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.

Poly(p-coumaric acid)nanoparticles alleviate temporomandibular joint osteoarthritis by inhibiting chondrocyte ferroptosis

Oxidative stress and inflammation are key drivers of osteoarthritis(OA)pathogenesis and disease progression.Herein we report the synthesis of poly(p-coumaric)nanoparticles(PCA NPs)from p-courmaic acid(p-CA),a naturally occurring phytophenolic acid,to be a multifunctional and drug-free therapeutic for temporomandibular joint osteoarthritis(TMJOA).Compared to hyaluronic acid(HA)that is clinically given as viscosupplementation,PCA NPs exhibited long-term efficacy,superior anti-oxidant and anti-inflammatory properties in alleviating TMJOA and repairing the TMJ cartilage and subchondral bone in a rat model of TMJOA.Notably,TMJ repair mediated by PCA NPs could be attributed to their anti-oxidant and anti-inflammatory properties in enhancing cell proliferation and matrix synthesis,while reducing inflammation,oxidative stress,matrix degradation,and chondrocyte ferroptosis.Overall,our study demonstrates a multifunctional nanoparticle,synthesized from natural p-coumaric acid,that is stable and possess potent antioxidant,anti-inflammatory properties and ferroptosis inhibition,beneficial for treatment of TMJOA.

Edaravone-loaded poly(amino acid) nanogel inhibits ferroptosis for neuroprotection in cerebral ischemia injury

Neurological injury caused by ischemic stroke is a major cause of permanent disability and death. The currently available neuroprotective drugs fail to achieve desired therapeutic efficacy mainly due to short circulation half-life and poor blood−brain barrier (BBB) permeability. For that, an edaravone-loaded pH/glutathione (pH/GSH) dual-responsive poly(amino acid) nanogel (NG/EDA) was developed to improve the neuroprotection of EDA. The nanogel was triggered by acidic and EDA-induced high-level GSH microenvironments, which enabled the selective and sustained release of EDA at the site of ischemic injury. NG/EDA exhibited a uniform sub-spherical morphology with a mean hydrodynamic diameter of 112.3 ± 8.2 nm. NG/EDA efficiently accumulated at the cerebral ischemic injury site of permanent middle cerebral artery occlusion (pMCAO) mice, showing an efficient BBB crossing feature. Notably, NG/EDA with 50 µM EDA significantly increased neuron survival (29.3%) following oxygen and glucose deprivation by inhibiting ferroptosis. In addition, administering NG/EDA for 7 d significantly reduced infarct volume to 22.2% ± 7.2% and decreased neurobehavioral scores from 9.0 ± 0.6 to 2.0 ± 0.8. Such a pH/GSH dual-responsive nanoplatform might provide a unique and promising modality for neuroprotection in ischemic stroke and other central nervous system diseases.

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 CELL COMPATIBILITY OF FUNCTIONALIZED BIODEGRADABLE POLY(DL-LACTIDE-co-RS-β-MALIC ACID)

In order to create a functionalized biodegradable polymer for vascular tissue engineering application,poly(DL- lactide-co-RS-β-malic acid)(PDLLMAc)was synthesized.PDLLMAc was obtained after hydrogenolysis of poly(DL- lactide-co-RS-β-benzyl malolactonate)(PDLLMA),which was from the ring-opening polymerization of DL-lactide(DLLA) and RS-β-benzyl malolactonate(MA)using stannous octoate as catalyst.The copolymers were characterized by ~1H-NMR, FTIR,GPC and DSC.The tensile strength and water uptake of the copoly...

High-performance and robust high-temperature polymer electrolyte membranes with moderate microphase separation by implementation of terphenyl-based polymers

Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.

