Synthesis,characterization, and biodegradation of carboxymethylchitosan‐g‐medium chain length polyhydroxyalkanoates

Grafting of medium chain length polyhydroxyalkanoates (mcl‐PHA) produced by Comamonas testosteroni onto carboxymethylchitosan (CMCH) using ceric ammonium nitrate (CAN) as an initiator was carried out under nitrogen atmosphere in aqueous medium. The grafting composition was 2 g CMCH, 0.2M CAN, and 0.5 g mcl‐PHA. The reaction was carried out at 40°C ± 1°C for 4.5 h, and reaction product was extracted by acetone precipitation. The CMCH‐g‐mcl‐PHA copolymers were characterized by Fourier transform infrared spectroscopy, Thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. The data obtained showed successful grafting of mcl‐PHA onto CMCH polymer. TGA results indicated that the graft was stable up to 380°C, and the solubility studies revealed a high % grafting efficiency. Biodegradation studies of the graft in terms of microbial growth, extracellular protein concentration, and % weight loss in the graft were carried out for 30 days using a bacterial isolate Burkholderia cepacia 202 and a fungal isolate Aspergillus fumigatus 202. 93% weight loss of the graft was obtained in case of A. fumigatus 202, whereas B. cepacia 202 showed 76% loss in weight of the graft. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Chemical characterization of medium‐chain‐length polyhydroxyalkanoates (PHAs) recovered by enzymatic treatment and ultrafiltration

BACKGROUND: Medium‐chain‐length polyhydroxyalkanoates (PHAs) are biodegradable polyesters accumulated intracellularly as energy resources by bacterial species such as Pseudomonas putida. The most popular method for PHA recovery is solvent extraction using trichloromethane (chloroform) and methyl alcohol (methanol). An alternative method is enzymatic treatment, which eliminates usage of these hazardous solvents. This research focuses on the characterization of PHAs recovered by enzymatic treatments and ultrafiltration. Comparisons are made with conventional solvent extracted PHA. RESULTS: The purity of PHA in water suspension recovered by enzymatic treatments as analyzed by gas chromatography was 92.6%. Enzymatically recovered PHA was comparable to conventional solvent‐extracted PHA, which had a purity of 95.5%. PHA was further characterized for functional group analysis, structural composition analysis and molecular weight determination. It was found that the molecular weight of the PHA recovered by enzymatic treatment was less than solvent‐extracted PHA, probably due to degradation of the lipopolysaccharide layer. However, functional group and structural composition analyses showed similar results for PHA recovered by both methods. CONCLUSION: PHAs recovered through enzymatic digestion treatment have good comparability with solvent‐extracted PHAs. Thus enzymatic digestion has great potential as an alternative recovery method. Copyright © 2007 Society of Chemical Industry     

Kinetics of thermodegradation of palm kernel oil derived medium‐chain‐length polyhydroxyalkanoates

Oligomeric hydroxyalkanoic acids have potential industrial, medical, and pharmaceutical applications and they can be produced from the degradation of high molecular weight polyhydroxyalkanoates by a number of different ways. Thermal decomposition takes place in the absence of organic solvent and other chemicals and this justified the method of producing low molecular weight PHA as green chemistry. The kinetics for thermal degradation of medium‐chain‐length polyhydroxyalkanoates (mcl‐PHA) prepared from saponified palm kernel oil (SPKO) was studied by thermogravimetric analysis (TGA) technique. Employing the nonisothermal Kissinger's method, the degradation activation energy, E_d, and pre‐exponential factor, A, were 129 kJ mol^?1 and 1.15 × 10¹⁰ s^?1, respectively. Specific degradation rate constant, k was found to increase at higher heating rate. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Novel amphiphilic poly(ester‐urethane)s based on poly[(R)‐3‐hydroxyalkanoate]: synthesis,biocompatibility and aggregation in aqueous solution

