Efficient Alcoholysis of Poly(ethylene terephthalate) by Using Supercritical Carbon Dioxide as a Green Solvent.

In order to reduce the environmental impact of poly(ethylene terephthalate) (PET) plastic waste, supercritical fluids were used to facilitate effective recovery via improved solvent effects. This work focuses on the mechanisms of supercritical CO2 (ScCO2) during the alcoholysis processing of PET using systematic experiments and molecular dynamics (MD) simulations. The results of the alcoholysis experiment indicated that PET chips can be completely depolymerized within only an hour at 473 K assisted with ScCO2 at an optimal molar ratio of CO2/ethanol of 0.2. Random scission of PET dominates the early stage of the depolymerization reaction process, while specific scission dominates the following stage. Correspondingly, molecular dynamics (MD) simulations revealed that the solubilization and self-diffusion properties of ScCO2 facilitate the transportation of alcohol molecules into the bulk phase of PET, which leads to an accelerated diffusion of both oligomers and small molecules in the system. However, the presence of excessive CO2 has a negative impact on depolymerization by weakening the hydrogen bonding between polyester chain segments and ethanol, as well as decreasing the swelling degree of PET. These data provide a deep understanding of PET degradation by alcohols and the enhancement of ScCO2. It should be expected to achieve an efficient and high-yield depolymerization process of wasted polyesters assisted with ScCO2 at a relatively low temperature.

Effects of Chemical Composition and Cross-Linking Degree on the Thermo-Mechanical Properties of Bio-Based Thermosetting Resins: A Molecular Dynamics Simulation Study.

Bio-based epoxy resins have received significant attention in terms of concerns regarding carbon emission. Epoxidized soybean oil (ESO) derived from sustainable feedstock has been widely used to blend with traditional diglycidyl ether of bisphenol-A (DGEBA) to replace some of the petroleum-based components. In this work, molecular dynamics (MD) simulations were applied to track the network formation and predict the performance of methyl hexahydrophthalic anhydride (MHHPA)-cured ESO/DGEBA blend systems. The effects of ESO content and cross-linking degree on the mass density, volumetric shrinkage, glass transition temperature (Tg), coefficient of thermal expansion (CTE), Young's modulus, yield strength, and Poisson's ratio of the epoxy resin were systematically investigated. The results show that systems with high ESO content achieve gelation at low cross-linking degree. The Tg value, Young's modulus, and yield strength increase with the increase in cross-linking degree, but the CTE at the glassy state and Poisson's ratio decrease. The comparison results between the simulated and experimental data demonstrated that the MD simulations can accurately predict the thermal and mechanical properties of ESO-based thermosets. This study gains insight into the variation in thermo-mechanical properties of anhydride-cured ESO/DGEBA-based epoxy resins during the cross-linking process and provides a rational strategy for optimizing bio-based epoxy resins.

Influences of Polyphenols on the Properties of Crosslinked Acellular Fish Swim Bladders: Experiments and Molecular Dynamic Simulations.

Acellular fish swim bladders (AFSBs) are a promising biomaterial in tissue engineering, however, they may suffer from rapid degradation due to enzyme invasion. In this work, natural polyphenols, including epigallocatechin gallate (EGCG), proanthocyanidin (PC), tannic acid (TA) and protocatechuic acid (PCA), were utilized to improve the properties of AFSBs through crosslinking modifications. Fourier transform infrared (FTIR) results indicate that the triple helix of the collagen in AFSBs is well preserved after crosslinking. The differential scanning calorimetry (DSC), water contact angle (WCA) and in vitro degradation tests indicate that the polyphenol-crosslinked AFSBs exhibit improved thermal stability, enzymatic stability, hydrophilicity and mechanical properties. Among them, EGCG with multiple phenolic hydroxyl groups and low potential resistance is more favorable for the improvement of the mechanical properties and enzymatic stability of AFSBs, as well as their biocompatibility and integrity with the collagen triple helix. Moreover, the crosslinking mechanism was demonstrated to be due to the hydrogen bonds between polyphenols and AFSBs, and was affected by the molecular size, molecular weight and the hydroxyl groups activity of polyphenol molecules, as clarified by molecular dynamic (MD) simulations. The approach presented in this work paves a path for improving the properties of collagen materials.

Polyimide Films Based on ß-Cyclodextrin Polyrotaxane with Low Dielectric and Excellent Comprehensive Performance.

