Poly(Propylene Carbonate)-Based Biodegradable and Environment-Friendly Materials for Biomedical Applications.

Poly(propylene carbonate) (PPC) is an emerging "carbon fixation" polymer that holds the potential to become a "biomaterial of choice" in healthcare owing to its good biocompatibility, tunable biodegradability and safe degradation products. However, the commercialization and wide application of PPC as a biomedical material are still hindered by its narrow processing temperature range, poor mechanical properties and hydrophobic nature. Over recent decades, several physical, chemical and biological modifications of PPC have been achieved by introducing biocompatible polymers, inorganic ions or small molecules, which can endow PPC with better cytocompatibility and desirable biodegradability, and thus enable various applications. Indeed, a variety of PPC-based degradable materials have been used in medical applications including medical masks, surgical gowns, drug carriers, wound dressings, implants and scaffolds. In this review, the molecular structure, catalysts for synthesis, properties and modifications of PPC are discussed. Recent biomedical applications of PPC-based biomaterials are highlighted and summarized.

Effect of Poly(propylene carbonate) on Properties of Polylactic Acid-Based Composite Films.

To enrich the properties of polylactic acid (PLA)-based composite films and improve the base degradability, in this study, a certain amount of poly(propylene carbonate) (PPC) was added to PLA-based composite films, and PLA/PPC-based composite films were prepared by melt blending and hot-press molding. The effects of the introduction of PPC on the composite films were analyzed through in-depth studies on mechanical properties, water vapor and oxygen transmission rates, thermal analysis, compost degradability, and bacterial inhibition properties of the composite films. When the introduction ratio coefficient of PPC was 30%, the tensile strength of the composite film increased by 19.68%, the water vapor transmission coefficient decreased by 14.43%, and the oxygen transmission coefficient decreased by 18.31% compared to that of the composite film without PPC, the cold crystallization temperature of the composite film increased gradually from 96.9 °C to 104.8 °C, and PPC improved the crystallization ability of composite film. The degradation rate of the composite film with PPC increased significantly compared to the previous one, and the degradation rate increased with the increase in the PPC content. The degradation rate was 49.85% and 46.22% faster on average than that of the composite film without PPC when the degradation was carried out over 40 and 80 days; the composite film had certain inhibition, and the maximum diameter of the inhibition circle was 2.42 cm. This study provides a strategy for the development of PLA-based biodegradable laminates, which can promote the application of PLA-based laminates in food packaging.

Optimizing the Ion Conductivity and Mechanical Stability of Polymer Electrolyte Membranes Designed for Use in Lithium Ion Batteries: Combining Imidazolium-Containing Poly(ionic liquids) and Poly(propylene carbonate).

State-of-the-art Li batteries suffer from serious safety hazards caused by the reactivity of lithium and the flammable nature of liquid electrolytes. This work develops highly efficient solid-state electrolytes consisting of imidazolium-containing polyionic liquids (PILs) and lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). By employing PIL/LiTFSI electrolyte membranes blended with poly(propylene carbonate) (PPC), we addressed the problem of combining ionic conductivity and mechanical properties in one material. It was found that PPC acts as a mechanically reinforcing component that does not reduce but even enhances the ionic conductivity. While pure PILs are liquids, the tricomponent PPC/PIL/LiTFSI blends are rubber-like materials with a Young's modulus in the range of 100 MPa. The high mechanical strength of the material enables fabrication of mechanically robust free-standing membranes. The tricomponent PPC/PIL/LiTFSI membranes have an ionic conductivity of 10-6 S·cm-1 at room temperature, exhibiting conductivity that is two orders of magnitude greater than bicomponent PPC/LiTFSI membranes. At 60 °C, the conductivity of PPC/PIL/LiTFSI membranes increases to 10-5 S·cm-1 and further increases to 10-3 S·cm-1 in the presence of plasticizers. Cyclic voltammetry measurements reveal good electrochemical stability of the tricomponent PIL/PPC/LiTFSI membrane that potentially ranges from 0 to 4.5 V vs. Li/Li+. The mechanically reinforced membranes developed in this work are promising electrolytes for potential applications in solid-state batteries.

