Measuring Erosion of Biodegradable Polymers in Brimonidine Drug Delivery Implants by Quantitative Proton NMR Spectroscopy (q-HNMR).

Erosion of biodegradable polymeric excipients, such as polylactic acid (PLA) and polylactic-co-glycolic acid (PLGA), is generally characterized by microbalance for the remaining mass of PLA and/or PLGA and Gel Permeation Chromatography (GPC) for molecular weight (MW) decrease. For polymer erosion studies of intravitreal sustained release brimonidine implants, however, both microbalance and GPC present several challenges. Mass loss measurement by microbalance does not have specificity for excipient polymers and drug substances. Accuracy of the remaining mass by weighing could also be low due to sample mass loss through retrieval-drying steps, especially at later drug release (DR) time points. When measuring the decrease of polymer MW by GPC, trace amounts of polymeric degradants (oligomers and/or monomers) trapped inside the implants during DR tests may not be measurable due to sensitivity limitations of the GPC detector and column MW range. Previous efforts to measure remained PLGA weight of dexamethasone micro-implants using qNMR with external calibration have been performed, however, these measurements do not account for chemical structure changes (i.e. LA to GA ratio changes from time zero) of PLGA implants during drug release tests. Here, a qNMR method with an internal standard was developed to monitor the following changes in micro-implants during drug release tests: 1. The remaining overall PLA/PLGA mass. 2. The remaining lactic acid (LA), glycolic acid (GA) unit and PLGA's lauryl ester end group percentages. 3. The trace content of PLA/PLGA oligomers as degradants retained in the implants. Unlike microbalance analysis, qNMR has both specificity for drug substance, excipient polymer, and accuracy due to minimal implant loss during sample preparation. Compared to the overall PLA/PLGA remaining mass generally monitored in erosion studies, the percentage of remaining LA, GA, and the ester end group provide more information about the microstructure change (such as hydrophobicity) of PLA/PLGA. Additionally, the qNMR method can complement GPC methods by measuring the change of remaining PLA and PLGA oligomer concentrations in brimonidine implants, with tenfold less sample and no MW cutoff. The qNMR method can be used as a sensitive tool for both polymer excipient characterization and kinetics studies of brimonidine implant erosion.

Facilely Promoting the Concentration of Baicalin in Polylactic Acid Fiber for UV Shielding and Antibacterial Functions: A Customized and Sustainable Approach.

There is a significant trend towards the integration of natural substances with bio-polymers for fully bio-based functional composites. Polylactic acid is regarded as a promising biodegradable polymer for replacing synthetic polymers. Differing from the case of natural fiber, the incompatibility of polylactic acid with bio-based molecules prevents it from being used to fabricate high-quality sustainable composites. This work presents a simultaneous ultraviolet shielding and antibacterial finishing process of polylactic acid combined with bioactive baicalin and an eco-friendly ester, which is highlighted for (a) the lack of synthetic chemicals involved in such process, (b) adsorption enhancement achieved at a mild temperature, and (c) marginal color change on treated polylactic acid. A response surface methodology was adopted to analyze the impacts of various factors on the baicalin quantity in polylactic acid, and to optimize the treatment condition. The uptake ratio of baicalin in polylactic acid was drastically promoted from 8.5 mg/g to 21.1 mg/g using methyl cinnamate. The response surface methodology based on a central composite design experiment indicated that the usage of baicalin was the most significant factor followed by methyl cinnamate and temperature. After optimization, a very faint color depth of 1.2 was apparent, but UPF 50+ and 92% bacterial reduction could be achieved. In all, the success in strengthening of the functionalities of polylactic acid extends the applications of polylactic acid products.

Reinforcing Efficiency of Recycled Carbon Fiber PLA Filament Suitable for Additive Manufacturing.