BACKGROUND: The aim of this work was to develop polyhydroxyalkanoates (PHAs) for blood contact applications, and to study their self‐assembly behavior in aqueous solution when the PHAs are incorporated with hydrophilic segments. To do this, poly(ester‐urethane) (PU) multiblock copolymers were prepared from hydroxyl‐terminated poly(ethylene glycol) (PEG) and hydroxylated poly[(R)‐3‐hydroxyalkanoate] (PHA‐diol) using 1,6‐hexamethylene diisocyanate as a coupling reagent. The PEG segment functions as a soft, hydrophilic and crystalline portion and the poly[(R)‐3‐hydroxybutyrate] segment behaves as a hard, hydrophobic and crystalline portion. In another series of PU multiblock copolymers, crystalline PEG and completely amorphous poly[((R)‐3‐hydroxybutyrate)‐co‐(4‐hydroxybutyrate)] behaved as hydrophobic and hydrophilic segments, respectively. RESULTS: The formation of a PU series of block copolymers was confirmed by NMR, gel permeation chromatography and infrared analyses. The thermal properties showed enhanced thermal stability with semi‐crystalline morphology via incorporation of PEG. Interestingly, the changes of the hydrophilic/hydrophobic ratio led to different formations in oil‐in‐water emulsion and surface patterning behavior when cast into films. Blood compatibility was also increased with increasing PEG content compared with PHA‐only polymers. CONCLUSION: For the first time, PHA‐based PU block copolymers have been investigated in terms of their blood compatibility and aggregation behavior in aqueous solution. Novel amphiphilic materials with good biocompatibility for possible blood contact applications with hydrogel properties were obtained. Copyright © 2008 Society of Chemical Industry     

Polyhydroxyalkanoate‐based drug delivery systems

Microbial polyhydroxyalkanoates (PHAs) have been a subject of significant research interest in the past few decades. The recent development of novel functionalized PHAs has opened up new possibilities to combine the good biocompatibility of PHA‐based drug delivery systems to, for example, improve drug loading and release properties, targeting or imaging functionalities. This mini‐review presents some recent scientific developments in the preparation of functionalized PHAs, PHA–drug and PHA–protein conjugates, multifunctional PHA nanoparticles and micelles as well as biosynthetic PHA particles for drug delivery. These developments in combination with the generally excellent biocompatibility of PHA materials are expected to further expand the interest in PHA materials for drug delivery and other therapeutic applications. © 2016 Society of Chemical Industry     

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

The 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 T_g of PS towards higher temperatures, indicating chemical interaction of PS‐PHA.

     

In vitro synthesis of polyhydroxyalkanoate catalyzed by class II and III PHA synthases: a useful technique for surface coatings of a hydrophobic support with PHA

In vitro synthesis of polyhydroxyalkanoates (PHAs) on a hydrophobic support, i.e. highly oriented pyrolytic graphite (HOPG), was performed using class II PHA synthase (PhaC1_Pp) from Pseudomonas putida and class III PHA synthase (PhaEC_Av) from Allochromatium vinosum. Using PhaC1_Pp and 3‐hydroxyoctanoyl‐CoA, a poly(3‐hydroxyoctanoate) [P(3HO)] film was formed on the hydrophobic support with a thickness of a few nanometers, as revealed by atomic force microscopy (AFM). A poly(3‐hydroxybutyrate) [P(3HB)] film was also formed using PhaEC_Av and 3‐hydroxybutyryl‐CoA. AFM observations of the HOPG surface during P(3HB) film formation revealed that polymerized P(3HB) covered HOPG surface within the reaction time, resulting in the formation of a homogeneous ultra‐thin film. This method of ultra‐thin PHA film formation on a hydrophobic support may be applicable to the surface‐coating technique of materials with biodegradable, bioabsorbable, and biocompatible PHAs. Copyright © 2009 Society of Chemical Industry     

Bioconversion of residual soybean oil into polyhydroxyalkanoates

The aim of this study is to evaluate the bioconversion of residual soybean oil (RSO) into polyhydroxyalkanoates (PHAs) by selecting microorganism and fermentation condition in order to increase PHAs production. PHAs production by Cupriavidus necator IPT 026 using glucose (PHA 1) and RSO (PHA 2) as substrate is 1.15 ± 0.21 and 2.84 ± 0.04 g L^?1, respectively. FTIR spectra of PHAs were similar to data reported in literature. PHAs presented low crystallinity (PHA 1: 42.69%; PHA 2: 46.44%), high thermal stability (PHA 1: 271.78 °C; PHA 2: 272.52 °C), and low M_W (PHA 1: 140.69 kDa; PHA 2: 254.54 kDa). PHAs produced by RSO are potential candidates for industrial applications, especially ones that demand higher temperatures. This is the first study on the production and characterization of PHAs obtained by C. necator IPT 026 in culture with RSO. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46255.     

