Defect healing and doping of CVD graphene by thermal sulfurization.

CVD graphene layers are intrinsically polycrystalline; depending on grain size, their structure at the atomic level is scarcely free of defects, which affects the properties of graphene. On the one hand, atomic-scale defects act as scattering centers and lead to a loss of carrier mobility. On the other hand, structural disorder at grain boundaries provides additional resistance in series that affects material conductivity. Graphene chemical functionalization has been demonstrated to be an effective way to improve its conductivity mainly by increasing carrier concentration. The present study reports the healing effects of sulfur doping on the electrical transport properties of single-layer CVD graphene. A post-growth thermal sulfurization process operating at 250 °C is applied on single layers of graphene on Corning-glass and Si/SiO2 substrates. XPS and Raman analyses reveal the covalent attachment of sulfur atoms in graphene carbon lattice without creating new C-sp3 defects. Measurements of transport properties show a significant improvement in hole mobility as revealed by Hall measurements and related material conductivity. Typically, Hall mobility values as high as 2500 cm2 V-1 s-1 and sheet resistance as low as 400 Ohm per square are measured on single-layer sulfurized graphene.

Drug Delivery through Epidermal Tissue Cells by Functionalized Biosilica from Diatom Microalgae.

Diatom microalgae are a natural source of fossil biosilica shells, namely the diatomaceous earth (DE), abundantly available at low cost. High surface area, mesoporosity and biocompatibility, as well as the availability of a variety of approaches for surface chemical modification, make DE highly profitable as a nanostructured material for drug delivery applications. Despite this, the studies reported so far in the literature are generally limited to the development of biohybrid systems for drug delivery by oral or parenteral administration. Here we demonstrate the suitability of diatomaceous earth properly functionalized on the surface with n-octyl chains as an efficient system for local drug delivery to skin tissues. Naproxen was selected as a non-steroidal anti-inflammatory model drug for experiments performed both in vitro by immersion of the drug-loaded DE in an artificial sweat solution and, for the first time, by trans-epidermal drug permeation through a 3D-organotypic tissue that better mimics the in vivo permeation mechanism of drugs in human skin tissues. Octyl chains were demonstrated to both favour the DE adhesion onto porcine skin tissues and to control the gradual release and the trans-epidermal permeation of Naproxen within 24 h of the beginning of experiments. The evidence of the viability of human epithelial cells after permeation of the drug released from diatomaceous earth, also confirmed the biocompatibility with human skin of both Naproxen and mesoporous biosilica from diatom microalgae, disclosing promising applications of these drug-delivery systems for therapies of skin diseases.

Raman, WAXS, and Solid-State NMR Characterizations of Regenerated Silk Fibroin Using Lanthanide Ions as Chaotropic Agents.

Bombyx mori silk fibroin (SF) has been reported as a convenient natural material for regenerative medicine, optoelectronics, and many other technological applications. SF owes its unique features to the hierarchical organization of the fibers. Many efforts have been made to set up protocols for dissolution since many applications of SF are based on regenerated solutions and fibers, but chaotropic conditions required to disassemble the packing of the polymer afford solutions with poor crystalline behavior. Our previous research has disclosed a dissolution and regeneration process of highly crystalline fibers involving lanthanide ions as chaotropic agents, demonstrating that each lanthanide has its own unique interaction with SF. Herein, we report elucidation of the structure of Ln-SF fibers by the combined use of Raman spectroscopy, wide-angle X-ray scattering (WAXS), and solid-state NMR techniques. Raman spectra confirmed the coordination of metal ions to SF, WAXS results highlighted the crystalline content of fibers, and solid-state NMR enabled the assessment of different ratios of secondary structures in the protein.

Boronic Acid Moieties Stabilize Adhesion of Microalgal Biofilms on Glassy Substrates: A Chemical Tool for Environmental Applications.

Photosynthetic organisms such as diatoms microalgae provide innovative routes to eco-friendly technologies for environmental pollution bioremediation. Living diatoms are capable to incorporate in vivo a wide variety of chemical species dispersed in seawater, thus being promising candidates for eco-friendly removal of toxic contaminants. However, their exploitation requires immobilization methods that allow to confine microalgae during water treatment. Here we demonstrate that a biofilm of Phaeodactylum tricornutum diatom cells grown on the surface of a glassy substrate bearing boronic acid protruding moieties is stably anchored to the substrate resisting mechanical stress and it is suitable for removal of up to 80 % metal ions (As, Cr, Cu, Zn, Sn, Pb, Sb) in a model polluted water sample. Control experiments also suggest that stabilization of the biofilm adhesion occurs by interaction of boronic acid surface groups of the substrate with the hydroxyl groups of diatoms extracellular polysaccharides.

