Large-scale production of poly(3-hydroxyvaleric acid) by fermentation ofChromobacterium violaceum,processing, and characterization of the homopolyester

A fed-batch process was developed, which allowed biotechnological production of the homopolyester poly(3-hydroxyvaleric acid) [poly(3HV)], in a mineral salts medium containing valeric acid as carbon source and complex nutrients as supplements byChromobacterium violaceum at a 10- and 300-L fermentation scale. This process yielded up to 40 g dry cell matter per L fermentation broth, and the cells contained up to 70% (w/w) poly(3HV). Poly(3HV), which was extracted from the cells with chloroform and was precipitated from this solvent with ethanol, was processed to test bars by injection molding or by press processing and to fibers by melt spinning. The unprocessed and processed poly(3HV) material was characterized with respect to the molecular weight and with respect to thermal, rheological, and mechanical properties. It was shown that it is possible to process biodegradable poly(3HV) thermoplastically and to obtain a polymer suitable for applications with low strength requirements.     

A Novel Biodegradable Green Poly(l-Aspartic Acid-Citric Acid) Copolymer for Antimicrobial Applications

Poly (l-aspartic acid-citric acid) green copolymers were developed using thermal polymerization of aspartic acid (ASP) and citric acid (CA) followed by direct bulk melt condensation technique. Antibacterial properties of copolymer of aspartic acid based were investigated as a function of citric acid content. This study is focused on the microorganism inhibition performance of aspartic acid based copolymers. Results showed that inhibition properties increase with increasing citric acid content. Characterization of obtained copolymers was carried out with the help of infrared absorption spectra (FTIR), x-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA). The antibacterial activity of copolymers against bacteria like E-coli, Bacillus and pseudomonas was investigated. The copolymers showed excellent antimicrobial activities against three types of microorganisms. Overall studies indicated that the above copolymers possess a broad wound dressing activity against above three types of bacteria and may be useful as antibacterial agents.     

Aromatic Copolyester-based Nano-biocomposites: Elaboration, Structural Characterization and Properties

Biodegradable polymers are one of the most promising ways to replace non-degradable polymers. But, to be a real alternative to classical synthetic polymers and find applications, biopolymer (biodegradable polymer) properties have to be enhanced. Nano-biocomposites, which are obtained by incorporation of nanofillers into a biomatrix, are an interesting way to achieve these improvements. Modified and unmodified montmorillonites have been introduced into a biodegradable aromatic copolyester, poly(butylene adipate-co-terephthalate) (PBAT). Structural characterization, thermal and mechanical tests have been carried out to understand better the relations between the nanofillers structuring and the final nano-biocomposite properties. Main results show that clay incorporation and the obtained intercalated structures improve PBAT properties (enhanced thermal stability, increased stiffness) and thus may increase the attractiveness of this biopolymer.     

Use of Nutshells as Fillers in Polymer Composites

Nutshells are agricultural waste products that can be procured at relatively low cost. In this work we examined the possibility of using these biodegradable materials as fillers in poly(lactic acid) and low density polyethylene. The nutshells were ground into powder, blended with the polymer, and then injection molded with final weight varying from 10 to 40 weight %. The mechanical and thermal properties of the composites were then studied. In general, the addition of fillers caused reductions in mechanical properties to varying extents, but thermal properties were only slightly affected. The use of maleic anhydride and peroxide with the fillers had a negative effect on poly(lactic acid) but a slightly positive effect on the stiffness of polyethylene. The results suggested that polymer-nutshell composites may be usable in applications where cost is a concern and where some reductions in mechanical properties are acceptable.     

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.     

Molecular structure of extracellular poly(3-hydroxybutyrate) depolymerase fromAlcaligenes faecalis T1

The amino acid sequence of a peptide containing an active serine was examined with poly(3-hydroxybutyrate) (PHB) depolymerase ofAlcaligenes faecalis T1. The sequence Cys-Asn-Ala-Trp-Ala-Gly-Ser-Asn-Ala-Gly-Lys was obtained. This amino acid sequence around the active serine does not fit any reported sequence of other esterases and proteases. On the other hand, a segment of the amino acid sequence of PHB depolymerase ofA. faecalis was homologous to the type III sequence of fibronectin. Similar sequences have been reported in some type of bacterial chitinase and cellulases, and PHB depolymerase seems to have an overall similarity to these bacterial extracellular hydrolases.     

