Biodegradable compatibilized poly(L-lactide)/thermoplastic polyurethane blends:design, preparation and property testing

Biodegradable blends of poly(l-lactide) (PLL) toughened with a polycaprolactone-based thermoplastic polyurethane (TPU) elastomer and compatibilized with a purpose-designed poly(l-lactide-co-caprolactone) (PLLCL) copolymer were prepared. Both 2-component (PLL/TPU) and 3-component (PLL/TPU/PLLCL) blends of various compositions were prepared by melt mixing, hot-pressed into thin films and their properties tested. The results showed that, although the TPU could toughen the PLL, the blends were immiscible leading to phase separation with the TPU domains distributed in the PLL matrix. However, addition of the PLLCL copolymer could partially compatibilize the blend by improving the interfacial adhesion between the two phases. Biodegradability testing showed that the blends were biodegradable and that the PLLCL copolymer could increase the rate of biodegradation under controlled composting conditions. The 3-component blend of composition PLL/TPU/PLLCL = 90/10/10 parts by weight was found to exhibit the best all-round properties

Preparation and property testing of compatibilized poly(l-lactide)/thermoplastic polyurethane blends

Poly(l-lactide) (PLL) has been blended with a polycaprolactone-based thermoplastic polyurethane (TPU) elastomer as a toughening agent and a poly(l-lactide-co-caprolactone) (PLLCL) copolymer as a compatibilizer. Both 2-component (PLL/TPU) and 3-component (PLL/TPU/PLLCL) blends were prepared by melt mixing, characterized, hot-pressed into thin sheets and their tensile properties tested. The results showed that, although the TPU could toughen the PLL, the blends were largely immiscible leading to phase separation. However, addition of the PLLCL copolymer improved blend compatibility. The best all-round properties were found for the 3-component blend of composition PLL/TPU/PLLCL = 90/10/10 parts by weight

Physical and thermal properties of l-lactide/ϵ-caprolactone copolymers:the role of microstructural design

Understanding the underlying role of microstructural design in polymers allows for the manipulation and control of properties for a wide range of specific applications. As such, this work focuses on the study of microstructure–property relationships in l-lactide/ϵ-caprolactone (LL/CL) copolymers. One-step and two-step bulk ring-opening polymerization (ROP) procedures were employed to synthesize LL/CL copolymers of various compositions and chain microstructures. In the one-step procedure, LL and CL were simultaneously copolymerized to yield P(LL-stat-CL) statistical copolymers. In the two-step procedure, poly(l-lactide) (PLL) and poly(ϵ-caprolactone) (PCL) prepolymers were synthesized in the first step before CL and LL respectively were added in the second step to yield P[LL-b-(CL-stat-LL)-b-LL] and P[CL-b-(LL-stat-CL)-b-CL] block copolymers as the final products. The findings reveal that, in addition to the copolymerization procedure employed, the length and type of the prepolymer play important roles in determining the chain microstructure and thereby the overall properties of the final copolymer. Moreover, control over the degree of crystallinity and the type of crystalline domains, which is controlled during the polymer chemistry process, heavily influences the physical and mechanical properties of the final polymer. In summary, this work describes an interesting approach to the microstructural design of biodegradable copolymers of LL and CL for potential use in biomedical applications

Multifunctional core‐shell electrospun nanofibrous fabrics of poly(vinyl alcohol)/silk sericin (core) and poly(lactide‐ co ‐glycolide) (shell)

Core–shell fibres (CSFs) offer a simple route to multifunctional hybrid materials for a wide range of applications. Herein, we report the design of a core–shell electrospun nanofibrous fabric containing a hydrophilic core and hydrophobic shell. CSFs were fabricated for the first time from poly(vinyl alcohol)/silk sericin (from silk cocoons) as the core and poly(lactide-co-glycolide) as the shell. The core serves as a potential carrier for water-soluble bioactive agents, and the shell works as a barrier to prevent premature release of water-soluble agents from the core. The effect of the molecular weight of poly(lactide-co-glycolide) and the loading of silk sericin on the morphology of fibres was studied. The parameters that significantly influence the core–shell electrospinning process were studied to elucidate the most effective conditions to create our multifunctional nanofibrous fabrics with smooth fibre morphology (diameters in the range 800–1300 nm) and low bead formation. Our CSFs were shown to degrade in saline buffer solution (pH 7.4) and were readily rendered with anti-bacterial properties against Staphylococcus aureus and Escherichia coli by the post-spinning deposition of silver nanoparticles (AgNPs, 40 nm diameter) or cinnamon essential oil (CEO). The fibres were non-toxic to normal human dermal fibroblast cell lines, as the cells were shown to attach and proliferate on CSFs, CSF/AgNPs and CSF/CEO with good cell tolerance for 72 h of incubation. These smart multifunctional CSFs show great potential towards smart delivery fabrics/dressings capable of carrying water-soluble bioactive agents surrounded by a protective, but degradable, antibacterial shell to guard the cargo for more effective controlled release

