TiO2 Phase Ratio's Contribution to the Photocatalytic Activity.

Photocatalysis is one of the approaches for solving environmental issues derived from extremely harmful pollution caused by industrial dyes, medicine, and heavy metals. Titanium dioxide is among the most promising photocatalytic semiconductors; thus, in this work, TiO2 powders were prepared by a hydrothermal synthesis using titanium tetrachloride TiCl4 as a Ti source. The effect of the hydrochloric acid (HCl) concentration on TiO2 formation was analyzed, in which a thorough morpho-structural analysis was performed employing different analysis methods like XRD, Raman spectroscopy, SEM/TEM, and N2 physisorption. EPR spectroscopy was employed to characterize the paramagnetic defect centers and the photogeneration of reactive oxygen species. Photocatalytic properties were tested by photocatalytic degradation of the rhodamine B (RhB) dye under UV light irradiation and using a solar simulator. The pH value directly influenced the formation of the TiO2 phases; for less acidic conditions, the anatase phase of TiO2 crystallized, with a crystallite size of ≈9 nm. Promising results were observed for TiO2, which contained 76% rutile, showing a 96% degradation of RhB under the solar simulator and 91% under UV light after 90 min irradiation, and the best result showed that the sample with 67% of the anatase phase after 60 min irradiation under the solar simulator had a 99% degradation efficiency.

Modulated Laser Cladding of Implant-Type Coatings by Bovine-Bone-Derived Hydroxyapatite Powder Injection on Ti6Al4V Substrates-Part I: Fabrication and Physico-Chemical Characterization.

The surface physico-chemistry of metallic implants governs their successful long-term functionality for orthopedic and dentistry applications. Here, we investigated the feasibility of harmoniously combining two of the star materials currently employed in bone treatment/restoration, namely, calcium-phosphate-based bioceramics (in the form of coatings that have the capacity to enhance osseointegration) and titanium alloys (used as bulk implant materials due to their mechanical performance and lack of systemic toxicity). For the first time, bovine-bone-derived hydroxyapatite (BHA) was layered on top of Ti6Al4V substrates using powder injection laser cladding technology, and then subjected, in this first stage of the research, to an array of physical-chemical analyses. The laser processing set-up involved the conjoined modulation of the BHA-to-Ti ratio (100 wt.% and 50 wt.%) and beam power range (500-1000 W). As such, on each metallic substrate, several overlapped strips were produced and the external surface of the cladded coatings was further investigated. The morphological and compositional (SEM/EDS) evaluations exposed fully covered metallic surfaces with ceramic-based materials, without any fragmentation and with a strong metallurgical bond. The structural (XRD, micro-Raman) analyses showed the formation of calcium titanate as the main phase up to maximum 800 W, accompanied by partial BHA decomposition and the consequential advent of tetracalcium phosphate (markedly above 600 W), independent of the BHA ratio. In addition, the hydrophilic behavior of the coatings was outlined, being linked to the varied surface textures and phase dynamism that emerged due to laser power increment for both of the employed BHA ratios. Hence, this research delineates a series of optimal laser cladding technological parameters for the adequate deposition of bioceramic layers with customized functionality.

The Physico-Chemical Properties and Exploratory Real-Time Cell Analysis of Hydroxyapatite Nanopowders Substituted with Ce, Mg, Sr, and Zn (0.5-5 at.%).

Cation-substituted hydroxyapatite (HA), standalone or as a composite (blended with polymers or metals), is currently regarded as a noteworthy candidate material for bone repair/regeneration either in the form of powders, porous scaffolds or coatings for endo-osseous dental and orthopaedic implants. As a response to the numerous contradictions reported in literature, this work presents, in one study, the physico-chemical properties and the cytocompatibility response of single cation-doped (Ce, Mg, Sr or Zn) HA nanopowders in a wide concentration range (0.5-5 at.%). The modification of composition, morphology, and structure was multiparametrically monitored via energy dispersive X-ray, X-ray photoelectron, Fourier-transform infrared and micro-Raman spectroscopy methods, as well as by transmission electron microscopy and X-ray diffraction. From a compositional point of view, Ce and Sr were well-incorporated in HA, while slight and pronounced deviations were observed for Mg and Zn, respectively. The change of the lattice parameters, crystallite size, and substituting cation occupation factors either in the Ca(I) or Ca(II) sites were further determined. Sr produced the most important HA structural changes. The in vitro biological performance was evaluated by the (i) determination of leached therapeutic cations (by inductively coupled plasma mass spectrometry) and (ii) assessment of cell behaviour by both conventional assays (e.g., proliferation-3-(4,5-dimethyl thiazol-2-yl) 5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium assay; cytotoxicity-lactate dehydrogenase release assay) and, for the first time, real-time cell analysis (RTCA). Three cell lines were employed: fibroblast, osteoblast, and endothelial. When monophasic, the substituted HA supported the cells' viability and proliferation without signs of toxicity. The RTCA results indicate the excellent adherence of cells. The study strived to offer a perspective on the behaviour of Ce-, Mg-, Sr-, or Zn-substituted HAs and to deliver a well-encompassing viewpoint on their effects. This can be highly important for the future development of such bioceramics, paving the road toward the identification of candidates with highly promising therapeutic effects.