Biodegradable and Toughened Composite of Poly(Propylene Carbonate)/Thermoplastic Polyurethane (PPC/TPU): Effect of Hydrogen Bonding.

The blends of Poly(propylene carbonate) (PPC) and polyester-based thermoplastic polyurethane (TPU) were melt compounded in an internal mixer. The compatibility, thermal behaviors, mechanical properties and toughening mechanism of the blends were investigated using Fourier transform infrared spectra (FTIR), tensile tests, impact tests, differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and dynamic mechanical analysis technologies. FTIR and SEM examination reveal strong interfacial adhesion between PPC matrix and suspended TPU particles. Dynamic mechanical analyzer (DMA) characterize the glass transition temperature, secondary motion and low temperature properties. By the incorporation of TPU, the thermal stabilities are greatly enhanced and the mechanical properties are obviously improved for the PPC/TPU blends. Moreover, PPC/TPU blends exhibit a brittle-ductile transition with the addition of 20 wt % TPU. It is considered that the enhanced toughness results in the shear yielding occurred in both PPC matrix and TPU particles of the blends.

A novel sustained release fluoride strip based Poly(propylene carbonate) for preventing caries.

Low-level fluoride in the oral environment for a long sustained period is more effective for preventing caries. However, the current fluoride delivery methods have a short fluoride retention time and high-dose fluoride administration may increase the risk of dental fluorosis. This study developed a novel fluoride strip based poly(propylene carbonate) (PPC), which can improve oral fluoride retention for desirable anticaries effect with minimal side effects. The fluoride strips based PPC (NaF-PPC strips) with different fluoride contents (0, 1.25, 2.5 and 5 wt.%) were developed by melt-blending method. The physico-chemical characteristics, drug loading, drug release properties, remineralization and antibacterial efficacy and biocompatibility of NaF-PPC strips were investigated. The in vitro drug release studies indicated that fluoride release in a sustained manner with no initial burst release and approximately 100% of fluoride ions were released from PPC strips over 24 days. NaF-PPC strips exhibited excellent remineralization and antibacterial potential when fluoride content up to 5%. Combination with biocompatibility, 2.5% NaF-PPC strips could be a promising fluoride application for preventing caries. This work provides an effective and novel topical fluoride delivery for general use.

Biodegradable Films of PLA/PPC and Curcumin as Packaging Materials and Smart Indicators of Food Spoilage.

Bio-based and biodegradable packaging combined with chemical sensors and indicators has attracted great attention as they can provide protection combined with information on the actual freshness of foodstuffs. In this study, we present an effective, biodegradable, mostly bio-sourced material ideal for sustainable packaging that can also be used as a smart indicator of ammonia (NH3) vapor and food spoilage. The developed material comprises a blend of poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) loaded with curcumin (CCM), which is fabricated via the scalable techniques of melt extrusion and compression molding. Due to the structural similarity of PLA and PPC, they exhibited good compatibility and formed hydrogen bonds within their blends, as proven by Fourier transform infrared (FTIR) and X-ray diffraction (XRD). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis confirmed that the blends were thermally stable at the used processing temperature (180 °C) with minimal crystallinity. The rheological and mechanical properties of the PLA/PPC blends were easily tuned by changing the ratio of the biopolymers. Supplementing the PLA/PCC samples with CCM resulted in efficient absorption of UV radiation, yet the transparency of the films was preserved (T700 ∼ 68-84%). The investigation of CCM extract in ethanol with the DPPH• assay demonstrated that the samples could also provide effective antioxidant action, due to the tunable release of the CCM. Analyses for water vapor and oxygen permeability showed that the PPC improved the barrier properties of the PLA/PPC blends, while the presence of CCM did not hinder barrier performance. The capacity for real-time detection of NH3 vapor was quantified using the CIELab color space analysis. A change in color of the sample from a yellowish shade to red was observed by the naked eye. Finally, a film of PLA/PPC/CCM was successfully applied as a sticker indicator to monitor the spoilage of shrimps over time, demonstrating an evident color change from yellow to light orange, particularly for the PPC-containing blend. The developed system, therefore, has the potential to serve as a cost-effective, easy-to-use, nondestructive, smart indicator for food packaging, as well as a means for NH3 gas monitoring in industrial and environmental applications.