Removal of manganese from waste water by complexation-ultrafiltration using copolymer of maleic acid and acrylic acid

Copolymer of maleic acid and acrylic acid （PMA-100）, combining with polyvinyl butyral （PVB） ultrafiltration membrane was used for the removal of Mn（II） from waste water by complexation-ultrafiltration. The carboxylic group content of PMA-100 and the rate of complexation reaction were measured. Effects of the mass ratio of PMA-100 to Mn（II） （n）, pH, background electrolyte, etc on the rejection rate （R） and permeate flux （J） were investigated. The results show that carboxylic group content of PMA-100 is 9.5 mmol/g. The complexation of Mn（II） with PMA-100 is rapid and completed within 5 min at pH 6.0. Both R and J increase with pH increasing in the range of 2.5-7.0, and R increases with the increase of n at pH 6.0 while J is little affected. The background electrolyte leads to the decrease of R, and CaCl2 has much greater effect on R than NaCl at the same ionic strength.

Antimicrobial Expanded Polytetrafluoroethylene Film Prepared by 3-ray Radiation Induced Grafting of Poly（acrylic acid）

The simultaneous γ-ray-radiation-induced grafting polymerization of acrylic acid on ex- panded polytetrafluoroethylene （ePTFE） film was investigated. It was found that the degree of grafting （DG） of poly（acrylic acid） （PAA） can be controlled by the monomer concentration, absorbed dose, and dose rate under an optimal inhibitor concentration of [Fe2＋]=18 mmol/L. SEM observation showed that the macroporous structure in ePTFE films would be covered gradually with the increase of the DG of PAA. The prepared ePTFE-g-PAA film was im- mersed in a neutral silver nitrate solution to fabricate an ePTFE-g-PAA/Ag hybrid film after the addition of NaBH4 as a reduction agent of Ag＋ to Ag atom. SEM, XRD, and XPS results proved that Ag nanoparticles with a size of several tens of nanometers to 100 nanometers were in situ immobilized on ePTFE film. The loading capacity of Ag nanoparticles could be tuned by the DG of PAA, and determined by thermal gravimetric analysis. The quart- titative antibacterial activity of the obtained ePTFE-g-PAA/Ag hybrid films was measured using counting plate method. It can kill all the Escherichia coli in the suspension in 1 h. Moreover, this excellent antibacterial activity can last at least for 4 h. This work provides a facile and practical way to make ePTFE meet the demanding antimicrobial requirement in more and more practical application areas.

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）.

CLAY CATALYZED SYNTHESIS OF BIO-DEGRADABLE POLY(GLYCOLIC ACID)

Glycolic acid was polymerized under vacuum in the presence and absence of nano sized clay.The added clay catalyzed the condensation polymerization which can be confirmed by recording FTIR spectroscopy and intrinsic viscosity (Ⅳ)values.The relative intensity of C=O/CH is increased while increasing the amount of clay.DSC showed the appearance of multiple endotherms of poly(glycolic acid).TGA showed the percentage weight residue remain above 750℃for polymer-nano composite system was 21% and hence proved the fl...

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.

A Hybrid Membrane of Poly(vinyl alcohol) and Phosphotungstic Acid for Fuel Cells

Proton conducting membranes composed of phosphotungstic acid (PWA) and poly(vinyl alcohol) (PVA)were prepared. Conductivity and Fourier transform infrared spectrometer(FTIR) measurements show that most ofthe acid embedded are stable in the PVA matrix when the membrane is immerged in water or methanol solution atroom temperature. Conductivity of the composite membranes scatters around 10-3 S.cm-1 at room temperature.The methanol crossover through the membranes is about an order of magnitude lower than that through Nafion117 membrane.

Synthesis and Characterization of a Novel Biomaterial: Maleic Anhydride-modified Poly(dl-lactic acid)

A novel modified poly(dl-lactic acid) (PDLLA) was obtained by covalently grafting of maleic anhydride onto the backbone of PDLLA, attempting to improve PDLLA’s hydrophilicity and cell affinity and to provide reactive groups for further chemical modification. FTIR, 13C NMR and DSC were used to characterize the maleic anhydride-modified PDLLA.

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).

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.

