Epitaxial highly ordered Sb:SnO2 nanowires grown by the vapor liquid solid mechanism on m-, r- and a-Al2O3

Epitaxial, highly ordered Sb:SnO(2) nanowires were grown by the vapor–liquid–solid mechanism on m-, r- and a-Al(2)O(3) between 700 °C and 1000 °C using metallic Sn and Sb with a mass ratio of Sn/Sb = 0.15 ± 0.05 under a flow of Ar and O(2) at 1 ± 0.5 mbar. We find that effective doping and ordering can only be achieved inside this narrow window of growth conditions. The Sb:SnO(2) nanowires have the tetragonal rutile crystal structure and are inclined along two mutually perpendicular directions forming a rectangular mesh on m-Al(2)O(3) while those on r-Al(2)O(3) are oriented in one direction. The growth directions do not change by varying the growth temperature between 700 °C and 1000 °C but the carrier density decreased from 8 × 10(19) cm(−3) to 4 × 10(17) cm(−3) due to the re-evaporation and limited incorporation of Sb donor impurities in SnO(2). The Sb:SnO(2) nanowires on r-Al(2)O(3) had an optical transmission of 80% above 800 nm and displayed very long photoluminescence lifetimes of 0.2 ms at 300 K. We show that selective area location growth of highly ordered Sb:SnO(2) nanowires is possible by patterning the catalyst which is important for the realization of novel nanoscale devices such as nanowire solar cells

Magnetically‐actuated microcages for cells entrapment, fabricated by laser direct writing via two photon polymerization

The manipulation of biological materials at cellular level constitutes a sine qua non and provocative research area regarding the development of micro/nano‐medicine. In this study, we report on 3D superparamagnetic microcage‐like structures that, in conjunction with an externally applied static magnetic field, were highly efficient in entrapping cells. The microcage‐like structures were fabricated using Laser Direct Writing via Two‐Photon Polymerization (LDW via TPP) of IP‐L780 biocompatible photopolymer/iron oxide superparamagnetic nanoparticles (MNPs) composite. The unique properties of LDW via TPP technique enabled the reproduction of the complex architecture of the 3D structures, with a very high accuracy i.e., about 90 nm lateral resolution. 3D hyperspectral microscopy was employed to investigate the structural and compositional characteristics of the microcage‐like structures. Scanning Electron Microscopy coupled with Energy Dispersive X‐Ray Spectroscopy was used to prove the unique features regarding the morphology and the functionality of the 3D structures seeded with MG‐63 osteoblast‐like cells. Comparative studies were made on microcage‐like structures made of IP‐L780 photopolymer alone (i.e., without superparamagnetic properties). We found that the cell‐seeded structures made by IP‐L780/MNPs composite actuated by static magnetic fields of 1.3 T were 13.66 ± 5.11 folds (p < 0.01) more efficient in terms of cells entrapment than the structures made by IP‐L780 photopolymer alone (i.e., that could not be actuated magnetically). The unique 3D architecture of the microcage‐like superparamagnetic structures and their actuation by external static magnetic fields acted in synergy for entrapping osteoblast‐like cells, showing a significant potential for bone tissue engineering applications

Laser Direct Writing of Dual-Scale 3D Structures for Cell Repelling at High Cellular Density

The fabrication of complex, reproducible, and accurate micro-and nanostructured interfaces that impede the interaction between material’s surface and different cell types represents an important objective in the development of medical devices. This can be achieved by topographical means such as dual-scale structures, mainly represented by microstructures with surface nanopatterning. Fabrication via laser irradiation of materials seems promising. However, laser-assisted fabrication of dual-scale structures, i.e., ripples relies on stochastic processes deriving from laser–matter interaction, limiting the control over the structures’ topography. In this paper, we report on laser fabrication of cell-repellent dual-scale 3D structures with fully reproducible and high spatial accuracy topographies. Structures were designed as micrometric “mushrooms” decorated with fingerprint-like nanometric features with heights and periodicities close to those of the calamistrum, i.e., 200–300 nm. They were fabricated by Laser Direct Writing via Two-Photon Polymerization of IP-Dip photoresist. Design and laser writing parameters were optimized for conferring cell-repellent properties to the structures, even for high cellular densities in the culture medium. The structures were most efficient in repelling the cells when the fingerprint-like features had periodicities and heights of ≅200 nm, fairly close to the repellent surfaces of the calamistrum. Laser power was the most important parameter for the optimization protocol

