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...

pH-Compensation Effect of Lysine on the Acidic Degradation of Electrospun Poly( lactide-co-glycolide) Fibers in PBS

Electrospun aligned ultrafine fibers of poly( lactide-coglycolide)( PLGA) can be used to construct biomimetic scaffolds for engineering those structurally anisotropic and dense tissues( e. g.,tendon,ligament,etc.). But the acidic degradation products of the PLGA could result in p H decrease in the vicinity of the scaffolds,which may give rise to biocompatibility concerns. To address the noted problem, this study was designed to evaluate the p Hcompensation capacity of using Lysine( Lys) —a kind of basic amino acid on the acidic degradation products of PLGA. Ultrafine PLGA( 50∶ 50) fibers with 0,10%,20%,and 30% by weight of Lys loadings were prepared by a stable jet electrospinning( SJES)approach. The morphology,structure,and mechanical properties of the electrospun aligned fibrous mats of Lys-incorporated PLGA( 50∶50) were characterized by scanning electron microscope( SEM),Fourier transform infrared spectroscopy( FTIR),and tensile testing,respectively. Thereafter,the fibrous PLGA( 50 ∶50) scaffolds were subjected to degradation by being immersed in phosphate buffered saline( PBS,p H 6. 86) solution at 37 ℃ for 5weeks. Our results show that the formed Lys / PLGA composite ultrafine fibers have a well-aligned and uniform morphology with a fineness of ca. 1 #m in diameter. Introduction of Lys led to increased mechanical performance; that is,when the Lys loading is less than 30%,tensile strength and Young's modulus of the aligned Lys / PLGA fibers reached up to the impressive values of 84. 5 MPa and 2. 4 GPa,respectively. Degradation results show that the p H of the PLGA group fell to 5. 6 in 5 weeks while the p H of the Lys /PLGA groups with 10%,20%, and 30% of Lys loadings was maintained at 6. 3, 6. 5 and 6. 7, respectively. This work demonstrated that incorporation of Lys into electrospun PLGA fibers could be an effective approach in mediating the p H decrease caused by the acidic degradation products of the PLGA.

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.

Preparation of poly(lactide-co-glycolide)microspheres and evaluation of pharmacokinetics and tissue distribution of BDMC-PLGA-MS in rats

The aim of the present study was to develop a novel long-acting Poly(lactic-co-glycolic acid)(PLGA)-based microspheres formulation of Bisdemethoxycurcum(BDMC) by emulsionsolvent evaporation method. Meanwhile, the effects of the volume ratio of the dispersed phase and continuous phase, the concentration of PLGA and PVA, the theoretical drug loading and stirring speed were investigated. The mean diameter of the microspheres was 8.5 μm and the size distribution was narrow. The encapsulation efficiency(EE) and drug loading efficiency(DLE) of BDME loaded PLGA microspheres(BDMC-PLGA-MS) was 94.18% and 8.14%,respectively. In an in vitro study of drug release, it can be concluded that the BDMC-PLGAMS exhibited sustained and long-term release properties for 96 h. Stability studies suggested that the microspheres we prepared had a very good stability. Furthermore, the results of an in vivo study indicated that the BDMC-PLGA-MS had sustained release effect and was mainly distributed in the lung tissue, and less distribution in other tissues, which indicated that microspheres could be an effective parenteral carrier for the delivery of BDMC in lung cancer treatment.

Microwave-assisted Polymerization of D,L-Lactide with Stannous Octanoate as Catalyst

Poly (lactic acid) (PLA) was synthesized by microwave-assisted ring-opening polymerization of D, L-lactide with stannous octanoate (SnOct(2)) as catalyst. Its weight-average molar mass (M-w) ranged from 39000 to 67000 and the polydispersity index from 1.3 to 1.7. The polymerization rate was much faster than that of the conventional thermal polymerization. A degradation of newly formed PLA in reaction mixture by microwave irradiation was observed.

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.

A STUDY OF STRUCTURE AND PROPERTY CHANGES OF BIODEGRADABLE POLYGLYCOLIDE AND POLY(GLYCOLIDE-co-LACTIDE)FIBERS DURING PROCESSING AND IN VITRO DEGRADATION

Structure and properties of bioabsorbable polyglycolide (PGA) and poly(glycolide-co-lactide) (PGA-co-PLA)fibers were investigated during several industrial processing stages and in vitro degradation by means of wide-angle X-raydiffraction (WAXD), dynamic mechanical analysis (DMA) and mechanical property tests. In the orientation stage, the PGAfibers were found to have higher degrees of crystallinity than corresponding PGA-co-PLA samples produced under similarconditions. In the hot-stretching and post-annealing stages, after fibers were braided, PGA samples were found to gain morecrystallinity and higher T_g than PGA-co-PLA samples. The higher crystallinity in PGA fibers resulted in a slower rate ofdegradation. DMA results showed that a great deal of internal stress that was built during orientation and hot-stretchingstages was released in the post-annealing stage for a1l PGA and PGA-co-PLA samples. During earlier stages of in vitrodegradation, both PGA and PGA-co-PLA samples exhibited the typical cleavage-induced crystallization mechanism. Theheat shrinkage in the glass transition area was found to disappear after 6-8 days of degradation for all PGA and PGA-co-PLAsamples, indicating the amorphous portions of the polymers lost orientation after a short period in the buffer solution, mostlikely due to relaxation of the cleaved chains.

