Efficient and selective upcycling of waste polylactic acid into acetate using nickel selenide

The conversion of waste polylactic acid(PLA)plastics into high-value-added chemicals through electrochemical methods is a promising and sustainable approach.However,developing efficient and highly selective catalysts for lactic acid oxidation reaction(LAOR)and understanding the reaction process are challenging.Here,we report the electrooxidation of waste PLA to acetate at a high current density of 100 mA cm-2 with high Faraday efficiency(~95%)and excellent stability(>100 h)over a nickel selenide nanosheet catalyst.In addition,a total Faraday efficiency of up to 190%was achieved for carboxylic acids,including acetic acid and formic acid,by coupling with the cathodic CO_(2) reduction reaction.In situ experimental results and theoretical simulations revealed that the catalytic activity center of LAOR was dynamically formed NiOOH species,and the surface-adsorbed SeO_(x) species accelerated the formation of Ni~(3+)species,thus promoting catalytic activity.The mechanism of lactic acid electrooxidation was further elucidated.Lactic acid was dehydrogenated to produce pyruvate first and then formed CH_3CO due to preferential C-C bond cleavage,resulting in the presence of acetate.This work demonstrated a sustainable method for recycling waste PLA and CO_(2) into high-value-added products.

Synergism of Zinc Oxide/Organoclay-Loaded Poly(lactic acid) Hybrid Nanocomposite Plasticized by Triacetin for Sustainable Active Food Packaging

The synergistic effect of organoclay(OC)and zinc oxide(ZnO)nanoparticles on the crucial properties of poly(lactic acid)(PLA)nanocompositefilms was systematically investigated herein.After their incorporation into PLA via the solvent casting technique,the water vapor barrier property of the PLA/OC/ZnOfilm improved by a maximum of 86%compared to the neat PLAfilm without the deterioration of Young’s modulus or the tensile strength.Moreover,thefilm’s self-antibacterial activity against foodborne pathogens,including gram-negative(Escherichia coli,E.coli)and gram-positive(Staphylococcus aureus,S.aureus)bacteria,was enhanced by a max-imum of approximately 98–99%compared to the neat PLAfilm.Furthermore,SEM images revealed the homo-geneous dispersion of both nano-fillers in the PLA matrix.However,the thermal stability of thefilm decreased slightly after the addition of the OC and ZnO.Thefilm exhibited notable light barrier properties in the UV-Vis range.Moreover,the incorporation of a suitable biodegradable plasticizer significantly decreased the Tg and notably enhanced theflexibility of the nanocompositefilm by increasing the elongation at break approxi-mately 1.5-fold compared to that of the neat PLAfilm.This contributes to its feasibility as an active food packa-ging material.

Poly(lactic acid)-aspirin microspheres prepared via the traditional and improved solvent evaporation methods and its application performances

Drug-loaded microspheres are significant for the development of modern pharmaceutical products. It is well known that the taken of aspirin for long-term increases the risk of serious gastrointestinal complications, therefore a controllable delivery of aspirin is of importance to lighten those side effects. In this work, poly(lactic acid)(PLA) was chosen as the carrier to prepare PLA-aspirin microspheres by using the traditional and the improved solvent evaporation methods. It was found that no matter which experimental condition was, the encapsulation efficiency of aspirin was higher by using the improved method than that of the traditional method. Specifically, when the concentration of polyvinyl alcohol = 1%(mass),the polymer concentration = 1:20, the oil/water rate = 1:2.5, PLA-aspirin microspheres were obtained via the improved method with a high yield of 82.83%(mass) and an encapsulation efficiency of 44.09%. PLAaspirin microspheres were then prepared continuously using the improved method, which further enhanced the encapsulation efficiency to 54.56%. Approximate 85% aspirin released from microspheres within 7 days. Obvious degradation which was represented by reduction on hardness was observed by soaking microspheres in PBS for 60 days. This work is of interest because it provides a continuous route to prepare PLA-aspirin microspheres continuously with a high drug encapsulation efficiency.

