A comprehensive review on polylactic acid (PLA) - Synthesis, processing and application in food packaging.

Plastics play an essential role in food packaging; their primary function is to preserve the nature of the food, ensure adequate shelf life and ensure food safety. Plastics are being produced on a global scale in excess of 320 million tonnes annually, with demand rising to reflect the material in wide range of applications. Nowadays, the packaging industry is a significant consumer of synthetic plastic made from fossil fuels. Petrochemical-based plastics are regarded as the preferred material for packaging. Nonetheless, using these plastics in large quantities results in a long-standing environment. Environmental pollution and the depletion of fossil fuels have prompted researchers and manufacturers to develop eco-friendly biodegradable polymers to replace petrochemical-based polymers. As a result, the production of eco-friendly food packaging material has sparked increased interest as a viable alternative to petrochemical-based polymers. Polylactic acid (PLA) is one of the compostable thermoplastic biopolymers that is biodegradable and renewable in nature. High-molecular-weight PLA can be used to produce fibres, flexible, non-wovens, hard and durable materials (100,000 Da or even higher).The chapter focuses on food packaging techniques, food industry waste, biopolymers, their classification, PLA synthesis, the importance of PLA properties for food packaging, and technologies used to process PLA in food packaging.

Biological matrix composites from cultured plant cells.

We present an approach to fabricate biological matrix composites made entirely from cultured plant cells. We utilize the cell's innate ability to synthesize nanofibrillar cell walls, which serve as the composite's fundamental building blocks. Following a controlled compression/dehydration process, the cells arrange into lamellar structures with hierarchical features. We demonstrate that the native cell wall nanofibrils tether adjacent cells together through fibrillar interlocking and intermolecular hydrogen bonding. These interactions facilitate intercellular adhesion and eliminate the need for other binders. Our fabrication process utilizes the entire plant cell, grown in an in vitro culture; requires no harsh chemical treatments or waste-generating extraction or selection processes; and leads to bulk biocomposites that can be produced in situ and biodegrade in soil. The final mechanical properties are comparable to commodity plastics and can be further modulated by introducing filler particles.

Biodegradability, physical, mechanical and antimicrobial attributes of starch nanocomposites containing chitosan nanoparticles.

This study aimed to develop a plasticized starch (PS) based film loaded with chitosan nanoparticles (CNPs, 1, 2, 3, and 4%) as a reinforcing and antibacterial agent. We examined the morphology, biodegradability, mechanical, thermo-mechanical, and barrier properties of the PS/CNPs films. The antimicrobial activity against both Gram-positive (S. aureus) and Gram-negative (E. coli) bacteria was investigated by colony forming unit (CFU) and disc diffusion methods. A dense structure was obtained for all PS/CNPs films and, thus, their complete biodegradation occurred in more days than neat PS. The increase in the CNPs percentage led to improved mechanical behaviour and barrier properties. PS-CNPs composite films revealed inhibition zones against both E. coli and S. aureus, with the 100% reduction in CFU against S. aureus. The current study exhibited that PS-CNPs films were more effective in inhibiting bacteria growth than neat PS film, confirming the composite films potential application as antimicrobial food packaging.

Improved Synthesis of a Novel Biodegradable Tunable Micellar Polymer Based on Partially Hydrogenated Poly(ß-malic Acid-co-benzyl Malate).