Solvent-Free Polymerization of l-Aspartic Acid in the Presence of d-Sorbitol to Obtain Water Soluble or Network Copolymers

l-Aspartic acid was thermally polymerized in the presence of d-sorbitol with the goal of synthesizing new, higher molecular weight water soluble and absorbent copolymers. No reaction occurred when aspartic acid alone was heated at 170 or 200 °C. In contrast, heating sorbitol and aspartic acid neat or with ammonium hydroxide gave a mixture of water soluble and insoluble copolymers of polysuccinimide and sorbitol. In the presence of phosphoric acid, sorbitol aspartate ester copolymers having both water soluble and highly swollen gel components were formed. These results indicate that polysaccharides such as sorbitol can readily react to form copolymer ester/amides with aspartic acid and such copolymers may have utility as biodegradable water soluble and swellable polyampholytes.     

Biodegradation of thermally synthesized polyaspartate

Polyaspartate synthesized using thermal methods (thermal polyaspartate; TPA) has been shown to have dispersant and crystallization inhibition activities. These activities suggest that the polymer may be used in water treatment and paper processing and as a detergent and paint additive. The commercial potential for TPA is enhanced by the fact that it may be synthesized on a large scale. Therefore, a study of the biodegradation of the polymer was undertaken. TPA was produced by hydrolysis of a polysuccinimide synthesized by dry thermal polymerization of aspartic acid. The resulting polymer was a poly(,-dl-aspartate) having a 70% structure and containing a racemic mixture of aspartic acid. TPA was incubated with both dilute effluent and activated sludge from a wastewater treatment plant. Low-biomass effluent experiments showed changes in molecular size of TPA concomitant with oxygen demand induced by the polymer, suggesting susceptibility of TPA to at least partial biodegradation. Low-biomass sludge experiments (SCAS, modified Sturm) yielded approximately 70% mineralization of 20 mg L^–1 TPA by 28 days, suggesting that a significant portion of the polymer was labile. High-biomass sludge experiments using¹⁴C-TPA at 1 mg L^–1 revealed approximately 30% mineralization and 95% total removal of TPA carbon from solution in 23 days, with most of the mineralization and removal taking place in less than 5 days. Additional short-term studies using a variety of particulate substrates, including activated sludge, confirmed that TPA is subject to removal from solution by adsorption. From these studies with labeled TPA, it was concluded that TPA is subject to rapid removal and at least partial degradation in a wastewaster treatment plant. Using gel and thin-layer chromatography, it was determined that at least part of the unmineralized residue from the high biomass assays was polyaspartate. It is speculated that the unusual structure of TPA compared to natural proteins may limit the rate of proteolysis of the polymer and thus its overall degradation rate.     

Comparative Biodegradation in Soil Behaviour of two Biodegradable Polymers Based on Renewable Resources

This work presents the last phase of long-term experimental studies on the biodegradation in soil behaviour of polymers destined for agricultural applications. The paper focuses on comparative studies between the biodegradation in soil behaviour of two important biodegradable polymers based on renewable resources: poly(lactic acid) (PLA) versus polyhydroxyalkanoates (PHA). Full-scale experiments were carried out during the period June 2008–January 2009. Different methods of exposure were applied in the case of polyhydroxyalkanoates, simulating the agricultural biodegradable mulching films use and their fate in soil after the end of their useful lifetime. The field results were compared with the results of biodegradation under controlled laboratory conditions simulating biodegradation in soil, using soil from the experimental field. Further, the field results were compared against the results of biodegradation under farm composting conditions.     

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.     

Natural and Artificial Functionalized Biopolyesters I. Chemoenzymatic Mediated Synthesis of Chiral Precursors

Design of optically active polymeric materials for temporary therapeutic and environmental applications requires the working-out of functionalized polymers with structures and properties adjusted to the considered applications. Biocompatibility of selected polymers is a required property in regard to the interactions between living organisms and macromolecular systems. It is therefore important to prepare highly optically active monomers and their corresponding hydrolyzable and biocompatible polymers. Bacterium Clostridium tetanomorphum is an useful source of enzymes for bioconversion and particularly in the chemoenzyrnatic route to optically active alkylmalolactonic acid esters and their optically pure stereoisomers. 3-Methylaspartase, involved in the glutamate fermentation pathway, is a very interesting enzyme, which can provide chiral precursors with high optically purity. This chemoenzymatic strategy can be used to prepare the four stereoisomers of 3-methylmalolaconic acid esters, by enzymatic resolution of natural and artificial stereoisomers of 3-methylaspartic acid. A series of 3-alkymalolactonic acid esters with alkyl equal to ethyl or isopropyl, have been also synthesized and transformed into corresponding optically active polyesters.     