Bioactivity of bioresorbable composite based on bioactive glass and poly-L-lactide

Bioactive and bioresorbable composite was fabricated by a solvent evaporation technique using poly-L-lactide(PLLA) and bioactive glass (average particle size: 6.8 μm). Bioactive glass granules are homogeneously distributed in the composite with microcrack structure. The formation of hydroxyapatite(HA) on the composite in simulated body fluid(SBF) was analyzed by scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), X-ray diffraction(XRD), and Raman spectra. Rod-like HA crystals deposit on the surface of PLLA/bioactive glass composite after soaking for 3 d. Both rod-like crystals and HA layer form on the surface for 14 d in SBF. The high bioactivity of PLLA/bioactive glass composite indicates the potential of materials for integration with bone.

Preparation and characterization of poly(D,L-lactide) and its porous biomaterials

Poly(D,L-lactide) was synthesized by indirect method from D,L-lactic acid and characterized by infrared spectrum and proton nuclear magnetic resonance. The influences of monomer purity, initiator concentration, polymerization temperature and polymerization time on the relative molecular mass of poly(D, L-lactide) were investigated. The polylactide was made into porous materials by using solvent-casting particulate-leaching method. Under the optimized conditions, polylactides with a viscosity average molecular mass up to 1.82×105 are obtained and the results are fairly reproducible. Scanning electron microscope observation indicates that the sample is highly porous and well-distributed with good interconnections between pores and the pore size of porous materials is in the range from 200 μm to 500 μm and it can be used as scaffold for bone tissue engineering.

Poly(L-lactide)-Poly(ethylene glycol) Multiblock Copolymers: Synthesis and Properties

Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as better miscibility between the two components, low crystallinity and better hydrophilicity, which can be modulated by adjusting the block lengths of the two components.

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.

NON-ISOTHERMAL CRYSTALLIZATION OF POLY(L-LACTIDE)(PLLA) UNDER QUIESCENT AND STEADY SHEAR CONDITIONS

The non-isothermal crystallization of poly（L-lactide） （PLLA） under quiescent and steady shear flow conditions was in situ investigated by using polarizing optical microscopy （POM） with a hot shear stage and wide-angle X-ray diffraction （WAXD）. The shear rate and the cooling rate both play a significant role in the final crystalline morphology and crystallinity. Under quiescent conditions, the morphology assumes different sized spherulites, and its crystallinity dramatically reduces with increasing the cooling rate. On the other hand, the shear flow increases the onset crystallization temperature, and enhances the final crystallinity. When the shear rate is above 5 s^-1, cylindrite-like crystals are observed, furthermore, their content depends on the cooling rate.

Different crystallinity of poly(d,l-lactide-co-p-dioxanone) copolymers acquired by control of chain microstructure

Poly（d,l-lactide-co-p-dioxanone） （P（LA-co-PDO）） copolymers with different chain microstructures were synthesized by onestep or two-step bulk ring-opening polymerizations of d,l-lactide （LA） and p-dioxanone （PDO） monomers using stannous octoate [Sn（Oct）2]/n-dodecanol as the initiating system. The average sequence lengths of the lactidyl （LLA） and dioxanyl （LpDo） units were calculated from the ^1H NMR spectra. It was found that both LLA and Lpoo values from the two-step syntheses were significantly longer than those from the corresponding one-step syntheses, indicating more blocky structure achieved for the twostep copolymers. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline, while the one-step copolymers were completely amorphous. In conclusion, the crystallinity of P（LA-co-PDO） copolymers could be adjusted conveniently to meet specific applications by changing the microstructure of the copolymers via different polymerization routes.

RING-OPENING COPOLYMERIZATION OF DL-LACTIDE AND POLY(ETHYLENE GLYCOL) INITIATED BY LANTHANUM ACETATE AND APPLICATION OF THE COPOLYMER AS MATRIX OF MICROSPHERES CONTAINING VIBRIO CHOLERA ANTIGENS

Poly-dl-lactide-poly(ethylene glycol) (PELA) triblock copolymers were synthesized with lanthanum acetate as the initiator. PELA microspheres with entrapped Vibrio Cholera antigen and outer membrane protein (OMP) were prepared by a double emulsion W/O/W based on solvent extraction methods. The obtained microspheres showed smooth and spherical surface and their size varied between 0.5 and 5.0 mu m, which are suitable for oral targeting delivery system. The distribution tests in rabbits and mice through scanning electronic micrography and fluorescence microscope indicated that microspheres have successfully reached the immunization-related tissues, such as the liver, spleen and intestinal peyer's patches, following oral administration. The PELA microspheres were also evaluated as an efficient antigen delivery system by enhancing a higher protective ratio against live Vibrios Cholera.