Poly(benzyl malate) (PBM), together with its derivatives, have been studied as nanocarriers for biomedical applications due to their superior biocompatibility and biodegradability. The acquisition of PBM is primarily from chemical routes, which could offer polymer-controlled molecular weight and a unique controllable morphology. Nowadays, the frequently used synthesis from L-aspartic acid gives an overall yield of 4.5%. In this work, a novel synthesis route with malic acid as the initiator was successfully designed and optimized, increasing the reaction yield up to 31.2%. Furthermore, a crystalline form of PBM (PBM-2) that polymerized from high optical purity benzyl-ß-malolactonate (MLABn) was discovered during the optimization process. X-ray diffraction (XRD) patterns revealed that the crystalline PBM-2 had obvious diffraction peaks, demonstrating that its internal atoms were arranged in a more orderly manner and were different from the amorphous PBM-1 prepared from the racemic MLABn. The differential scanning calorimetry (DSC) curves and thermogravimetric curves elucidated the diverse thermal behaviors between PBM-1 and PBM-2. The degradation curves and scanning electron microscopy (SEM) images further demonstrated the biodegradability of PBM, which have different crystal structures. The hardness of PBM-2 implied the potential application in bone regeneration, while it resulted in the reduction of solubility when compared with PBM-1, which made it difficult to be dissolved and hydrogenated. The solution was therefore heated up to 75 °C to achieve benzyl deprotection, and a series of partially hydrogenated PBM was sequent prepared. Their optimal hydrogenation rates were screened to determine the optimal conditions for the formation of micelles suitable for drug-carrier applications. In summary, the synthesis route from malic acid facilitated the production of PBM for a shorter time and with a higher yield. The biodegradability, biosafety, mechanical properties, and adjustable hydrogenation widen the application of PBM with tunable properties as drug carriers.

Highly Efficient Modular Construction of Functional Drug Delivery Platform Based on Amphiphilic Biodegradable Polymers via Click Chemistry.

Amphiphilic copolymers with pendant functional groups in polyester segments are widely used in nanomedicine. These enriched functionalities are designed to form covalent conjugates with payloads or provide additional stabilization effects for encapsulated drugs. A general method is successfully developed for the efficient preparation of functional biodegradable PEG-polyester copolymers via click chemistry. Firstly, in the presence of mPEG as initiator, Sn(Oct)2-catalyzed ring-opening polymerization of the α-alkynyl functionalized lactone with D,L-lactide or ε-caprolactone afforded linear mPEG-polyesters bearing multiple pendant alkynyl groups. Kinetic studies indicated the formation of random copolymers. Through copper-catalyzed azide-alkyne cycloaddition reaction, various small azido molecules with different functionalities to polyester segments are efficiently grafted. The molecular weights, polydispersities and grafting efficiencies of azido molecules of these copolymers were investigated by NMR and GPC. Secondly, it is demonstrated that the resulting amphiphilic functional copolymers with low CMC values could self-assemble to form nanoparticles in aqueous media. In addition, the in vitro degradation study and cytotoxicity assays indicated the excellent biodegradability and low cytotoxicity of these copolymers. This work provides a general approach toward the preparation of functional PEG-polyester copolymers in a quite efficient way, which may further facilitate the application of functional PEG-polyesters as drug delivery materials.

Preparation of effective ultraviolet shielding poly (lactic acid)/poly (butylene adipate-co-terephthalate) degradable composite film using co-precipitation and hot-pressing method.

Biodegradable poly (lactide) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) composite films were made by a co-precipitation and hot-pressing method. The property of composite films like the chemical interaction, phase morphology, mechanical properties, and thermal properties were studied. The Fourier transform infrared spectroscopy (FTIR) test manifested that there was a small amount of the transesterifications between the PBAT and PLA during hot pressing, which could improve the compatibility of the two phases. The tensile strength of the film only reduced by 7.4%, while the elongation at break was increased by 119.1% compared with PLA after adding 4%wt PBAT. The composite films showed a high Ultraviolet-visible (UV) light barrier property. The UV blocking rate of the composite after adding 4%wt PBAT was 6.95 times higher than that of pure PLA at 380 nm. The PLA/PBAT composite films with excellent thermal stability, satisfactory mechanical properties and UV-light barrier have high a possibility for an UV screening packaging application.

Biodegradable Polymersomes with Structure Inherent Fluorescence and Targeting Capacity for Enhanced Photo-Dynamic Therapy.

Biodegradable nanostructures displaying aggregation-induced emission (AIE) are desirable from a biomedical point of view, due to the advantageous features of loading capacity, emission brightness, and fluorescence stability. Herein, biodegradable polymers comprising poly (ethylene glycol)-block-poly(caprolactone-gradient-trimethylene carbonate) (PEG-P(CLgTMC)), with tetraphenylethylene pyridinium-TMC (PAIE) side chains have been developed, which self-assembled into well-defined polymersomes. The resultant AIEgenic polymersomes are intrinsically fluorescent delivery vehicles. The presence of the pyridinium moiety endows the polymersomes with mitochondrial targeting ability, which improves the efficiency of co-encapsulated photosensitizers and improves therapeutic index against cancer cells both in vitro and in vivo. This contribution showcases the ability to engineer AIEgenic polymersomes with structure inherent fluorescence and targeting capacity for enhanced photodynamic therapy.

