Synthesis, Properties, and Enzymatic Hydrolysis of Poly(lactic acid)-co-Poly(propylene adipate) Block Copolymers Prepared by Reactive Extrusion.
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ABSTRACT:
SUBMITTER: Terzopoulou Z
PROVIDER: S-EPMC8659515 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:In the present study, novel block copolymers of poly(l-lactide)-block-poly(propylene adipate) (PLLA-b-PPAd) were synthesized in two ratios, 90/10 and 75/25 w/w and were further investigated as long-acting injectable (LAI) polymeric matrices in naltrexone base microparticle formulations. The synthesized polymers were characterized by 1H-NMR, 13C-NMR, FTIR, XRD, TGA and DSC. NMR and FTIR spectroscopies confirmed the successful synthesis of copolymers while DSC showed that these are block copolymers with well-defined and separated blocks. Microparticles were prepared by single emulsification method and were further characterized. Nanoparticles in the range of 0.4-4.5 ?m were prepared as indicated by SEM, with copolymers giving the lowest particle size. By XRD and DSC it was found that naltrexone was present in the amorphous state in its microparticles. Dissolution study showed a drug release extending over seven days, indicating that these novel PLLA-b-PPAd copolymers could be promising matrices for naltrexone's LAI formulations. It was evidenced that drug release depended on the copolymer composition. Model release studies showed that drug release is controlled by diffusion.
| S-EPMC7240759 | biostudies-literature
Project description:The presented study focuses on the development of flax fiber (FF) reinforced composites prepared with the use of poly(lactic acid)/poly(butylene adipate-co-terephthalate)-PLA/PBAT blend system. This type of modification was aimed to increase impact properties of PLA-based composites, which are usually characterized by high brittleness. The PLA/PBAT blends preparation was carried out using melt blending technique, while part of the samples was prepared by reactive extrusion process with the addition of chain extender (CE) in the form of epoxy-functionalized oligomer. The properties of unreinforced blends was evaluated using injection molded samples. The composite samples were prepared by compression molding technique, while flax fibers reinforcement was in the form of plain fabric. The properties of the laminated sheets were investigated during mechanical test measurements (tensile, flexural, impact). Differential scanning calorimetry (DSC) analysis was used to determine the thermal properties, while dynamic mechanical thermal analysis (DMTA) and heat deflection temperature (HDT) measurements were conducted in order to measure the thermomechanical properties. Research procedure was supplemented with structure evaluation using scanning electron microscopy (SEM) analysis. The comparative study reveals that the properties of PLA/PBAT-based composites were more favorable, especially in the context of impact resistance improvement. However, for CE modified samples also the modulus and strength was improved. Structural observations after the impact tests confirmed the presence of the plastic deformation of PLA/PBAT matrix, which confirmed the favorable properties of the developed materials. The use of PBAT phase as the impact modifier strongly reduced the PLA brittleness, while the reactive extrusion process improves the fiber-matrix interactions leading to higher stiffness and strength.
| S-EPMC8003650 | biostudies-literature
Project description:Polypropylene oxide (PPO) and poly(9-(2,3-epoxypropyl) carbazole) (PEPK) di-block copolymers are prepared in one pot via sequential monomer addition by using i-PrONa/i-Bu3Al as an anionic catalytic system. An almost 100% monomer conversion is obtained, and the length of each block is controlled through the monomer/catalyst ratio used. Copolymer molecular weights are quite close to theoretical values calculated assuming the formation of one polymer chain per catalyst; therefore, it is hypothesized that the polymerization reaction proceeds with a living character. The synthesis appears to be particularly efficient and versatile. The calorimetric properties of copolymers obtained in this work are remarkable, since they show two distinct Tg values, corresponding to the PPO and PEPK blocks. The optical measurements of di-block copolymers show more analogous features than those of PEPK homopolymer. Copolymer solution emission spectra just exhibit isolated carbazole fluorescence, whereas in the solid state, film spectra show excimer fluorescence.