The synthesis of PHA‐g‐(PTHF‐b‐PMMA) multiblock/graft copolymers by combination of cationic and radical polymerization

A new and promising method for the diversification of microbial polyesters based on chemical modifications is introduced. Poly(3‐hydroxy alkanoate)‐g‐(poly(tetrahydrofuran)‐b‐poly(methyl methacrylate)) (PHA‐g‐(PTHF‐b‐PMMA)) multigraft copolymers were synthesized by the combination of cationic and free radical polymerization. PHA‐g‐PTHF graft copolymer was obtained by the cationic polymerization of THF initiated by the carbonium cations generated from the chlorinated PHAs, poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), and poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBHx) in the presence of AgSbF₆. Therefore, PHA‐g‐PTHF graft copolymers with hydroxyl ends were produced. In the presence of Ce⁺⁴ salt, these hydroxyl ends of the graft copolymer can initiate the redox polymerization of MMA to obtain PHA‐g‐(PTHF‐b‐PMMA) multigraft copolymer. Polymers obtained were purified by fractional precipitation. In this manner, their γ‐values (volume ratio of nonsolvent to the solvent) were also determined. Their molecular weights were determined by GPC technique. The structures were elucidated using ¹H‐NMR and FTIR spectroscopy. Thermal analyses of the products were carried out using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Comparative analysis of different properties of polyhydroxyalkanoates isolated from two different bacterial strains: Alkaliphilus oremlandii OhILAs and recombinant Escherichia coli XL1B

We synthesized poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(3‐HB‐co‐3‐HV)] copolymer having different contents of 3‐hydroxyvalerate (3‐HV) units (16.04, 16.3, 24.95, 25.62, and 16.52 mol % 3‐HV) with different yields of polyhydroxyalkanoates (PHAs) by feeding with different cooking oils and with Alkaliphilus oremlandii OhILAs strain. The PHA production efficiency of the Alkaiphilus strain was compared with that of the control strain, Bacillus cereus. The synthesis of each PHA biopolymer was performed with different toxic spent oils as the sole carbon source in an oil‐in‐water‐based microemulsion medium. We observed that the productivity of the poly(3‐hydroxybutyrate) [P(3‐HB)] copolymer from the Alkaliphilus strain was higher than those of the PHAs isolated from B. cereus and the Escherichia coli XL1B strain. The synthesized PHA copolymers were characterized by ¹H‐NMR and Fourier transform infrared (FTIR) spectroscopy. In the ¹H‐NMR spectra, a doublet resonance peak at 1.253 ppm of the/ methyl protons of the 3‐hydroxybutyrate (3‐HB) side group and one at 0.894 ppm due to the methyl protons of the 3‐HV side group indicated the presence of 3‐HB and 3‐HV units in the copolymer. The chemical shift values at 1.25 and 2.2 ppm, due to the resonance absorption peaks of the methyl protons and methylene protons, confirmed the synthesis of the P(3‐HB) homopolymer. From the FTIR spectra, a strong C?O stretching frequency in the range of 1745–1727 cm^?1, together with strong C? O stretching bands near 1200 cm^?1 and a strong band near 3400 cm^?1, confirmed the synthesis of P(3‐HB‐co‐3‐HV) and P(3‐HB). Thus, waste cooking oil as a substrate provided an alternate route for the formation of P(3‐HB‐co‐3‐HV) and P(3‐HB) by Alkaliphilus and E. coli strains, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41080.     