Polypseudorotaxane and polydopamine linkage-based hyaluronic acid hydrogel network with a single syringe injection for sustained drug delivery.

Polypseudorotaxane structure and polydopamine bond-based crosslinked hyaluronic acid (HA) hydrogels including donepezil-loaded microspheres were developed for subcutaneous injection. Both dopamine and polyethylene glycol (PEG) were covalently bonded to the HA polymer for catechol polymerization and inclusion complexation with alpha-cyclodextrin (α-CD), respectively. A PEG chain of HA-dopamine-PEG (HD-PEG) conjugate was threaded with α-CD to make a polypseudorotaxane structure and its pH was adjusted to 8.5 for dopamine polymerization. Poly(lactic-co-glycolic acid) (PLGA)/donepezil microsphere (PDM) was embedded into the HD-PEG network for its sustained release. The HD-PEG/α-CD/PDM 8.5 hydrogel system exhibited an immediate gelation pattern, injectability through single syringe, self-healing ability, and shear-thinning behavior. Donepezil was released from the HD-PEG/α-CD/PDM 8.5 hydrogel in a sustained pattern. Following subcutaneous injection, the weight of excised HD-PEG/α-CD/PDM 8.5 hydrogel was higher than the other groups on day 14. These findings support the clinical feasibility of the HD-PEG/α-CD/PDM 8.5 hydrogel for subcutaneous injection.

Alkenyl succinic anhydride modified tree-gum kondagogu: A bio-based material with potential for food packaging.

Tree gums are a class of abundantly available carbohydrate polymers that have not been explored thoroughly in film fabrication for food packaging. Films obtained from pristine tree gums are often brittle, hygroscopic, and lack mechanical strength. This study focuses on the chemical modification of gum kondagogu using long-chain alkenyl groups of dodecenyl succinic anhydride (DDSA), an esterifying agent that introduces a 12-carbon hydrophobic chain to the kondagogu structure. The esterification reaction was confirmed by 1H nuclear magnetic resonance and Fourier-transform infrared spectroscopy. The effect of nano-cellulose as an additive on various film properties was investigated. The developed films were characterized for their mechanical, morphological, optical, barrier, antibacterial, and biodegradable properties. The inclusion of long-chain carbon groups acted as internal plasticizers and resulted in an amorphous structure with better film-forming ability, improved hydrophobicity, and higher elongation at break values. The modified films exhibited antibacterial properties and excellent biodegradability under aerobic conditions.

Development and characterization of chitosan and acrylic acid-based novel biodegradable polymeric films for soil conditioning.

In this study, biodegradable polymeric films (BPFs) based on chitosan and acrylic acid cross-linked with 3-aminopropyl triethoxysilane (APTES) were developed for water retention and soil-conditioning applications in areas sufferings from water scarcity. A series of BPFs were prepared by varying the amount of silica nanoparticles (SiNPs) (0.67% to 2.6%) and a correlation of the optimum amount of SiNPs with thermal stability, morphology, swellability (at various pH), degradability, and anti-microbial activity were deduced. The obtained results showed that the NP 8 (containing 2.51% of SiNPs) exhibited the maximum absorption capacity (1815%) in distilled water, whereas NP6 (including 1.88% of SiNPs) expressed the maximum thermal stability (T50% at 375.61 °C). The microscopic images further strengthen this observation because the maximum number of micro-porous cavities was shown on the surface of NP8. The time-dependent swelling response in distilled water accomplished that hydrophilicity (percentage swelling) of films was enhanced with an increase in the concentration of SiNPs. All BPFs samples exhibited inhibitory response against both gram-positive (for Staphylococcus aureus was 2.9 cm for NP6) and gram-negative (for Escherichia coli was 0.9 cm for NP8) bacteria. The biodegradation test inferred that the degradation of BPFs in soil did not affect the soil fertility as nano-silica is proven as growth-promoting miniatures. It can be concluded that these BPFs may be efficiently employed in the agriculture sector for water retention and as a soil conditioner.