The use of 3D printing technology for manufacturing new products based on sustainable materials enables one to take advantage of secondary raw materials derived from recycling. This work investigates the structural performances of 3D printing composite filaments based on polylactic acid (PLA), as a matrix, reinforced by recycled carbon fiber (rCF). Carbon fibers were recovered from industrial scraps by a patented thermal process and used to produce thermoplastic composite filaments for additive manufacturing without any additional treatment and additives. The influence of the recovered carbon fiber (rCF) content on the thermal properties, mechanical properties and microstructure of the composites was studied in the range of 3-20 wt%. The recorded TGA curves exhibited a one-stage weight loss within the temperature range 290-380 °C for all samples and the residual rCF content was in good agreement with the theoretical fiber loading. The Young modulus of the extruded filaments strongly increased below a critical content (5 wt%), while at higher content the improvement was reduced. An increase in the storage modulus of 54% compared to neat PLA 3D printed sample resulted in a printed specimen with a higher rCF content. SEM images highlighted a strong rCF prevailing alignment in the direction of the extrusion flow, creating almost unidirectional reinforcement inside the filament. These findings suggest that homogeneous composite filaments reinforced with well-dispersed recycled CF without additional chemical modification and additives are suitable materials for additive manufacturing. The effect of rCF topological distribution within the material on the mechanical performances has been discussed, highlighting that the isolated fibers could efficiently transfer loads with respect to the percolated 3D network and have been correlated with the microstructure.

Carbon Fiber-Reinforced PLA Composite for Fused Deposition Modeling 3D Printing.

Polylactic acid (PLA) composite serve as widely used filaments in fused deposition modeling (FDM) 3D printing. This study investigates the enhancement of PLA composite's comprehensive mechanical properties and thermal stability through the incorporation of carbon fiber (CF). The influence of FDM process parameters on the mechanical properties of PLA composite is also analyzed. Results show that adding 5 wt.% CF significantly enhances the stiffness and comprehensive mechanical properties of PLA composite. The order of printing factors affecting the tensile strength of the PLA composite product is as follows: printing layer thickness, bottom plate temperature, printing speed, and nozzle temperature. Finally, optimal tensile strength is achieved under specific conditions: 0.1 mm layer thickness, 60 °C bottom plate temperature, 40 mm/s printing speed, and 215 °C nozzle temperature.

Influence of Carbonyl Iron Particles (CIP) and Glass Microspheres on Thermal Properties of Poly(lactic acid) (PLA).

In this investigation, composite poly(lactic acid) (PLA) systems of hollow glass microspheres (MS) and carbonyl iron particles (CIP) were processed and characterized to investigate the effects of using conductive and insulating particles as additives in a polymer system. PLA-MS and PLA-CIP were set at the two levels of 3.94 and 7.77 vol.% for each particle type to study the effects of the particle material type and loading on neat PLA's thermal properties. It was observed during the twin-screw extrusion that the addition of CIP greatly decreased the viscosity of the PLA melt during processing. Correlations determined using thermogravimetric analysis, differential scanning calorimetry, thermal conductivity, and shear rheology provided insights into how thermal stability was affected. The incorporation of MS and CIP altered thermal properties such as the glass transition temperature (Tg), melting temperature (Tm), and cold crystallization temperature (Tcc). The metal CIP-filled systems had large increases in their thermal conductivity values and viscoelastic transitions compared to those with PLA that were correlated with the observed overheating during extrusion.

Synergistic effect of TiO2 nanoparticles and poly (ethylene-co-vinyl acetate) on the morphology and crystallization behavior of polylactic acid.

The impact of adding ethylene vinyl acetate copolymer (EVA 80) and 1 wt% TiO2 nanoparticles on the morphology and crystallization behavior of poly(lactic acid) blends was investigated using DSC, SEM, and POM. Thermal analysis revealed the enhancement of crystallinity of PLA in the presence of TiO2 and higher EVA 80 content in the blend. The PLA and EVA 80 components showed compatibility, as evidenced by the shift of the glass transition temperatures of the PLA phase in the blend to lower values compared to neat PLA. The lower temperature shift of the cold crystallization of the PLA and the formation of the small spherulites of the PLA in the blends indicated that the EVA 80 and TiO2 act as a nucleating agent for crystallization. The non-isothermal crystallization parameters of the composites were evaluated using Avrami's modified model, the MO approach, and Friedman's isoconversional method. The Avrami's modified rate constant (K) and the effective activation energy values significantly increased with the incorporation of EVA 80 and TiO2 nanoparticles. Furthermore, the thermogravimetric analysis (TGA) showed improved thermal stability of PLA by adding EVA 80 and TiO2.

