Reduced TiO2 Nanotubes/Silk Fibroin/ZnO as a Promising Hybrid Antibacterial Coating.

The current research aims to elucidate the influence of reduction process of TiO2 nanostructures on the surface properties of a bioinspired Ti modified implant, considering that the interface between a biomaterial surface and the living tissue plays an important role for this interaction. The production of reduced TiO2 nanotubes (RNT) with lower band gap is optimized and their performance is compared with those of simple TiO2 nanotubes (NT). The more conductive surfaces provided by the presence of RNT on Ti, allow a facile deposition of silk fibroin (SF) film using the electrochemical deposition method. This hybrid film is then functionalized with ZnO nanoparticles, to improve the antibacterial effect of the coating. The modified Ti surface is evaluated in terms of surface chemistry, morphology and roughness, wettability, surface energy, surface charge and antibacterial properties. Surface analysis such as SEM, AFM, FTIR and contact angle measurements were performed to obtain topographical features and wettability. FT-IR analysis confirms that SF was effectively attached to TiO2 nanotubes surfaces. The electrochemical deposition of SF and SF-ZnO reduced the interior diameter of nanotubes from ~85 nm to approx. 50-60 nm. All modified surfaces have a hydrophilic character.

Synthesis and characterization of polyurethane flexible foams provided from PET derivatives, fly ash, and glass wastes.

The aim of this study involved the synthesis and characterization of polyurethane (PUR) foams obtained from poly(ethylene terephthalate) (PET) depolymerization products and two types of filling agents, namely fly ash and glass waste. The depolymerized PET-based products were obtained by zinc acetate-catalyzed glycolysis process in diethylene glycol (DEG) as a co-reactant. The resulting glycolysis products were contacted with methylene diphenyl diisocyanate, castor oil, and reinforcing agents. The resulting PUR specimens were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), EDX mapping, mechanical tests, and thermal analysis. The analysis confirmed that the best mechanical performances were registered by the specimens with the lowest concentration of filling agent, while the highest thermal resistance was achieved by the PUR foams with the highest concentration of reinforcing agent.

Cu(II) and Hg(II) detection under photo-assisted accumulation in an open circuit potential at a polyazulene-EDTA like modified electrode.

The influence of UV light irradiation on the metal ion open-circuit accumulation process is determined using a glassy carbon modified electrode with poly(2,2'-(ethan-1,2-diylbis((2-(azulen-2-ylamino)-2-oxoethyl)azandiyl))diacetic acid (polyL). A correlation analysis between the semiconductive properties of polyL film and sensing properties is performed. Photo-assisted metal ion open circuit accumulation led to the simultaneous detection of Cu(II) and Hg(II) which allowed a detection limit of 0.4 nM and 0.7 nM for Cu(II) and Hg(II), respectively.

TiO2 Nanotubes Functionalized with Icariin for an Attenuated In Vitro Immune Response and Improved In Vivo Osseointegration.

Due to their superior mechanical and chemical properties, titanium (Ti) and its alloys have been widely used as orthopedic implantable devices. However, their bioinertness represents a limitation, which can be overcome by employing various surface modifications, such as TiO2 nanotube (TNT) fabrication via electrochemical anodization. Anodic TNTs present tunable dimensions and unique structures, turning them into feasible drug delivery platforms. In the present work, TNTs were loaded with icariin (Ica) through an adhesive intermediate layer of polydopamine (DP), and their in vitro and in vivo biological performance was evaluated. The successful fabrication of the modified surfaces was verified by scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), and contact angle measurements (CA), while the in vitro release of Ica was evaluated via UV-VIS spectrophotometry. In terms of in vitro behaviour, comparative studies on RAW 264.7 macrophages demonstrated that the TNT substrates, especially TNT-DP-Ica, elicited a lower inflammatory response compared to the Ti support. Moreover, the in vivo implantation studies evinced generation of a reduced fibrotic capsule around this implant and increased thickness of the newly formed bone tissue at 1 month and 3 months post-implantation, respectively. Overall, our results indicate that the controlled release of Ica from TNT surfaces could result in an improved osseointegration process.

In Vitro and In Vivo Evaluation of Silver Nanoparticles Phytosynthesized Using Raphanus sativus L. Waste Extracts.