Molding Method, Thermal and Mechanical Properties of Jute/PLA Injection Molding

Natural composites have been important materials system due to preservation of earth environments. Natural fibers such as jute, hemp, bagasse and so on are very good candidate of natural composites as reinforcements. On the other hand regarding matrix parts thermosetting polymer and thermoplastic polymer deriver form petrochemical products are not environmental friendly material, even if thermoplastic polymer can be recycled. In order to create fully environmental friendly material (FEFM) biodegradable polymer which can be deriver from natural resources is needed. Therefore poly(lactic acid) (PLA) polymer is very good material for the FEFM. In this paper jute fiber filled PLA resin (jute/PLA) composites was fabricated by injection moldings and mechanical properties were measured. It is believable that industries will have much attention to FEFM, so that injection molding was adopted to fabricate the composites. Long fiber pellet fabricated by pultrusion technique was adopted to prepare jute/PLA pellet. Because it is able to fabricate composite pellets with relative long length fibers for injection molding process, where, jute yarns were continuously pulled and coated with PLA resin. Here two kinds of PLA materials were used including the one with mold releasing agent and the other without it. After pass through a heated die whereby PLA resin impregnates into the jute yarns and sufficient cooling, the impregnated jute yarns were cut into pellets. Then jute/PLA pellets were fed into injection machine to make dumbbell shape specimens. In current study, the effects of temperature of PLA melting temperature i.e. impregnation temperature and the kinds of PLA were focused to get optimum molding condition. The volume fractions of jute fiber in pellet were measured by several measuring method including image analyzing, density measurement and dissolution methods. Additionally, thermal and mechanical properties were investigated. It is found that 250° is much suitable for jute/PLA long fiber pultrusion process because of its less heat degradation of jute, better impregnation, acceptable mechanical property and higher production efficiency. Additionally the jute fibers seem much effective to increase deflection temperature under load, tensile modulus and Izod strength.     

Organic–Inorganic Hybrid Coatings for the Modification of Barrier Properties of Poly(lactic acid) Films for Food Packaging Applications

Organic–inorganic hybrid coatings based on poly(ε-caprolactone), poly(ethylene oxide) or poly(lactic acid) as organic phase and silica from tetraethoxysilane as inorganic phase were prepared by the sol–gel approach. Coatings were applied onto poly(lactic acid) films for food packaging in order to improve its barrier properties towards oxygen and water vapour. All the prepared coatings were dense, homogeneous layers characterized by a good adhesion to the substrate. The permeance of the coating layers resulted one order of magnitude lower than that of the uncoated poly(lactic acid) (PLA) film. The hydrophilic character of the coating did not permit to gain a significant decrease in the water vapour permeance. The perfect visual transparency of the coatings allows their application without worsening of the esthetical properties of the substrate PLA film.     

Starch-plastic materials—Preparation,physical properties,and biodegradability (a review of recent USDA research)

Recent starch-plastic research at the National Center for Agricultural Utilization Research is reviewed and related worldwide efforts are noted. Properties of starch that influence its formulation and performance in plastics are discussed. Methods are given for preparation of starch-poly(methyl acrylate) graft copolymer, starch-poly(ethylene-co-acrylic acid), and starch-poly(ethylene-co-acrylic acid)-polyethylene plastics. Their physical properties are discussed, as is degradability by enzymes or amylolytic organisms from soil, ponds, and streams.The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

Synthesis and Characterization of Lactic Acid Oligomers: Evaluation of Performance as Poly(Lactic Acid) Plasticizers

The use of fully bio-based and biodegradable materials for massive applications, such as food packaging, is an emerging tendency in polymer research. But the formulations proposed in this way should preserve or even increase the functional properties of conventional polymers, such as transparency, homogeneity, mechanical properties and low migration of their components to foodstuff. This is not always trivial, in particular when brittle biopolymers, such as poly(lactic acid) (PLA), are considered. In this work the formulation of innovative materials based on PLA modified with highly compatible plasticizers, i.e. oligomers of lactic acid (OLAs) is proposed. Three different synthesis conditions for OLAs were tested and the resulting additives were further blended with commercial PLA obtaining transparent and ductile materials, able for films manufacturing. These materials were tested in their structural, thermal and tensile properties and the best formulation among the three materials was selected. OLA with molar mass (M_n) around 1,000 Da is proposed as an innovative and fully compatible and biodegradable plasticizer for PLA, able to replace conventional plasticizers (phthalates, adipates or citrates) currently used for films manufacturing in food packaging applications.     

Novel Fabrication of PAA/PVA/Yeast Superabsorbent with Interpenetrating Polymer Network for pH-Dependent Selective Adsorption of Dyes

Traditional superabsorbent polymers have wide application potential as an adsorbent, but the poor physical and mechanical properties limit their further applications. To tentatively overcome this dilemma, a novel poly(acrylic acid)/poly(vinyl alcohol)/yeast superabsorbent polymers (PAA/PVA/yeast SAPs) with interpenetrating polymer networks (IPNs) were fabricated herein via solution polymerization. The mechanical stability tests showed that the resulting products could desirably resist the destruction of shear flow (<5000 rpm) and load pressure (<3 kg). The effects of yeast content, pH, contact time, initial dye concentration and temperature were systematically studied to evaluate their adsorption properties. Consecutive five cycles of adsorption–desorption indicated that their easy regeneration and reusability. More importantly, the PVA/PAA/yeast SAPs displayed brilliant pH-dependent selective adsorption for dyes in dye mixtures. It is believed hereby that the PAA/PVA/yeast SAPs can be expected to be economically and technically feasible for the scalable treatment of dyes wastewater.     

