Magnetite-Based Nanostructured Coatings Functionalized with Nigella sativa and Dicloxacillin for Improved Wound Dressings.

In this study, we report the performance improvement of wound dressings by covering them with magnetite-based nanostructured coatings. The magnetite nanoparticles (Fe3O4 NPs) were functionalized with Nigella sativa (N. sativa) powder/essential oil and dicloxacillin and were synthesized as coatings by matrix assisted pulsed laser evaporation (MAPLE). The expected effects of this combination of materials are: (i) to reduce microbial contamination, and (ii) to promote rapid wound healing. The crystalline nature of core/shell Fe3O4 NPs and coatings was determined by X-ray diffraction (XRD). Differential Scanning Calorimetry (DSC) and Thermo Gravimetric Analysis (TGA) have been coupled to investigate the stability and thermal degradation of core/shell nanoparticle components. The coatings' morphology was examined by scanning electron microscopy (SEM). The distribution of chemical elements and functional groups in the resulting coatings was evidenced by Fourier transform infrared (FTIR) spectrometry. In order to simulate the interaction between wound dressings and epithelial tissues and to evaluate the drug release in time, the samples were immersed in simulated body fluid (SBF) and investigated after different durations of time. The antimicrobial effect was evaluated in planktonic (free-floating) and attached (biofilms) bacteria models. The biocompatibility and regenerative properties of the nanostructured coatings were evaluated in vitro, at cellular, biochemical, and the molecular level. The obtained results show that magnetite-based nanostructured coatings functionalized with N. sativa and dicloxacillin are biocompatible and show an enhanced antimicrobial effect against Gram positive and Gram negative opportunistic bacteria.

Rhodamine B Photodegradation in Aqueous Solutions Containing Nitrogen Doped TiO2 and Carbon Nanotubes Composites.

In this work, new results concerning the potential of mixtures based on nitrogen doped titanium dioxide (TiO2:N) and carbon nanotubes (CNTs) as possible catalyst candidates for the rhodamine B (RhB) UV photodegradation are reported. The RhB photodegradation was evaluated by UV-VIS absorption spectroscopy using samples of TiO2:N and CNTs of the type of single-walled carbon nanotubes (SWNTs), double-wall carbon nanotubes (DWNTs), multi-wall carbon nanotubes (MWNTs), and single-walled carbon nanotubes functionalized with carboxyl groups (SWNT-COOH) having various concentrations of CNTs. The best photocatalytic performance was obtained for sample containing TiO2:N and 2.5 wt.% SWNTs-COOH, when approx. 85% of dye removal was achieved after 300 min. of UV irradiation. The reaction kinetics of RhB aqueous solutions containing TiO2:N/CNT mixtures followed a complex first-order kinetic model. The TiO2:N/CNTs catalyst induced higher photodegradation efficiency of RhB than TiO2:N due to the presence of CNTs, which act as adsorbent and dispersing agent and capture the photogenerated electrons of TiO2:N hindering the electron-hole recombination.

Reduced Graphene Oxide Sheets as Inhibitors of the Photochemical Reactions of α-Lipoic Acid in the Presence of Ag and Au Nanoparticles.

The influence of Ag and Au nanoparticles and reduced graphene oxide (RGO) sheets on the photodegradation of α-lipoic acid (ALA) was determined by UV-VIS spectroscopy. The ALA photodegradation was explained by considering the affinity of thiol groups for the metallic nanoparticles synthesized in the presence of trisodium citrate. The presence of excipients did not induce further changes when ALA interacts with Ag and Au nanoparticles with sizes of 5 and 10 nm by exposure to UV light. Compared to the Raman spectrum of ALA powder, changes in Raman lines' position and relative intensities when ALA has interacted with films obtained from Au nanoparticles with sizes between 5 and 50 nm were significant. These changes were explained by considering the chemical mechanism of surface-enhanced Raman scattering (SERS) spectroscopy. The photodegradation of ALA that had interacted with metallic nanoparticles was inhibited in the presence of RGO sheets.

Multifunctional GaFeO3 Obtained via Mechanochemical Activation Followed by Calcination of Equimolar Nano-System Ga2O3-Fe2O3.