The aim of the current paper is the development of phytosynthesized silver nanoparticles mediated by Raphanus sativus L. extracts obtained through two extraction methods (temperature and microwave) and to test their potential application for controlling apple crops pathogens. The phytosynthesized materials were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. All the materials were evaluated in terms of antioxidant and in vitro antimicrobial activity (against bacteria, molds, and yeast: Escherichia coli ATCC 8738, Staphylococcus aureus ATTC 25923, Pseudomonas aeruginosa ATCC 9027, Salmonella typhimurium ATCC 14028, Candida albicans ATCC 10231, Venturia inaequalis, Podosphaera leucotricha, Fusarium oxysporum ATCC 48112, Penicillium hirsutum ATCC 52323, and Aspergillus niger ATCC 15475). Considering the results obtained in the in vitro assays, formulations based on nanoparticles phytosynthesized using Raphanus sativus L. waste extracts (RS1N) were evaluated as potential antifungal agents for horticultural crops protection, against Venturia inaequalis and Podosphaera leucotricha through in vivo assays. For the DPPH assay, the inhibition (%) varied between 37.06% (for RS1N at 0.8 mg/mL concentration) and 83.72% (for RS1N at 7.2 mg/mL concentration) compared to 19.97% (for RS2N at 0.8 mg/mL) and only 28.91% (for RS2N at 7.2 mg/mL). Similar results were obtained for RS3N (85.42% inhibition at 7.2 mg/mL) compared with RS4N (21.76% inhibition at 7.2 mg/mL). Regarding the ABTS assay, the highest scavenger activity values were recorded for samples RS1N (91.43% at 1.6 mg/mL) and RS3N (96.62% at 1.6 mg/mL).

Titanium industrial residues surface modification towards its reuse as antimicrobial surfaces.

In this study, a new material obtained from titanium ingots residue was coated with natural carotenoids having antibacterial properties. The waste is a no recycling titanium scrap from technological production process which was pressed and transformed into disks titanium samples. Through anodization and annealing procedures of the titanium disk, a nanostructured titanium dioxide surface with photocatalytic and antibacterial properties was successfully obtained. The titanium scrap impurities (V, Al, and N), unwanted for production process, have shown to improve electrochemical and semiconductor properties of the residue surfaces. The nanostructured titanium scrap surface was modified with two different carotenoids, torularhodin and ß-carotene, to potentiate the antibacterial properties. The bactericidal tests were performed against Salmonella typhimurium and Escherichia coli, both Gram-negative. The best bactericidal effect is obtained for nanostructured titanium scrap disks immersed in torularhodin, with a percentage of growth inhibition around 60% against both tested bacteria. The results suggest that this low-cost waste material is suitable for efficient reuse as antibacterial surface after a few simple and inexpensive treatments.

Improving the Voltammetric Determination of Hg(II): A Comparison Between Ligand-Modified Glassy Carbon and Electrochemically Reduced Graphene Oxide Electrodes.

A new thiosemicarbazone ligand was immobilized through a Cu(I)-catalyzed click reaction on the surface of glassy carbon (GC) and electrochemically reduced graphene oxide (GC-ERGO) electrodes grafted with phenylethynyl groups. Using the accumulation at open circuit followed by anodic stripping voltammetry, the modified electrodes showed a significant selectivity and sensibility for Hg(II) ions. A detection limit of 7 nM was achieved with the GC modified electrodes. Remarkably, GC-ERGO modified electrodes showed a significantly improved detection limit (0.8 nM), sensitivity, and linear range, which we attribute to an increased number of surface binding sites and better electron transfer properties. Both GC and GC-ERGO modified electrodes proved their applicability for the analysis of real water samples.

Influence of red mud and waste glass on the microstructure, strength, and leaching behavior of bottom ash-based geopolymer composites.

The influence of waste glass and red mud addition as alternative source of aluminosilicate precursors on the microstructural, mechanical, and leaching properties of bottom ash-based geopolymer was studied in this work through mineralogical, morphological, and spectroscopic analysis, as well as by conducting compressive strength and leaching tests. The bottom ash-based geopolymer composites were synthesized by adding a constant amount of waste glass (10% by weight) and increasing amounts of red mud (up to 30% by weight). The results derived from FTIR, 29Si and 27Al MAS NMR, and SEM-EDX revealed that adding up to 10% (by weight) red mud to the synthesis mixes leads to an increase in the degree of geopolymerization of the activated mixes. The compressive strength followed the same trend. An increase of more than 10% (by weight) red mud added to the synthesis mixes results in a significant decrease of compressive strength of the geopolymer composites. A low leachability of geopolymer composites in regard with their contaminants was revealed especially for those with good compressive strength.

Residual titanium flakes as a novel material for retention and recovery of rare earth and relatively rare earth elements.