In order to prepare polyimide (PI) films with a low dielectric constant and excellent comprehensive performance, a two-step method was employed in this study to integrate ß-cyclodextrin into a semi-aromatic fluorine-containing polyimide ternary system. By introducing trifluoromethyl groups to reduce the dielectric constant, the dielectric constant was further reduced to 2.55 at 10 MHz. Simultaneously, the film exhibited noteworthy thermal stability (a glass transition temperature exceeding 300 °C) and a high coefficient of thermal expansion. The material also demonstrated outstanding mechanical properties, boasting a strength of 122 MPa and a modulus of 2.2 GPa, along with high optical transparency (transmittance reaching up to 89% at 450 nm). Moreover, the inherent high transparency of colorless polyimide (CPI) combined with good stretchability contributed to the attainment of a low dielectric constant. This strategic approach not only opens up new opportunities for novel electroactive polymers but also holds potential applications in flexible displays, circuit printing, and chip packaging.

Dynamic Crosslinked Injectable Mussel-Inspired Hydrogels with Adhesive, Self-Healing, and Biodegradation Properties.

The non-invasive tissue adhesives with strong tissue adhesion and good biocompatibility are ideal for replacing traditional wound treatment methods such as sutures and needles. The self-healing hydrogels based on dynamic reversible crosslinking can recover their structure and function after damage, which is suitable for the application scenario of tissue adhesives. Herein, inspired by mussel adhesive proteins, we propose a facile strategy to achieve an injectable hydrogel (DACS hydrogel) by grafting dopamine (DOPA) onto hyaluronic acid (HA) and mixing it with carboxymethyl chitosan (CMCS) solution. The gelation time and rheological and swelling properties of the hydrogel can be controlled conveniently by adjusting the substitution degree of the catechol group and the concentration of raw materials. More importantly, the hydrogel exhibited rapid and highly efficient self-healing ability and excellent biodegradation and biocompatibility in vitro. Meanwhile, the hydrogel exhibited ~4-fold enhanced wet tissue adhesion strength (21.41 kPa) over the commercial fibrin glue. This kind of HA-based mussel biomimetic self-healing hydrogel is expected to be used as a multifunctional tissue adhesive material.

Preparation of extracellular matrix of fish swim bladders by decellularization with supercritical carbon dioxide.

Fish swim bladders used to be considered as byproducts or waste in fishery; however, they are potential materials for biological medicine with abundant collagen. In this work, an efficient noncytotoxic decellularization process using sodium dodecyl sulfate (SDS) ternary system assisted with supercritical carbon dioxide (scCO2) as the green extraction fluid and ethanol (ET) as the cosolvent has been developed to harvest acellular fish swim bladders (AFSBs). The experimental results show that the tissue treated by SDS assisted with scCO2 and ethanol at 37 °C and 25 MPa can be decellularized thoroughly and maintains intact fibers and uniform pore distribution, which resulting in a tensile strength of 5.61 MPa and satisfactory biocompatibility. Meanwhile, the residual SDS content in scCO2/SDS/ET ternary system is 0.0122% which is significantly lower than it in scCO2/SDS system due to the enhanced mass transfer rate of SDS in tissues by scCO2 with ethanol. The synergy between SDS and ethanol can enhance the diffusion coefficient and the solubility of SDS in scCO2, which reduced the contact time between SDS and tissues. Meaningfully, the results obtained in this work can not only provide a novel strategy to produce acellular matrix with superior properties, but also offer a further understanding of the decellularization through scCO2 extraction processing with the synergy of suitable detergent/cosolvent.

Facile Preparation of Tunicate-Inspired Chitosan Hydrogel Adhesive with Self-Healing and Antibacterial Properties.

In order to replace traditional wound treatments such as sutures, tissue adhesives with strong wet tissue adhesion and biocompatibility have attracted more attention to the applications of non-invasive wound closure. Herein, inspired by tunicate adhesive protein, a series of 2,3,4-trihydroxybenzaldehyde (TBA)-modified chitosan hydrogels (CS-TBA-Fe) were prepared by easily mixing the solutions of chitosan-FeCl3 and TBA via the Schiff-base reaction and the coordination between Fe3+ and pyrogallol groups. The gelation time was greatly shortened to only several seconds after induced even trace Fe3+. The hydrogel (CS-TBA-Fe) exhibited ~12-fold enhanced wet tissue adhesion strength (60.3 kPa) over the commercial fibrin glue. Meanwhile, the hydrogel also showed robust adhesion to various substrates such as wood, PMMA, and aluminum. The swelling ratio and rheological property can be simply controlled by changing the concentrations of chitosan, TBA, and Fe3+. Moreover, the hydrogel displayed a rapid and highly efficient self-healing ability and an excellent antibacterial activity against E. coli. The overall results show that the CS-TBA-Fe hydrogel with enhanced wet adhesiveness will be a promising tissue adhesive material.