Preparation and properties of short natural fiber reinforced poly(lactic acid) composites

The natural fiber/poly(lactic acid) (PLA) composites were prepared with ramie and jute short fiber as reinforcement and PLA as matrix. The mechanical and thermal properties of the composites were investigated. The results show that the properties of the composites are better than those of plain PLA. When the content of the fiber is 30%, the composites can get the best mechanical properties. The dynamic mechanical analysis results show that the storage moduli of the PLA/ramie and PLA/jute composites increase with respect to the plain PLA. The Vicat softening temperature of the composites is greatly higher than that of PLA. The results of thermogravimetric analysis show that adding fiber to the PLA matrix can improve the degradation temperature of PLA.

Morphological, Mechanical and Thermal Properties of Poly(lactic acid)(PLA)/Cellulose Nanofibrils(CNF) Composites Nanofiber for Tissue Engineering

Composite nanofiber membranes based on biodegradable poly(lactic acid)(PLA) and cellulose nanofibrils(CNF) were produced via electrospinning. The influence of CNF content on the morphology, thermal properties, and mechanical properties of PLA/CNF composite nanofiber membranes were characterized by field scanning electron microscopy(FE-SEM), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA), and dynamic mechanical analysis(DMA), respectively. The results show that the PLA/CNF composite nanofibers with smooth, free-bead surface can be successfully fabricated with various CNF contents. The introduction of CNF is an effective approach to improve the crystalline ability, thermal stability and mechanical properties for PLA/CNF composite fibers. The Young's moduli and tensile strength of the PLA/CNF composite nanofiber reach 106.6 MPa and 2.7 MPa when the CNF content is 3%, respectively, which are one times higher and 1.5 times than those of pure PLA nanofiber. Additionally, the water contact angle of PLA/CNF composite nanofiber membranes decreases with the increase of the CNF loading, resulting in the enhancement of their hydrophilicity.

The Green Composites: Millet Husk Fiber (MHF) Filled Poly Lactic Acid (PLA) and Degradability Effects on Environment

This study provides an overview on green composites degradability. Practically, the main drawbacks of using natural fibers are their poor dimensional stability, degradability and high degree of moisture absorption. While, end use of product from natural fiber filled or reinforced composites has become subject of concern to material engineers and scientist. The major properties of natural fiber reinforced polymer composites are greatly dependent on the hydrophilic tendency and dimensional stability of the fibers used, morphology aspect ratio for long fiber, while voids for powder fibers. The effects of chemical treatments on cellulosic fibers that are used as reinforcements for thermoplastics were studied. The chemical source for the treatments is alkalization. The significance of chemically-treated natural fibers is seen through the improvement of mechanical properties. The untreated fiber composites degrade faster in municipal soil compared to treated fiber composites.

A novel artificial nerve graft for repairing longdistance sciatic nerve defects:a self-assembling peptide nanofiber scaffold-containing poly (lactic-co-glycolic acid) conduit

In this study, we developed a novel artificial nerve graft termed self-assembling peptide nanofiber scaffold （SAPNS）-containing poly（lactic-co-glycolic acid） （PLGA） conduit （SPC） and used it to bridge a 10-mm-long sciatic nerve defect in the rat. Retrograde tracing, behavioral testing and histomorphometric analyses showed that compared with the empty PLGA conduit implantation group, the SPC implantation group had a larger number of growing and extending axons, a markedly increased diameter of regenerated axons and a greater thickness of the myelin sheath in the conduit. Furthermore, there was an increase in the size of the neuromuscular junction and myofiber diameter in the target muscle. These findings suggest that the novel artificial SPC nerve graft can promote axonal regeneration and remyelination in the transected peripheral nerve and can be used for repairing peripheral nerve injury.

Reactive Compatibilization of Short-Fiber Reinforced Poly(lactic acid)Biocomposites

Poor interfacial adhesion between biobased thermoplastics and natural fibers is recognized as a major drawback for biocomposites.To be applicable for the large-scale production,a simple method to handle is of importance.This work presented poly(lactic acid)(PLA)reinforced with short-fiber and three reactive agents including anhydride and epoxide groups were selected as compatibilizers.Biocomposites were prepared by one-step meltmixing methods.The influence of reactive agents on mechanical,dynamic mechanical properties and morphology of PLA biocomposites were investigated.Tensile strength and storage modulus of PLA biocomposites incorporated with epoxide-based reactive agent was increased 13.9%and 37.4%compared to non-compatibilized PLA biocomposite,which was higher than adding anhydride-based reactive agent.SEM micrographs and Molau test exhibited an improvement of interfacial fiber-matrix adhesion in the PLA biocomposites incorporated with epoxide-based reactive agent.FTIR revealed the chemical reaction between the fiber and PLA with the presence of epoxide-based reactive agents.