The aim of this study was the valorization of titanium flakes (waste) from titanium and titanium alloy ingot production factories and using in applications related to metals recovery as retention bed for some trace metals. The titanium flakes were anodized for surface nanostructuration with TiO2 nanotubes and then annealed in order to increase the surface stability. The nanostructured titanium flakes were loaded and pressed in a retention column linked with inductively coupled plasma spectrometer (ICP-OES). This system allowed determination of trace elements such as beryllium, lanthanum, lutetium, and ytterbium from sample solutions. Beryllium recovery percentage was over 90%, while lanthanides have just a satisfactory recovery percentage (about 65% Yb and Lu and 50% La). The TiO2 nanotube architecture was not affected during utilization being able to perform for a long time. A thermodynamic and kinetic study was done for beryllium due to its successful adsorption recovery percentage. The obtained results showed that the titanium waste is a promising material for rare earth and relatively rare earth elements retention and recovery. Graphical abstract Graphical abstract.

3D hybrid structures based on biomimetic membranes and Caryophyllus aromaticus - "green" synthesized nano-silver with improved bioperformances.

The paper describes an innovative bio-design of some hybrid nanoarchitectures containing bioartificial membranes and silver nanoparticles phytogenerated by using a natural extract Caryophyllus aromaticus (cloves) that contains many bioactive compounds. Two kinds of liposomes with and without chlorophyll a (Chla) obtained through thin film hydration method were used to achieve bio-green-generated hybrids by a simple, cost effective bottom-up approach. The characteristic peaks of CE-nAg monitored by UV-Vis absorption have firstly demonstrated the biohybrids formation. The slightly blue shift and fluorescence quenching observed by fluorescence emission spectra highlighted the formation of hybrid systems by biointeraction between lipid vesicles and silver nanoparticles. The incorporation of silver nanoparticles in lipid vesicles resulted in significant changes of FT-IR spectra of liposomes, indicating a reorganization of biomimetic membranes. All the microscopic methods (SEM, AFM and TEM) confirmed the biosynthesis of "green" AgNPs together with associated biohybrids, their spherical and quasi-spherical shapes with nano-scaled size. By TEM assay it was shown that CE-nAg are surrounded by petal like cloud structures that consist of biopolymers like proteins or polysaccharides and other phytochemicals arising from clove extract. EDS spectra confirmed the formation of phyto-nanoAg and also the presence of silver in the biohybrids. In addition, Selected Area Electron Diffraction showed characteristic polycrystalline ring patterns for a cubic structure of the clove-generated AgNPs. The hybrid materials showed efficient physical stability,i.e. ξ value of -28.0 mV (for biohybrids without Chla, BH) and of -31.7 mV (for biohybrids labelled with Chla, Chla-BH), assured by strong electrostatic repulsive forces between particles. The "green" nano-silver particles (CE-nAg) showed remarkable antioxidant activity (AA = 90.2%). The biohybrids loaded with clove-AgNPs proved to be more effective, scavenging about 98.8% of free radicals (in case of Chla-BH), and of 92.6% (in case of BH). The antibacterial effectiveness showed that green AgNPs combine in a synergistic manner the antibacterial properties of clove extract with those of silver, resulting in an enhancement of inhibition diameter, by 20%. Chla-BH proved to be more potent against Escherichia coli, than BH, exhibiting an inhibition diameter of 42 mm. Regarding the in vitro cytotoxicity against tumour cells, the CE-nAg concentration significantly influenced the cell viability, i.e. IC50 was 3.6% (v/v) for HT-29 cells. Chla-BH was more effective against HT-29 cancer cells at the concentrations ranging from 0 to 18% (v/v), when the normal cells were not affected. Clove-generated AgNPs exhibited haemolytic activity against hRBCs, while the biohybrids were haemocompatible. The action mechanism on the two cell lines (mouse fibroblast L929 cells and human colorectal adenocarcinoma HT-29 cells) investigated by fluorescence microscopy demonstrated that CE-nAg killed almost all the cells (94%) through necrosis at a concentration of 33.4% (v/v). The treatment of HT-29 cells with BH resulted in: 71.5% viable cells, 19.5% apoptotic and only 9% necrotic cells, while in the case of Chla-BH treatment, only 77.5% cells were viable, 16% cells were apoptotic and 6.5% were necrotic. In this way, the developed silver-based nanoparticles can represent viable promoters to develop new biohybrids with improved features, e.g. antioxidant and antibacterial effectiveness, haemolytic activity and greater specificity towards tumour cells.

Nitrodopamine vs dopamine as an intermediate layer for bone regeneration applications.