Photothermal methods and atomic force microscopy images applied to the study of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) dense membranes

Thermal and transport properties of some polyhydroxyalkanoates (PHAs), poly‐3‐hydroxybutyrate and poly‐3‐hydroxybutyrate‐co‐3‐hydroxyvalerate copolymers at different concentrations (8, 14, and 22%), were studied by using photoacoustic and photothermal techniques. Mass diffusion coefficients were obtained for carbon dioxide and oxygen by using a gas analyzer. Specific heat capacity measurements were performed by monitoring temperature of the samples under white light illumination against time. Thermal diffusivities were determined by using the open photoacoustic cell configuration. The results were discussed considering the incorporation of hydroxyvalerate units in the poly(3‐hydroxybutyrate) unit cell and were correlated with atomic force microscopy images of the upper surface of membranes. New information on transport properties of PHAs is provided. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1491–1497, 2005     

Reactions of palm oil‐based mcl‐PHAs with epoxidized natural rubber

A palm oil‐based medium‐chain‐length polyhydroxyalkanoate (mcl‐PHA) was allowed to react with epoxidized natural rubber (ENR). There was no noticeable reaction at ambient temperature for short reaction times. However, after 30 min at 170°C, the mcl‐PHA underwent thermal degradation to generate carboxylic terminal groups that attacked the epoxy groups of the ENR. Evidence of the ring‐opening reaction was provided by both FTIR and ¹H‐NMR. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improvement of the production of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxybutyrate) terpolyester by manipulating the culture condition

BACKGROUND: The aim of this work is to enhance the production of terpolyester poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxybutyrate) (P(3HB‐co‐3HV‐co‐4HB)) produced by a locally isolated bacterium, Cupriavidus sp. USMAA2‐4. The monomer composition was varied by supplementing different carbon precursors and by manipulating the culture condition through one‐stage cultivation. The effect of C/N ratio and different concentrations of carbon source and precursors were investigated in order to produce higher content of this terpolyester. Although research on this biodegradable polyester is abundant, studies on terpolyester P(3HB‐co‐3HV‐co‐4HB) are still limited. RESULTS: Supplementation of oleic acid in accumulation medium increased the bacterial growth and polyhydroxyalkanoate (PHA) accumulation. It was also shown that medium consisting of assorted carbon precursors at C/N 20 gave relatively high dry cell weight and P(3HB‐co‐3HV‐co‐4HB) content. Various compositions of terpolyester were obtained when the concentration of oleic acid and 4HB precursors were manipulated. The combination of oleic acid with γ‐butyrolactone and 1‐pentanol was found to be the best combination to produce high PHA content (81 wt%). The composition of monomer in P(3HB‐co‐3HV‐co‐4HB) was produced in the range 8–13 mol% for 3HV and 9–24 mol% for 4HB, respectively. CONCLUSIONS: The production of P(3HB‐co‐3HV‐co‐4HB) in shake‐flasks successfully produced 81 wt% of PHA content. This manipulated culture condition can be used at larger scale to provide modeling for the production of terpolyester in a bioreactor. Copyright © 2012 Society of Chemical Industry     

Development of tunable biodegradable polyhydroxyalkanoates microspheres for controlled delivery of tetracycline for treating periodontal disease

This article was aimed at preparation and characterization of drug delivery carriers made from biodegradable polyhydroxyalkanoates (PHAs) for slow release of tetracycline (TC) for periodontal treatment. Four PHA variants; polyhydroxybutyrate (PHB), poly(hydroxybutyrate‐co‐hydroxyvalerate) with 5, 12, and 50% hydroxyvalerate were used to formulate TC‐loaded PHA microspheres by double emulsion‐solvent evaporation method. We also compared the effect of different molecular weight (M_w) of polyvinyl alcohol (PVA) acting as surface stabilizer on particle size, drug loading, encapsulation efficiency, and drug release profile. The TC‐loaded PHA microspheres exhibited microscale and nanoscale spherical morphology under scanning electron microscopy. Among formulations, TC‐loaded PHB:low M_w PVA demonstrated the highest TC loading with slow release behavior. Our results showed that the release rate from PHA microspheres was influenced by both the type of PHA and M_w of PVA stabilizer. Lastly, TC‐loaded PHB microspheres showed efficient killing activity against periodontitis‐causing bacteria, suggesting its potential application for treating periodontal disease. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44128.     