Poly (Acrylamide-co-Acrylic Acid) Hydrogel Induced by Glow-Discharge Electrolysis Plasma and Its Adsorption Properties for Cationic Dyes

In this paper, poly （acrylamide-co-acrylic acid） （P（AM-co-AA）） hydrogel was pre- pared in an aqueous solution by using glow-discharge electrolysis plasma （GDEP） induced copoly- merization of acrylamide （AM） and acrylic acid （AA）, in which N,N＇-methylenebisacrylamide （MBA） was used as a crosslinker. A mechanism for the synthesis of P（AM-co-AA） hydrogel was proposed. To optimize the synthesis condition, the following parameters were examined in detail： the discharge voltage, discharge time, the content of the crosslinker, and the mass ratio of AM to AA. The results showed that the optimum pH range for cationic dyes removal was found to be 5.0-10.0. The P（AM-co-AA） hydrogel exhibits a very high adsorption potential and the ex- perimental adsorption capacities for Crystal violet （CV） and Methylene blue （MB） were 2974.3 mg/g and 2303.6 mg/g, respectively. The adsorption process follows a pseudo-second-order kinetic model. In addition, the adsorption mechanism of P（AM-co-AA） hydrogel for cationic dyes was also discussed.

Transplantation of Nogo-66 receptor gene-silenced cells in a poly(D,L-lactic-co-glycolic acid) scaffold for the treatment of spinal cord injury

Inhibition of neurite growth, which is in large part mediated by the Nogo-66 receptor, affects neural regeneration following bone marrow mesenchymal stem cell transplantation. The tissue engineering scaffold poly（D,L-lactide-co-glycolic acid） has good histocompatibility and can promote the growth of regenerating nerve fibers. The present study used small interfering RNA to silence Nogo-66 receptor gene expression in bone marrow mesenchymal stem cells and Schwann cells, which were subsequently transplanted with poly（D,L-lactide-co-glycolic acid） into the spinal cord lesion regions in rats. Simultaneously, rats treated with scaffold only were taken as the control group. Hematoxylin-eosin staining and immunohistochemistry revealed that at 4 weeks after transplantation, rats had good motor function of the hind limb after treatment with Nogo-66 receptor gene-silenced ceils prus the poly（O,L-lactide-co-glycolic acid） scaffold compared with rats treated with scaffold only, and the number of bone marrow mesenchymal stem cells and neuron-like cells was also increased. At 8 weeks after transplantation, horseradish peroxidase tracing and transmission electron microscopy showed a large number of unmyelinated and myelinated nerve fibers, as well as intact regenerating axonal myelin sheath following spinal cord hemisection injury. These experimental findings indicate that transplantation of Nogo-66 receptor gene-silenced bone marrow mesenchymal stem cells and Schwann cells plus a poly（D,L-lactide-co-glycolic acid） scaffold can significantly enhance axonal regeneration of spinal cord neurons and improve motor function of the extremities in rats following spinal cord injury.

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.

Effect of a Novel Nucleating Agent on Isothermal Crystallization of Poly（L-lactic acid）

The effect of a novel active nucleating agent(TBC8-eb) on the isothermal crystallization of poly(L-lactic acid) (PLLA) was studied by differential scanning calorimetry(DSC) and Fourier transform infrared spectroscopy(FTIR) . The analysis on kinetics demonstrates that TBC8-eb can not only accelerate the crystallization rate but also transform most of the original spherulite crystals of PLLA into sheaf-like crystals. Furthermore,the free energy of folding(σe) of PLLA and PLLA with TBC8-eb is 0.15 and 0.06 J·m-2,respectively,which suggests that the addition of TBC8-eb favors the regular folding of molecule chains in the crystallization of PLLA,improv-ing its crystallization rate. The FTIR results show that TBC8-eb can accelerate the conformational ordering of PLLA in the isothermal crystallization. The conformational ordering of PLLA nucleated with TBC8-eb begins with the interchain interaction of CH3,and then a short helix emerges where a couple of CH3 groups interact.