Semi-Crystalline Poly(thioether) Prepared by Visible-Light-Induced Organocatalyzed Thiol-ene Polymerization in Emulsion.

A photocatalytic thiol-ene aqueous emulsion polymerization under visible-light is described to prepare linear semicrystalline latexes using 2,2'-dimercaptodiethyl sulfide as dithiol and various dienes. The procedure involves low irradiance (3 mW cm-2 ), LED irradiation source, eosin-Y disodium as organocatalyst, low catalyst loading (<0.05% mol), and short reaction time scales (<1 h). The resulting latexes have molecular weights of about 10 kg mol-1 , average diameters of 100 nm, and a linear structure consisting only of thioether repeating units. Electron-transfer reaction from a thiol to the triplet excited state of the photocatalyst is suggested as the primary step of the mechanism (type I), whereas oxidation by singlet oxygen generated by energy transfer has a negligible effect (type II). Only polymers prepared with aliphatic dienes such as diallyl adipate or di(ethylene glycol) divinyl ether exhibit a high crystallization tendency as revealed by differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction. Ordering and crystallization are driven by molecular packing of poly(thioether) chains combining structural regularity, compactness, and flexibility.

Synergistic Toughening of Epoxy Composite with Cellulose Nanofiber and Continuous Pineapple Leaf Fiber as Sustainable Reinforcements.

In this work, the effect of cellulose nanofiber (CNF) on the mechanical properties of long pineapple leaf fiber (PALF)-reinforced epoxy composites was investigated. The content of PALF was fixed at 20 wt.% and the CNF content was varied at 1, 3, and 5 wt.% of the epoxy matrix. The composites were prepared by hand lay-up method. Comparison was conducted between CNF-, PALF- and CNF-PALF-reinforced composites. It was found that the introduction of these small amounts of CNF into epoxy resin caused very small effects on flexural modulus and strength of neat epoxy. However, impact strength of epoxy with 1 wt.% CNF increased to about 115% that of neat epoxy, and, as the content of CNF increased to 3 and 5 wt.%, the impact strength decreased to that of neat epoxy. Observation of the fractured surface under electron microscope revealed the change in failure mechanism from a smooth surface to a much rougher surface. For epoxy containing 20 wt.% PALF, both flexural modulus and strength increased significantly to about 300% and 240% that of neat epoxy. The composite impact strength increased to about 700% that of the neat epoxy. For hybrid systems containing both CNF and PALF, there were few changes observed in both flexural modulus and strength compared to the PALF epoxy system. However, much improvement in impact strength was obtained. By using epoxy containing 1 wt.% CNF as the matrix, the impact strength increased to about 220% that of 20 wt.% PALF epoxy or 1520% that of neat epoxy. It thus could be deduced that the spectacular improvement in impact strength was due to the synergistic effect of CNF and PALF. The failure mechanism leading to the improvement in impact strength will be discussed.

Development of novel and ecological keratin/cellulose-based composites for absorption of oils and organic solvents.

Keratin/cellulose cryogels were successfully fabricated using chicken feathers (CF) and cardboard (C) from environmental waste for the first time, to be exploited in oil/solvent absorption. The keratin/cellulose-based composites were obtained by combining the dissolution of CF and C waste in 1-butyl-3-methylimidazolium chloride (Bmim-Cl+) ionic liquid green solvent via regeneration, simply by the freeze-drying method. The characterization analysis of the synthesized keratin/cellulose-based composites was performed using Fourier transform infrared spectrometry, X-ray diffractometry, scanning electron microscopy, and thermogravimetry. The as-prepared cryogel can absorb various oils and organic solvents. Moreover, its sorption capacity can reach up to 6.9-17.7 times the weight of the initial cryogel. This kind of CF/C cryogel revealed good and fast absorption efficiency. It could also be reused by simple absorption/distillation and absorption/desorption methods. Through the kinetic analysis, it was found that the pseudo-second-order model was more appropriate for the keratin/cellulose cryogel oil absorption process. Besides, owing to its low cost, good absorption capacity, and excellent reusability, this cryogel has potential for spill cleanup of oils and organic solvents.