Examination of primary aromatic amines content in polylactic acid straws and migration into food simulants using SERS with LC-MS.

Polylactic acid (PLA) straws hold eco-friendly potential; however, residual diisocyanates used to enhance the mechanical strength can generate carcinogenic primary aromatic amines (PAAs), posing health risks. Herein, we present a rapid, comprehensive strategy to detecting PAAs in 18 brands of food-grade PLA straws and assessing their migration into diverse food simulants. Surface-enhanced Raman spectroscopy was conducted to rapidly screen straws for PAAs. Subsequently, qualitative determination of migrating PAAs into various food simulants (4 % acetic acid, 10 % ethanol, 50 % ethanol) occurred at 70 °C for 2 h using liquid chromatography-mass spectrometry. Three PAAs including 4,4'-methylenedianiline, 2,4'-methylenedianiline, and 2,4-diaminotoluene were detected in all straws. Specifically, 2,4-diaminotoluene in 50 % ethanol exceeded specific migration limit of 2 µg/kg, raising safety concerns. Notably, PAAs migration to 10 % and 50 % ethanol surpassed that to 4 % acetic acid within a short 2-hour period. Moreover, PLA straws underwent varying degrees of shape changes before and after migration. Straws with poly(butylene succinate) resisted deformation compared to those without, indicating enhanced heat resistance, while poly(butyleneadipate-co-terephthalate) improved hydrolysis resistance. Importantly, swelling study unveiled swelling effect wasn't the primary factor contributing to the increased PAAs migration in ethanol food simulant, as there was no significant disparity in swelling degrees across different food simulants. FT-IR and DSC analysis revealed higher PAAs content in 50 % ethanol were due to highly concentrated polar ethanol disrupting hydrogen bonds and van der Waal forces holding PLA molecules together. Overall, minimizing contact between PLA straws and alcoholic foods is crucial to avoid potential safety risks posed by PAAs.

Characteristics of biofilms on polylactic acid microplastics and their inhibitory effects on the growth of rice seedlings: A comparative study of petroleum-based microplastics.

Increasing evidence highlights the negative effects of microplastics (MPs) on crops and bio-based plastics offer an alternative to conventional plastics. However, there is limited knowledge on the impacts and mechanisms of bio-based MPs on crop physiology. In this study, bio-based polylactic acid (PLA) and petroleum-based MPs [polyamide (PA) and polypropylene (PP)] were added to hydroponic cultures planted with rice (Oryza sativa L.) seedlings to assess their toxicity. Compared to PA and PP MPs, PLA MPs experienced greater aging after 28 days of exposure, and their surfaces were loaded with more rod-shaped microorganisms with potential plastic degradation ability, such as Proteobacteria and Bacteroidota, which competed with rice seedlings for carbon and nitrogen sources for self-multiplication, thus altering the carbon fixation and nitrogen cycling processes during rice seedling growth. Down-regulation of amino acid and lipid metabolisms in the PLA treatment inhibited the normal synthesis of chlorophyll in rice seedling leaves. Consequently, decreases in the biomass and height of rice seedling roots and shoots were observed in the PLA MP treatment. This study provides evidence that bio-based MPs may have a more severe impact on crop growth than petroleum-based MPs.

Fluorescent Polylactic acid composite incorporating lignin-based carbon quantum dots for sustainable 4D printing applications.