Facile Synthesis of Thermoplastic Polyamide Elastomers Based on Amorphous Polyetheramine with Damping Performance.

Novel thermoplastic polyamide elastomers (TPAEs) consisting of long-chain semicrystalline polyamide 1212 (PA1212) and amorphous polyetheramine were synthesized via one-pot melt polycondensation. The method provides accessible routes to prepare TPAEs with a high tolerance of compatibility between polyamide and polyether oligomers compared with the traditional two-step method. These TPAEs with 10 wt % to 76 wt % of soft content were obtained by reaction of dodecanedioic acid, 1,12-dodecanediamine, and poly(propylene glycol) (PPG) diamine. The structure-property relationships of TPAEs were systematically studied. The chemical structure and the morphologic analyses have revealed that microphase separation occurs in the amorphous region. The TPAEs that have long-chain PPG segments consist of a crystalline polyamide domain, amorphous polyamide-rich domain, and amorphous polyetheramine-rich domain, while the ones containing short-chain PPG segments comprise of a crystalline polyamide domain and miscible amorphous polyamide phase and amorphous polyetheramine phase due to the compatibility between short-chain polyetheramine and amorphous polyamide. These novel TPAEs show good damping performance at low temperature, especially the TPAEs that incorporated 76 wt % and 62 wt % of PPG diamine. The TPAEs exhibit high elastic properties and low residual strain at room temperature. They are lightweight with density between 1.01 and 1.03 g/cm3. The long-chain TPAEs have well-balanced properties of low density, high elastic return, and high shock-absorbing ability. This work provides a route to expand TPAEs to damping materials with special application for sports equipment used in extremely cold conditions such as ski boots.

Analysis of Bubble Growth in Supercritical CO2 Extrusion Foaming Polyethylene Terephthalate Process Based on Dynamic Flow Simulation.

Bubble growth in the polymer extrusion foaming process occurs under a dynamic melt flow. For non-Newtonian fluids, this work successfully coupled the dynamic melt flow simulation with the bubble growth model to realize bubble growth predictions in an extrusion flow. The initial thermophysical properties and dynamic rheological property distribution at the cross section of the die exit were calculated based on the finite element method. It was found that dynamic rheological properties provided a necessary solution for predicting bubble growth during the supercritical CO2 polyethylene terephthalate (PET) extrusion foaming process. The introduction of initial melt stress could effectively inhibit the rapid growth of bubbles and reduce the stable size of bubbles. However, the initial melt stress was ignored in previous work involving bubble growth predictions because it was not available. The simulation results based on the above theoretical model were consistent with the evolution trends of cell morphology and agreed well with the actual experimental results.

Fabrication of PCL Scaffolds by Supercritical CO2 Foaming Based on the Combined Effects of Rheological and Crystallization Properties.

Polycaprolactone (PCL) scaffolds have recently been developed via efficient and green supercritical carbon dioxide (scCO2) melt-state foaming. However, previously reported gas-foamed scaffolds sometimes showed insufficient interconnectivity or pore size for tissue engineering. In this study, we have correlated the thermal and rheological properties of PCL scaffolds with their porous morphology by studying four foamed samples with varied molecular weight (MW), and particularly aimed to clarify the required properties for the fabrication of scaffolds with favorable interconnected macropores. DSC and rheological tests indicate that samples show a delayed crystallization and enhanced complex viscosity with the increasing of MW. After foaming, scaffolds (27 kDa in weight-average molecular weight) show a favorable morphology (pore size = 70-180 µm, porosity = 90% and interconnectivity = 96%), where the lowest melt strength favors the generation of interconnected macropore, and the most rapid crystallization provides proper foamability. The scaffolds (27 kDa) also possess the highest Young's modulus. More importantly, owing to the sufficient room and favorable material transportation provided by highly interconnected macropores, cells onto the optimized scaffolds (27 kDa) perform vigorous proliferation and superior adhesion and ingrowth, indicating its potential for regeneration applications. Furthermore, our findings provide new insights into the morphological control of porous scaffolds fabricated by scCO2 foaming, and are highly relevant to a broader community that is focusing on polymer foaming.

A comparable study of polyglycolic acid's degradation on macrophages' activation.

