Flow Metal‐Free Ar?C Bond Formation via Photogenerated Phenyl Cations

A convenient photochemical flow protocol for the formation of aryl‐carbon bonds via photogenerated phenyl cations has been developed. A wide range of phenylated products, including biaryls, allylarenes, 2‐arylacetals and benzyl γ‐lactones, was smoothly synthesized in satisfactory yields under metal‐free conditions. The adoption of a flow reactor often allowed us to adopt higher concentrations of substrates and shorter irradiation times compared to those usually employed in batch systems.

     

Precursor gas chemistry determines the crystallinity of carbon nanotubes synthesized at low temperature

Despite significant progress in carbon nanotube (CNT) synthesis by thermal chemical vapor deposition (CVD), the factors determining the structure of the resulting carbon filaments and other graphitic nanocarbons are not well understood. Here, we demonstrate that gas chemistry influences the crystal structure of carbon filaments grown at low temperatures (500 °C). Using thermal CVD, we decoupled the thermal treatment of the gaseous precursors (C₂H₄/H₂/Ar) and the substrate-supported catalyst. Varying the preheating temperature of the feedstock gas, we observed a striking transition between amorphous carbon nanofibers (CNFs) and crystalline CNTs. These results were confirmed using both a hot-wall CVD system and a cold-wall CVD reactor. Analysis of the exhaust gases (by ex situ gas chromatography) showed increasing concentrations of specific volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbons (PAHs) that correlated with the structural transition observed (characterized using high-resolution transmission electron microscopy). This suggests that the crystallinity of carbon filaments may be controlled by the presence of specific gas phase precursor molecules (e.g., VOCs and PAHs). Thus, direct delivery of these molecules in the CVD process may enable selective CNF or CNT formation at low substrate temperatures. The inherent scalability of this approach could impact many promising applications, especially in the electronics industry.     

On the Viscoelastic Properties of Collagen‐Gel‐Based Lattices under Cyclic Loading: Applications for Vascular Tissue Engineering

Reconstituted collagen gels are widely used as scaffolds even though their low strength and poor elasticity limit their applications in VTE. Here, two approaches are adopted to modify their mechanical behavior: in the first, gels prepared under physiologic conditions are remodeled by cell‐mediated contraction; in the second, gels prepared in non‐physiologic conditions are chemically crosslinked. Samples are tested under cyclic loading and their viscoelastic behavior is assessed. The results show that both approaches result in lattices with adequate strength, and crosslinking significantly reduces hysteresis and permanent deformation. SEM shows that SMCs are capable of contracting and remodeling all the lattices, confirming that these are suitable supports for tissue regeneration.

     

Unpatterned Bioactive Poly(Butylene 1,4-Cyclohexanedicarboxylate)-Based Film Fast Induced Neuronal-Like Differentiation of Human Bone Marrow-Mesenchymal Stem Cells

Herein, we present poly(butylene 1,4-cyclohexanedicarboxylate) (PBCE) films characterized by an unpatterned microstructure and a specific hydrophobicity, capable of boosting a drastic cytoskeleton architecture remodeling, culminating with the neuronal-like differentiation of human bone marrow-mesenchymal stem cells (hBM-MSCs). We have used two different filming procedures to prepare the films, solvent casting (PBCE) and compression-moulding (PBCE*). PBCE film had a rough and porous surface with spherulite-like aggregations (Ø = 10–20 μm) and was characterized by a water contact angle = 100°. PBCE* showed a smooth and continuous surface without voids and visible spherulite-like aggregations and was more hydrophobic (WCA = 110°). Both surface characteristics were modulated through the copolymerization of different amounts of ether-oxygen-containing co-units into PBCE chemical structure. We showed that only the surface characteristics of PBCE-solvent-casted films steered hBM-MSCs toward a neuronal-like differentiation. hBM-MSCs lost their canonical mesenchymal morphology, acquired a neuronal polarized shape with a long cell protrusion (≥150 μm), expressed neuron-specific class III β-tubulin and microtubule-associated protein 2 neuronal markers, while nestin, a marker of uncommitted stem cells, was drastically silenced. These events were observed as early as 2-days after cell seeding. Of note, the phenomenon was totally absent on PBCE* film, as hBM-MSCs maintained the mesenchymal shape and behavior and did not express neuronal/glial markers.     