Tetracycline-Loaded Electrospun Poly(L-lactide-co-ε-caprolactone) Membranes for One-Step Periodontal Treatment

In this research, a one-step periodontal membrane, with the required function and properties, has been designed as an alternative method of tissue regenerative treatments. Designed nanoporous prototypes from poly(l-lactide-co-ε-caprolactone) (PLCL, 70:30 mol %) were fabricated by electrospinning, denoted as S-PLCL. They were subsequently loaded with tetracycline (TC) in order to enhance periodontal regeneration and deliver an anti-inflammatory and antibiotic drug. It was found that TC loading did not have any significant effect on the fiber diameter but did increase hydrophilicity. With the increase in TC loading, the water vapor permeability (WVP) of the S-PLCL membrane decreased within the range of 31–56% when compared with neat S-PLCL membranes, while in the solvent-cast film (F-PLCL), no significant change in WVP was observed. Moreover, S-PLCL demonstrated a controllable slow release rate of TC. S-PLCL loaded with 1500 μg/mL of TC showed a release concentration of 30 ppm over a certain time period to promote greater levels of human oral fibroblast and human oral keratinocyte cell proliferation and plaque inhibition. In conclusion, a TC-loaded S-PLCL fibrous membrane has been designed and fabricated to provide the ideal conditions for cell proliferation and antibiotic activity during treatment, outperforming nonfibrous F-PLCL loaded with TC at the same concentration

3D-printed PLA/PEO blend as biodegradable substrate coating with CoCl2 for colorimetric humidity detection

This study aimed to fabricate biodegradable substrate with colorimetric humidity indicator for detective moisture in food packaging. The poor properties of poly(lactic acid) (PLA) were enhanced by melt blending PLA with non-toxic poly(ethylene oxide) PEO at 180 °C. Specifically, three-dimensional (3D) substrates of PLA/PEO blends were fabricated by solvent-cast 3D printing. Furthermore, cobalt chloride (CoCl2) solution was printed onto the substrate with an inkjet printer to serve as a colorimetric humidity sensing indicator. It found that the flexibility and thermal stability of the PLA were improved and the hydrophilicity was increased with an increase in PEO content. Color changes and the sensitivity of this material were confirmed using image analysis and total color difference. The CoCl2 indicator displayed color changes that ranged from blue to pink under ambient conditions (above 60%RH), revealing suitable potential for frozen food packaging material with aim to detect amount of moisture in the packaging

Ring-opening polymerization of ε-caprolactone initiated by tin(II) octoate/n-hexanol: DSC isoconversional kinetics analysis and polymer synthesis

The kinetics of ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) initiated by 1.0, 1.5 and 2.0 mol% of stannous(II) octoate/n-hexanol (Sn(Oct)2/n-HexOH) wase successfully studied by non-isothermal differential scanning calorimetry (DSC) at heating rates of 5, 10, 15 and 20 °C/min. The DSC polymerization kinetic parameters of ε-CL were calculated using differential (Friedman) and integral isoconversional methods (Kissinger-Akahira-Sunose, KAS). The average activation energy (Ea) values obtained from Friedman and KAS methods were in the range of 64.9–70.5 kJ/mol and 64.9–80.4 kJ/mol, respectively. The values of frequency factor (A) were determined from model fitting method using Avrami-Erofeev reaction model. The average values of A for the ROP of ε-CL initiated by 1.0, 1.5 and 2.0 mol% of Sn(Oct)2/n-HexOH (1:2) were 7.3x107, 2.8x106 and 1.2x106 min−1, respectively. From kinetics studied, the polymerization rate of ε-CL increased with increasing initiator concentration. The performance of Sn(Oct)2/n-HexOH in the synthesis of poly(ε-caprolactone) (PCL) was investigated by bulk polymerization at temperatures of 140, 160 and 180 °C. Sn(Oct)2/n-HexOH (1:2) could produce high number average molecular weight ($$\overline {{M_{\rm{n}}}}$$= 9.0 × 104 g/mol) and %yield (89%) of PCL in a short period of time at Sn(Oct)2 concentration of 0.1 mol% and temperature of 160°C. The mechanism of the ROP of ε-CL with Sn(Oct)2/n-HexOH was proposed through the coordination-insertion mechanism