Improvement of rBMSCs Responses to Poly(propylene carbonate) Based Biomaterial through Incorporation of Nanolaponite and Surface Treatment Using Sodium Hydroxide.

Poly(propylene carbonate) (PPC) has aroused extensive attention in the biomaterial field because of its excellent biocompatibility and appropriate degradability, but surface hydrophobicity and bioinertness limit its applications for bone repair and tissue engineering. In this study, a bioactive PPC/laponite (LAP) nanocomposite (PL) was prepared by a melt-blending method, and a microporous surface on PPC and PL (PT and PLT) was created by sodium hydroxide (NaOH) treatment. The results demonstrated that the surface roughness, hydrophilicity, surface energy, and degradability as well as protein adsorption of PLT were obviously improved compared with PPC. Moreover, the degradability of PLT was remarkably enhanced with a slight increase of pH values in Tris-HCl solution. Furthermore, adhesion and proliferation as well as osteogenic differentiation of rat bone marrow mesenchymal stem cells (rBMSCs) to PLT were significantly promoted compared with PPC. The results suggested that incorporating LAP into PPC obviously improved the surface performance of PL (with nanotopography), and surface treatment with NaOH further enhanced surface properties of PLT (with micronanotopography and hydrophilic groups), which significantly promoted responses of rBMSCs. In short, PLT displayed excellent cytocompatibility, which would have great potential for bone regeneration.

Transparent Bioplastic Derived from CO2-Based Polymer Functionalized with Oregano Waste Extract toward Active Food Packaging.

Active packaging materials, biodegradable and from renewable resources, are the most promising substitutes of nonbiodegradable, petroleum-based plastics, toward green and sustainable packaging solutions. In this study, an innovative bioplastic system, composed of carbon dioxide-derived poly(propylene carbonate) (PPC) and nature-originated cellulose acetate (CA), was developed. The extract from oregano waste was incorporated into the bioplastics as a low-cost and effective antioxidant resource. Thin, freestanding, and flexible PPC.CA bioplastic films were obtained by a simple, easily scalable solvent casting technique. The pristine films, without the oregano extract, featured good transparency and high water vapor barrier ability, along with suitable mechanical and thermal properties that are comparable to commercial plastics used for packaging. Interestingly, the incorporation of oregano waste extract added to the bioplastics high UV protection and high antioxidant activity, suitable features for active food packaging applications, without compromising the intriguing properties of the pristine films. The biocomposite films were not only biocompatible but also started biodegrading after just 1 week in seawater. The reported biocomposites are foreseen as promising candidates for several packaging applications, but in particular for sustainable active food packaging.

Ecofriendly UV-protective films based on poly(propylene carbonate) biocomposites filled with TiO2 decorated lignin.