The aim of this paper was to present a parallel investigation of the poly(dopamine) (DP) and nitrodopamine (NDP) structures deposited on titanium surface (Ti) and titanium oxide nanotubes (NT-TiO2/Ti) and to highlight their advantages and drawbacks to serve as an intermediary layer for bone regeneration applications. This study outlines some hypotheses regarding the manner in which these compounds are able to form a stable film that could serve as bioadhesive. The paper is also a study of structuring and evolution of film architecture for two coatings, polydopamine and nitrodopamine in terms of surface structure, stability, wettability, morphology, adhesion and ability to protect the titanium surface. All investigations are based on the data provided by surface characterization techniques: SEM, RAMAN, XRD, XPS, wettability and flexural strength. The impact of polydopamine and nitrodopamine coatings on the biocompatibility of titanium nanotubes was investigated in vitro. Cell morphology, viability, proliferation and pre-osteoblast differentiation were examined in detail. It was highlighted that both DP and NDP functionalized TiO2 nanotubes display good cell response in terms of cell spreading, formation of focal adhesions, cell viability and proliferation, suggesting their suitability for applications in bone regeneration field. However, NDP coated TiO2 nanotubes demonstrated an enhanced osteogenic potential compared to DP coated substrates.

Production and characterization of cellulose acetate - titanium dioxide nanotubes membrane fraxiparinized through polydopamine for clinical applications.

The present paper introduces a study on the preparation and characterization of cellulose acetate - TiO2 nanotubes membrane. In order to be used as a hemodialysis membrane, fraxiparinized nanotubes have been incorporated into the cellulose matrix. Fraxiparine embedding was performed via strong binding ability of dopamine. Composite membrane was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and water contact angle measurement. Electrochemical impedance spectroscopy was used to correlate the morphology of composite membrane with its electrochemical properties. Mott-Schottky test proved titanium dioxide semiconductor incorporation in composite membrane. Permeation test was made to determine pure water flux. The obtained results showed that addition of nanotubes had a positive impact on membrane permeation compared with a control polymeric membrane.

Enhancing antimicrobial activity of TiO2/Ti by torularhodin bioinspired surface modification.

Implant-associated infections are a major cause of morbidity and mortality. This study was performed using titanium samples coated by anodization with a titanium dioxide (TiO2) shielded nanotube layer. TiO2/Ti surface was modified by simple immersion in torularhodin solution and by using a mussel-inspired method based on polydopamine as bio adhesive for torularhodin immobilization. SEM analysis revealed tubular microstructures of torularhodin and the PDA ability to function as a catchy anchor between torularhodin and TiO2 surface. Corrosion resistance was associated with TiO2 barrier oxide layer and nano-organized oxide layer and the torularhodin surface modification does not bring significant changes in resistance of the oxide layer. Our results demonstrated that the torularhodin modified TiO2/Ti surface could effectively prevent adhesion and proliferation of Escherichia coli, Staphylococcus aureus, Enterococcus faecalis, Bacillus subtilis, and Pseudomonas aeruginosa. The new modified titanium surface showed good biocompatibility and well-behaved haemocompatibility. This biomaterial with enhanced antimicrobial activity holds great potential for future biomedical applications.

Electrochemical impedance spectroscopy in understanding the influence of ultrasonic dental scaling on the dental structure-dental filling interface.

The purpose of this study was to investigate the effect of ultrasonic scaling on teeth restored with a light-cured resin. Ultrasonic scaling is a very popular periodontal therapy among dentists, and used for the removal of dental plaque and calculus in order to reduce and eliminate inflammation. Given the fact that most ultrasonic devices are used at high frequencies to perform scaling, undesirable consequences, such as loss of adhesion and increase in surface roughness, may occur in teeth that have been restored with light-cured resins. Electrochemical impedance spectroscopy (EIS) and scanning electron microscopy were used to investigate the effects of ultrasonic treatments at the dental material-hard dental tissue interface. After ultrasonic scaling, EIS measurements were performed on a human tooth that had been restored with a light-cured resin filling. The data were analyzed and the influence of ultrasound was shown after visualization of the hard dental tissues and the dental material as equivalent electrical circuits. The study revealed, through EIS measurements, that ultrasonic scaling affected the resistance of the light-cured resin filling and dentin, whereas the enamel was affected only slightly. Scanning electron microscopy revealed an increase in roughness of the dental material.

Improved antibacterial behavior of titanium surface with torularhodin-polypyrrole film.

