experiments allowed the characterization of elastomeric materials with a melting point T m near 50 °C, enthalpy of fusion Δ H m from 27 to 32 J/g, and glass transition temperature T g of −43 °C. Molecular weights ranged from 175,000 to 358,000 g/mol. On the basis of the phenotypical features and genotypic investigations, strain TE9 was assigned to the Pseudomonas genus and the name of Pseudomonas raguenesii sp. nov. is proposed.

Autoxidation of Medium Chain Length Polyhydroxyalkanoate

Polyhydroxyalkanoates (PHAs) are a class of biopolymers that are currently the subject of intensive research for various applications (packaging, consumer products, medical applications, etc.). It is known from synthetic polymers that all plastic materials show more or less pronounced autoxidation (aging induced by UV radiation, temperature, heavy metal ions, etc.). There is less knowledge as yet regarding the autoxidation behavior of biopolymers. The autoxidative behavior of medium chain length poly[(R)-3-hydroxyalkanoate] (mcl-PHA) was therefore investigated. mcl-PHA (co)polymers with amounts of 0, 10, 50, and 75 mol % of olefinic side chains with terminal double bonds were tempered at 60 degrees C in air for 3 months. After 1, 2, 4, 8, and 12 weeks, samples were removed and analyzed for changes in chemical and physical properties by sol-gel analysis (Soxhlet extraction), size exclusion chromatography (SEC), infrared analysis (IR), and gas chromatography/flame ionization detection (GC/FID). It became apparent that the content of double bonds greatly influences the autoxidation of mcl-PHA. A low amount of unsaturated moiety (0 and 10 mol %) resulted in chain scission, whereas samples with 50 and 75 mol % olefinic side chains showed cross-linking and became insoluble after a few weeks. Kinetic data of oxidation behavior were investigated by performing isothermal DSC experiments at elevated temperatures. The kinetic data combined with the experiment enabled the gelation time to be predicted and the shelf-life of mcl-PHA to be estimated. Because of the detected sensitivity of mcl-PHA regarding autoxidation, it is recommended that these biopolymers should be stored cold (at least -5 degrees C) and in an inert gas atmosphere or stabilized by suitable additives (antioxidants).

Biosynthesis of medium chain length poly(3-hydroxyalkanoates) (mcl-PHAs) by Comamonas testosteroni during cultivation on vegetable oils

Comamonas testosteroni has been studied for its ability to synthesize and accumulate medium chain length poly(3-hydroxyalkanoates) (mcl-PHAs) during cultivation on vegetable oils available in the local market. Castor seed oil, coconut oil, mustard oil, cotton seed oil, groundnut oil, olive oil and sesame oil were supplemented in the mineral medium as a sole source of carbon for growth and PHAs accumulation. The composition of PHAs was analysed by a coupled gas chromatography/mass spectroscopy (GC/MS). PHAs contained C 6 to C 14 3-hydroxy acids, with a strong presence of 3-hydroxyoctanoate when coconut oil, mustard oil, cotton seed oil and groundnut oil were supplied. 3-Hydroxydecanoate was incorporated at higher concentrations when castor seed oil, olive oil and sesame oil were the substrates. Purified PHAs samples were characterized by Fourier Transform Infrared (FTIR) and 13C NMR analysis. During cultivation on various vegetable oils, C. testosteroni accumulated PHAs up to 78.5–87.5% of the cellular dry material (CDM). The efficiency of the culture to convert oil to PHAs ranged from 53.1% to 58.3% for different vegetable oils. Further more, the composition of the PHAs formed was not found to be substrate dependent as PHAs obtained from C. testosteroni during growth on variety of vegetable oils showed similar compositions; 3-hydroxyoctanoic acid and/or 3-hydroxydecanoic acid being always predominant. The polymerizing system of C. testosteroni showed higher preference for C 8 and C 10 monomers as longer and smaller monomers were incorporated less efficiently.

