Nanostructuring Biobased Epoxy Resin with PEO-PPO-PEO Block Copolymer.

A biobased diglycidyl ether of vanillin (DGEVA) epoxy resin was nanostructured by poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-PPO-PEO) triblock copolymer. Due to the miscibility/immiscibility properties of the triblock copolymer in DGEVA resin, different morphologies were obtained depending on the triblock copolymer amount. A hexagonally packed cylinder morphology was kept until reaching 30 wt% of PEO-PPO-PEO content, while a more complex three-phase morphology was obtained for 50 wt%, in which large worm-like PPO domains appear surrounded by two different phases, one of them rich in PEO and another phase rich in cured DGEVA. UV-vis measurements show that the transmittance is reduced with the increase in triblock copolymer content, especially at 50 wt%, probably due to the presence of PEO crystals detected by calorimetry.

Semi-paracrystallinity in semi-conducting polymers.

Precise determination of structural organization of semi-conducting polymers is of paramount importance for the further development of these materials in organic electronic technologies. Yet, prior characterization of some of the best-performing materials for transistor and photovoltaic applications, which are based on polymers with rigid backbones, often resulted in conundrums in which X-ray scattering and microscopy yielded seemingly contradicting results. Here we solve the paradox by introducing a new structural model, i.e., semi-paracrystalline organization. The model establishes that the microstructure of these materials relies on a dense array of small paracrystalline domains embedded in a more disordered matrix. Thus, the overall structural order relies on two parameters: the novel concept of degree of paracrystallinity (i.e., paracrystalline volume/mass fraction, introduced here for the first time) and the lattice distortion parameter of paracrystalline domains (g-parameter from X-ray scattering). Structural parameters of the model are correlated with long-range charge carrier transport, revealing that charge transport in semi-paracrystalline materials is particularly sensitive to the interconnection of paracrystalline domains.

An Ideal Spin Filter: Long-Range, High-Spin Selectivity in Chiral Helicoidal 3-Dimensional Metal Organic Frameworks.

An enantiopure, conductive, and paramagnetic crystalline 3-D metal-organic framework (MOF), based on Dy(III) and the l-tartrate chiral ligand, is proved to behave as an almost ideal electron spin filtering material at room temperature, transmitting one spin component only, leading to a spin polarization (SP) power close to 100% in the ±2 V range, which is conserved over a long spatial range, larger than 1 µm in some cases. This impressive spin polarization capacity of this class of nanostructured materials is measured by means of magnetically polarized conductive atomic force microscopy and is attributed to the Chirality-Induced Spin Selectivity (CISS) effect of the material arising from a multidimensional helicity pattern, the inherited chirality of the organic motive, and the enhancing influence of Dy(III) ions on the CISS effect, with large spin-orbit coupling values. Our results represent the first example of a MOF-based and CISS-effect-mediated spin filtering material that shows a nearly perfect SP. These striking results obtained with our robust and easy-to-synthesize chiral MOFs constitute an important step forward in to improve the performance of spin filtering materials for spintronic device fabrication.

Improvement of macroscale properties of TiO2/cellulose acetate hybrid films by solvent vapour annealing.

Two different methods were employed for the preparation of cellulose triacetate (CTA) based nanocomposites without and with poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (EPE) triblock copolymer and modified with sol-gel synthesised titanium dioxide nanoparticles (TiO2). The hybrid nanocomposites were prepared by solvent casting (SC) and solvent vapour annealing (SVA) methods. The hybrid nanocomposite films obtained by SVA presented smoother surfaces, and consequently, higher gloss values. As for transparency, only the hybrid nanocomposites prepared by SVA remained completely transparent even with high sol-gel content due to the nanostructuration of EPE triblock copolymer. Furthermore, the UV-shielding properties provided by the TiO2 nanoparticles were not modified regardless of the employed preparation method. Finally, the nanocomposites prepared by SVA presented a higher Young's modulus and tensile strength than the SC nanocomposites. The obtained results proved the efficiency of the SVA method to control the relationship between the morphology and the final properties of the hybrid nanocomposite films leading to materials with enhanced surface, optical, and mechanical properties.

Flexible photochromic cellulose triacetate based bionanocomposites modified with sol-gel synthesized V2O5 nanoparticles.