Improving the In Vitro Removal of Indoxyl Sulfate and p-Cresyl Sulfate by Coating Diatomaceous Earth (DE) and Poly-vinyl-pyrrolidone-co-styrene (PVP-co-S) with Polydopamine.

Polydopamine (PDA) is a synthetic eumelanin polymer mimicking the biopolymer secreted by mussels to attach to surfaces with a high binding strength. It exhibits unique adhesive properties and has recently attracted considerable interest as a multifunctional thin film coating. In this study, we demonstrate that a PDA coating on silica- and polymer-based materials improves the entrapment and retention of uremic toxins produced in specific diseases. The low-cost natural nanotextured fossil diatomaceous earth (DE), an abundant source of mesoporous silica, and polyvinylpyrrolidone-co-Styrene (PVP-co-S), a commercial absorbent comprising polymeric particles, were easily coated with a PDA layer by oxidative polymerization of dopamine at mild basic aqueous conditions. An in-depth chemical-physical investigation of both the resulting PDA-coated materials was performed by SEM, AFM, UV-visible, Raman spectroscopy and spectroscopic ellipsometry. Finally, the obtained hybrid systems were successfully tested for the removal of two uremic toxins (indoxyl sulfate and p-cresyl sulfate) directly from patients' sera.

Polydopamine coating of living diatom microalgae.

Many microorganisms produce specific structures, known as spores or cysts, to increase their resistance to adverse environmental conditions. Scientists have started to produce biomimetic materials inspired by these natural membranes, especially for industrial and biomedical applications. Here, we present biological data on the biocompatibility of a polydopamine-based artificial coating for diatom cells. In this work, living Thalassiosira weissflogii diatom cells are coated on their surface with a polydopamine layer mimicking mussel adhesive protein. Polydopamine does not affect diatoms growth kinetics, it enhances their resistance to degradation by treatment with detergents and acids, and it decreases the uptake of model staining emitters. These outcomes pave the way for the use of living diatom cells bearing polymer coatings for sensors based on living cells, resistant to artificial microenvironments, or acting as living devices for cells interface study.

Synthesis and Investigation of Electro-Optical Properties of H-Shape Dibenzofulvene Derivatives.

We have synthetized two classes of dibenzofulvene-arylamino derivatives with an H-shape design, for a total of six different molecules. The molecular structures consist of two D-A-D units connected by a thiophene or bitiophene bridge, using diarylamino substituents as donor groups anchored to the 2,7- (Group A) and 3,6- (Group B) positions of the dibenzofulvene backbone. The donor units and the thiophene or bithiophene bridges were used as chemico-structural tools to modulate electro-optical and morphological-electrical properties. A combination of experiments, such as absorption measurements (UV-Vis spectroscopy), cyclic voltammetry, ellipsometry, Raman, atomic force microscopy, TD-DFT calculation and hole-mobility measurements, were carried out on the synthesized small organic molecules to investigate the differences between the two classes and therefore understand the relevance of the molecular design of the various properties. We found that the anchoring position on dibenzofulvene plays a crucial key for fine-tuning the optical, structural, and morphological properties of molecules. In particular, molecules with substituents in 2,7 positions (Group A) showed a lower structural disorder, a larger molecular planarity, and a lower roughness.

Graphene CVD growth on copper and nickel: role of hydrogen in kinetics and structure.

Understanding the chemical vapor deposition (CVD) kinetics of graphene growth is important for advancing graphene processing and achieving better control of graphene thickness and properties. In the perspective of improving large area graphene quality, we have investigated in real-time the CVD kinetics using CH(4)-H(2) precursors on both polycrystalline copper and nickel. We highlighted the role of hydrogen in differentiating the growth kinetics and thickness of graphene on copper and nickel. Specifically, the growth kinetics and mechanism is framed in the competitive dissociative chemisorption of H(2) and dehydrogenating chemisorption of CH(4), and in the competition of the in-diffusion of carbon and hydrogen, being hydrogen in-diffusion faster in copper than nickel, while carbon diffusion is faster in nickel than copper. It is shown that hydrogen acts as an inhibitor for the CH(4) dehydrogenation on copper, contributing to suppress deposition onto the copper substrate, and degrades quality of graphene. Additionally, the evidence of the role of hydrogen in forming C-H out of plane defects in CVD graphene on Cu is also provided. Conversely, resurfacing recombination of hydrogen aids CH(4) decomposition in the case of Ni. Understanding better and providing other elements to the kinetics of graphene growth is helpful to define the optimal CH(4)/H(2) ratio, which ultimately can contribute to improve graphene layer thickness uniformity even on polycrystalline substrates.