In Vitro Degradation of Electrospun Poly(Lactic-Co-Glycolic Acid) (PLGA) for Oral Mucosa Regeneration.

Poly(lactic-co-glycolic acid) (PLGA) has been used in the field of tissue engineering as a scaffold due to its good biocompatibility, biodegradability and mechanical strength. With the aim to explore the degradability of PLGA electrospun nonwoven structures for oral mucosa tissue engineering applications, non-irradiated and gamma irradiated nonwovens were immersed in three different solutions, in which simulated body fluid (SBF) and artificial saliva are important for future oral mucosa tissue engineering. The nonwovens were immersed for 7, 15 and 30 days in SBF, culture media (DMEM) and artificial saliva at 37 °C. Before immersion in the solutions, the dosage of 15 kGy was applied for sterilization in one assay and compared with non-irradiated samples at the same timepoints. Samples were characterized using different techniques such as scanning electron microscopy (SEM), differential scanning calorimetric (DSC) and gel permeation chromatography (GPC) to evaluate the nonwoven degradation and Fourier-transform infrared spectroscopy (FTIR) to evaluate the chain scissions. Our results showed that PLGA nonwovens were constituted by semicrystalline fibers with moderate degradation properties up to thirty days. The non-irradiated samples exhibited slower kinetics of degradation than irradiated nonwovens. For immersion times longer than 7 days in the three different solutions, the mean diameter of irradiated fibers stayed in the same range, but significantly different from the control sample. On non-irradiated samples, the degradation kinetics was slower and the plateau in the diameter value was only attained after 30 days of immersion in the fluids. Plasticization (fluid absorption into the fiber structure) occurred in the bulk material, as confirmed by a decrease in Tg observed by DSC analyses of non-irradiated and irradiated nonwovens, in comparison with the respective controls. In addition, artificial saliva showed a higher capacity of influencing PLGA crystallization than SBF and DMEM. FTIR analyses showed typical PLGA chemical functional groups changes. These results will be important for future application of those PLGA electrospun nonwovens for oral mucosa regeneration.

Combining a ligand photogenerator and a Ru precatalyst: a photoinduced approach to cross-linked ROMP polymer films.

Although metathesis photoinduced catalysis is now well established, there is little development in thin film preparation using photochemically activated ring-opening metathesis polymerization (ROMP). Herein, a N-heterocyclic carbene (NHC) photogenerator (1,3-bis(mesityl)imidazolium tetraphenylborate) is combined with an inactive metathesis catalyst ([RuCl2(p-cymene)]2) to generate under UV irradiation an active catalyst (p-cymene)RuCl2 (NHC), that is capable of producing in a single step cross-linked copolymer films by ROMP of norbornene with dicyclopentadiene. The study shows that the photoinitiated catalytic system can be optimized by increasing the yield of photogenerated NHC through a sensitizer (2-isopropylthioxanthone), and by choosing [RuI2(p-cymene)]2 as precatalyst to provide a long-term photolatency. The cross-linked polymer structure is investigated by a range of techniques including gel content measurement, FT-IR and solid-state 13C NMR spectroscopy, TGA and DSC, which reveal a cross-linking mechanism proceeding through both metathesis and olefin coupling.

Direct Laser Writing of Crystallized TiO2 and TiO2 /Carbon Microstructures with Tunable Conductive Properties.

Metal oxides are an important class of materials for optoelectronic applications. In this context, developing simple and versatile processes for integrating these materials at the microscale and nanoscale has become increasingly important. One of the major remaining challenges is to control the microstructuration and electro-optical properties in a single step. It is shown here that near-infrared femtosecond laser irradiation can be successfully used to prepare amorphous or crystallized TiO2 microstructures in a single step using a direct laser writing (DLW) approach from a TiO2 precursor thin film doped with a suitable dye. When laser writing is conducted under a nitrogen atmosphere, simultaneous to the crosslinking of the Ti-oxide precursor, the graphitization of the organic species embedded in the initial film is observed. In this case, a carbon network is generated within the TiO2 matrix, which significantly increases the conductivity. Moreover, the TiO2 /C nanocomposite exhibits piezoresistive behavior that is used in a pressure sensor device. Using this route, it is possible to use DLW to fabricate microsized pressure sensors.