Transparent and flexible bionanocomposites with photochromic properties based on cellulose triacetate (CTA) and sol-gel synthesized V2O5 nanoparticles were prepared. Poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (EPE) triblock copolymer was added to achieve nanostructured materials and simultaneously control the dispersion of synthesized V2O5 nanoparticles. Investigated bionanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), atomic force microscopy (AFM), tensile tests, and UV-vis spectroscopy. FTIR results confirmed the presence of hydrogen bonds in the bionanocomposites. The miscibility between components improved with the increase of sol-gel content resulting in a decrease of the Tg and Tm of CTA phase as indicated by DSC results. Addition of EPE triblock copolymer enhanced the photochromic properties of bionanocomposites reducing the time of recovery to the initial state after 5 min of UV light irradiation. The biocompatibility of pure CTA and EPE/CTA blends as well as the photochromic properties provided by synthesized V2O5 nanoparticles make their transparent and flexible bionanocomposites ideal for possible future applications.

Effect of in situ modification of bacterial cellulose with carboxymethylcellulose on its nano/microstructure and methotrexate release properties.

Bacterial cellulose/carboxymethylcelullose (BC/CMC) biocomposites with different DS-CMC (DS from 0.7 to 1.2) were developed in order to evaluate their impact as a drug delivery system. Biocomposites were loaded with methotrexate (MTX) as an alternative for the topical treatment of psoriasis. Scanning electron microscopy and atomic force microscopy showed that the CMC coated the cellulose nanofibers, leading to the decrease of the elastic modulus as the DS of CMC increased. BC/CMC0.9 exhibited the lower liquid uptake (up to 11 times lower), suggesting that the more linear structure of the intermediate substitute CMC grade (0.9) was able to interact more strongly with BC, resulting in a denser structure. All samples showed a typical burst release effect in the first 15min of test, however the BC/CMC0.9 biocomposite promoted a slight lowering of MTX release rates, suggesting that the DS of CMC can be considered the key factor to modulate the BC properties.

Hydrothermal synthesis of bacterial cellulose-copper oxide nanocomposites and evaluation of their antimicrobial activity.

In this work, for the first time bacterial cellulose (BC) hydrogel membranes were used for the fabrication of antimicrobial cellulosic nanocomposites by hydrothermal deposition of Cu derivative nanoparticles (i.e.Cu(0) and CuxOy species). BC-Cu nanocomposites were characterized by FTIR, SEM, AFM, XRD and TGA, to study the effect of hydrothermal processing time on the final physicochemical properties of final products. XRD result show that depending on heating time (3-48h), different CuxOy phases were achieved. SEM and AFM analyses unveil the presence of the Cu(0) and copper CuxOy nanoparticles over BC fibrils while the surface of 3D network became more compact and smother for longer heating times. Furthermore, the increase of heating time placed deleterious effect on the structure of BC network leading to decrease of BC crystallinity as well as of the on-set degradation temperature. Notwithstanding, BC-Cu nanocomposites showed excellent antimicrobial activity against E. coli, S. aureus and Salmonella bacteria suggesting potential applications as bactericidal films.

Optical sensor platform based on cellulose nanocrystals (CNC) - 4'-(hexyloxy)-4-biphenylcarbonitrile (HOBC) bi-phase nematic liquid crystal composite films.

The preparation of composite materials has gained tremendous attention due to the potential synergy of the combined materials. Here we fabricate novel thermal/electrical responsive photonic composite films combining cellulose nanocrystals (CNC) with a low molecular weight nematic liquid crystal (NLC), 4'-(hexyloxy)-4-biphenylcarbonitrile (HOBC). The obtained composite material combines both intense structural coloration of photonic cellulose and thermal and conductive properties of NLC. Scanning electron microscopy (SEM) results confirmed that liquid crystals coated CNC films maintain chiral nematic structure characteristic of CNC film and simultaneously, transversal cross-section scanning electron microscopy images indicated penetration of liquid crystals through the CNC layers. Investigated composite film maintain NLC optical properties being switchable as a function of temperature during heating/cooling cycles. The relationship between the morphology and thermoresponsive in the micro/nanostructured materials was investigated by using transmission optical microscopy (TOM). Conductive response of the composite films was proved by Electrostatic force microscopy (EFM) measurement. Designed thermo- and electro-responsive materials open novel simple pathway of fabrication of CNC-based materials with tunable properties.

Transparent nanostructured cellulose acetate films based on the self assembly of PEO-b-PPO-b-PEO block copolymer.

In this study fabrication and characterization of transparent nanostructured composite films based on cellulose triacetate (CTA) and poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (EPE) triblock copolymer were presented. The effect of the addition of EPE triblock copolymer on the thermal stability, morphology, and mechanical properties of cellulose triacetate films was investigated. The triblock EPE was chosen since PEO blocks interact favorably with CTA, whereas, PPO blocks remain immiscible which provokes a microphase separation. This allows to obtain EPE/CTA composite films with ordered microphase-separated structures where PPO spherical microdomains are well-dispersed in PEO/CTA matrix by simple solvent-evaporation process. During this process, PEO block chains selectively interact with CTA by strong interpolymer hydrogen-bonding while PPO block microseparated. The addition even 40wt% of EPE leads to nanostructured EPE/CTA composite. The cytotoxicity assay of CTA and EPE/CTA composite films confirm non-toxic character of designed transparent nanostructured composites based on sustainable matrices.