Preparation,Characterization,and Antitumor Efficacy of Camptothecine-Loaded Hydroxyapatite / Poly( lactic-co-glycolic acid ) Composite Nanofibers via Electrospinning

In the past decade, various medicated nanofibrous scaffolds have been developed as effective drug delivery systems for postsurgical cancer treatment.In this study, hydroxyapatite nanoparticles( HANPs) were used as carriers to load an anticancer agent—camptothecine( CPT),and the CPT-loaded HANPs( CPT@ HANPs) was then incorporated into poly( lactic-co-glycolic acid)( PLGA) nanofibers via electrospinning.Thus fabricated medicated nanofibrous mats( PLGA / CPT @ HANPs) were characterized by field emission scanning electron microscope( FESEM),transmission electron microscope( TEM), attenuated total reflection Fourier transform infrared spectroscopy( ATR-FTIR) and X-ray diffraction( XRD).The release profiles of CPT from the medicated electrospun mats were obtained and their in vitro anticancer efficacy against HeL a cells was also evaluated.The results showed that the CPT was successfully loaded onto the surface of HANPs,and the prepared electrospun mats exhibited a homogeneous and continuous morphology.Furthermore,the loaded CPT exhibited a sustained release behavior from the nanofibrous mats and the released CPT showed a long-term anticancer efficacy against HeL a cells.Therefore,the prepared medicated electrospun mats may be served as an effective drug delivery device for local antitumor treatment.

Preparation and phase change performance of Na_2HPO_4·12H_2O@poly(lactic acid) capsules for thermal energy storage

Micro-encapsulated phase-change materials(micro PCMs) with Na_2 HPO_4·12 H_2 O encapsulated in poly(lactic acid)(PLA) shell were prepared by a solvent evaporation–precipitation method that involves the use of a coaxial needle. The effects of PLA concentration, stirring speed, injection rate of core and shell solutions, and polyvinyl alcohol(PVA) concentration on phase change properties were investigated. The thermal properties of microP CMs were characterized by differential scanning calorimetry(DSC). The capsules prepared under the optimal conditions are about 2 mm in diameter and show a latent heat of up to 122.2 J·g^(-1).

Synergistic effect of MXene on the flame retardancy and thermal degradation of intumescent flame retardant biodegradable poly(lactic acid)composites

The effect of Ti3C2 MXene nanosheets on the intumescent flame retardant(IFR)poly(lactic acid)(PLA)composites was investigated among a series of PLA/IFR/MXene,which were prepared by melt blending 0-2.0 wt%MXene,10.0 wt%-12.0 wt%IFR and PLA together.The results of limiting oxygen index(LOI)and vertical burning(UL-94)discover that the combination of 0.5 wt%MXene and 11.5 wt%IFR synergistically improves the fire safety of PLA to reach UL-94 V-0 rating with LOI value of 33.0%.The PLA/IFR/MXene composites perform an obvious reduction in peak of heat release rate(HRR)in cone calorimeter tests(CCTs).Furthermore,the carbon residues after CCTs were characterized by scanning electron microscope(SEM),laser Raman spectroscopy(LRS),X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS).It is demonstrated that both the titanium composition of the MXene structure and the characteristics of the two-dimensional material enhance the PLA/IFR/MXene composite materials’ability to produce a dense barrier layer to resist burnout during thermal degradation.

Blends of Poly(lactic acid) with Thermoplastic Acetylated Starch

Blends of poly（lactic acid）（PLA） and thermoplastic acetylated starch（ATPS） were prepared by means of the melt mixing method. The results show that PLA and ATPS were partially miscible, which was confirmed with the measurement of Tg by dynamic mechanical analysis（DMA） and differrential scanning calorimetry（DSC）. The mechanical and thermal properties of the blends were improved. With increasing the ATPS content, the elongation at break and impact strength were increased. The elongation at break increased from 5% of neat PLA to 25% of the blend PLA/ATPS40. It was found that the cold crystallization behavior of PLA changed evidently by addition of ATPS. The cold crystallization temperature（Tcc） of each of PLA/ATPS blends was found to shift to a lower temperature and the width of exothermic peak became narrow compared with that of neat PLA. The thermogravimetry analysis（TGA） results showed that the peak of derivative weight for ATPS moved to higher temperature with increasing PLA content in PLA/ATPS blends. It can be concluded that PLA could increase the thermal stability of ATPS. The rheological measurement reveals the melt elasticity and viscosity of the blends decreased with the increased concentration of ATPS, which was favorable to the processing properties of PLA.