Dual cure (thermal/photo) composite hydrogel derived from chitosan/collagen for in situ 3D bioprinting.

In situ 3D printing technologies is a new frontier for highly personalized medicine, which requires suitable bioink with rheology, biocompatibility, and gelation kinetics to support the right shape and mechanical properties of the printed construct. To this end, a facile design of thermo/photo dual cure composite hydrogel was proposed using MHBC and soluble collagen in this study. M/C composite hydrogel exhibited rapid thermo-induced sol-gel transition and contraction, tunable mechanical properties, proper microstructure and biodegradability for 3D cell culture, as well as improve cyto-compatibility, all of which were dependent upon the methacrylation degree of MHBC and M/C ratios. The printability of the optimal formulation (3% MHBC/1% collagen) was validated by its mild printing condition, rapid gelation of bioink at 37 °C and simple postprocessing manipulation. Both desirable printability and cyto-compatibility enable M/C composite hydrogel a potential candidate as bioink to be applied for in situ 3D bioprinting.

Chitosan-poly(vinyl alcohol) intelligent films fortified with anthocyanins isolated from Clitoria ternatea and Carissa carandas for monitoring beverage freshness.

Biodegradable chitosan-poly(vinyl alcohol) films containing natural anthocyanin-rich extracts were prepared using solvent casting method and employed as intelligent indicators for monitoring beverages freshness. The surface and cross-sectional scanning electron micrograph indicated a compact structure for the intelligent films, whereas the atomic force micrograph indicated a 16.22 and 20.31 nm increase in surface roughness for Clitoria ternatea and Carissa carandas extract incorporated films, respectively. Moreover, the test films demonstrated enhanced radical scavenging efficacy. The extracts and anthocyanin incorporated films presented excellent colorimetric changes at pH 2 to 8. In addition, the C. ternatea test films showed changes in color for juice stored at 25 °C after 72 h. Photo-degradability results indicated stability of test films stored in dark at 4 °C and 25 °C, whereas leaching study indicated the release of ≤2.0% anthocyanin after 24 h. The cytocompatibilty assay showed that the test and control films were biocompatible with a viability of >80% on HaCat cells. The results demonstrated that the incorporation of anthocyanins-rich extracts into chitosan-poly(vinyl alcohol) did not significantly interfere with the films properties (p > 0.05). The natural anthocyanin incorporated films demonstrated good pH sensing property that could be further explored for monitoring of beverages freshness.

Additive Manufacturing Using Melt Extruded Thermoplastics for Tissue Engineering.

Melt extrusion of thermoplastic materials is an important technique for fabricating tissue engineering scaffolds by additive manufacturing methods. Scaffold manufacturing is commonly achieved by one of the following extrusion-based techniques: fused deposition modelling (FDM), 3D-fiber deposition (3DF), and bioextrusion. FDM needs the input material to be strictly in the form of a filament, whereas 3DF and bioextrusion can be used to process input material in several forms, such as pellets or powder. This chapter outlines a common workflow for all these methods, going from the material to a scaffold, while highlighting the special requirements of particular methods. A few ways of characterizing the scaffolds are also briefly described.

Properties of hydric and biodegradability of cassava starch-based bioplastics reinforced with thermally modified kaolin.

In this study, hydric and biodegradability properties of cassava starch-based bioplastics reinforced with crude kaolin or treated kaolinitic clay at 700 °C called metakaolin were investigated using water adsorption and microbiological tests. Non-reinforced bioplastics (BP) and those containing 5 wt.% crude kaolin (BPKB) or metakaolin (BPMKB) were manufactured using the casting/evaporation method. Results obtained showed a decrease in the solubility and in the water diffusion and permeability of clay-reinforced bioplastics with respect to the ones without reinforcement. This improvement of the hydric properties has been attributed to the reduction in the free volumes existing between the starch macromolecules due to their interactions with clay platelets. These interactions might favor a more homogeneous and compact microstructure. The biodegradability of the clay reinforced bioplastics was significantly improved due to the bacterial proliferation. The thermal treatment of kaolinitic clay further improved the hydric and biodegradability properties of starch-based bioplastics.