One A3B Porphyrin Structure—Three Successful Applications

Porphyrins are versatile structures capable of acting in multiple ways. A mixed substituted A3B porphyrin, 5-(3-hydroxy-phenyl)-10,15,20-tris-(3-methoxy-phenyl)-porphyrin and its Pt(II) complex, were synthesised and fully characterised by 1H- and 13C-NMR, TLC, UV-Vis, FT-IR, fluorescence, AFM, TEM and SEM with EDX microscopy, both in organic solvents and in acidic mediums. The pure compounds were used, firstly, as sensitive materials for sensitive and selective optical and fluorescence detection of hydroquinone with the best results in the range 0.039–6.71 µM and a detection limit of 0.013 µM and, secondly, as corrosion inhibitors for carbon–steel (OL) in an acid medium giving a best performance of 88% in the case of coverings with Pt-porphyrin. Finally, the electrocatalytic activity for the hydrogen and oxygen evolution reactions (HER and OER) of the free-base and Pt-metalated A3B porphyrins was evaluated in strong alkaline and acidic electrolyte solutions. The best results were obtained for the electrode modified with the metalated porphyrin, drop-casted on a graphite substrate from an N,N-dimethylformamide solution. In the strong acidic medium, the electrode displayed an HER overpotential of 108 mV, at i = −10 mA/cm2 and a Tafel slope value of 205 mV/dec

Coating Dependent In Vitro Biocompatibility of New Fe-Si Nanoparticles

Magnetic nanoparticles offer multiple utilization possibilities in biomedicine. In this context, the interaction with cellular structures and their biological effects need to be understood and controlled for clinical safety. New magnetic nanoparticles containing metallic/carbidic iron and elemental silicon phases were synthesized by laser pyrolysis using Fe(CO)5 vapors and SiH4 gas as Fe and Si precursors, then passivated and coated with biocompatible agents, such as l-3,4-dihydroxyphenylalanine (l-DOPA) and sodium carboxymethyl cellulose (CMC-Na). The resulting magnetic nanoparticles were characterized by XRD, EDS, and TEM techniques. To evaluate their biocompatibility, doses ranging from 0–200 µg/mL hybrid Fe-Si nanoparticles were exposed to Caco2 cells for 24 and 72 h. Doses below 50 μg/mL of both l-DOPA and CMC-Na-coated Fe-Si nanoparticles induced no significant changes of cellular viability or membrane integrity. The cellular internalization of nanoparticles was dependent on their dispersion in culture medium and caused some changes of F-actin filaments organization after 72 h. However, reactive oxygen species were generated after exposure to 25 and 50 μg/mL of both Fe-Si nanoparticles types, inducing the increase of intracellular glutathione level and activation of transcription factor Nrf2. At nanoparticles doses below 50 μg/mL, Caco2 cells were able to counteract the oxidative stress by activating the cellular protection mechanisms. We concluded that in vitro biological responses to coated hybrid Fe-Si nanoparticles depended on particle synthesis conditions, surface coating, doses and incubation time

Novel Nanocomposites Based on Functionalized Magnetic Nanoparticles and Polyacrylamide: Preparation and Complex Characterization

This paper reports the synthesis and complex characterization of nanocomposite hydrogels based on polyacrylamide and functionalized magnetite nanoparticles. Magnetic nanoparticles were functionalized with double bonds by 3-trimethoxysilyl propyl methacrylate. Nanocomposite hydrogels were prepared by radical polymerization of acrylamide monomer and double bond modified magnetite nanoparticles. XPS spectra for magnetite and modified magnetite were recorded to evaluate the covalent bonding of silane modifying agent. Swelling measurements in saline solution were performed to evaluate the behavior of these hydrogels having various compositions. Mechanical properties were evaluated by dynamic rheological analysis for elastic modulus and vibrating sample magnetometry was used to investigate the magnetic properties. Morphology, geometrical evaluation (size and shape) of nanostructural characteristics and the crystalline structure of the samples were investigated by SEM, HR-TEM and selected area electron diffraction (SAED). The nanocomposite hydrogels will be further tested for the soft tissue engineering field as repairing scaffolds, due to their mechanical and magnetization behavior that can stimulate tissue regeneration

Laser Direct Writing via Two-Photon Polymerization of 3D Hierarchical Structures with Cells-Antiadhesive Properties