Poly(vinyl alcohol-co-lactic acid)/Hydroxyapatite Composites: Synthesis and Characterization

There is a wide range of applications where calcium phosphate and hydroxyapatite (HA) are used as biomaterials, e.g. as synthetic bone grafts, coating on metal prostheses (like hip endoprostheses or dental implants) and drug carriers. In the study, the design and synthesis of composites based on poly(vinyl alcohol-co-lactic acid)/hydroxyapatite (PVA-co-LA/HA) with potential for biomedical applications, they are presented. The hydroxyapatite particles were surface-grafted with l(+)-lactic acid in the presence of manganese acetate as catalyst, resulting in modified hydroxyapatite (HA_m) with improved capacity of bonding, respectively for the preparation of the composite based on PVA-co-LA/HA_m. FT-IR spectra further confirmed the existence of PLA polymer on the surface of HA particles. In synthesis of PVA-co-LA copolymer the different molar ratios PVA/LA (2/1, 1/1, 1/2), toluene/water: 1/2 (as azeotrope solvent mixture) and manganese acetate as catalyst, were used. The composite materials were synthesized in situ with 10 wt% HA, and respectively HA_m (reported to PVA and lactic acid components). The composite materials were characterized by FTIR spectroscopy, thermal analyses (DSC, DTG), ¹H-NMR spectroscopy, particle size distribution and zeta potential.     

Biodegradable Polymers- A Review on Recent Trends and Emerging Perspectives

Recent trends in biodegradable polymers indicate significant developments in terms of novel design strategies and engineering to provide advanced polymers with comparably good performance. However, there are several inadequacies in terms of either technology or cost of production especially in the case of applications in environmental pollution. So, there is a need to have a fresh perspective on the design, properties and functions of these polymers with a view to developing strategies for future developments. The paper reviews the present state-of-art on biodegradable polymers and discusses the salient features of the design and properties of biodegradable polymers. Special emphasis is given to the problems and prospects of (1) approaches adopted to make non-biodegradable synthetic polymers such as polyethylene biodegradable and (2) biodegradable polymers and copolymers made from renewable resources especially poly(lactic acid) based polymers and copolymers which are emerging as the candidate biodegradable materials for the future.     

Enhanced production of poly(3-hydroxybutyrate) by filamentation-suppressed recombinantEscherichia coli in a defined medium

Fed-batch cultures of recombinantEscherichia coli strains were carried out for the production of poly(3-hydroxybutyric acid) (PHB) in a chemically defined medium. TheE. coli strains used were XL1-Blue, harboring pSYL105, a stable high-copy number plasmid containing theAlcaligenes eutrophus polyhydroxyalkanoate (PHA) genes, and XL1-Blue, harboring pSYL107, which is pSYL105 containing theE. coli ftsZ gene to suppress filamentation. With XL1-Blue(pSYL105) the final cell mass and PHB concentration obtained in 62 h were 102 and 22.5 g/L, respectively. Fed-batch culture of XL1-Blue(pSYL107) under identical conditions resulted in a final cell mass and PHB concentration of 127.5 and 48.2 g/L, respectively. The PHB contents obtained with XL1-Blue(pSYL105) and XL1-Blue(pSYL107) were 22.1 and 37.8%, respectively. Therefore, PHB was more efficiently produced in a defined medium by employing filamentation-suppressed recombinantE. coli.     

The biodegradation of lactic acid-based poly(ester-urethanes)

The biodegradability of lactic acid based poly(ester-urethanes) was studied using the headspace test method, which was performed at several elevated temperatures. The poly(ester-urethanes) were prepared using a straight two-step lactic acid polymerization process. The lactic acid is first condensation polymerized to a low molecular weight hydroxyl-terminated telechelic prepolymer and then the molecular weight is increased with a chain extender such as diisocyanate. In the biodegradation studies the effect of different stereostructures (different amounts of D-units in the polymer chain), the length of ester units, and the effect of crosslinking on the biodegradation rate were studied. The results indicate that poly(ester-urethanes) do not biodegrade at 25‡C, but at elevated temperatures they biodegrade well. The different stereostructures and crosslinking have a strong influence on the biodegradation rate. The length of ester units in the polymer chain also affects the biodegradation rate, but much less than crosslinking and stereostructure.