Inducing Crystallinity of Metal Thin Films with Weak Magnetic Fields without Thermal Annealing

Since the discovery of thin films, it has been known that higher crystallinity demands higher temperatures, making the process inadequate for energy-efficient and environmentally friendly methods of thin film fabrication. We resolved this problem by sparking metal wires in a 0.4 Tesla magnetic field at ambient conditions under ultra-pure nitrogen flow to replace the annealing of thin films, and thus designed an environmentally friendly and energy-efficient thin film fabrication method. We employed grazing incidence X-Ray Diffraction spectroscopy to characterize crystallinity of Iron, Nickel, Copper and Tungsten thin films prepared by a sparking discharge process in the presence of 0.4 T magnetic field at an ambient temperature of 25 °C. Control experiment was conducted by sparking without a magnetic field present and using ultra-pure nitrogen flow and ambient air containing oxygen. The Iron thin film prepared in ultra-pure nitrogen flow preserved crystallinity even after one year of ageing. Nickel exhibited higher crystallinity when sparked in nitrogen gas flow than when sparked in atmospheric air and was the only element to crystalize under atmospheric air. Tungsten successfully crystalized after just 40 min of sparking and aluminium failed to crystalize at all, even after 12 h of sparking under nitrogen flow

Novel Color Change Film as a Time–Temperature Indicator Using Polydiacetylene/Silver Nanoparticles Embedded in Carboxymethyl Cellulose

Time–temperature indicators (TTIs) can be important tools in product applications to monitor food quality losses, especially for fruits and vegetables. In this context, the effects of silver nanoparticles (AgNPs) and glycerol on the color change of polydiacetylene/AgNPs (PDA/AgNPs) embedded in carboxymethyl cellulose (CMC) film as time–temperature indicators (TTIs) were investigated. A CMC film prepared with 30 mg/L AgNPs and a 1:3 (v/v) PDA:AgNP ratio exhibited a faster color change than under other conditions. At 35 °C, the films with PDA/AgNPs changed color from purplish-blue to purple and purple to reddish-purple over time due to the higher thermal conductivity of AgNPs and larger PDA surface area exposed to specific temperatures. The total color difference (TCD) of PDA/AgNP-embedded CMC film directly changed with regard to time and temperature. However, adding glycerol to the system resulted in a symmetrical chemical structure, a factor that delayed the color change. Scanning electron micrographs showed AgNPs embedded in the CMC films. Transmission electron micrographs indicated a core-shell structure of PDA/AgNP vesicles in the CMC matrix. PDA/AgNP vesicles were confirmed by second derivative Fourier transform infrared spectroscopy, with a new peak at 1390–1150 cm−1. The kinetics of TTIs from PDA/AgNP-embedded CMC films yielded an activation energy of 58.70 kJ/mol

Synthesis and characterization of semi-IPN hydrogels composed of sodium 2-acrylamido-2-methylpropanesulfonate and poly(ε-caprolactone) diol for controlled drug delivery

Semi-interpenetrating polymer network (semi-IPN) hydrogel of sodium 2-acrylamido-2-methylpropane sulfonate (Na-AMPS) and poly(ε-caprolactone) (PCL) diol for drug delivery applications was synthesized via free radical UV-photopolymerization technique using 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone as an initiator and poly(ethylene glycol) diacrylate (PEGDA) as a crosslinker. The hydrogels' chemical structure and internal morphology have been explored using Fourier-transform infrared spectroscopy and scanning electron microscopy. The influence of PCL diol and PEGDA concentrations on the synthesized semi-IPN hydrogel properties was investigated. The semi-IPN hydrogel can increase the elasticity of the hydrogel while simultaneously providing enough water uptake and water retention. Furthermore, the semi-IPN hydrogel was non-cytotoxic to mouse fibroblasts L929 cells. Finally, ciprofloxacin (CIP) was used as a model drug and was efficiently encapsulated into the semi-IPN hydrogels. Drug loading capacity was enhanced with increasing PCL diol and CIP content. It was also observed that the PCL diol and CIP contents had a marked influence on the release profiles. Thus, the rate of release could be designed by changing the Na-AMPS to PCL diol ratio and CIP content. Drug release was found to be both diffusion and swelling-controlled in accordance with the Fickian and non-Fickian transport mechanisms. In the light of the results obtained, their easy formability, their appropriate mechanical and physical properties make P(Na-AMPS)/PCL diol semi-IPN hydrogels are the potential candidates for use as drug carrier and controlled drug release materials in the biomedical field