We report the design and fabrication by laser direct writing via two photons polymerization of innovative hierarchical structures with cell-repellency capability. The structures were designed in the shape of “mushrooms”, consisting of an underside (mushroom’s leg) acting as a support structure and a top side (mushroom’s hat) decorated with micro- and nanostructures. A ripple-like pattern was created on top of the mushrooms, over length scales ranging from several µm (microstructured mushroom-like pillars, MMP) to tens of nm (nanostructured mushroom-like pillars, NMP). The MMP and NMP structures were hydrophobic, with contact angles of (127 ± 2)° and (128 ± 4)°, respectively, whereas flat polymer surfaces were hydrophilic, with a contact angle of (43 ± 1)°. The cell attachment on NMP structures was reduced by 55% as compared to the controls, whereas for the MMP, a reduction of only 21% was observed. Moreover, the MMP structures preserved the native spindle-like with phyllopodia cellular shape, whereas the cells from NMP structures showed a round shape and absence of phyllopodia. Overall, the NMP structures were more effective in impeding the cellular attachment and affected the cell shape to a greater extent than the MMP structures. The influence of the wettability on cell adhesion and shape was less important, the cellular behavior being mainly governed by structures’ topography

Grafting versus Crosslinking of Silk Fibroin-g-PNIPAM via Tyrosine-NIPAM Bridges

This paper reports the synthesis and complex characterization of novel polymeric networks based on the crosslinking of Bombyx mori silk fibroin via poly(N-isopropylacrylamide) bridges generated by an ammonium cerium nitrate redox system. The research study gives an understanding of the polymerization mechanism in terms of the generation of radical sites, radical growth and termination reaction, as well as the involvement of modifications on silk fibroin structure and properties. The physico-chemical characterization was carried out by FTIR-ATR, X-ray photoelectron spectroscopy and RAMAN spectroscopy with unravelling the chemical modification. The structural characterization and spatial arrangement by secondary structure were carried out by X-ray diffraction and circular dichroism. The thermal behavior and thermal stability were evaluated by differential scanning calorimetry and thermogravimetric analysis. The novel complex polymer network is intended to be used in the field of smart drug delivery systems

Polymeric Carbon Nitrides for Photoelectrochemical Applications: Ring Opening-Induced Degradation

Active and stable materials that utilize solar radiation for promoting different reactions are critical for emerging technologies. Two of the most common polymeric carbon nitrides were prepared by the thermal polycondensation of melamine. The scope of this work is to investigate possible structural degradation before and after photoelectrochemical testing. The materials were characterized using synchrotron radiation and lab-based techniques, and subsequently degraded photoelectrochemically, followed by post-mortem analysis. Post-mortem investigations reveal: (1) carbon atoms bonded to three nitrogen atoms change into carbon atoms bonded to two nitrogen atoms and (2) the presence of methylene terminals in post-mortem materials. The study concludes that polymeric carbon nitrides are susceptible to photoelectrochemical degradation via ring opening

Beyond Nitrogen in the Oxygen Reduction Reaction on Nitrogen-Doped Carbons: A NEXAFS Investigation

Polymer electrolyte membrane fuel cells require cheap and active electrocatalysts to drive the oxygen reduction reaction. Nitrogen-doped carbons have been extensively studied regarding their oxygen reduction reaction. The work at hand looks beyond the nitrogen chemistry and brings to light the role of oxygen. Nitrogen-doped nanocarbons were obtained by a radio-frequency plasma route at 0, 100, 250, and 350 W. The lateral size of the graphitic domain, determined from Raman spectroscopy, showed that the nitrogen plasma treatment decreased the crystallite size. Synchrotron radiation photoelectron spectroscopy showed a similar nitrogen chemistry, albeit the nitrogen concentration increased with the plasma power. Lateral crystallite size and several nitrogen moieties were plotted against the onset potential determined from oxygen reduction reaction curves. There was no correlation between the electrochemical activity and the sample structure, as determine from Raman and synchrotron radiation photoelectron spectroscopy. Near-edge X-ray absorption fine structure (NEXAFS) was performed to unravel the carbon and nitrogen local structure. A difference analysis of the NEXAFS spectra showed that the oxygen surrounding the pyridinic nitrogen was critical in achieving high onset potentials. The work shows that there were more factors at play, other than carbon organization and nitrogen chemistry