It is highly desirable to develop biodegradable UV-shielding materials from the renewable resources as the ever-increasing demand for the sustainable environment. In this work, TiO2 decorated lignin particles (TiO2@lignin) were synthesized successfully by hydrothermal method in aqueous solution to improve the UV shielding performance of lignin particles. The poly(propylene carbonate) (PPC) composite films (thickness of ~23 µm) with different contents of TiO2@lignin were prepared via a blade-casting method. Morphological analysis showed that the TiO2@lignin dispersed uniformly in the PPC matrix with a good miscibility. UV-vis transmission spectra results revealed that the PPC composite film containing 5 wt% TiO2@lignin could absorb about 90% of UV light in the full UV band (200-400 nm), indicating the TiO2@lignin had a good UV-shielding property. Moreover, the presence of TiO2@lignin could significantly improve the thermal stability of the PPC/TiO2@lignin composite films. The DMA results showed that the introduction of TiO2@lignin could enhance the storage modulus and glass transition temperature simultaneously.

Employing the Sirolimus-Eluting Poly (Propylene Carbonate) Mesh for the Prevention of Arteriovenous Graft Stenosis in Rats.

Poly (propylene carbonate, PPC) is a new member of the aliphatic polyester family. An outstanding feature of PPC is that it produces mainly water and carbon dioxide when degraded in vivo, causing minimal side effects. This unique property together with excellent biocompatibility and biodegradability makes PPC a promising material for drug delivery. In this study, we explored the effect of the sirolimus (an inhibitor of cell growth)-eluting PPC mesh on graft stenosis and its possible mechanisms in a rat arteriovenous grafting model. The PPC mesh was prepared by electrospinning. A jugular vein to abdominal aortic autograft transplantation model was established in rats. The graft was then treated by wrapping with the drug mesh or the drug-free mesh or left untreated. Four weeks posttransplantation, neointima was measured with hematoxylin and eosin staining, matrix metalloproteinase-2 (MMP-2), and MMP-9, and proliferating cell nuclear antigen (PCNA) in the grafts were assayed by Western blotting and immunohistochemistry, respectively. In vitro rat aortic adventitial fibroblast cell (RAAFC) migration was assessed using the Boyden chamber assay, and phospho-mammalian target of rapamycin (mTOR) levels in RAAFCs were determined by Western blotting. Animals with the drug mesh had an intimal area index of 4.87% ± 0.98%, significantly lower than that of the blank group (14.21% ± 2.56%) or the PPC group (15.03% ± 2.35%, both P < .05). The sirolimus mesh markedly suppressed MMP-2 and MMP-9 expression, decreased PCNA-positive cell numbers, inhibited RAAFC migration, and reduced phospho-mTOR levels. Our data suggest that the sirolimus-eluting PPC mesh might be potentially applied for the management of grafting stenosis.

Synthesis and characterization of amphiphilic block polymer poly(ethylene glycol)-poly(propylene carbonate)-poly(ethylene glycol) for drug delivery.

A novel amphiphilic block polymer poly(ethylene glycol)-poly(propylene carbonate)-poly(ethylene glycol) (PEG-PPC-PEG) was synthesized via the dicyclohexylcarbodiimide condensation reaction of double PEG-bis-amine and HOOC-PPC-COOH. The obtained copolymer was characterized by NMR to determine its structure. Using the PEG-PPC-PEG as the carrier and using doxorubicin (DOX) as a model drug, DOX-loaded nanoparticles with core shell structure were synthesized by self-assembly in water. The nanoparticles properties such as particle size, drug loading, encapsulation efficiency (EE) and drug release behavior were investigated as a function of the hydrophobic block length of PPC segments and compared with each other. The results showed that the EE was up to 88.8%. Nanoparticles were found to have a certain effect on the controlled release of DOX.

Reinforced Poly(Propylene Carbonate) Composite with Enhanced and Tunable Characteristics, an Alternative for Poly(lactic Acid).

