Surface-Modified Polypyrrole-Coated PLCL and PLGA Nerve Guide Conduits Fabricated by 3D Printing and Electrospinning.

The efficiency of nerve guide conduits (NGCs) in repairing peripheral nerve injury is not high enough yet to be a substitute for autografts and is still insufficient for clinical use. To improve this efficiency, 3D electrospun scaffolds (3D/E) of poly(l-lactide-co-ε-caprolactone) (PLCL) and poly(l-lactide-co-glycolide) (PLGA) were designed and fabricated by the combination of 3D printing and electrospinning techniques, resulting in an ideal porous architecture for NGCs. Polypyrrole (PPy) was deposited on PLCL and PLGA scaffolds to enhance biocompatibility for nerve recovery. The designed pore architecture of these "PLCL-3D/E" and "PLGA-3D/E" scaffolds exhibited a combination of nano- and microscale structures. The mean pore size of PLCL-3D/E and PLGA-3D/E scaffolds were 289 ± 79 and 287 ± 95 nm, respectively, which meets the required pore size for NGCs. Furthermore, the addition of PPy on the surfaces of both PLCL-3D/E (PLCL-3D/E/PPy) and PLGA-3D/E (PLGA-3D/E/PPy) led to an increase in their hydrophilicity, conductivity, and noncytotoxicity compared to noncoated PPy scaffolds. Both PLCL-3D/E/PPy and PLGA-3D/E/PPy showed conductivity maintained at 12.40 ± 0.12 and 10.50 ± 0.08 Scm-1 for up to 15 and 9 weeks, respectively, which are adequate for the electroconduction of neuron cells. Notably, the PLGA-3D/E/PPy scaffold showed superior cytocompatibility when compared with PLCL-3D/E/PPy, as evident via the viability assay, proliferation, and attachment of L929 and SC cells. Furthermore, analysis of cell health through membrane leakage and apoptotic indices showed that the 3D/E/PPy scaffolds displayed significant decreases in membrane leakage and reductions in necrotic tissue. Our finding suggests that these 3D/E/PPy scaffolds have a favorable design architecture and biocompatibility with potential for use in peripheral nerve regeneration applications.

Ethyl cellulose composite membranes containing a 2D material (MoS2) and helical carbon nanotubes for efficient solar steam generation and desalination.

With the increasing water consumption, water evaporators have been investigated for clean water production. Herein, the fabrication of electrospun composite membrane evaporators based on ethyl cellulose (EC), with the incorporation of light-absorption enhancers 2D MoS2 and helical carbon nanotubes, for steam generation and solar desalination is described. Under natural sunlight, the maximum water evaporation rate was 2.02 kg m-2 h-1 with an evaporation efficiency of 93.2 % (1 sun) and reached 2.42 kg m-2 h-1 at 12:00 pm (1.35 sun). The composite membranes demonstrated self-floating on the air-water interface and minimal accumulation of superficial salt during the desalination process due to the hydrophobic character of EC. For concentrated saline water (21 wt% NaCl), the composite membranes maintained a relatively high evaporation rate of up to ~79 % compared to the freshwater evaporation rate. The composite membranes are robust due to the thermomechanical stability of the polymer even while operating under steam-generating conditions. Over repeated use, they exhibited excellent reusability with a relative water mass change of >90 % compared to the first evaporation cycle. Moreover, desalination of artificial seawater produced a lower cation concentration (~3-5 orders of magnitude) and thereby yielded potable water, indicating the potential for solar-driven freshwater generation.

Carboxymethyl cellulose/poly(vinyl alcohol) blended films reinforced by buckypapers of carbon nanotubes and 2D material (MoS2): Enhancing mechanical strength, toughness, and barrier properties.

Plastic waste is one cause of climate change. To solve this problem, packaging films are increasingly produced from biodegradable polymers. Eco-friendly carboxymethyl cellulose and its blends have been developed for such a solution. Herein, a unique strategy is demonstrated to improve the mechanical and barrier properties of carboxymethyl cellulose/poly(vinyl alcohol) (CMC/PVA) blended films for the packaging of nonfood dried products. The blended films were impregnated with buckypapers containing different combinations of multiwalled carbon nanotubes, two-dimensional molybdenum disulfide (2D MoS2) nanoplatelets, and helical carbon nanotubes (HCNTs). Compared to the blend, the polymer composite films exhibit significant increases in tensile strength (~105 %, from 25.53 to 52.41 MPa), Young's modulus (~297 %, from 155.48 to 617.48 MPa), and toughness (~46 %, from 6.69 to 9.75 MJ m-3). Polymer composite films containing HCNTs in buckypapers offer the highest toughness. For barrier properties, the polymer composite films are opaque. The water vapor transmission rate of the blended films decreases (~52 %, from 13.09 to 6.25 g h-1 m-2). Moreover, the maximum thermal-degradation temperature of the blend rises from 296 to 301 °C, especially for the polymer composite films with buckypapers containing MoS2 nanosheets that contribute to the barrier effect for both water vapor and thermal-decomposition gas molecules.