Polyglycolic acid (PGA) is a faster biodegradable polymer for various implants, frequently causing different macrophages' activation. In this study, we undertook a comparable study of PGA's degradation on macrophages' activation with different PGA crystallinity (in porous and fibrous 3D scaffolding format) in an in vitro and in vivo model. The incubation medium containing PGA degradation products, with different pH value of 7.1, 6.1 and 3.6, was added to RAW 264.7 macrophages' culture to simulate different degradation phases. The addition of hydrochloric acid with the same pH values in the culture media was used to compare and simplify the acid types' effect on macrophages. The scaffolds were implanted to mouse subcutaneously for 6 weeks. To correlate the degradation rate between the in vitro and in vivo models, PGA scaffolds were grafted by rhodamine-b covalently enabling the detection of PGA degradation through fluorescence intensity decay. It was confirmed that porous PGA degraded faster than fibrous scaffolds due to lower crystallinity. The acidic PGA degradation products (GA) did not promote IL-10 production, but inhibited IL-1ß, IL-6 and TNF-α production in 7-days' culture significantly. The use of HCl with the same pH value as PGA degradation products in culture did not produce the same inhibition effect as GA. The mouse model showed that the degradation of PGA scaffolds was accelerated in vivo in the first two weeks, mainly due to tissue ingrowth. The fast degradation of porous scaffolds triggered M1 macrophages into the implantation site, whilst the slow degradation of PGA fibers promoted the polarization of macrophages into M2 pro-healing phenotypes. This study provides a good foundation to study and design biodegradable biomaterials toward immunomodulation.

Supercritical CO2 foamed composite scaffolds incorporating bioactive lipids promote vascularized bone regeneration via Hif-1α upregulation and enhanced type H vessel formation.

Bone tissue engineering has substantial potential for the treatment of massive bone defects; however, efficient vascularization coupled with bone regeneration still remains a challenge in this field. In the current study, supercritical carbon dioxide (scCO2) foaming technique was adopted to fabricate mesoporous bioactive glasses (MBGs) particle-poly (lactic-co-glycolic acid) (PLGA) composite scaffolds with appropriate mechanical and degradation properties as well as in vitro bioactivity. The MBG-PLGA scaffolds incorporating the bioactive lipid FTY720 (designated as FTY/MBG-PLGA) exhibited simultaneously sustained release of the bioactive lipid and ions. In addition to providing a favorable microenvironment for cellular adhesion and proliferation, FTY/MBG-PLGA scaffolds significantly facilitated the in vitro osteogenic differentiation of rBMSCs and also markedly stimulated the upregulation of Hif-1α expression via the activation of the Erk1/2 pathway, which mediated the osteogenic and pro-angiogenic effects on rBMSCs. Furthermore, FTY/MBG-PLGA extracts induced superior in vitro angiogenic performance of HUVECs. In vivo evaluation of critical-sized rat calvarial bone defects indicated that FTY/MBG-PLGA scaffolds potently promoted vascularized bone regeneration. Notably, the significantly enhanced formation of type H vessels (CD31hiEmcnhi neo-vessels) was observed in newly formed bone tissue in FTY/MBG-PLGA group, strongly suggesting that FTY720 and therapeutic ions released from the scaffolds synergistically induced more type H vessel formation, which indicated the coupling of angiogenesis and osteogenesis to achieve efficiently vascularized bone regeneration. Overall, the results indicated that the foamed porous MBG-PLGA scaffolds incorporating bioactive lipids achieved desirable vascularization-coupled bone formation and could be a promising strategy for bone regenerative medicine. STATEMENT OF SIGNIFICANCE: Efficacious coupling of vascularizationandbone formation is critical for the restoration of large bone defects. Anoveltechnique was used to fabricate composite scaffolds incorporating bioactive lipids which possessedsynergistic cues of bioactive lipids and therapeutic ions to potently promotebone regenerationas well as vascularization. The underlying molecular mechanism for the osteogenic and pro-angiogenic effects of the compositescaffolds was unveiled. Interestingly, the scaffolds were furtherfoundto enhance the formation oftype H capillarieswithin the bone healing microenvironment to couple angiogenesis to osteogenesis to achieve satisfyingvascularizedbone regeneration.These findings provide a novel strategy to develop efficiently vascularized engineering constructs to treat massive bone defects.

A mussel-inspired carboxymethyl cellulose hydrogel with enhanced adhesiveness through enzymatic crosslinking.