Impact of nano-morphology, lattice defects and conductivity on the performance of graphene based electrochemical biosensors.

Diverse properties of graphenic materials have been extensively explored to determine properties that make good electrochemical nanomaterial-based biosensors. These are reviewed by critically examining the influence of graphene nano-morphology, lattice defects and conductivity. Stability, reproducibility and fabrication are discussed together with sensitivity and selectivity. We provide an outlook on future directions for building efficient electrochemical biosensors.

Review of Graphene Growth From a Solid Carbon Source by Pulsed Laser Deposition (PLD).

Graphene is a remarkable two-dimensional (2D) material that is of great interest to both academia and industry. It has outstanding electrical and thermal conductivity and good mechanical behavior with promising applications in electronic devices, supercapacitors, batteries, composite materials, flexible transparent displays, solar cells, and sensors. Several methods have been used to produce either pristine graphene or doped graphene. These include chemical vapor deposition (CVD), mechanical exfoliation, decomposition of SiC, liquid-phase exfoliation, pulsed laser deposition (PLD). Among these methods, PLD, which is routinely used for growing complex oxide thin films has proved to be an alternative to the more widely reported CVD method for producing graphene thin films, because of its advantages. Here we review the synthesis of graphene using PLD. We describe recent progress in preparing pristine graphene and doped graphene by PLD, including deposition processes and characterization. The goal of this complete survey is to describe the advantages of using the technique for graphene growth. The review will also help researchers to better understand graphene synthesis using the PLD technique.

Cationic Substitutions in Hydroxyapatite: Current Status of the Derived Biofunctional Effects and Their In Vitro Interrogation Methods.

High-performance bioceramics are required for preventing failure and prolonging the life-time of bone grafting scaffolds and osseous implants. The proper identification and development of materials with extended functionalities addressing socio-economic needs and health problems constitute important and critical steps at the heart of clinical research. Recent findings in the realm of ion-substituted hydroxyapatite (HA) could pave the road towards significant developments in biomedicine, with an emphasis on a new generation of orthopaedic and dentistry applications, since such bioceramics are able to mimic the structural, compositional and mechanical properties of the bone mineral phase. In fact, the fascinating ability of the HA crystalline lattice to allow for the substitution of calcium ions with a plethora of cationic species has been widely explored in the recent period, with consequent modifications of its physical and chemical features, as well as its functional mechanical and in vitro and in vivo biological performance. A comprehensive inventory of the progresses achieved so far is both opportune and of paramount importance, in order to not only gather and summarize information, but to also allow fellow researchers to compare with ease and filter the best solutions for the cation substitution of HA-based materials and enable the development of multi-functional biomedical designs. The review surveys preparation and synthesis methods, pinpoints all the explored cation dopants, and discloses the full application range of substituted HA. Special attention is dedicated to the antimicrobial efficiency spectrum and cytotoxic trade-off concentration values for various cell lines, highlighting new prophylactic routes for the prevention of implant failure. Importantly, the current in vitro biological tests (widely employed to unveil the biological performance of HA-based materials), and their ability to mimic the in vivo biological interactions, are also critically assessed. Future perspectives are discussed, and a series of recommendations are underlined.

Versatile graphene biosensors for enhancing human cell therapy.

Technological advances in engineering and cell biology stimulate novel approaches for medical treatment, in particular cell-based therapy. The first cell-based gene therapy against cancer was recently approved by the US Food and Drug Administration. Progress in cancer diagnosis includes a blood test detecting five cancer types. Numerous stem cell phase I/II clinical trials showing safety and efficacy will soon pursue qualifying criteria for advanced therapy medicinal products (ATMP), aspiring to join the first stem-cell therapy approved by the European Medicines Agency. Cell based therapy requires extensive preclinical characterisation of biomarkers indicating mechanisms of action crucial to the desired therapeutic effect. Quantitative analyses monitoring critical functions for the manufacture of optimal cell and tissue-based clinical products include successful potency assays for implementation. The challenge to achieve high quality measurement is increasingly met by progress in biosensor design. We adopt a cell therapy perspective to highlight recent examples of graphene-enhanced biointerfaces for measurement of biomarkers relevant to cancer treatment, diagnosis and tissue regeneration. Graphene based biosensor design problems can thwart their use for health care transformative point of care testing and real-time applications. We discuss concerns to be addressed and emerging solutions for establishing clinical grade biosensors to accelerate human cell therapy.

