The production of poly(3-hydroxybutyrate) [P(3HB)] from untreated raw palm oil mill effluent (urPOME), the first wastewater discharge from crude palm oil extraction, is discussed. The mutant strain Azotobacter vinelandii ΔAvin_16040, which lacks the S-layer protein but has a better P(3HB) synthesis capability than the wild type strain ATCC 12,837, was chosen for this study. UrPOME substrate, with high biological oxygen demand (BOD), chemical oxygen demand (COD) and suspended solids, was used without pre-treatment. DSMZ-Azotobacter medium which was devoid of laboratory sugar(s) was used as the basal medium (BaM). Initially, Azotobacter vinelandii ΔAvin_16040 generated 325.5, 1496.3, and 1465.7 mg L-1 of P(3HB) from BaM with 20% urPOME, 2BaM with 20% urPOME and 20 g L-1 sucrose, and 2BaM with 20% urPOME and 2 mL L-1 glycerol, respectively. P(3HB) generation was enhanced by nearly tenfold using statistical optimization, resulting in 13.9 g L-1. Moreover, the optimization reduced the compositions of mineral salts and sugar in the medium by 48 and 97%, respectively. The urPOME-based P(3HB) product developed a yellow coloration most possibly attributed to the aromatic phenolics content in urPOME. Despite the fact that both were synthesised by ΔAvin_16040, thin films of urPOME-based P(3HB) had superior crystallinity and tensile strength than P(3HB) produced only on sucrose. When treated with 10 and 50 kGy of electron beam irradiation, these P(3HB) scissioned to half and one-tenth of their original molecular weights, respectively, and these cleavaged products could serve as useful base units for specific polymer structure construction.
Interests in the use of biodegradable polymers as biomaterials have grown. Among the different polymeric composites currently available, the blend of starch and polycaprolactone (PCL) has received the most attention since the 1980s. Novamont is the first company that manufactured a PCL/starch (SPCL) composite under the trademark Mater-Bi®. The properties of PCL (a synthetic, hydrophobic, flexible, expensive polymer with a low degradation rate) and starch (a natural, hydrophilic, stiff, abundant polymer with a high degradation rate) blends are interesting because of the composite components have completely different structures and characteristics. PCL can adjust humidity sensitivity of starch as a biomaterial; while starch can enhance the low biodegradation rate of PCL. Thus, by appropriate blending, SPCL can overcome important limitations of both PCL and starch components and promote controllable behavior in terms of mechanical properties and degradation which make it suitable for many biomedical applications. This article reviewed the different fabrication and modification methods of the SPCL composite; different properties such as structural, physical, and chemical as well as degradation behavior; and different applications as biomaterials.
Poly (lactic) acid (PLA) composites have made their way into various applications that may require thermoforming to produce 3D shapes. Wrinkles are common in many forming processes and identification of the forming parameters to prevent them in the useful part of the mechanical component is a key consideration. Better prediction of such defects helps to significantly reduce the time required for a tooling design process. The purpose of the experiment discussed here is to investigate the effects of different test parameters on the occurrence of deformations during sheet forming of double curvature shapes with bamboo fabric reinforced-PLA composites. The results demonstrated that the domes formed using hot tooling conditions were better in quality than those formed using cold tooling conditions. Wrinkles were more profound in the warp direction of the composite domes compared to the weft direction. Grid Strain Analysis (GSA) identifies the regions of severe deformation and provides useful information regarding the optimisation of processing parameters.
Nucleic acid segregation and compartmentalization were likely essential functions that primitive compartment systems resolved during evolution. Recently, polyester microdroplets generated from dehydration synthesis of various α-hydroxy acids (αHA) were suggested as potential primitive compartments. Some of these droplets can differentially segregate and compartmentalize organic dyes, proteins, and nucleic acids. However, the previously studied polyester microdroplets included limited αHA chemical diversity, which may not reflect the chemical diversity available in the primitive Earth environment. Here, we increased the chemical diversity of polyester microdroplet systems by combinatorially adding an αHA monomer with a basic side chain, 4-amino-2-hydroxybutyric acid (4a2h), which was incorporated with different ratios of other αHAs containing uncharged side chains to form combinatorial heteropolyesters via dehydration synthesis. Incorporation of 4a2h in the polymers resulted in the assembly of some polyester microdroplets able to segregate fluorescent RNA or potentially acquire intrinsic fluorescent character, suggesting that minor modifications of polyester composition can significantly impact the functional properties of primitive compartments. This study suggests one process by which primitive chemical systems can increase diversity of compartment "phenotype" through simple modifications in their chemical composition.