| S-EPMC7957571 | biostudies-literature
Project description:The lipid headgroup plays an important role in the association of polymers with lipid bilayer membranes. Herein, we report how a glycerol headgroup versus a choline headgroup affects the interaction of poly(ethylene oxide)-b-poly(propylene oxide) (PEO-PPO) block copolymers with lipid bilayer vesicles. Unilamellar vesicles composed of phosphatidylcholine and phosphatidylglycerol at various molar ratios were used as model membranes. The interactions between the block copolymers and lipid bilayers were quantified by pulsed-field gradient nuclear magnetic resonance (PFG-NMR) based on the distinctly different mobilities of free and bound polymers. All the investigated polymer species showed significantly higher binding with 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) sodium salt (POPG) liposomes than with 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) liposomes, indicating stronger association with the glycerol headgroup compared to the choline headgroup. This effect did not become significant until the composition of mixed POPC/POPG liposomes contained more than 20 mol % POPG. A plausible explanation for the enhanced polymer binding with POPG invokes the role of hydrogen bonding between the glycerol headgroup and the ether moieties of the polymers.
| S-EPMC7302449 | biostudies-literature
Project description:In this report, poly(lactic acid) (PLA) and Poly(butylene adipate-co-terephthalate) (PBAT) with three kinds of compatibilizers were melt blended under intensive shear flow. A self-made parallel three-screw extruder was developed to generate such flow during the process. Mechanical properties, chemical reactions among PLA, PBAT and compatibilizers, rheological behavior and morphology were investigated. The mechanical tests showed that the notched impact strength of super-tough composite with 10 wt% EGMA is about 20 times than that of pure PLA. The Fourier transform infrared spectroscopy (FT-IR) results showed that the epoxy functional groups or maleic anhydride functional groups of KT-20, KT-915 and EGMA reacted with the hydroxyl groups of PLA or PBAT macromolecules, resulting in a bridge of PLA and PBAT. About rheological properties, the tan ?-angular frequency curves and the ?''- ?' curves confirmed the chemical reactions mentioned above and indicated better compatibility of ?''- ?' between PLA and PBAT, respectively. Meanwhile, the loss modulus and storage modulus-angular frequency curves demonstrated the discrepancy of different compatibilizer components. In particular, from scanning electron microscopy (SEM) images, it can be seen that the phase size and dispersion uniformity of PBAT adjusted by compatibilizer, corresponding to better compatibility that is described in the ?''- ?' curves. The approach for producing super-tough PLA/PBAT/compatibilizer by intensive shear flow provides a viable direction for further improving PLA performance.
| S-EPMC7254402 | biostudies-literature
Project description:In the present work, Risperidone microparticles from poly(lactic acid)/poly(hexylene succinate) (PLA-b-PHSu) block copolymers in different ratios, 95/05, 90/10 and 80/20 w/w, were examined as long-acting injectable formulations. Nuclear magnetic resonance (NMR) was used to verify the successful synthesis of copolymers. Enzymatic hydrolysis showed an increase in weight loss as the content of PHSu increased, while the cytotoxicity studies confirmed the biocompatibility of the copolymers. The polyesters were further used to encapsulate Risperidone by spray drying. The drug-loaded microparticles were studied by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). SEM microphotographs confirmed that spherically shaped microparticles were prepared with sizes about 5-12 μm, while XRD and differential scanning calorimetry (DSC) studies evidenced that Risperidone was encapsulated in amorphous form. The drug loading and the entrapment efficiency of Risperidone were studied as well as the in vitro release from the prepared microparticles. As the content of PHSu increased, a higher release of Risperidone was observed, with PLA-b-PHSu 80/20 w/w succeeding to release 100% of RIS within 12 days. According to theoretical modeling, the kinetics of RIS release from PLA-b-PHSu microparticles is complex, governed by both diffusion and polymer erosion.
| S-EPMC9571843 | biostudies-literature
Project description:The aliphatic-aromatic copolyester poly(butylene adipate-co-butylene terephthalate) (PBAT), also known as ecoflex, contains adipic acid, 1,4-butanediol and terephthalic acid and is proven to be compostable [1], [2], [3]). We describe here data for the synthesis and analysis of poly(butylene adipate-co-butylene terephthalate variants with different adipic acid:terephatalic acid ratios and 6 oligomeric PBAT model substrates. Data for the synthesis of the following oligomeric model substrates are described: mono(4-hydroxybutyl) terephthalate (BTa), bis(4-(hexanoyloxy)butyl) terephthalate (HaBTaBHa), bis(4-(decanoyloxy)butyl) terephthalate (DaBTaBDa), bis(4-(tetradecanoyloxy)butyl) terephthalate (TdaBTaBTda), bis(4-hydroxyhexyl) terephthalate (HTaH) and bis(4-(benzoyloxy)butyl) terephthalate (BaBTaBBa). Polymeric PBAT variants were synthesized with adipic acid:terephatalic acid ratios of 100:0, 90:10, 80:20, 70:30, 60:40 and 50:50. These polymeric and oligomeric substances were used as ecoflex model substrates in enzymatic hydrolysis experiments in the article "Substrate specificities of cutinases on aliphatic-aromatic polyesters and on their model substrates" [4].