Use of a Mixture of Polyols Based on Metasilicic Acid and Recycled PLA for Synthesis of Rigid Polyurethane Foams Susceptible to Biodegradation.

Two polyol raw materials were obtained in the conducted research, one based on metasilicic acid (MSA), the other based on poly(lactic acid) (PLA) waste. The obtained polyols were characterized in terms of their applicability for the production of rigid polyurethane foams (RPUFs). Their basic analytical properties (hydroxyl number, acid number, elemental analysis) and physicochemical properties (density, viscosity) were determined. The assumed chemical structure of the obtained new compounds was confirmed by performing FTIR and 1H NMR spectroscopic tests. Formulations for the synthesis of RPUFs were developed on the basis of the obtained research results. A mixture of polyols based on MSA and PLA in a weight ratio of 1:1 was used as the polyol component in the polyurethane formulation. The reference foam in these tests was a foam that was synthesized only on the basis of MSA-polyol. The obtained RPUFs were tested for basic functional properties (apparent density, compressive strength, water absorption, thermal conductivity coefficient etc.). Susceptibility to biodegradation in soil environment was also tested. It was found that the use of mixture of polyols based on MSA and PLA positively affected the properties of the obtained foam. The polyurethane foam based on this polyol mixture showed good thermal resistance and significantly reduced flammability in comparison with the foam based MSA-polyol. Moreover, it showed higher compressive strength, lower thermal conductivity and biodegradability in soil. The results of the conducted tests confirmed that the new foam was characterized by very good performance properties. In addition, this research provides information on new waste management opportunities and fits into the doctrine of sustainable resource management offered by the circular economy.

Progress in the Preparation of Functional and (Bio)Degradable Polymers via Living Polymerizations.

This review presents the latest developments in (bio)degradable approaches and functional aliphatic polyesters and polycarbonates prepared by typical ring-opening polymerization (ROP) of lactones and trimethylene carbonates. It also considers several recent innovative synthetic methods including radical ring-opening polymerization (RROP), atom transfer radical polyaddition (ATRPA), and simultaneous chain- and step-growth radical polymerization (SCSRP) that produce aliphatic polyesters. With regard to (bio)degradable approaches, we have summarized several representative cleavable linkages that make it possible to obtain cleavable polymers. In the section on functional aliphatic polyesters, we explore the syntheses of specific functional lactones, which can be performed by ring-opening copolymerization of typical lactone/lactide monomers. Last but not the least, in the recent innovative methods section, three interesting synthetic methodologies, RROP, ATRPA, and SCSRP are discussed in detail with regard to their reaction mechanisms and polymer functionalities.

Antibacterial tragacanth gum-based nanocomposite films carrying ascorbic acid antioxidant for bioactive food packaging.

Food packaging has a pivotal share to improve protection, safety and shelf-life time of foods and bioproducts. Herein, we prepared bioactive nanocomposite films that composed of tragacanth (TG), polyvinyl alcohol, ZnO nanoparticles (NPs) and ascorbic acid (AA) using glycerol as a plasticizer and citric acid as a cross-linker for food packaging. The SEM images showed a homogenous distribution of ZnO NPs with low aggregation in nanocomposite films. The water solubility of nanocomposite films reduced from 15.65 % to 10.81 with increasing of TG and ZnO NPs contents. The incorporation of AA and ZnO NPs into nanocomposite films improved antioxidant activity from 50 % to 66 % in 95 % ethanolic solution. Also, the nanocomposite films showed good antibacterial activity against Gram-negative and -positive bacteria. Soil degradation rate of nanocomposite films increased from 80 % to 91.46 as the wt% of TG increased. Therefore, prepared nanocomposite films could be employed as a promising candidate for food packaging applications.

Stiffening, strengthening, and toughening of biodegradable poly(butylene adipate-co-terephthalate) with a low nanoinclusion usage.