Nano-Architecture of nitrogen-doped graphene films synthesized from a solid CN source.

New synthesis routes to tailor graphene properties by controlling the concentration and chemical configuration of dopants show great promise. Herein we report the direct reproducible synthesis of 2-3% nitrogen-doped 'few-layer' graphene from a solid state nitrogen carbide a-C:N source synthesized by femtosecond pulsed laser ablation. Analytical investigations, including synchrotron facilities, made it possible to identify the configuration and chemistry of the nitrogen-doped graphene films. Auger mapping successfully quantified the 2D distribution of the number of graphene layers over the surface, and hence offers a new original way to probe the architecture of graphene sheets. The films mainly consist in a Bernal ABA stacking three-layer architecture, with a layer number distribution ranging from 2 to 6. Nitrogen doping affects the charge carrier distribution but has no significant effects on the number of lattice defects or disorders, compared to undoped graphene synthetized in similar conditions. Pyridinic, quaternary and pyrrolic nitrogen are the dominant chemical configurations, pyridinic N being preponderant at the scale of the film architecture. This work opens highly promising perspectives for the development of self-organized nitrogen-doped graphene materials, as synthetized from solid carbon nitride, with various functionalities, and for the characterization of 2D materials using a significant new methodology.

Robust Electrografting on Self-Organized 3D Graphene Electrodes.

Improving graphene-based electrode fabrication processes and developing robust methods for its functionalization are two key research routes to develop new high-performance electrodes for electrochemical applications. Here, a self-organized three-dimensional (3D) graphene electrode processed by pulsed laser deposition with thermal annealing is reported. This substrate shows great performance in electron transfer kinetics regarding ferrocene redox probes in solution. A robust electrografting strategy for covalently attaching a redox probe onto these graphene electrodes is also reported. The modification protocol consists of a combination of diazonium salt electrografting and click chemistry. An alkyne-terminated phenyl ring is first electrografted onto the self-organized 3D graphene electrode by in situ electrochemical reduction of 4-ethynylphenyl diazonium. Then the ethynylphenyl-modified surface efficiently reacts with the redox probe bearing a terminal azide moiety (2-azidoethyl ferrocene) by means of Cu(I)-catalyzed alkyne-azide cycloaddition. Our modification strategy applied to 3D graphene electrodes was analyzed by means of atomic force microscopy, scanning electron microscopy, Raman spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy (XPS). For XPS chemical surface analysis, special attention was paid to the distribution and chemical state of iron and nitrogen in order to highlight the functionalization of the graphene-based substrate by electrochemically grafting a ferrocene derivative. Dense grafting was observed, offering 4.9 × 10(-10) mol cm(-2) surface coverage and showing a stable signal over 22 days. The electrografting was performed in the form of multilayers, which offers higher ferrocene loading than a dense monolayer on a flat surface. This work opens highly promising perspectives for the development of self-organized 3D graphene electrodes with various sensing functionalities.

Opening an electrical band gap of bilayer graphene with molecular doping.

The opening of an electrical band gap in graphene is crucial for its application for logic circuits. Recent studies have shown that an energy gap in Bernal-stacked bilayer graphene can be generated by applying an electric displacement field. Molecular doping has also been proposed to open the electrical gap of bilayer graphene by breaking either in-plane symmetry or inversion symmetry; however, no direct observation of an electrical gap has been reported. Here we discover that the organic molecule triazine is able to form a uniform thin coating on the top surface of a bilayer graphene, which efficiently blocks the accessible doping sites and prevents ambient p-doping on the top layer. The charge distribution asymmetry between the top and bottom layers can then be enhanced simply by increasing the p-doping from oxygen/moisture to the bottom layer. The on/off current ratio for a bottom-gated bilayer transistor operated in ambient condition is improved by at least 1 order of magnitude. The estimated electrical band gap is up to ∼111 meV at room temperature. The observed electrical band gap dependence on the hole-carrier density increase agrees well with the recent density-functional theory calculations. This research provides a simple method to obtain a graphene bilayer transistor with a moderate on/off current ratio, which can be stably operated in air without the need to use an additional top gate.