Fluorescent 4D printing materials, as innovative materials that combine fluorescent characteristics with 4D printing technology, have attracted widespread interest and research. In this study, green lignin-derived carbon quantum dots (CQDs) were used as the fluorescent module, and renewable poly(propylene carbonate) polyurethane (PPCU) was used for toughening. A new low-cost fluorescent polylactic acid (PLA) composite filament for 4D printing was developed using a simple melt extrusion method. The strength of the prepared composite was maintained at 32 MPa, while the elongation at break increased 8-fold (34 % increase), demonstrating excellent shape fixed ratio (∼99 %), recovery ratio (∼92 %), and rapid shape memory recovery speed. The presence of PPCU prevented fluorescence quenching of the CQDs in the PLA matrix, allowing the composite to emit bright green fluorescence under 365 nm ultraviolet light. The composite exhibited shear thinning behavior and had an ideal melt viscosity for 3D printing. The results obtained demonstrated the versatility of these easy-to-manufacture and low-cost filaments, opening up a novel and convenient method for the preparation of strong, tough, and multifunctional PLA materials, increasing their potential application value.

Vanillin-based flame retardant enables polylactic acid high-efficiency fireproof, anti-UV and oxygen barrier for food packaging.

Polylactic acid (PLA) is widely known for its biocompatibility, biodegradability, and high transparency. However, it still has varied limitations such as flammability, UV sensitivity, and poor oxygen barrier properties. To address these issues, a bio-based compound, hexasubstituted cyclotriphosphazene (HVP), was synthesized by using vanillin and hexachlorocyclotriphosphazene to enhance the overall performance of PLA. The resulting PLA/HVP composites demonstrated improved mechanical strength and UV resistance. Specifically, PLA/3HVP, with a 3 wt% HVP loading, achieved a UL-94 V-0 rating and a high limiting oxygen index of 26.5 %. Cone calorimeter tests revealed that PLA/3HVP possessed a significantly longer ignition time and a lower peak heat release rate compared to pure PLA. These burning testing results indicated the enhanced fire resistance. Additionally, the oxygen transmission rate of PLA/3HVP was reduced by 81.1 % compared to pure PLA. When used as food packaging, the weight loss of mangoes covered with PLA/3HVP film was 2.2 % after 7 days, compared to 2.5 % with pure PLA film, highlighting its potential for food preservation applications.

Three-dimensional-printed femoral diaphysis for biomechanical testing-Optimization and validation.

Polylactic acid (PLA) models of normal human femoral diaphyses were designed using three-dimensional (3D) printing technology to create inexpensive, accessible, and reproducible specimens for flexural biomechanical studies. These models were subjected to three-point bending and their response to loading was characterized. The anisotropic mechanical behavior of the 3D-printed femurs and the influence of printing orientations, infill density, wall layers, resolution, and other printing parameters were explored to develop a design space. The objective of the design space was set to emulate the flexural biomechanical response of the normal human femur bones. Results show the 3D-printed PLA diaphyseal femurs with 5% infill density, two-four wall layers, and a resolution of 200 µm resulted in a flexural strength of 184.8 ± 8.18 MPa. Models with 20% infill density and six wall layers resulted in a flexural modulus of 18.54 ± 0.543 GPa. These results emulate the biomechanical response of the normal human femur, as determined by historical target values derived from prior cadaveric and 3D printing data. With further research, inclusive of modeling the proximal and distal femur and more comprehensive biomechanical testing, 3D-printed femurs may ultimately serve as a cheap, accessible biomechanical resource for surgeons and researchers.

A new strategy for the preparation of polylactic acid composites with UV resistance, light conversion, and antibacterial properties.

A novel rare earth complex, Eu(IAA)2(phen)2 (EuIP), was synthesized by solution-based synthesis method. Then, EuIP and polylactic acid (PLA) were melt-blended at 190 °C to obtain a multifunctional PLA/EuIP composite. The incorporation of EuIP provided PLA/EuIP composites with good light conversion ability. Under UV irradiation, PLA/EuIP composites converted the absorbed UV light into red light. Moreover, the PLA/1.0EuIP composite exhibited excellent light transmittance of 88 % in the visible region and showed strong red emission under UV light. After UV irradiation for 96 h, the molecular weights and mechanical properties of neat PLA decreased dramatically. Interestingly, the molecular weights and mechanical properties of PLA/EuIP composites did not deteriorate after 96 h of UV irradiation. The reason was that EuIP could absorb UV light and utilize the absorbed energy to emit red fluorescence. Furthermore, PLA/EuIP composites showed good antibacterial activities against E. coli and S. aureus. In addition, in vitro cell experiments showed that PLA/EuIP composites was suitable for the growth of murine breast cancer (4 T1) cells. Besides, enzymatic degradation testing also proved that PLA/EuIP composites had good biodegradability. This work provides an ingenious design strategy for the preparation of PLA/EuIP composites possessing light conversion ability, UV resistance, and antibacterial properties.