Morphologies and mechanical properties of polylactide blends with medium chain length poly(3‐hydroxyalkanoate) and chemically modified poly(3‐hydroxyalkanoate)

AbstractBlends of bacterial poly(3‐hydoroxyalkanoate) (PHA) with a medium‐length side chain and polylactide (PLA), and blends of the chemically modified PHA (ePHA) with PLA, were prepared. The morphologies, some physical properties, and thermal behavior of the blends based on PLA were investigated by electron microscopies, testing machines, and a differential scanning calorimeter, respectively. A blend of uncrystallized rubbery second components, PHA and ePHA, produced an increase in the impact toughness of the PLA blends in contrast to a decrease in the tensile strength value. PHA, especially, with an inserted epoxy group side chain was more effective in improving the morphology and the physical properties than PHA. The ePHA particles existed in the PLA domain as a dispersed phase having a size of 0.1–1 μm. The results of the biodegradation test demonstrated that the PLA blends still maintained their biodegradability and were more accessible to hydrolysis and microbial attack, resulting in a greater weight loss than the pure PLA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2363–2369, 2004

Glucose/Lipid Mixed Substrates as a Means of Controlling the Properties of Medium Chain Length Poly(hydroxyalkanoates)

Glucose-triacylglycerol (TAG) mixed substrates were used to modulate the physical and mechanical properties of medium-chain-length poly(hydroxyalkanoates) (mcl-PHAs). Pseudomonas resinovorans NRRL B-2649 grew and produced mcl-PHAs on glucose and TAGs (coconut oil, C; soybean oil, S) after 24 h in a shake flask culture. However, with the exception of coconut oil, maximum cell productivity was not reached in any of the cultures until 72 h post-inoculation. Here, 50:50 mixtures of glucose and coconut oil (glc/C) or glucose and soybean oil (glc/S) resulted in intermediate cell productivities with a maximum of 57% and 48% of the CDW at 72 h, respectively. In addition, mixed substrates resulted in mcl-PHAs with compositions that varied slightly over time. PHA-glc/C and PHA-glc/S were composed of 7 mol % and 8 mol % 3-hydroxydodecenoic acid (C(12:1)), respectively at 72 h. These concentrations were intermediate to the C(12:1) concentration of PHA-glc and respective PHA-TAG. Also, significant amounts of 3-hydroxytetradecanoic acid (C(14:0)), 3-hydroxytetradecenoic acid (C(14:1)), and 3-hydroxytetradecadienoic acid (C(14:2)) were present in PHA-glc/C and PHA-glc/S, which were derived from the respective TAG, as glucose resulted in almost no C(14:)(X) monomers. The molar masses of each of the polymers remained relatively constant between 24 and 96 h. At 72 h, the number-average molar masses (M(n)) of PHA-glc/C and PHA-glc/S were 178,000 and 163,000 g/mol, respectively, which were also intermediate to the M(n) of PHA-glc (225,000 g/mol) and the respective PHA-TAG (PHA-C = 153,000 g/mol; PHA-S = 75,000 g/mol). These physical differences caused variations in the mechanical properties of mcl-PHA films, thus providing a new and effective method of modifying their properties.

Viscoelastic properties of linseed oil-based medium chain length poly(hydroxyalkanoate) films: effects of epoxidation and curing

Medium-chain-length poly(hydroxyalkanoate) (mcl-PHA) polymers derived from linseed oil (PHA-L) have a relatively small molar mass and contain a high concentration of unsaturated side-chains. As such, these polymers are amorphous and take on the consistency of a viscous liquid at room temperature. In order to increase the application potential of this material, the side-chain olefinic groups of PHA-L were converted to epoxy derivatives (PHA-LE) using m-chloroperoxybenzoic acid ( m-CPBA). Epoxidation resulted in a 37% conversion of olefinic to epoxy groups. The epoxy groups enhanced the PHA-LE film susceptibility to crosslinking upon exposure to air. PHA-LE films began to crosslink and stiffen in less than 25 days, whereas PHA-L films began to crosslink between days 50 and 75. The PHA-LE films showed an increase in tensile strength (TS, from 4.8 to 20.7 MPa) and Young's modulus (YM, from 12.9 to 510.6 MPa) between 25 and 100 days. In contrast, PHA-L had a TS of 25.0 MPa and YM of 767.8 MPa after 100 days. Epoxidation helped induce crosslink formation; however, aging for 100 days ultimately resulted in crosslinked films from both PHA-L and PHA-LE with higher strength and durability than the original materials.

Perspectives of medium chain length poly(hydroxyalkanoates), a versatile set of bacterial bioplastics

Medium chain length (mcl) poly(hydroxyalkanoic acids) (PHAs) are polyesters accumulated by fluorescent Pseudomonads and other bacteria. Work on the genetics of mcl-PHA formation has led to polymer synthesis in recombinant bacteria and plants. Several high and medium cost applications are now emerging. With optimized bacterial mcl-PHA synthesis on inexpensive agro-substrates and the development of plant-based mcl-PHAs in the next decade, the production economics of these bioplastics will ultimately permit their sustainable production for bulk applications.