The equimolar oxide mixture ß-Ga2O3-α-Fe2O3 was subjected to high-energy ball milling (HEBM) with the aim to obtain the nanoscaled GaFeO3 ortho-ferrite. X-ray diffraction, 57Fe Mössbauer spectroscopy, and transmission electron microscopy were used to evidence the phase structure and evolution of the equimolar nano-system ß-Ga2O3-α-Fe2O3 under mechanochemical activation, either as-prepared or followed by subsequent calcination. The mechanical activation was performed for 2 h to 12 h in normal atmosphere. After 12 h of HEBM, only nanoscaled (~20 nm) gallium-doped α-Fe2O3 was obtained. The GaFeO3 structure was obtained as single phase, merely after calcination at 950 °C for a couple of hours, of the sample being subjected to HEBM for 12 h. This temperature is 450 °C lower than used in the conventional solid phase reaction to obtain gallium orthoferrite. The optical and magnetic properties of representative nanoscaled samples, revealing their multifunctional character, were presented.

X-ray Crystal Structure, Geometric Isomerism, and Antimicrobial Activity of New Copper(II) Carboxylate Complexes with Imidazole Derivatives.

Five new copper(II) acrylate complexes (acr is the acrylate anion: C3H3O2) with imidazole derivatives (2-methylimidazole/2-MeIm, 5-methylimidazole/5-MeIm, 2-ethylimidazole/2-EtIm) of type: cis-[Cu(2-RIm)2(acr)2]·xH2O ((1): R = ⁻CH3, x = 2; (4): R = ⁻CH2⁻CH3, x = 0), trans-[Cu(2-RIm)2(acr)2] ((2): R = ⁻CH3; (5): R = ⁻CH2⁻CH3) and trans-[Cu(5-RIm)2(acr)2] ((3): R = ⁻CH3) have been prepared and characterized by elemental analysis, Fourier Transform Infrared spectrometry (FTIR), Electron Paramagnetic Resonance (EPR), electronic reflectance spectroscopy, scanning electron microscopy, and mass spectrometry. The single crystal X-ray diffraction study of complexes (2) and (5) reveals that the copper(II) ion is located on an inversion center and show elongated octahedral geometry completed by two coplanar bidentate acrylates and two unidentate imidazole derivatives displayed in trans positions. For complex (4) the single crystal X-ray diffraction shows that the copper(II) ion is in a distorted octahedral environment which can be easily confused with a trigonal prism completed by two bidentate acrylates and two unidentate imidazole derivatives displayed in cis positions. These results indicate the fact that complexes (4) and (5) are the geometric isomers of the same compound bis(acrylate)-bis(2-ethylimidazole)-copper(II). Complexes (1) and (2), as well as (4) and (5), were produced simultaneously in the reaction of the corresponding copper(II) acrylate with imidazole derivatives in methanol solution. Furthermore, in order to be able to formulate potential applications of the obtained compounds, our next goal was to investigate the in vitro antimicrobial activity of the synthesized complexes against Gram-positive and Gram-negative bacteria, as well as fungal strains, of both clinical and ecological importance (biodeterioration of historical buildings). The trans isomers (2) and (5), followed by (4) have shown the broadest range of antimicrobial activity. In case of (1) and (2) isomers, the trans isomer (2) was significantly more active than cis (1), while the cis isomer (4) proved to be more active than trans (5). Taken together, the biological evaluation results indicate that the trans (2) was the most active complex, demonstrating its potential for the development of novel antimicrobial agents, with potential applications in the biomedical and restoration of architectural monuments fields.

Polyaniline photoluminescence quenching induced by single-walled carbon nanotubes enriched in metallic and semiconducting tubes.

The influence of single-walled carbon nanotubes enriched in semiconductor (S-SWNTs) and metallic (M-SWNTs) tubes on the photoluminescence (PL) of polyaniline (PANI), electrosynthesized in the presence of the H2SO4 and HCl solutions, is reported. The emission bands peaked at 407-418 and 440-520 nm indicate that the electropolymerization of aniline (ANI) leads to the formation of short and longer macromolecular chains (MCs), respectively. We demonstrate that the reaction product consists of ANI tetramers (TT) and trimers (TR) as well as PANI-salt. Using Raman scattering and IR absorption spectroscopy, a covalent functionalization of SWNTs with shorter and longer MCs of PANI-salt is demonstrated. The presence of S-SWNTs and M-SWNTs induces a decrease in ANI TT weight in the reaction product mass consisting in S-SWNTs and M-SWNTs covalently functionalized with PANI-emeraldine salt (ES) and PANI-leucoemeraldine salt (LS), respectively. A PANI PL quenching is reported to be induced of the S-SWNTs and M-SWNTs. A de-excitation mechanism is proposed to explain PANI PL quenching.