Novel lipase isolated from a Pseudomonas strain and its application in the synthesis of S(+)‐2‐O‐benzylglycerol‐1‐acetate

Isolation of a novel microbial lipase (EC 3.1.1.3) having specific catalytic activity for the synthesis of optically pure 2‐O‐benzylglycerol‐1‐acetate, the building block for the preparation of many β‐blockers, phospholipase A2 inhibitors and other biologically active compounds was the aim of this investigation. A Pseudomonas (strain G6), recently isolated from soil, produced an extracellular lipase. SDS–PAGE analysis showed that the lipase protein was a hexamer. The molecular weight of the sub‐units of the lipase protein were 10, 19, 29, 30, 47 and 53. The catalytic activity of the lipase was exploited for the synthesis of 2‐O‐benzylglycerol‐1‐acetate from 2‐O‐benzylglycerol through transesterification using vinyl acetate as acylating agent. High selectivity of the lipase towards the monoacetate product was demonstrated. A 97% enantiomeric excess (ee) of S(+)‐2‐O‐benzylglycerol‐1‐acetate was obtained when the reaction was carried out at room temperature with shaking. The lipase was highly active in anhydrous organic microenvironments and in non‐polar organic solvents with log P values above 2.5. © 2002 Society of Chemical Industry     

Polyhydroxyalkanoates,a family of natural polymers,and their applications in drug delivery

Polyhydroxyalkanoates (PHAs) are natural biopolymers produced by various microorganisms as a reserve of carbon and energy. PHA synthesis generally occurs during fermentation under nutrient limiting conditions with excess carbon. There are two main types of PHAs, short chain length PHAs (scl‐PHAs) and medium chain length PHAs (mcl‐PHAs). The mechanical and thermal properties of PHAs depend mainly on the number of carbons in the monomer unit and its molecular weight. PHAs are promising materials for biomedical applications because they are biodegradable, non‐toxic and biocompatible. The large range of PHAs, along with their varying physical properties and high biocompatibility, make them highly attractive biomaterials for use in drug delivery. They can be used to produce tablets, micro‐ and nanoparticles as well as drug eluting scaffolds. A large range of different PHAs have been explored and the results obtained suggest that PHAs are excellent candidates for controlled and targeted drug delivery systems. © 2015 Society of Chemical Industry     

Effect of orotic acid as a nucleating agent on the crystallization of bacterial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) copolymers

The kinetics of crystallization induced by orotic acid (OA) and boron nitride (BN) as nucleating agents were investigated for bacterial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)s (P(HB‐co‐HH)s) containing from 0 to 18% HH monomer units. The nucleation efficiency of these two chemicals was investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that both orotic acid and boron nitride are able to nucleate the crystallization of PHB. In the case of P(HB‐co‐HH) copolymers, orotic acid showed an outstanding nucleating effect. The comparison of half‐crystallization times shows that for P(HB‐co‐10% HH), the crystallization initiated by orotic acid is more than three time faster than the one induced by boron nitride (t_1/2BN/t_1/2OA(60°C) = 3.7 and t_1/2BN/t_1/2OA(90°C) = 4.5). According to the fact that orotic acid is a biodegradable, biocompatible and a nontoxic chemical, this nucleating agent is a promising solution for PHAs used in medical applications such as implants. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Storage of biodegradable polymers by an enriched microbial community in a sequencing batch reactor operated at high organic load rate