RELEASE OF IBUPROFEN FROM PEG-PLLA ELECTROSPUN FIBERS CONTAINING POLY(ETHYLENE GLYCOL)-b-POLY(α-HYDROXY OCTANOIC ACID) AS AN ADDITIVE

Poly（a-hydroxy octanoic acid） was first used as an additive for the preparation of electrospun ultra-fine fibers of poly（ethylene glycol）-b-poly（L-lactide） （PEG-PLLA）. Ibuprofen was loaded in the electrospun ultra-fine fibers. The results from environmental scanning electron microscopy （ESEM）, wide angle X-ray diffraction （WAXD） and differential scanning calorimetry （DSC） demonstrated that ibuprofen could be perfectly entrapped in the fibers electrospun from PEG-PLLA using a-hydroxy octanoic acid or PEG-b-poly（a-hydroxy octanoic acid） （PEG-PHOA） as additives. Compared with electrospun PEG-PLLA fibers which entrapped 20 wt% ibuprofen, the PEG-PLLA electrospun fibers containing PEG-PHOA exhibited integral and robust after 1 week incubated in 37℃, pH 7.4 phosphate buffer solution with 10 μg/mL proteinase K. Compared with electrospun fibers without PEG-PHOA, the concentration ofproteinase K in release media had less effect on the release rate of ibuprofen. An unique release profile was found from PEG-PLLA fiber after the incorporation of PEG-PHOA. Enzyme degradation experiments demonstrated that PEG-PHOA but not a-hydroxy octanoic acid monomer was the crucial factor for integrity maintenance of the electrospun fibers, which may be due to the enzyme degradation tolerance property of the PEG-PHOA polymer additive.

Preparation and Characterization of Poly Lactic Acid/Graphene Oxide/Nerve Growth Factor Scaffold with Electrical Stimulation for Peripheral Nerve Regeneration in vitro

A novel conductive drug-loading system was prepared by using an improved emulsion electrostatic spinning method which contained polylactic acid (PLA),graphene oxide (GO),and nerve growth factor (NGF) coated with bovine serum albumin (BSA) nanoparticles.Firstly,the structure,mechanical properties,morphology and electrical conductivity of PLA/GO electro spun fiber membranes with different GO ratios were characterized.PLA/GO scaffolds can exhibit superior porosity,hydrophilic and biomechanical properties when the GO incorporation rate is 0.5%.The addition of GO in the PLA/GO electro spun fiber membranes can also create appropriate pH environment for the repair of injured nerve when the GO incorporation rate is above 0.5%.Secondly,PLA/GO/BSA/Genipin/NGF particles (with a ratio of BSA/NGF=3:1) prepared by modified emulsion electro spinning method will release more NGF than PLA/GO/NGF particles.In addition,PLA/0.5%GO/NGF scaffold can maintain its structure stability for at least 8 weeks observed by scanning electron microscope (SEM).Moreover,the degradation of PLA/0.5%GO/NGF scaffold is consistent with its weight loss.Finally,in vitro assay confirmes that PLA/GO composite scaffold exhibits low cytotoxicity to RSC96 cells.Cellular results have demonstrated that PLA/0.5%GO/NGF sustained-release drug sustained-release system with appropriate electrical stimulation (ES) can promote PC12 cell proliferation,and it can maintain its differentiation capability for at least 3 weeks.In conclusion,PLA/0.5%GO/NGF sustained-release drug sustained-release system can maintain its biological activity for at least 3 weeks and promote cell proliferation with appropriate ES.