The acidic nature of the degradation products of polyesters often leads to unpredictable clinical complications, such as necrosis of host tissues and massive immune cell invasions. In this study, poly(propylene carbonate) (PPC) and starch composite is introduced with superior characteristics as an alternative to polyester-based polymers. The degradation products of PPC-starch composites are mainly carbon dioxide and water; hence, the associated risks to the acidic degradation of polyesters are minimized. Moreover, the compression strength of PPC-starch composites can be tuned over the range of 0.2±0.03 MPa to 33.9±1.51 MPa by changing the starch contents of composites to address different clinical needs. More importantly, the addition of 50 wt % starch enhances the thermal processing capacity of the composites by elevating their decomposition temperature from 245 to 276 °C. Therefore, thermal processing methods, such as extrusion and hot melt compression methods can be used to generate different shapes and structures from PPC-starch composites. We also demonstrated the cytocompatibility and biocompatibility of these composites by conducting in vitro and in vivo tests. For instance, the numbers of osteoblast cells were increased 2.5 fold after 7 days post culture. In addition, PPC composites in subcutaneous mice model resulted in mild inflammatory responses (e.g., the formation of fibrotic tissue) that were diminished from two to 4 weeks postimplantation. The long-term in vivo biodegradation of PPC composites are compared with poly(lactic acid) (PLA). The histochemical analysis revealed that after 8 weeks, the biodegradation of PLA leads to massive immune cell infusion and inflammation at the site, whereas the PPC composites are well-tolerated in vivo. All these results underline the favorable properties of PPC-starch composites as a benign biodegradable biomaterial for fabrication of biomedical implants.

Electrospun aligned poly(propylene carbonate) microfibers with chitosan nanofibers as tissue engineering scaffolds.

In this study, parallel-aligned poly(propylene carbonate) (PPC) microfibers with a fiber diameter of 1.48±0.42 µm were prepared by electrospinning and modified by oxygen plasma treatment. Next, chitosan nanofibers with a fiber diameter size of 278±98 nm were introduced into the PPC fiber mats by freeze drying. Morphological analyses showed that the PPC scaffolds treated with 0.05 mg/ml chitosan solution provided the best micro and nanofiber structure with abundant chitosan nanofibers but without the formation of films. Surface chemical properties were analyzed by X-ray photoelectron spectroscopy (XPS). The initial water contact angle of the scaffolds decreased from 122.3±0.4° for neat PPC scaffolds to 53.8±1.6° for scaffolds with plasma treatment and chitosan nanofibers. The mechanical properties of the scaffolds were affected by plasma treatment with Young's modulus experiencing a reduction of 63%. Meanwhile, Young's modulus experienced a 26% improvement after the introduction of chitosan nanofibers. Fibroblast cells were cultured on the scaffolds to study the effects of both the plasma treatment and the introduction of chitosan nanofibers on cell adhesion, proliferation, and morphology. The scaffolds with PPC microfibers and chitosan nanofibers showed a superior cell response in terms of cell attachment, cell proliferation, and cell-scaffold interactions over the other scaffolds.

Sustained delivery of dbcAMP by poly(propylene carbonate) micron fibers promotes axonal regenerative sprouting and functional recovery after spinal cord hemisection.

This study describes the use of poly(propylene carbonate) (PPC) electrospun fibers as vehicle for the sustained delivery of dibutyryl cyclic adenosine monophosphate (dbcAMP) to the hemisected spinal cord. The dbcAMP and PPC were uniformly mixed with acetonitrile; then, electrospinning was used to generate micron fibers. The release of dbcAMP was assessed by ELISA in vitro. Our results showed that the encapsulation of dbcAMP in the fibers led to stable and prolonged release in vitro. The PPC micron fibers containing dbcAMP and the PPC micron fibers without dbcAMP were then implanted into the hemisected thoracic spinal cord, followed by testing of the functional recovery and immunohistochemistry. Compared with the control group, sustained delivery of dbcAMP promoted axonal regenerative sprouting and functional recovery and reduced glial scar formation, and the PPC micron fibers without dbcAMP did not have these effects. Our findings demonstrated the feasibility of using PPC electrospun fibers containing dbcAMP for spinal cord injury. The approach described here also will provide a platform for the potential delivery of other axon-growth-promoting or scar-inhibiting agents.