SYNTHESIS,CHARACTERIZATION AND NANOPARTICLE FORMATION OF STAR-SHAPED POLY(L-LACTIDE)WITH SIX ARMS

Well-defined star-shaped poly(L-lactide)with six arms(sPLLA)was synthesized via the ring-opening polymerization of L-lactide using dipentaerythritol as initiator and stannous octoate as catalyst in bulk at 125~C.The effects of molar ratios of both monomer to initiator and monomer to catalyst on the molecular weights of as-synthesized sPLLA polymers were in detail investigated.The molecular weights of sPLLA polymers linearly increased with the molar ratio of monomer to initiator,and the molecular weight dist...

Silk Fibroin/Poly-L-lactide Lactone Bi-layered Membranes for Guided Bone Regeneration

After removal of the caries or diseased teeth,the alveolar ridge will undergo absorption and atrophy.When the amount of alveolar bone is insufficient,it will cause an inability to perform effective dental implant restoration.In order to control the absorption and promote the repair and regeneration of alveolar ridge,a method of implanting guided bone regeneration(GBR)membranes at the extraction site is often used.In this study,silk fibroin(SF)and poly-L-lactide lactone(PLCL)were used to prepare bilayered guided bone regeneration membranes,and its morphology,hydrophilicity,surface roughness and mechanical properties were studied.At the same time,the drug release behaviors and cell compatibility of the bilayered membranes were studied.The results showed that SF/PLCL bi-layered membranes had good mechanical properties and surface hydrophilicity,and the drug-loaded bi-layered membranes had good cell compatibility.The bilayered membranes fabricated in this study are of potential for applying in the oral health field to promote bone regeneration.

Biodegradation of Absorbable Hydroxyapatite/Poly-DL-lactide Composites in Different Environment

To develop a new generation of absorbable fracture fixation devices with enhanced biocompatibility, the biodegradation mechanism and its influence on the cellular response at the tissue/implant interface of hydroxyapatite/ poly DL lactide (HA/PDLLA) composites were investigated in vitro and in vivo.HA/PDLLA rods were immersed in phosphate buffered saline,or implanted in muscle and bony tissue for 52 weeks.Scanning electron microscopic and histological studies were done.The degradation rate was the slowest in vitro,slower in muscle tissue and fast in bone.In vitro, the composites degraded heterogeneously and a hollow structure was formed.In bone,the limited clearing capacity leads to the accumulation of oligomeric debris,which contribute totally to the autocatalytic effect.So,the fastest degradation and intense tissue response were seen.In muscle tissue,oligomeric debris migrated into vicinal fibers over a long distance from the original implant cavity and the tissue reactions were,however, quite moderate.For the same size organic/inorganic composite,the environment where it was placed is the major factor in determining its biodegradation process and cellular reaction.In living tissue,factors such as cells,enzymes and mechanical stress have an obvious influence on the biodegradation and biological process at the tissue/implant interface.The biocompatibility of the HA/PDLLA composites is enhanced with the incorporating of the resorbable HA microparticles.

MISCIBILITY AND CRYSTALLIZATION BEHAVIOR OF BIODEGRADABLE BLEND OF POLY(β—HYDROXYBUTYRATE)AND POLY(D,L—LACTIDE)—CO—POLY(ETHYLENE GLYCOL)

Studies on the miscibility of PHB/PELA blends showed that PHB and PELA were miscible in amorphous state.The crystallization behavior of PHB in the blend was strongly de- pendent on the addition of PELA component.

MISCIBILITY AND MORPHOLOGICAL STRUCTURE OF BIODEGRADABLE BLEND OF POLY(β—HYDROXYBUTYRATE)AND POLY(D,L—LACTIDE)

The poly(β-hydroxybutyrate)/poly(d,1-lactide)(PHB/PLA)blend was found to be immiscible,the melting point and the phase crystallinity of PHB were independent of the blend composition.Comparing with plain PHB,the blend exhibited the crystallization change and a certain improvement of the mechanical property.

Preparation and biocompatibility evaluation of poly(D,L-lactide-co-glycine)

D,L-lactide was prepared from D,L-lactic acid by means of polymerization and depolymerization at low vacuum level.Morpholine-2,5-dione(MD) was synthesized from the cyclization of chloroacetyl glycine which was made from chloroacetyl chloride and glycine in the basic condition.A novel copolymer(PLAMD) with D,L-lactide(D,L-LA) and morpholine-2,5-dione(MD) was synthesized using stannous octoate as initiator,and characterized with FT-IR and 1HNMR.The biocompatibility of PLAMD and PLA was investigated by MTT and microscope.The results show that amino acid is introduced into PDLLA main chain.PLAMD has better cell affinity than PLA,so it is a promising biomaterial.