Comparison of morphological and functional outcomes of mouse sciatic nerve repair with three biodegradable polymer conduits containing poly (lactic acid)

Poly（lactic acid）（PLA）-containing nerve guidance conduits（NGCs） are currently being investigated for nerve repair as an alternative to autograft, which leads to permanent functional impairment in the territory innervated by the removed nerve. Combination of polymers modifies the physical properties of the conduits, altering their nerve-guidance properties. Conduits made from PLA-only or combined with other polymers have been used successfully for nerve repair, but their efficiency has not been compared. We compared the morphological and functional outcomes of peripheral nerve repair by using NGCs made of poly（lactic acid） and combined or not with polycaprolactone（PLA/PCL） or polyvinylpyrrolidone（PLA/PVP）. To assess the functional recovery, we employed a mechanical hyperalgesia analysis, sciatic functional index（SFI）, and electroneuromyography. The mechanical hyperalgesia analysis showed that the PLA group improved more rapidly than the PLA/PVP and PLA/PCL groups; similarly, in the electroneuromyography assay, the PLA group exhibited higher amplitude than the PLA/PCL and PLA/PVP groups. However, the SFI improvement rates did not differ among the groups. Morphologically, the PLA group showed more vascularization, while the nerve fiber regeneration did not differ among the groups. In conclusion, the PLA-only conduits were superior to the other NGCs tested for nerve repair.

Melt Synthesis and Characterization of Poly(L-lactic Acid) Chain Linked by Multifunctional Epoxy Compound

High molecular weight（Mw） poly（L-lactic acid）s（PLLAs） were synthesized using multifunctional epoxy compound（Joncryl-ADR4370） as chain extender. The products were characterized by gel permeation chromatography（GPC） and spectroscopy（1HNMR and FTIR）. The results indicated that the Mw of PLLA increased with the increasing of the ratio of epoxy compound and the extending of reaction time. The highest Mw of PLLA reached 360 000 g/mol when the ratio of epoxy compound was 1.5 wt%. However, the reactants turned to cross-linking when the ratio of epoxy compound was over 1.5 wt%. Differential scanning calorimetry（DSC） measurements demonstrated that the glass transition（Tg） and melting temperatures（Tm） of products increased slightly as the increase of the molecular weight. Analysis of the hydrolytic degradation in vitro showed that the branched PLLA possessed the quicker degradability than that of the linear PLLA.

Fabrication and Characterization of Poly Lactic Acid Scaffolds by Fused Deposition Modeling for Bone Tissue Engineering

Three-dimensional porous poly-lactic acid(PLA) scaffold was fabricated using fused deposition modeling(FDM) method including 30%, 50% and 70% nominal porosity. Study of phases in initial polymeric material and printed scaffolds was done by X-ray diffraction(XRD), and no significant phase difference was observed due to the manufacturing process, and the poly-lactic acid retains its crystalline properties. The results of the mechanical properties evaluation by the compression test show that the mechanical properties of the scaffold have decreased significantly with increasing the porosity of scaffold. The microstructure of scaffolds were studied by scanning electron microscope(SEM), showing that the pores had a regular arrangement and their morphology changed with porosity change. The mechanical properties of the poly-lactic acid scaffolds printed using fused deposition modeling, can be adapted to the surrounding tissue, by porosity change.

Influence of Mica Particles on the Rheological Properties and Thermal Stability of Poly( lactic acid)

The influence of mica particles on the rheological and thermal properties of poly( lactic acid)( PLA) / mica composites were investigated by capillary rheometer and thermogravimetric( TG)analysis. The results show that the PLA / mica blends are nonNewtonian pseudoplastic and display shear-thinning. The value of non-Newtonian index of the blends melt decreased obviously with the addition of mica particles but somehow even increased when shear rate exceeded 4 500 s- 1. In this work,it could be indicated that appropriate amount of mica particles could somehow enhance the resistance of PLA melt under high shear rate to deviate from Newtonian fluid. TG analysis shows that the thermal stability of PLA decreases a little after the incorporation of the mica particles.As mica particles decompose in a completely different way in contrast to PLA,this abnormal decrease of thermal stability of PLA / mica composite may be attributed to moisture stored between mica layers released at high temperature.

Synthesis of the Biomimetic Polymer: Aliphatic Diamine and RGDS Modified Poly(d,l-lactic acid)

A novel poly（d, /-lactic acid） （PDLLA） based biomimetic polymer was synthesized by grafting maleic anhydride, butanediamine and arg-gly-asp-ser （RGDS） peptides onto the backbone of PDLLA, aiming to overcome the acidity and auto-accelerating degradation of PDLLA during degradation and to improve its biospecificity and biocompatibility. The synthetic copolymer was characterized by FTIR, ^13C NMR and amino acid analyzer （AAA）.