Synthesis and factorial design applied to a novel chitosan/sodium polyphosphate nanoparticles via ionotropic gelation as an RGD delivery system.

Chitosan nanoparticles have been extensively studied for both drug and protein/peptide delivery. The aim of this study was to develop an optimized chitosan nanoparticle, by ionotropic gelation method, using 32 full factorial design with a novel polyanion, sodium polyphosphate, well known under the trade name Graham salt. The effects of these parameters on the particle size, zeta potential, and morphology and association efficiency were investigated. The optimized nanoparticles showed an estimated size of 166.20±1.95nm, a zeta potential of 38.7±1.2mV and an efficacy of association of 97.0±2.4%. The Atomic Force Microscopy (AFM) and Scanning Electronic Microscopy (SEM) revealed spherical nanoparticles with uniform size. Molecular interactions among the components of the nanoparticles and peptide were evaluated by Fourier Transform Infrared Spectra (FTIR) and Differential Scanning Calorimetry (DSC). The obtained results indicated that, the developed nanoparticles demonstrated high biocompatible, revealing no or low toxicity in the human cancer cell line (Caco-2). In conclusion, this work provides parameters that contribute to production of chitosan nanoparticles and sodium polyphosphate with desirable size, biocompatible and enabling successful use for protein/peptides delivery.

A multipurpose natural and renewable polymer in medical applications: Bacterial cellulose.

Bacterial cellulose (BC) produced by some bacteria, among them Gluconacetobacter xylinum, which secrets an abundant 3D networks fibrils, represents an interesting emerging biocompatible nanomaterial. Since its discovery BC has shown tremendous potential in a wide range of biomedical applications, such as artificial skin, artificial blood vessels and microvessels, wound dressing, among others. BC can be easily manipulated to improve its properties and/or functionalities resulting in several BC based nanocomposites. As example BC/collagen, BC/gelatin, BC/Fibroin, BC/Chitosan, etc. Thus, the aim of this review is to discuss about the applicability in biomedicine by demonstrating a variety of forms of this biopolymer highlighting in detail some qualities of bacterial cellulose. Therefore, various biomedical applications ranging from implants and scaffolds, carriers for drug delivery, wound-dressing materials, etc. that were reported until date will be presented.

Komagataeibacter rhaeticus as an alternative bacteria for cellulose production.

A strain isolated from Kombucha tea was isolated and used as an alternative bacterium for the biosynthesis of bacterial cellulose (BC). In this study, BC generated by this novel bacterium was compared to Gluconacetobacter xylinus biosynthesized BC. Kinetic studies reveal that Komagataeibacter rhaeticus was a viable bacterium to produce BC according to yield, thickness and water holding capacity data. Physicochemical properties of BC membranes were investigated by UV-vis and Fourier transform infrared spectroscopies (FTIR), thermogravimetrical analysis (TGA) and X-ray diffraction (XRD). Additionally, scanning electron microscopy (SEM) and atomic force microscopy (AFM) were also used for morphological characterization. Mechanical properties at nano and macroscale were studied employing PeakForce quantitative nanomechanical property mapping (QNM) and dynamic mechanical analyzer (DMA), respectively. Results confirmed that BC membrane biosynthesized by Komagataeibacter rhaeticus had similar physicochemical, morphological and mechanical properties than BC membrane produced by Gluconacetobacter xylinus and can be widely used for the same applications.

Switchable photoluminescence liquid crystal coated bacterial cellulose films with conductive response.

Three different low molecular weight nematic liquid crystals (LCs) were used to impregnate bacterial cellulose (BC) film. This simple fabrication pathway allows to obtain highly transparent BC based films. The coating of BC film with different liquid crystals changed transmittance spectra in ultraviolet-visible region and allows to design UVC and UVB shielding materials. Atomic force microscopy results confirmed that liquid crystals coated BC films maintain highly interconnected three-dimensional network characteristic of BC film and simultaneously, transversal cross-section scanning electron microscopy images indicated penetration of liquid crystals through the three-dimensional network of BC nanofibers. Investigated BC films maintain nematic liquid crystal properties being switchable photoluminiscence as a function of temperature during repeatable heating/cooling cycles. Conductive response of the liquid crystal coated BC films was proved by tunneling atomic force microscopy measurement. Moreover, liquid crystal coated BC films maintain thermal stability and mechanical properties of the BC film. Designed thermoresponsive materials possessed interesting optical and conductive properties opening a novel simple pathway of fabrication liquid crystal coated BC films with tuneable properties.