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-4-hydroxybutyrate) [P(3HB-co-3HV-co-4HB)] terpolymer was produced using Cupriavidus sp. USMAA2-4 via one-step cultivation process through combination of various carbon sources such as 1,4-butanediol or γ-butyrolactone with either 1-pentanol, valeric acid, or 1-propanol. Oleic acid was added to increase the biomass production. The composition of 3HV and 4HB monomers were greatly affected by the concentration of 1,4-butanediol and 1-pentanol. Terpolymers with 3HV and 4HB molar fractions ranging from 2 to 41 mol.% and 5 to 31 mol.%, respectively, were produced by varying the concentration of carbon precursors. The thermal and mechanical properties of the terpolymers containing different proportions of the constituent monomers were characterized using gel permeation chromatography (GPC), DSC, and tensile machine. GPC analysis showed that the molecular weights (M (w)) of the terpolymer produced were within the range of 346 to 1,710 kDa. The monomer compositions of 3HV and 4HB were also found to have great influences on the thermal and mechanical properties of the terpolymer P(3HB-co-3HV-co-4HB) produced.
Global awareness of material sustainability has increased the demand for bio-based polymers like poly(lactic acid) (PLA), which are seen as a desirable alternative to fossil-based polymers because they have less environmental impact. PLA is an aliphatic polyester, primarily produced by industrial polycondensation of lactic acid and/or ring-opening polymerization of lactide. Melt processing is the main technique used for mass production of PLA products for the medical, textile, plasticulture, and packaging industries. To fulfill additional desirable product properties and extend product use, PLA has been blended with other resins or compounded with different fillers such as fibers, and micro- and nanoparticles. This paper presents a review of the current status of PLA mass production, processing techniques and current applications, and also covers the methods to tailor PLA properties, the main PLA degradation reactions, PLA products' end-of-life scenarios and the environmental footprint of this unique polymer.
Tissue-engineered substitutes have shown great promise as a potential replacement for current tissue grafts to treat tendon/ligament injury. Herein, we have fabricated aligned polycaprolactone (PCL) and gelatin (GT) nanofibers and further evaluated their physicochemical properties and biocompatibility. PCL and GT were mixed at a ratio of 100:0, 70:30, 50:50, 30:70, 0:100, and electrospun to generate aligned nanofibers. The PCL/GT nanofibers were assessed to determine the diameter, alignment, water contact angle, degradation, and surface chemical analysis. The effects on cells were evaluated through Wharton's jelly-derived mesenchymal stem cell (WJ-MSC) viability, alignment and tenogenic differentiation. The PCL/GT nanofibers were aligned and had a mean fiber diameter within 200-800 nm. Increasing the GT concentration reduced the water contact angle of the nanofibers. GT nanofibers alone degraded fastest, observed only within 2 days. Chemical composition analysis confirmed the presence of PCL and GT in the nanofibers. The WJ-MSCs were aligned and remained viable after 7 days with the PCL/GT nanofibers. Additionally, the PCL/GT nanofibers supported tenogenic differentiation of WJ-MSCs. The fabricated PCL/GT nanofibers have a diameter that closely resembles the native tissue's collagen fibrils and have good biocompatibility. Thus, our study demonstrated the suitability of PCL/GT nanofibers for tendon/ligament tissue engineering applications.
Two-stage fermentation was normally employed to achieve a high poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] productivity with higher 4HB molar fraction. Here, we demonstrated single-stage fermentation method which is more industrial feasible by implementing mixed-substrate cultivation strategy. Studies on bioreactor scale show a remarkably high PHA accumulation of 73 wt%, contributing to a high PHA concentration and product yield of 8.6 g/L and 2.7 g/g, respectively. This fermentation strategy has resulted in copolymers with wider range of 4HB monomer composition, which ranges from 12 to 55 mol%. These copolymers show a broad range of weight average molecular weight (M w ) from 119.5 to 407.0 kDa. The copolymer characteristics were found to be predominantly affected by the nature of the substrates and the mixture strategies, regardless of the 4HB monomer compositions. This was supported by the determination of copolymer randomness using (13)C-NMR analysis. The study warrants significantly in the copolymer scale-up and modeling at industrial level.
Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [(P(3HB-co-4HB)] copolymer receives attention as next generation biomaterial in medical application. However, the exploitation of the copolymer is still constrained since such copolymer has not yet successfully been performed in industrial scale production. In this work, we intended to establish pilot production system of the copolymer retaining the copolymer quality which has recently discovered to have novel characteristic from lab scale fermentation. An increase of agitation speed has significantly improved the copolymer accumulation efficiency by minimizing the utilization of substrates towards cell growth components. This is evidenced by a drastic increase of PHA content from 28 wt% to 63 wt% and PHA concentration from 3.1 g/L to 6.5 g/L but accompanied by the reduction of residual biomass from 8.0 g/L to 3.8 g/L. Besides, fermentations at lower agitation and aeration have resulted in reduced molecular weight and mechanical strength of the copolymer, suggesting the role of sufficient oxygen supply efficiency in improving the properties of the resulting copolymers. The KLa-based scale-up fermentation was performed successfully in maintaining the yield and the quality of the copolymers produced without a drastic fluctuation. This suggests that the scale-up based on the KLa values supported the fermentation system of P(3HB-co-4HB) copolymer production in single-stage using mixed-substrate cultivation strategy.
The present study addressed the synthesis of a bi-layered nanostructured fluorine-doped hydroxyapatite (nFHA)/polycaprolactone (PCL) coating on Mg-2Zn-3Ce alloy via a combination of electrodeposition (ED) and dip-coating methods. The nFHA/PCL composite coating is composed of a thick (70-80 μm) and porous layer of PCL that uniformly covered the thin nFHA film (8-10 μm) with nanoneedle-like microstructure and crystallite size of around 70-90 nm. Electrochemical measurements showed that the nFHA/PCL composite coating presented a high corrosion resistance (R(p)=2.9×10(3) kΩ cm(2)) and provided sufficient protection for a Mg substrate against galvanic corrosion. The mechanical integrity of the nFHA/PCL composite coatings immersed in SBF for 10 days showed higher compressive strength (34% higher) compared with the uncoated samples, indicating that composite coatings can delay the loss of compressive strength of the Mg alloy. The nFHA/PCL coating indicted better bonding strength (6.9 MPa) compared to PCL coating (2.2 MPa). Immersion tests showed that nFHA/PCL composite-coated alloy experienced much milder corrosion attack and more nucleation sites for apatite compared with the PCL coated and uncoated samples. The bi-layered nFHA/PCL coating can be a good alternative method for the control of corrosion degradation of biodegradable Mg alloy for implant applications.
A new class of biocomposites based on oil palm empty fruit bunch fiber and poly(butylene adipate-co-terephthalate) (PBAT), which is a biodegradable aliphatic aromatic co-polyester, were prepared using melt blending technique. The composites were prepared at various fiber contents of 10, 20, 30, 40 and 50 wt% and characterized. Chemical treatment of oil palm empty fruit bunch (EFB) fiber was successfully done by grafting succinic anhydride (SAH) onto the EFB fiber surface, and the modified fibers were obtained in two levels of grafting (low and high weight percentage gain, WPG) after 5 and 6 h of grafting. The FTIR characterization showed evidence of successful fiber esterification. The results showed that 40 wt% of fiber loading improved the tensile properties of the biocomposite. The effects of EFB fiber chemical treatments and various organic initiators content on mechanical and thermal properties and water absorption of PBAT/EFB 60/40 wt% biocomposites were also examined. The SAH-g-EFB fiber at low WPG in presence of 1 wt% of dicumyl peroxide (DCP) initiator was found to significantly enhance the tensile and flexural properties as well as water resistance of biocomposite (up to 24%) compared with those of untreated fiber reinforced composites. The thermal behavior of the composites was evaluated from thermogravimetric analysis (TGA)/differential thermogravimetric (DTG) thermograms. It was observed that, the chemical treatment has marginally improved the biocomposites' thermal stability in presence of 1 wt% of dicumyl peroxide at the low WPG level of grafting. The improved fiber-matrix surface enhancement in the chemically treated biocomposite was confirmed by SEM analysis of the tensile fractured specimens.
Poly(3-hydroxybutyrate-co-38 mol%-3-hydroxyvalerate) [P(3HB-co-38mol%-3HV)] was produced by Cupriavidus sp. USMAA2-4 in the presence of oleic acid and 1-pentanol. Due to enormous production of empty fruit bunch (EFB) in the oil palm plantation and high production cost of P(3HB-co-3HV), oil palm EFB fibers were used for biocomposites preparation. In this study, maleic anhydride (MA) and benzoyl peroxide (DBPO) were used to improve the miscibility between P(3HB-co-3HV) and EFB fibers. Introduction of MA into P(3HB-co-3HV) backbone reduced the molecular weight and improved the thermal stability of P(3HB-co-3HV). Thermal stability of P(3HB-co-3HV)/EFB composites was shown to be comparable to that of commercial packaging product. Composites with 35% EFB fibers content have the highest tensile strength compared to 30% and 40%. P(3HB-co-3HV)/EFB blends showed less chemicals leached compared to commercial packaging.