Catalyst–support interactions and their influence in water-assisted carbon nanotube carpet growth

We report results from characterization studies focused on a diverse selection of catalyst support materials in order to understand what makes a good catalyst support during carbon nanotube (CNT) carpet growth via water-assisted chemical vapor deposition. The growth and catalyst morphological changes occurring for thin Fe layers deposited on Al₂O₃, MgO, TiN, and ZrO₂ are compared. The growth behaviors of the catalyst substrates were evidently different, with Al₂O₃/Fe supporting CNT carpet growth and showing the highest activity and longest lifetime. The TiN/Fe catalyst also supported CNT carpet growth, albeit with much lower activity, shorter lifetime, and lower CNT quality while MgO/Fe and ZrO₂/Fe did not support CNT carpet growth under standard growth conditions. Studies using a combination of atomic force microscopy and X-ray photoelectron spectroscopy revealed a general correlation between the catalyst behavior (activity and lifetime) and the 3D evolution of the catalyst for active catalysts (Al₂O₃/Fe and TiN/Fe). Analysis of inactive catalysts under standard conditions (MgO/Fe and ZrO₂/Fe) raise interesting questions related to additional chemical interactions between the substrate and catalyst that could influence nucleation and CNT growth. This work provides a step toward understanding the challenges that arise in engineering efficient CNT growth processes on a desired substrate.     

Quantifying dissipative contributions in nanoscale interactions

Imaging with nanoscale resolution has become routine practice with the use of scanning probe techniques. Nevertheless, quantification of material properties and processes has been hampered by the complexity of the tip-surface interaction and the dependency of the dynamics on operational parameters. Here, we propose a framework for the quantification of the coefficients of viscoelasticity, surface energy, surface energy hysteresis and elastic modulus. Quantification of these parameters at the nanoscale will provide a firm ground to the understanding and modelling of tribology and nanoscale sciences with true nanoscale resolution.     

Eumelanin for nature‐inspired UV‐absorption enhancement of plastics

In the human body, the black‐brown biopigment eumelanin blocks harmful ultraviolet (UV) radiation. In the plastics industry, additives are often added to polymers to increase their UV‐absorption properties. We herein report an assessment of the biopigment eumelanin as a nature‐inspired additive for plastics to enhance their UV absorption. Since eumelanin is produced by natural sources and is nontoxic, it is an interesting candidate in the field of sustainable plastic additives. In this work, the eumelanin‐containing films of commercial ethylene–vinyl acetate copolymer, a plastic used for packaging applications, were obtained by melt compounding and compression molding. The biopigment dispersion in the films was improved by means of the melanin free acid treatment. It was observed that eumelanin amounts as low as 0.8 wt% caused an increase of the UV absorption, up to one order of magnitude in the UVA range. We also evaluated the effect of eumelanin on the thermal stability and photostability of the films: the biopigment proved to be double‐edged, working both as UV‐absorption enhancer and photo‐prooxidant, as thermogravimetric analysis and infrared spectroscopy revealed. © 2019 Society of Chemical Industry     

Intensification of biopolymeric microparticles production by ultrasonic assisted atomization

In this work ultrasonic atomization process is applied to produce biopolymer microparticles with potential applications in pharmaceutical and nutraceutical fields. Natural polymer (alginate)/water solution is atomized by ultrasonic assisted process and the droplets spray is reticulated using a solution of copper sulfate, where the Cu²⁺ ions cause the formation of a network structure (hard porous gel). Several operating parameters (solution concentration, flow rate, atomization power) are changed to study their effects on the produced microparticles. Literature correlations able to predict the features of the droplets as functions of process parameters are optimized using a statistical approach. Furthermore, the energy requirement for the drops production is compared with the energy required by traditional techniques to evaluate the intensification effect of the ultrasonic on the atomization process.