Nano- and macroscale structural and mechanical properties of in situ synthesized bacterial cellulose/PEO-b-PPO-b-PEO biocomposites.

Highly transparent biocomposite based on bacterial cellulose (BC) mat modified with poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) block copolymer (EPE) were fabricated in situ during biosynthesis of bacterial cellulose in a static culture from Gluconacetobacter xylinum. The effect of the addition to the culture medium of water-soluble EPE block copolymer on structure, morphology, crystallinity, and final properties of the novel biocomposites was investigated at nano- and macroscale. High compatibility between components was confirmed by ATR-FTIR indicating hydrogen bond formation between the OH group of BC and the PEO block of EPE block copolymer. Structural properties of EPE/BC biocomposites showed a strong effect of EPE block copolymer on the morphology of the BC mats. Thus, the increase of the EPE block copolymer content lead to the generation of spherulites of PEO block, clearly visualized using AFM and MO technique, changing crystallinity of the final EPE/BC biocomposites investigated by XRD. Generally, EPE/BC biocomposites maintain thermal stability and mechanical properties of the BC mat being 1 wt % EPE/BC biocomposite material with the best properties. Biosynthesis of EPE/BC composites open new strategy to the utilization of water-soluble block copolymers in the preparation of BC mat based biocomposites with tunable properties.

Conductive photoswitchable vanadium oxide nanopaper based on bacterial cellulose.

A bacterial cellulose mat was used as a template for the fabrication of conductive photoswitchable hybrid nanopaper by the incorporation of sol-gel synthesized vanadium nanoparticles. The resulting nanopaper, prepared through a green pathway, was able to photoinduce a reversible color change. Conductive properties at the nano- and macroscales were confirmed by electrostatic force microscopy and semiconductor analysis measurements, respectively.

Conductive properties of TiO2/bacterial cellulose hybrid fibres.

Conductive properties of TiO(2) nanoparticles and TiO(2)/BC hybrid inorganic/organic fibres were investigated by electrostatic force microscopy (EFM). TiO(2)/BC hybrid composites were prepared based on bacterial cellulose produced by Gluconobacterxylinum, being the bacterial cellulose as a hydrophilic substrate for TiO(2) nanoparticles synthesized via sol-gel. Taken into account hydrophilic nature of the cellulose, TiO(2) nanoparticles were located on the surface of the fibres due to hydrogen bonding interactions. EFM was used to determine qualitatively conductive properties of TiO(2) nanoparticles and their TiO(2)/BC hybrid inorganic/organic fibres. Results indicate that TiO(2)/BC hybrid fibres respond to applied bias regardless of the sign of the applied voltage.

Conductive properties of switchable photoluminescence thermosetting systems based on liquid crystals.

Conductive properties of different thermosetting materials modified with nematic 4'-(hexyl)-4-biphenyl-carbonitrile (HBC) liquid crystal and rutile TiO(2) nanoparticles were successfully studied by means of tunneling atomic force miscroscopy (TUNA). Taking into account the liquid crystal state of the HBC at room temperature, depending on both the HBC content and the presence of TiO(2) nanoparticles, designed materials showed different TUNA currents passed through the sample. The addition of TiO(2) nanoparticles into the systems multiply the detected current if compared to the thermosetting systems without TiO(2) nanoparticles and simultaneously stabilized the current passed through the sample, making the process reversible since the absolute current values were almost the same applying both negative and positive voltage. Moreover, thermosetting systems modified with liquid crystals with and without TiO(2) nanoparticles are photoluminescence switchable materials as a function of temperature gradient during repeatable heating/cooling cycle. Conductive properties of switchable photoluminescence thermosetting systems based on liquid crystals can allow them to find potential application in the field of photoresponsive devices, with a high contrast ratio between transparent and opaque states.

Conductive behavior of high TiO2 nanoparticle content of inorganic/organic nanostructured composites.

Amphiphilic polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers with different block ratios were used as templates for the incorporation of a high content of titanium dioxide nanoparticles using the sol-gel method. Confinement of the inorganic part in the PEO block of the block copolymer allows the generation of nanostructured systems with a high nanoparticle content. As successfully demonstrated using tunneling atomic force microscopy, the investigated systems maintained the conductive properties of the TiO(2) nanoparticles. The obtained results confirmed that with increasing TiO(2) nanoparticle content, the local current value increased up to 15 pA, and this conductivity value strongly depended on the amount of the PEO block in the block copolymer template. Moreover, the results indicated that control of the ratio between the sol-gel and the PEO block allows the design of well-dispersed, conductive inorganic/organic hybrids with high inorganic content. These materials can provide attractive strategies in the field of dye-sensitized solar cells.