The development and characterization of environmentally friendly bilayer films from sugar palm starch (SPS) and poly(lactic acid) (PLA) were conducted in this study. The SPS-PLA bilayer films and their individual components were characterized for their physical, mechanical, thermal and water barrier properties. Addition of 50% PLA layer onto 50% SPS layer (SPS50-PLA50) increased the tensile strength of neat SPS film from 7.74 to 13.65MPa but reduced their elongation at break from 46.66 to 15.53%. The incorporation of PLA layer significantly reduced the water vapor permeability as well as the water uptake and solubility of bilayer films which was attributed to the hydrophobic characteristic of the PLA layer. Furthermore, scanning electron microscopy (SEM) image of SPS50-PLA50 revealed lack of strong interfacial adhesion between the SPS and PLA. Overall, the incorporation of PLA layer onto SPS films enhances the suitability of SPS based films for food packaging.
catena-Poly[dicyclohexylammonium [tributyltin-mu-(4-oxo-4H-pyran-2,6-dicarboxylato-O(2):O( 6))]], (C(12)H(24)N)[Sn(C(7)H(2)O(6))(C(4)H(9))(3)], consists of 4-oxo-4H-pyran-2,6-dicarboxylato groups that axially link adjacent tributyltin units into a linear polyanionic chain. The ammonium counter-ions surround the chain, and each cation forms a pair of hydrogen bonds to the double-bond carbonyl O atoms of the same dianionic group. The chain propagates in a zigzag manner along the c axis of the monoclinic cell. In catena-poly[methyl(phenyl)ammonium [tributyltin-mu-(pyridine-2,6-dicarboxylato-O(2):O(6))]], (C(7)H(10)N)[Sn(C(7)H(3)NO(4))(C(4)H(9))(3)], the pyridine-2, 6-dicarboxylato groups also link the tributyltin groups into a chain, but the hydrogen-bonded chain propagates linearly on the ac face of the monoclinic cell.
The utilization of nanocellulose has increasingly gained attentions from various research fields, especially the field of polymer nanocomposites owing to the growing environmental hazardous of petroleum based fiber products. Meanwhile, the searching of alternative cellulose sources from different plants has become the interests for producing nanocellulose with varying characterizations that expectedly suit in specific field of applications. In this content the long and strong bast fibers from plant species was gradually getting its remarkable position in the field of nanocellulose extraction and nanocomposites fabrications. This review article intended to present an overview of the chemical structure of cellulose, different types of nanocellulose, bast fibers compositions, structure, polylactic acid (PLA) and the most probable processing techniques on the developments of nanocellulose from different bast fibers especially jute, kenaf, hemp, flax, ramie and roselle and its nanocomposites. This article however more focused on the fabrication of PLA based nanocomposites due to its high firmness, biodegradability and sustainability properties in developed products towards the environment. Along with this it also explored a couple of issues to improve the processing techniques of bast fibers nanocellulose and its reinforcement in the PLA biopolymer as final products.
A packaging material that is environment-friendly with excellent mechanical and physicochemical properties, biodegradable and ultraviolet (UV) protection and thermal stability was prepared to reduce plastic waste. Six different concentrations of Pennisetum purpureum/Napier cellulose nanowhiskers (NWCs) (i.e. 0, 0.5, 1.0, 1.5, 2.0, and 3.0 wt%) were used to reinforce polylactic acid (PLA) by a solvent casting method. The resulting bionanocomposite film samples were characterised in terms of their morphology, chemical structure, crystallinity, thermal degradation and stability, light transmittance, water absorption, biodegradability, and physical and mechanical properties. Field-emission scanning electron microscopy showed the excellent dispersion of NWC in the PLA matrix occurred with NWC concentrations of 0.5-1.5 wt%. All the bionanocomposite film samples exhibited good thermal stability at approximately 343-359 °C. The highest water absorption was 1.94%. The lowest transparency at λ800 was 16.16% for the PLA/3.0% NWC bionanocomposite film, which also has the lowest UVA and UVB transmittance of 7.49% and 4.02%, respectively, making it suitable for packaging materials. The PLA/1.0% NWC film exhibited the highest crystallinity of 50.09% and high tensile strength and tensile modulus of 21.22 MPa and 11.35 MPa, respectively.