The production of polyhydroxyalkanoates (PHAs) from organic acids by mixed bacterial cultures using a process based on aerobic enrichment of activated sludge, that selects for mixed microbial cultures able to store PHAs at high rates and yields, is described. Enrichment resulted from the selective pressure established by periodic feeding the carbon source in a sequencing batch reactor (SBR); a mixture of acetic, lactic and propionic acids was fed at high frequency (2 hourly), high dilution rate (1 d⁻¹), and at high organic load rate (12.75 g chemical oxygen demand (COD) L⁻¹ d⁻¹). The performance of the SBR was assessed by microbial biomass and PHA production as well as the composition and polymer content of the biomass. A final batch stage was used to increase the polymer concentration of the excess sludge produced in the SBR and in which the behaviour of the biomass was investigated by determining PHA production rates and yields. The microbial biomass selected in the SBR produced PHAs at high rate [278 mg PHAs (as COD) g biomass (as COD)⁻¹ h⁻¹, with a yield of 0.39 mg PHAs (as COD) mg removed substrates (as COD)⁻¹], reaching a polymer content higher than 50% (on a COD basis). The stored polymer was the copolymer poly(3‐hydroxybutyrate/3‐hydroxyvalerate) [P(HB/HV)], with an HV fraction of 18% mol mol⁻¹. The microbial community selected in the SBR was analysed by DGGE (denaturing gradient gel electrophoresis). The operating conditions of the SBR were shown to select for a restricted microbial population which appeared quite different in terms of composition with respect to the initial microbial cenosis in the activated sludge used as inoculum. On the basis of the sequencing of the major bands in the DGGE profiles, four main genera were identified: a Methylobacteriaceae bacterium, Flavobacterium sp, Candidatus Meganema perideroedes, and Thauera sp. The effects of nitrogen depletion (ie absence of growth) and pH variation were also investigated in the batch stage and compared with the SBR operative mode. Absence of growth did not stimulate higher PHA production, so indicating that the periodic feed regime fully exploited the storage potential of the enriched culture. Polymer production rates remained high between pH 6.5 and 9.5, whereas the HV content in the stored polymer strongly increased as the pH value increased. This study shows that polymer composition in the final batch stage can readily be controlled independently from the feed composition in the SBR. Copyright © 2005 Society of Chemical Industry     

Grafting of poly(3‐hydroxyalkanoate) and linoleic acid onto chitosan

Poly(3‐hydroxy octanoate) (PHO), poly(3‐hydroxy butyrate‐co‐3‐hydroxyvalerate) (PHBV), and linoleic acid were grafted onto chitosan via condensation reactions between carboxylic acids and amine groups. Unreacted PHAs and linoleic acid were eliminated via chloroform extraction and for elimination of unreacted chitosan were used 2 wt % of HOAc solution. The pure chitosan graft copolymers were isolated and then characterized by FTIR, ¹³C‐NMR (in solid state), DSC, and TGA. Microbial polyester percentage grafted onto chitosan backbone was varying from 7 to 52 wt % as a function of molecular weight of PHAs, namely as a function of steric effect. Solubility tests were also performed. Graft copolymers were soluble, partially soluble or insoluble in 2 wt % of HOAc depending on the amount of free primary amine groups on chitosan backbone or degree of grafting percent. Thermal analysis of PHO‐g‐Chitosan graft copolymers indicated that the plastizer effect of PHO by means that they showed melting transitions T_ms at 80, 100, and 113°C or a broad T_ms between 60.5–124.5°C and 75–125°C while pure chitosan showed a sharp T_m at 123°C. In comparison of the solubility and thermal properties of graft copolymers, linoleic acid derivatives of chitosan were used. Thus, the grafting of poly(3‐hydroxyalkanoate) and linoleic acid onto chitosan decrease the thermal stability of chitosan backbone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:81–89, 2007     

Thermal properties and crystallization behavior of fractionated blocky and random polyhydroxyalkanoate copolymers from mixed microbial cultures

This study represents the first detailed analysis of the thermal, morphological, and crystallization properties of the blend components within a range of mixed‐culture polyhydroxyalkanoates (PHAs), with 3‐hydroxyvalerate content in the as‐produced materials and in the fractions ranging from low (12 mol %) to high (91 mol %). Both coarse and fine fractionation of the as‐produced copolymers confirmed that they were blends of nominally blocky and/or random copolymers of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate), with very broad compositional distributions as governed by the PHA accumulation strategy. The crystallization kinetics and thermal properties of the fractions were found to be very significantly different from each other, consistent with the hypothesis that the overall mechanical properties were primarily controlled by the more rapidly crystallizing components. Two materials produced using an alternating feeding strategy demonstrated unique crystallization and thermal properties in their fractions, which are considered to have contributed to distinctly more elastic mechanical properties in these particular samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40836.