Novel Poly(Methylenelactide-g-L-Lactide) Graft Copolymers Synthesized by a Combination of Vinyl Addition and Ring-Opening Polymerizations.

In this work, a novel poly (methylenelactide-g-L-lactide), P(MLA-g-LLA) graft copolymer was synthesized from poly(methylenelactide) (PMLA) and L-lactide (LLA) using 0.03 mol% liquid tin(II) n-butoxide (Sn(OnBu)2) as an initiator by a combination of vinyl addition and ring-opening polymerization (ROP) at 120 °C for 72 h. Proton and carbon-13 nuclear magnetic resonance spectroscopy (1H- and 13C-NMR) and Fourier-transform infrared spectroscopy (FT-IR) confirmed the grafted structure of P(MLA-g-LLA). The P(MLA-g-LLA) melting temperatures (Tm) range of 144-164 °C, which was lower than that of PLA (170-180 °C), while the thermal decomposition temperature (Td) of around 314-335 °C was higher than that of PLA (approx. 300 °C). These results indicated that the grafting reaction could widen the melt processing range of PLA and in doing so increase PLA's thermal stability during melt processing. The graft copolymers were obtained with weight-average molecular weights (M¯w) = 4200-11,000 g mol-1 and a narrow dispersity (D = 1.1-1.4).

Development of an Antimicrobial-Coated Absorbable Monofilament Suture from a Medical-Grade Poly(l-lactide-co-ε-caprolactone) Copolymer.

In this study, a medical-grade poly(l-lactide-co-ε-caprolactone) (PLC) copolymer with a monomer ratio of l-lactide (L) to ε-caprolactone (C) of 70:30 mol % for use as an absorbable surgical suture was synthesized via ring-opening polymerization (ROP) using a novel soluble liquid tin(II) n-butoxide (Sn(OnC4H9)2) as an initiator. In fiber fabrication, the process included copolymer melt extrusion with a minimal draw followed by sequential controlled hot-drawing and fixed-annealing steps to obtain oriented semicrystalline fibers with improved mechanical strength. For healing enhancement, the fiber was dip-coated with "levofloxacin" by adding the drug into a solution mixture of acetone, poly(ε-caprolactone) (PCL), and calcium stearate (CaSt) in the ratio of acetone/PCL/CaSt = 100:1% w/v:0.1% w/v. The tensile strength of the coated fiber was found to be increased to ∼400 MPa, which is comparable with that of commercial polydioxanone (PDS II) of a similar size. Finally, the efficiency of the drug-coated fiber regarding its controlled drug release and antimicrobial activity was investigated, and the results showed that the coated fiber was able to release the drug continuously for as long as 30 days. For fiber antimicrobial activity, it was found that a concentration of 1 mg/mL was sufficient to inhibit the growth of Staphylococcus aureus (MRSA), Escherichia coli O157:H7, and Pseudomonas aeruginosa, giving a clear inhibition zone range of 20-24 mm for 90 days. Cytotoxicity testing of the drug-coated fibers showed a %viability of more than 70%, indicating that they were nontoxic.

Efficiency of liquid tin(ii) n-alkoxide initiators in the ring-opening polymerization of l-lactide: kinetic studies by non-isothermal differential scanning calorimetry.

Novel soluble liquid tin(ii) n-butoxide (Sn(OnC4H9)2), tin(ii) n-hexoxide (Sn(OnC6H13)2), and tin(ii) n-octoxide (Sn(OnC8H17)2) initiators were synthesized for use as coordination-insertion initiators in the bulk ring-opening polymerization (ROP) of l-lactide (LLA). In order to compare their efficiencies with the more commonly used tin(ii) 2-ethylhexanoate (stannous octoate, Sn(Oct)2) and conventional tin(ii) octoate/n-alcohol (SnOct2/nROH) initiating systems, kinetic parameters derived from monomer conversion data were obtained from non-isothermal differential scanning calorimetry (DSC). In this work, the three non-isothermal DSC kinetic approaches including dynamic (Kissinger, Flynn-Wall, and Ozawa); isoconversional (Friedman, Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW)); and Borchardt and Daniels (B/D) methods of data analysis were compared. The kinetic results showed that, under the same conditions, the rate of polymerization for the 7 initiators/initiating systems was in the order of liquid Sn(OnC4H9)2 > Sn(Oct)2/nC4H9OH > Sn(Oct)2 ≅ liquid Sn(OnC6H13)2 > Sn(Oct)2/nC6H13OH ≅ liquid Sn(OnC8H17)2 > Sn(Oct)2/nC8H17OH. The lowest activation energies (E a = 52, 59, and 56 kJ mol-1 for the Kissinger, Flynn-Wall, and Ozawa dynamic methods; E a = 53-60, 55-58, and 60-62 kJ mol-1 for the Friedman, KAS, and OFW isoconversional methods; and E a = 76-84 kJ mol-1 for the B/D) were found in the polymerizations using the novel liquid Sn(OnC4H9)2 as the initiator, thereby showing it to be the most efficient initiator in the ROP of l-lactide.