Simultaneous stiffening, strengthening, and toughening of biodegradable polymers, such as poly(butylene adipate-co-terephthalate) (PBAT) and others, is necessary for their use in packaging and agriculture applications. However, a high content of nanoinclusions is usually required, leading to a tradeoff between composite toughness and strength or stiffness in the reinforcement. Herein, we report an iterative reinforcement strategy that uses one nanocomposite to reinforce PBAT. An in-situ grafting polymerized cellulose nanocrystal (CNC)/PBAT (CNC-g-PBAT) nanocomposite consisting of ungrafted/free PBAT (PBATf) was used as an inclusion directly to reinforce a commercial PBAT. At an exceptionally low CNC usage of 0.02 wt.%, we achieved a simultaneous enhancement of the Young's modulus by 26 %, tensile strength by 27 %, elongation at break by 37 %, and toughness by 56 % over those for PBAT. To the best of our knowledge, such reinforcement efficiency is the highest among similar biodegradable polymer nanocomposites reported in the literature. The rheology, differential scanning calorimetry, and wide-angle X-ray diffraction measurements confirmed the mechanical reinforcement attributed to a synergistic contribution from PBATf and CNC-g-PBAT. In particular, the use of PBATf enhanced both stiffness and toughness of the composites, while the CNC-g-PBAT interacted within the polymer matrix and increased the crystallinity of the polymer matrix, leading to the strengthening and toughening effect. The strategy proposed here is greatly beneficial to producing high-performance biodegradable polymer nanocomposite films for packaging and agricultural applications using a very low amount of nanoinclusion.

Balancing the decomposable behavior and wet tensile mechanical property of cellulose-based wet wipe substrates by the aqueous adhesive.

With the current global outbreak of novel coronaviruses, the fabrication of decomposable wet wipe with sufficient wet strength to meet daily use is promising but still challenging, especially when renewable cellulose was employed. In this work, a decomposable cellulose-based wet wipe substrate is demonstrated by introducing a synthetic N-vinyl pyrrolidone-glycidyl methacrylate (NVP-GMA) adhesive on the cellulose surface. Experimental results reveal that the NVP-GMA adhesive not only significantly facilitates the chemical bonding between cellulose fibers in the wet state, but also increase the surface wettability and water retention. The as-fabricated cellulose-based wet wipe substrate displays a superb water retention capacity of 1.9 times, an excellent water absorption capacity (completely wetted with 0° water contact angle), and a perfect wet tensile index of 3.32 N.m.g-1. It is far better than state-of-the-art wet toilet wipe on the market (non-woven). The prepared renewable and degradable cellulose-based substrate with excellent mechanical strength has potential application prospects in diverse commercially available products such as sanitary and medical wet wipes.

Properties of wood composite plastics made from predominant Low Density Polyethylene (LDPE) plastics and their degradability in nature.

To address concerns over plastics in the global environment, this project produced three wood plastics composites (WPCs) which could divert plastics from the waste stream into new materials. The three materials made had a ratio of 85%:15%, 90%:10%, and 95%:5% low density polyethylene (LDPE) to wood powder and were produced using the dissolution method. Physical and mechanical properties of each WPC were evaluated according to Japanese Industrial Standard (JIS) A 5908:2003. Their degradation in nature was evaluated through a graveyard test and assay test conducted in Coptotermes curvignathus termites. Results showed that density, moisture content, thickness swelling and water absorption of the WPCs fulfilled the JIS standard. The mechanical properties of these composites also met the JIS standard, particularly their modulus of elasticity (MOE). Modulus of rupture (MOR) and internal bonding (IB) showed in lower values, depending on the proportion of wood filler they contained. Discoloration of the WPCs was observed after burial in the soil with spectra alteration of attenuated transmission reflectance (ATR) in the band of 500-1000 cm-1 which could be assigned to detach the interphase between wood and plastics. As termite bait, the WPCs decreased in weight, even though the mass loss was comparatively small. Micro Confocal Raman Imaging Spectrometer revealed that termite guts from insects feeding on WPCs contained small amounts of LDPE. This indicated termite can consume plastics in the form of WPCs. Thus WPCs made predominantly of plastics can be degraded in nature. While producing WPCs can assist in decreasing plastics litter in the environment, the eventual fate of the LDPE in termites is still unknown.