| S-EPMC4776266 | biostudies-literature
Project description:Block copolymers composed of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) have been widely used in cell membrane stabilization and permeabilization. To explore the mechanism of interaction between PPO-PEO block copolymers and lipid membranes, we have investigated how polymer structure influences the polymer-lipid bilayer association by varying the overall molecular weight, the hydrophobic and hydrophilic block lengths, and the end-group structure systematically, using 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) unilamellar liposomes as model membranes. Pulsed-field-gradient NMR (PFG-NMR) was employed to probe polymer diffusion in the absence and presence of liposomes. The echo decay curves of free polymers in the absence of liposomes are single exponentials, indicative of simple translational diffusion, while in the presence of liposomes, the decays are biexponential, with the slower decay corresponding to polymers bound to liposomes. The binding percentage of polymer to the liposome was quantified by fitting the echo decay curves to a biexponential model. The NMR experiments show that increasing the total molecular weight and hydrophobicity of the polymer can significantly enhance the polymer-lipid bilayer association, as the binding percentage and liposome surface coverage both increase. We hypothesize that the hydrophobic PPO block inserts into the lipid bilayer due to the fact that little molecular exchange between bound and free polymers occurs on the time scale of the diffusion experiments. Additionally, as polymer concentration increases, the liposome surface coverage increases and approaches a limit. These results demonstrate that PFG-NMR is a simple yet powerful method to quantify interactions between polymers and lipid bilayers.
| S-EPMC6055234 | biostudies-literature
Project description:Injectable, thermoresponsive hydrogels are promising candidates for the delivery, maintenance and controlled release of adoptive cell therapies. Therefore, there is significant interest in the development of cytocompatible and biodegradable thermoresponsive hydrogels with appropriate gelling characteristics. Towards this end, a series of thermoresponsive copolymers consisting of poly(caprolactone) (PCL), poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG) segments, with various PEG:PPG ratios, were synthesised via ring-opening polymerisation (ROP) of ?-caprolactone and epoxy-functionalised PEG and PPG derivatives. The resultant PCL-PEG-PPG copolymers were characterised via proton nuclear magnetic resonance (1H NMR) spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The thermoresponsive characteristics of the aqueous copolymer solutions at various concentrations was investigated using the inversion method. Whilst all of the copolymers displayed thermoresponsive properties, the copolymer with a ratio of 1:2 PEG:PPG exhibited an appropriate sol-gel transition (28 °C) at a relatively low concentration (10 wt%), and remained a gel at 37 °C. Furthermore, the copolymers were shown to be enzymatically degradable in the presence of lipases and could be used for the encapsulation of CD4+ T-cell lymphocytes. These results demonstrate that the thermoresponsive PCL-PEG-PPG hydrogels may be suitable for use as an adoptive cell therapy (ACT) delivery vehicle.
| S-EPMC7077385 | biostudies-literature
Project description:The primary focus of this work is to present the current challenges of printing scaffolds with concentration gradients of nanoparticles with an aim to improve the processing of these scaffolds. Furthermore, we address how print fidelity is related to material composition and emphasize the importance of considering this relationship when developing complex scaffolds for bone implants. The ability to create complex tissues is becoming increasingly relevant in the tissue engineering community. For bone tissue engineering applications, this work demonstrates the ability to use extrusion-based printing techniques to control the spatial deposition of hydroxyapatite (HA) nanoparticles in a 3D composite scaffold. In doing so, we combined the benefits of synthetic, degradable polymers, such as poly(propylene fumarate) (PPF), with osteoconductive HA nanoparticles that provide robust compressive mechanical properties. Furthermore, the final 3D printed scaffolds consisted of well-defined layers with interconnected pores, two critical features for a successful bone implant. To demonstrate a controlled gradient of HA, thermogravimetric analysis was carried out to quantify HA on a per-layer basis. Moreover, we non-destructively evaluated the tendency of HA particles to aggregate within PPF using micro-computed tomography (μCT). This work provides insight for proper fabrication and characterization of composite scaffolds containing particle gradients and has broad applicability for future efforts in fabricating complex scaffolds for tissue engineering applications.
| S-EPMC5597446 | biostudies-literature