High toughness and fast home-compost biodegradable packaging films derived from polylactic acid/thermoplastic starch/para-rubber ternary blends.

This research aims to formulate biobased and biodegradable packaging films with high toughness and fast home-compost biodegradation using ternary blends of polylactic acid (PLA), Para rubber (NR), and thermoplastic starch (TPS) through blown-film extrusion. The TPS content in this work ranges from 5 to 20 wt%, while the PLA: NR ratio is fixed at 70:30. At this PLA: NR ratio, the blend with 10 wt% TPS (PNT10) exhibited the highest % elongation at break and tensile toughness. Peroxide radical initiator was investigated as a potential additive for improving the properties of the ternary blend. Our binary interaction study indicated that peroxide initiated grafting reactions of PLA-NR and NR-TPS pairs, while no grafting occurred between PLA and TPS. In ternary blends, the highest peroxide content (0.5 wt%) increased the % elongation at break up to 120%, with the tensile toughness reaching 7255 MJ/m3. The improved compatibility induced by peroxide addition was supported by enhanced dispersion of TPS in the PLA/NR matrices. Results from the room-temperature soil burial test indicated that the presence of TPS could significantly accelerate the home-compost degradation of PNT films compared to films produced from neat PLA and PLA/NR. This suggests its potential as both a cost reducer and a biodegradation accelerator.

DOX-PLGA Nanoparticles Effectively Suppressed the Expression of Pro-Inflammatory Cytokines TNF-a, IL-6, iNOS, and IL-1ß in MCF-7 Breast Cancer Cell Line.

Background: Inflammation contributes to cancer pathobiology through different mechanisms. Higher levels of pro-inflammatory cytokines can lead to hyperinflammation and promote cancer development and metastasis. For cancer treatment, Doxorubicin (DOX) can be encapsulated into the poly-lactic-glycolic acid (PLGA) nanoparticles. This study aimed to investigate the impact of doxorubicin-loaded PLGA nanoparticles (DOX-PLGA NP) on the expression of pro-inflammatory genes TNF-α, IL-6, iNOS, and IL-1ß in the MCF-7 cells. Methods: The DOX-PLGA NP was prepared by loading doxorubicin into PLGA and characterized using dynamic light scattering (DLS) and atomic force microscopy (AFM). The cytotoxic effect of the nanoparticles was determined by the MTT assay, and their impacts on the expression of pro-inflammatory genes were assessed by qRT-PCR. Results: The encapsulation efficiency and loading capacity were 60±1.5 and 1.13±0.21 percent, respectively. The zeta potential and mean DOX-PLGA nanoparticle size were -18±0.550 mV and 172±55.6 nm, respectively. The 50% inhibitory concentration (IC50) of the DOX-PLGA NP on MCF-7 cell viability was 24.55 µg/mL after 72 hours of treatment. The qRT-PCR results revealed that the 20 µg/mL concentration of the DOX-PLGA NP significantly suppressed the expression of the pro-inflammatory genes TNF-α, IL-6, iNOS, and IL-1ß compared to DOX alone (20 µg/mL). Additionally, the suppression effect of DOX-PLGA NP on the expression of these pro-inflammatory genes was dose-dependent. Conclusions: These results show that DOX-PLGA NP efficiently suppressed the expression of pro-inflammatory genes. Furthermore, encapsulation of DOX into PLGA nanoparticles significantly improved the effectiveness of DOX in suppressing pro-inflammatory genes in MCF-7 breast cancer cells.

5-Fluorouracil-Loaded PLGA Declined Expression of Pro-Inflammatory Genes IL-9, IL-17A, IL-23 and IFN- y; in the HT-29 Colon Cancer Cell Line.