In order to replace conventional sutures in wound closing applications, favorable hydrogels with strong wet tissue adhesion and biocompatibility have attracted considerable attention. Herein, inspired by mussel adhesive protein, a series of dopamine modified carboxymethyl cellulose (CMC-DA) hydrogels were prepared in situ using enzymatic crosslinking in the presence of horseradish peroxidase (HRP) and H2O2. The biomimetic CMC-DA hydrogel exhibited about 6-fold enhanced wet tissue adhesion strength (28.5 kPa) over the commercial fibrin glue. In addition, the gelation time, swelling ratio and rheological property of the hydrogel can be simply controlled by changing the concentrations of HRP, H2O2, and CMC-DA polymer. The gels also exhibited good biodegradation and biocompatibility in vitro. The overall results show that the CMC-DA hydrogel with enhanced wet adhesiveness will be a promising tissue adhesive material.

Electrospun PLGA membrane incorporated with andrographolide-loaded mesoporous silica nanoparticles for sustained antibacterial wound dressing.

AIM: To assess the wound-healing ability of poly(lactic-co-glycolic acid) (PLGA) nanofibrous wound dressing incorporated with andrographolide (Andro)-loaded mesoporous silica nanoparticles (MSNs). MATERIALS & METHODS: PLGA/Andro-MSNs nanofibrous membrane wound dressings were produced by electrospinning. The effects of MSNs on the hydrophilicity, degradation and mechanical strength of membranes were evaluated. The cumulative release of Andro in vitro was obtained. Cell culture and in vivo tests on infectious models were carried out. RESULTS: The PLGA/Andro-MSNs membrane showed a sustained release of Andro. The incorporation of MSNs into PLGA improved the hydrophilicity of the nanofibrous membranes. Cell culture and in vivo tests showed that PLGA/Andro-MSNs membrane can promote epidermal cell adhesion and reduce inflammation process. CONCLUSION: PLGA/Andro-MSNs nanofibrous membrane exhibited an efficient wound-healing ability.

Novel Fabricating Process for Porous Polyglycolic Acid Scaffolds by Melt-Foaming Using Supercritical Carbon Dioxide.

Polyglycolic acid (PGA) is a biocompatible and biodegradable polymer with high crystallinity. It is difficult to obtain PGA porous scaffolds with controllable morphology as well as outstanding mechanical properties without toxic solvents. The current study thus aimed to develop a novel melt-foaming strategy to prepare porous PGA scaffolds through the interaction between PGA molecules and supercritical carbon dioxide (scCO2). Before the design of foaming strategy, rheological properties of PGA were first studied by a Haake rheometer, whereas the effect of scCO2 on PGA was investigated by high-pressure differential scanning calorimetry (DSC). It was revealed that the elasticity and viscosity could be greatly improved by a temperature regulation operation to withstand the growth of bubbles at the initial depressurization. Meanwhile, the melting and crystallization temperatures of PGA were reduced because of the plasticization effect of scCO2. Through the dissolution of compressed CO2 into PGA melt and subsequent rapid depressurization at a relatively low temperature with high PGA melt strength, PGA scaffolds with porosity of 39-74%, average pore sizes ranging from 5 to 50 µm, and interconnectivity greater than 90% could be controllably fabricated. The effect of foaming temperature and pressure on morphology of PGA foams were then examined in detail. Special nanoscale morphology on the pore surface of resultant porous PGA foams was observed. These PGA foams also exhibited attractive compressive modulus of 68-116 MPa. The PGA foams with 74% porosity and average pore size of 38 µm, prepared at 208 °C and 20 MPa were then used as scaffolds for in vitro cellular evaluation. Fibroblasts seeded on the scaffold exhibited excellent spreading shape and good proliferation ability and in vivo implantation of PGA foams manifested as the notable tissue ingrowth and neovascularization process within the foams, ascertaining its potential applications for tissue engineering and regenerative medicine. This work presents a breakthrough to fabricate highly crystalline PGA into porous scaffolds instead of traditional fibrous ones.

Preparation of Desirable Porous Cell Structure Polylactide/Wood Flour Composite Foams Assisted by Chain Extender.

Polylactide (PLA)/wood flour composite foam were prepared through a batch foaming process. The effect of the chain extender on the crystallization behavior and dynamic rheological properties of the PLA/wood flour composites were investigated as well as the crystal structure and cell morphology of the composite foams. The incorporation of the chain extender enhanced the complex viscosity and storage modulus of PLA/wood flour composites, indicating the improved melt elasticity. The chain extender also led to a decreased crystallization rate and final crystallinity of PLA/wood flour composites. With an increasing chain extender content, a finer and more uniform cell structure was formed, and the expansion ratio of PLA/wood flour composite foams was much higher than without the chain extender. Compared to the unfoamed composites, the crystallinity of the foamed PLA/wood flour composites was improved and the crystal was loosely packed. However, the new crystalline form was not evident.