The problem of microorganisms attaching and proliferating on implants and medical devices surfaces is still attracting interest in developing research on different coatings based on antibacterial agents. The aim of this work is centered on modifying titanium (Ti) based implants surfaces through incorporation of a natural compound with antimicrobial effect, torularhodin (T), by means of a polypyrrole (PPy) film. This study tested the potential antimicrobial activity of the new coating against a range of standard bacterial strains: Escherichia coli, Staphylococcus aureus, Enterococcus faecalis, Bacillus subtilis and Pseudomonas aeruginosa. The morphology, physical and electrochemical properties of the synthesized films were assessed by SEM, AFM, UV-Vis, FTIR and cyclic voltammetry. In addition, biocompatibility of this new coating was evaluated using L929 mouse fibroblast cells. The results showed that PPy-torularhodin composite film acts as a corrosion protective coating with antibacterial activity and it has no harmful effect on cell viability.

Electrochemical impedance spectroscopy investigation on the clinical lifetime of ProTaper rotary file system.

The main objective of the current paper is to show that electrochemical impedance spectroscopy (EIS) could be a method for evaluating and predicting of ProTaper rotary file system clinical lifespan. This particular aspect of everyday use of the endodontic files is of great importance in each dental practice and has profound clinical implications. The method used for quantification resides in the electrochemical impedance spectroscopy theory and has in its main focus the characteristics of the surface titanium oxide layer. This electrochemical technique has been adapted successfully to identify the quality of the Ni-Ti files oxide layer. The modification of this protective layer induces changes in corrosion behavior of the alloy modifying the impedance value of the file. In order to assess the method, 14 ProTaper sets utilized on different patients in a dental clinic have been submitted for testing using EIS. The information obtained in regard to the surface oxide layer has offered an indication of use and proves that the said layer evolves with each clinical application. The novelty of this research is related to an electrochemical technique successfully adapted for Ni-Ti file investigation and correlation with surface and clinical aspects.

Surfactant-dependent macrophage response to polypyrrole-based coatings electrodeposited on Ti6Al7Nb alloy.

In this study, polypyrrole (PPy) films were successfully synthesized on Ti6Al7Nb alloy by potentiostatic polymerization in the presence of poly(sodium 4-styrenesulfonate) (NaPSS), t-octylphenoxy polyethoxyethanol (Triton X-100) and N-dodecyl-ß-D-maltoside (DM) surfactants. Atomic force microscopy (AFM) analysis of the PPy/surfactant composite films revealed a granular structure characterized by a lower surface roughness than un-modified PPy films. The results demonstrated that addition of surfactants, namely Triton X-100 and DM, can improve electrochemical film stability and corrosion resistance. Further, Triton X-100 enhanced the adhesive strength of PPy films to the substrate. The surfactant type also showed a great influence on the surface wettability, the highest hydrophilic character being observed in the case of PPy/PSS film. Few studies have been devoted to the elucidation of inflammatory cell response to PPy-based materials. Therefore, RAW 264.7 macrophages were cultured on PPy-surfactant films to determine whether they elicit a differential cell behavior in terms of cell adhesion, proliferation, cellular morphology and cytokine secretion. Our results highlight the dependence of macrophage response on the surfactants used in the pyrrole polymerization process and suggest that the immune response to biomaterials coated with PPy films might be controlled by the choice of surfactant molecules.

Green light effects on biological systems: a new biophysical phenomenon.

This paper reports a new phenomenon connected with the influence of green light (GL) on biological systems. Our experiments have revealed an antioxidant effect of GL on cells subjected to lethal doses of UV at the cellular level and a protective effect of GL on DNA denatured by UV, coupled with a structural modification of DNA macromolecules under GL irradiation, at the molecular level. Mouse melanocyte cultures are subjected to UV irradiations with L(50) fluxes of 16.0 J m(-2) s(-1). GL is obtained from a strontium aluminate pigment, which emits GL under UV activation. Cells grown in GL, prior to UV irradiation, present a clear surprising protective effect with surviving values close to the controls. A GL antioxidant effect is suggested to be mediated through GL influence on cellular water cluster dynamics. To test this hypothesis, reactive oxygen species (ROS) are determined in cell cultures. The results revealed a decrease of cellular ROS generation in the UV-irradiated samples protected by a previous 24 h of GL irradiation. At the DNA level, the same type of GL protection against UV damage is recorded by gel electrophoresis and by UV spectroscopy of the irradiated DNA molecules. Two physical methods, impedance spectroscopy and chronoamperometry, have revealed at the level of GL-irradiated DNA molecules spectral modifications that correlate with the UV spectroscopy results. The interaction between the chargeless photons and the field of water molecules from the cellular compartments is discussed in relation with the new field of macroscopic quantum coherence phenomena.