Background: Pro-inflammatory cytokines play critical roles in cancer pathobiology and have been considered potential targets for cancer management and therapy. Understanding the impact of cancer therapeutics such as 5-fluorouracil (5-FU) on their expression might shed light on development of novel combinational therapies. This study aimed to encapsulate 5-FU into PLGA and evaluate their effects on the expression of pro-inflammatory genes IL-9, IL-17-A, IL-23, and IFN-y; in the HT-29 cells. Methods: PLGA-5-FU NPs were constructed and characterized by Dynamic Light Scattering (DLS) and Atomic Force Microscopy (AFM). The cytotoxicity was evaluated by MTT test and, the IC50 was identified. HT-29 cells were treated with different concentrations of the PLGA-5-FU NPs for 48 hours and, gene expression levels were analyzed by qRT-PCR. Results: DLS and AFM analysis revealed that the prepared PLGA-5-FU NPs were negatively charged spherical-shaped particles with a mean size of 215.9 ± 43.3 nm. PLGA-5-FU NPs impacted the viability of HT-29 cells in a dose- and time-dependent manner. The qRT-PCR results revealed a dose-dependent decrease in the expression of IL-9, IL-17A, IL-23 and IFN-y; genes, and their expressions were significantly different in both 10 and 20 µg/mL treated groups compared to the control. However, although the treatment of HT-29 cells with 20 µg/mL free 5-FU resulted in decreased expression of the studied genes, the differences were not statistically significant compared to the control group. Conclusion: PLGA-5-FU NPs significantly suppressed expression of the IL-9, IL-17A, IL-23 and IFN-y; genes, and the encapsulation of 5-FU into PLGA improved considerably impact of the 5-FU on the HT-29 cells.

Development and characterization of polylactic acid/starch biocomposites - From melt blending to preliminary life cycle assessment.

This study presents a comprehensive analysis encompassing melt blending, characterization, life cycle assessment (LCA), and 3D printing of a range of polylactic acid (PLA)/starch biocomposites, with starch content varying from 0 to 50 wt%. To enhance compatibility between the starch particles and the PLA matrix, we utilized a solvent-free method to graft N-octadecyl isocyanate (ODI) molecules onto the surface of the starch particles, resulting in ODI-g-starch, which yielded several improved properties. Notably, toughness and elongation at break improved by approximately 170 % and 300 %, respectively. Moreover, the crystallinity increased from 11.6 % in plain PLA to 30.1 %, suggesting that the uniform dispersion of ODI-g-starch particles acted as nucleating sites for the crystallization of PLA chains. Additionally, viscosity decreased significantly with the introduction of ODI-g-starch particles, indicating their plasticizing effect, thereby enhancing the processability and ease of fabrication of the biocomposite. Crucially, our LCA analysis revealed a significant reduction in the carbon footprint of these biocomposites, up to 18 % and 63 %, compared to plain PLA and selected fossil-based plastics, respectively, upon the incorporation of ODI-g-starch. In summary, our research introduces the newly developed PLA/starch biocomposites as a sustainable and eco-friendly alternative to commercially available plain PLA and specific fossil-based plastics.

Influence of carboxy-terminated hyperbranched polyester and polyethylene glycol on the mechanical and thermal properties of polylactic acid/straw flour composites.

Polylactic acid (PLA) wood-plastic composites have a significant advantage over traditional petroleum-based plastics due to their biodegradability. However, PLA has several shortcomings, including high brittleness, low heat resistance, slow crystallization, and poor compatibility with biomass materials, which have limited its potential applications. In this paper, we investigated the effects of carboxy-terminated hyperbranched polyester (CHBP) on the mechanical, crystalline, and thermal properties of PLA/straw flour (SF) blends through extrusion injection molding. Additionally, we added the traditional plasticizer polyethylene glycol (PEG) to synergize with CHBP to enhance the toughness of PLA/SF composites. Our results showed that the appropriate addition of CHBP effectively improved the interfacial bonding between PLA and straw flour. The incorporation of CHBP also improved the tensile strength, bending strength, impact strength, elongation at break, thermal stability, and crystallization rate of the composites. Furthermore, the addition of both CHBP and PEG significantly improved the impact strength of the composites compared to using PEG alone. This method also improved the heat resistance of the material and reduced the migration of plasticizers. Our study demonstrates the feasibility of using hyperbranched polymers and plasticizers to enhance the toughness, thermal stability, and crystalline properties of PLA wood-plastic composites, providing a new approach to improving the properties of these composites.