Interaction of New-Developed TiO2-Based Photocatalytic Nanoparticles with Pathogenic Microorganisms and Human Dermal and Pulmonary Fibroblasts.

TiO2-based photocatalysts were obtained during previous years in order to limit pollution and to ease human daily living conditions due to their special properties. However, obtaining biocompatible photocatalysts is still a key problem, and the mechanism of their toxicity recently received increased attention. Two types of TiO2 nanoparticles co-doped with 1% of iron and nitrogen (TiO2-1% Fe-N) atoms were synthesized in hydrothermal conditions at pH of 8.5 (HT1) and 5.5 (HT2), and their antimicrobial activity and cytotoxic effects exerted on human pulmonary and dermal fibroblasts were assessed. These particles exhibited significant microbicidal and anti-biofilm activity, suggesting their potential application for microbial decontamination of different environments. In addition, our results demonstrated the biocompatibility of TiO2-1% Fe-N nanoparticles at low doses on lung and dermal cells, which may initiate oxidative stress through dose accumulation. Although no significant changes were observed between the two tested photocatalysts, the biological response was cell type specific and time- and dose-dependent; the lung cells proved to be more sensitive to nanoparticle exposure. Taken together, these experimental data provide useful information for future photocatalytic applications in the industrial, food, pharmaceutical, and medical fields.

Innovative Self-Cleaning and Biocompatible Polyester Textiles Nano-Decorated with Fe-N-Doped Titanium Dioxide.

The development of innovative technologies to modify natural textiles holds an important impact for medical applications, including the prevention of contamination with microorganisms, particularly in the hospital environment. In our study, Fe and N co-doped TiO2 nanoparticles have been obtained via the hydrothermal route, at moderate temperature, followed by short thermal annealing at 400 °C. These particles were used to impregnate polyester (PES) materials which have been evaluated for their morphology, photocatalytic performance, antimicrobial activity against bacterial reference strains, and in vitro biocompatibility on human skin fibroblasts. Microscopic examination and quantitative assays have been used to evaluate the cellular morphology and viability, cell membrane integrity, and inflammatory response. All treated PES materials specifically inhibited the growth of Gram-negative bacilli strains after 15 min of contact, being particularly active against Pseudomonas aeruginosa. PES fabrics treated with photocatalysts did not affect cell membrane integrity nor induce inflammatory processes, proving good biocompatibility. These results demonstrate that the treatment of PES materials with TiO2-1% Fe-N particles could provide novel biocompatible fabrics with short term protection against microbial colonization, demonstrating their potential for the development of innovative textiles that could be used in biomedical applications for preventing patients' accidental contamination with microorganisms from the hospital environment.

Room Temperature Ferromagnetic Mn:Ge(001).

We report the synthesis of a room temperature ferromagnetic Mn-Ge system obtained by simple deposition of manganese on Ge(001), heated at relatively high temperature (starting with 250 °C). The samples were characterized by low energy electron diffraction (LEED), scanning tunneling microscopy (STM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), superconducting quantum interference device (SQUID), and magneto-optical Kerr effect (MOKE). Samples deposited at relatively elevated temperature (350 °C) exhibited the formation of ~5-8 nm diameter Mn5Ge3 and Mn11Ge8 agglomerates by HRTEM, while XPS identified at least two Mn-containing phases: the agglomerates, together with a Ge-rich MnGe~2.5 phase, or manganese diluted into the Ge(001) crystal. LEED revealed the persistence of long range order after a relatively high amount of Mn (100 nm) deposited on the single crystal substrate. STM probed the existence of dimer rows on the surface, slightly elongated as compared with Ge-Ge dimers on Ge(001). The films exhibited a clear ferromagnetism at room temperature, opening the possibility of forming a magnetic phase behind a nearly ideally terminated Ge surface, which could find applications in integration of magnetic functionalities on semiconductor bases. SQUID probed the co-existence of a superparamagnetic phase, with one phase which may be attributed to a diluted magnetic semiconductor. The hypothesis that the room temperature ferromagnetic phase might be the one with manganese diluted into the Ge crystal is formulated and discussed.