Poly(lactic acid) (PLA), a bio-based polyester, has been extensively investigated in the recent past owing to its excellent mechanical properties. Several studies have been conducted on PLA blends, with a focus on improving the brittleness of PLA to ensure its suitability for various applications. However, the increasing use of PLA has increased the contamination of PLA-based products in the environment because PLA remains intact even after three years at sea or in soil. This review focuses on analyzing studies that have worked on improving the degradation properties of PLA blends and studies how other additives affect degradation by considering different degradation media. Factors affecting the degradation properties, such as surface morphology, water uptake, and crystallinity of PLA blends, are highlighted. In natural, biotic, and abiotic media, water uptake plays a crucial role in determining biodegradation rates. Immiscible blends of PLA with other polymer matrices cause phase separation, increasing the water absorption. The susceptibility of PLA to hydrolytic and enzymatic degradation is high in the amorphous region because it can be easily penetrated by water. It is essential to study the morphology, water absorption, and structural properties of PLA blends to predict the biodegradation properties of PLA in the blends.
The current research discusses the development of poly (lactic acid) (PLA) and poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) reinforced nanocrystalline cellulose bionanocomposites. The nanocrystalline cellulose was derived from waste oil palm empty fruit bunch fiber by acid hydrolysis process. The resulting nanocrystalline cellulose suspension was then surface functionalized by TEMPO-mediated oxidation and solvent exchange process. Furthermore, the PLA/PHBV/nanocrystalline cellulose bionanocomposites were produced by solvent casting method. The effect of the addition of nanocrystalline cellulose on structural, morphology, mechanical and barrier properties of bionanocomposites was investigated. The results revealed that the developed bionanocomposites showed improved mechanical properties and decrease in oxygen permeability rate. Therefore, the developed bio-based composite incorporated with an optimal composition of nanocrystalline cellulose exhibits properties as compared to the polymer blend.
Polyhydroxyalkanoate (PHA) is a type of biopolymer produced by most bacteria and archaea, resembling thermoplastic with biodegradability and biocompatibility features. Here, we report the complete genome of a PHA producer, Aquitalea sp. USM4, isolated from Perak, Malaysia. This bacterium possessed a 4.2 Mb circular chromosome and a 54,370 bp plasmid. A total of 4067 predicted protein-coding sequences, 87 tRNA genes, and 25 rRNA operons were identified using PGAP. Based on ANI and dDDH analysis, the Aquitalea sp. USM4 is highly similar to Aquitalea pelogenes. We also identified genes, including acetyl-CoA (phaA), acetoacetyl-CoA (phaB), PHA synthase (phaC), enoyl-CoA hydratase (phaJ), and phasin (phaP), which play an important role in PHA production in Aquitalea sp. USM4. The heterologous expression of phaC1 from Aquitalea sp. USM4 in Cupriavidus necator PHB-4 was able to incorporate six different types of PHA monomers, which are 3-hydroxybutyrate (3HB), 3-hydroxyvalerate (3HV), 4-hydroxybutyrate (4HB), 5-hydroxyvalerate (5HV), 3-hydroxyhexanoate (3HHx) and isocaproic acid (3H4MV) with suitable precursor substrates. This is the first complete genome sequence of the genus Aquitalea among the 22 genome sequences from 4 Aquitalea species listed in the GOLD database, which provides an insight into its genome evolution and molecular machinery responsible for PHA biosynthesis.
Poly-3-hydroxybutyrate (P(3HB)), a member of the polyhydroxyalkanoate (PHA) family, is a biodegradable polyester with diverse industrial applications. NADPH-dependent acetoacetyl-CoA reductase (phaB) is the enzyme which plays an essential role in P(3HB) synthesis by catalyzing the conversion of the intermediates. The expression of phaB enzyme using the recombinant Escherichia coli BL-21(DE3) and the purification of the synthesized enzyme were studied. The pET-B3 plasmid harbouring the phaB gene derived from Ralstonia eutropha H16, was driven by the lac promoter in E. coli BL-21(DE3). The enzyme was expressed with different induction time, temperatures and cell age. Results showed that the cell age of 4 h, induction time of 12 h at 37°C were identified as the optimal conditions for the enzyme reductase expression. A specific activity of 0.151 U mg-1 protein and total protein concentration of 0.518 mg mg-1 of dry cell weight (DCW) were attained. Affinity chromatography was performed to purify the His-tagged phaB enzyme, in which enhanced the specific activity (14.44 U mg-1) and purification fold (38-fold), despite relative low yield (44.6%) of the enzyme was obtained. The purified phaB showed an optimal enzyme activity at 30°C and pH 8.0. The findings provide an alternative for the synthesis of the reductase enzyme which can be used in the industrial-scale production of the biodegradable polymers.