Carrier cascade target delivery of 5-aminolevulinic acid nanoplatform to enhance antitumor efficiency of photodynamic therapy against lung cancer.

5-Aminolevulinic acid (5-ALA) is a prodrug of porphyrin IX (PpIX). Disadvantages of 5-ALA include poor stability, rapid elimination, poor bioavailability, and weak cell penetration, which greatly reduce the clinical effect of 5-ALA based photodynamic therapy (PDT). Presently, a novel targeting nanosystem was constructed using gold nanoparticles (AuNPs) as carriers loaded with a CSNIDARAC (CC9)-targeting peptide and 5-ALA via Au-sulphur and ionic bonds, respectively, and then wrapped in polylactic glycolic acid (PLGA) NPs via self-assembly to improve the antitumor effects and reduce the side effect. The successful preparation of ALA/CC9@ AuNPs-PLGA NPs was verified using ultraviolet-visible, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The analyses revealed good sphericity with a particle size of approximately140 nm, Zeta potential of 10.11 mV, and slow-controlled release characteristic in a weak acid environment. Confocal microscopy revealed targeting of NCL-H460 cells by NPs by actively internalising CC9 and avoiding the phagocytic action of RAW264.7 cells, and live fluorescence imaging revealed targeting of tumours in tumour-bearing mice. Compared to free 5-ALA, the nanosystem displayed amplified anticancer activity by increasing production of PpIX and reactive oxygen species to induce mitochondrial pathway apoptosis. Antitumor efficacy was consistently observed in three-dimensionally cultured cells as the loss of integrity of tumour balls. More potent anti-tumour efficacy was demonstrated in xenograft tumour models by decreased growth rate and increased tumour apoptosis. Histological analysis showed that this system was not toxic, with lowered liver toxicity of 5-ALA. Thus, ALA/CC9@AuNPs-PLGA NPs deliver 5-ALA via a carrier cascade, with excellent effects on tumour accumulation and PDT through passive enhanced permeability and retention action and active targeting. This innovative strategy for cancer therapy requires more clinical trials before being implemented.

Toughening Polylactic Acid with Ultrafine Fully Vulcanized Powdered Natural Rubber Graft-Copolymerized with Poly(styrene-co-acrylonitrile): Tailoring the Styrene-Acrylonitrile Ratio for Enhanced Interfacial Interactions.

This study investigated the sustainable toughening of polylactic acid (PLA) by incorporating ultrafine fully vulcanized powdered natural rubber graft-copolymerized with poly-styrene-co-acrylonitrile (UFPNR-SAN). We investigated the effect of the styrene-to-acrylonitrile ratio (ST:AN) used during the grafting process on the final UFPNR-SAN compatibility with PLA. The ST:AN ratio was systematically varied during the grafting reaction to prepare UFPNR-SAN with a range of different surface energies. The ST:AN ratio of 4:1 showed the highest compatibility with the PLA matrix, attributed to optimal interfacial interactions and improved dispersion, as indicated by contact angle measurements and SEM observations. This resulted in a remarkable toughening of the PLA/UFPNR-SAN composite. For instance, an obvious fully ductile behavior without crack formation and flexural strain of around 17.5% against 5% of the neat PLA was recorded. In addition, 3.5 times improvement in the impact strength of the composite at 25 wt% dosage of the UFPNR-SAN was also achieved without compromising thermal properties. Overall, this study established the suitable ST:AN ratio on the grafting onto natural rubber to enhance interfacial interactions with PLA and its effects on the properties of the resulting PLA/UFPNR-SAN bio-based composite.