Photocatalytic and antibacterial activity properties of Ti surface treated by femtosecond laser-a prospective solution to peri-implant disease.

Laser texturing seems to be a promising technique for reducing bacterial adhesion on titanium implant surfaces. This work aims to demonstrate the possibility of obtaining a functionally orientated surface of titanium implant elements with a specific architecture with specific bacteriological and photocatalytic properties. Femtosecond laser-generated surface structures, such as laser-induced periodic surface structures (LIPSS, wrinkles), grooves, and spikes on titanium, have been characterised by XRD, Raman spectroscopy, and scanning electron microscopy (SEM). The photocatalytic activity of the titanium surfaces produced was tested based on the degradation effect of methylene blue (MB). The correlation between the photocatalytic activity of TiO2 coatings and their morphology and structure has been analysed. Features related to the size, shape, and distribution of the roughness patterns were found to influence the adhesion of the bacterial strain on different surfaces. On the laser-structurised surface, the adhesion of Escherichia coli bacteria were reduced by 80% compared to an untreated reference surface.

Physical, mechanical and antibacterial properties of the orthodontic adhesive doped with S-TiO2.

Orthodontic adhesive doped with sulfur-modified TiO2 promotes antibacterial effect. The objective of the study was to characterize the physical, mechanical and antibacterial properties of the orthodontic bracket adhesive, doped with modified titanium dioxide nanoparticles. Sulfur-doped TiO2 was synthetized and morphological topography was analyzed with TEM and SEM imaging. The catalytic performance during the degradation of rhodamine B was assessed. Nanomaterial was added at four concentration (1, 3, 6, and 10 wt%) to a commercial orthodontic adhesive. The shear bond strength and microhardness of a resin-based orthodontic adhesive containing S-TiO2 were evaluated. The inhibitory effect of the pure and doped adhesives against Escherichia coli and Streptococcus mutans was examined. As the results, the highest antimicrobial activity and good adhesive properties were noticed for light-cured orthodontic adhesive doped with 3% of S-TiO2. In this case, orthodontic adhesives with strong and long-lasting bactericidal properties can be created through the incorporation of modified TiO2 without negatively influencing microhardnesses, and bonding ability. White spot lesion and demineralization, which occurs very often in patients during orthodontic treatment, can be therefore minimized.

Layered MoS2: effective and environment-friendly nanomaterial for photocatalytic degradation of methylene blue.

Photocatalytic degradation is a promising method for removing persistent organic pollutants from water because of its low cost (see solar-driven photocatalysis), high mineralisation of pollutants, and low environmental impact. Photocatalysts based on transition metal dichalcogenides (TMDs) have recently attracting high scientific interest due to their unique electrical, mechanical, and optical properties. A MoS2 photocatalyst of the layered structure was managed to photodegrade methylene blue (MB) under visible light irradiation. The catalyst was thoroughly characterised using SEM, AFM, powder XRD, UV-Vis, Raman, and XPS measurements. The photocatalytic degradation of the MB solution was conducted under the following conditions: (i) reductive and (ii) oxidative. The impact of optical and electronic properties, and the MoS2-MB interaction on photocatalytic activity, was discussed. The apparent rate constants (kapp) of degradation were 3.7 × 10-3; 7.7 × 10-3; 81.7 × 10-3 min-1 for photolysis, oxidative photocatalysis, and reductive photocatalysis. Comparison of the degradation efficiency of MB in reductive and oxidative processes indicates the important role of the reaction with the surface electron. In the oxidation process, oxygen reacts with an electron to form a superoxide anion radical involved in further transformations of the dye, whereas, in the reduction process, the addition of an electron destabilises the chromophore ring and leads to its rupture.

Photocatalytic activity of layered MoS2 in the reductive degradation of bromophenol blue.

Molybdenum disulphide (MoS2) is a layered material with interesting photocatalytic properties. In this study, a layered MoS2 was produced using a hydrothermal method. The obtained material was characterised by XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy), SEM (scanning electron microscopy), UV-Vis spectroscopy, DLS (dynamic light scattering), and zeta potential analysis. For the evaluation of the photocatalytic properties of layered MoS2, a solution of bromophenol blue (BPB) and the catalyst was illuminated for 120 minutes. According to the experimental results, MoS2 exhibited excellent catalytic activity in BPB degradation. The MoS2 preparation method enabled improved light harvesting, avoided fast charge recombination (related to bulk MoS2), and created a large number of suitable electron transfer sites for photocatalytic reactions. Simulation of BPB decay and bromide production was carried out for a further understanding of MoS2 photocatalytic action. The simulation results proved the reduction mechanism of BPB photodegradation.

Spectral and Angular Characteristics of the High-Contrast Dielectric Grating under the Resonant Interaction of a Plane Wave and a Gaussian Beam.

The resonant interaction of a plane wave and a one-dimensional Gaussian beam with a high-contrast dielectric grating was analyzed. Rigorous coupled wave analysis (RCWA) was used to numerically model the diffraction of a plane wave by the grating. RCWA, a discrete Fourier transform at the fulfillment (of the conditions) of the sampling theorem, was used to study diffraction of the Gaussian beam. The grating can be considered as a one-dimensional photonic crystal along which the waveguide mode propagates under resonance. The corresponding photonic crystal has both allowed and forbidden photonic bands for the propagating waveguide mode under resonance due to the high-contrast dielectric permittivity. There is no significant difference between the spectral and angular characteristics under the interaction of the plane wave or the Gaussian beam with grating, if the waveguide mode is in the forbidden photonic bandgap. The reflection coefficient from the grating is practically equal to unity for both cases. Resonant spectral and angular characteristics become wider at the Gaussian beam diffraction compared to the resonance curves for the plane wave in the case when the waveguide mode is in the allowed photon bandgap. The reflection coefficient from the grating becomes less than unity and its value tends to unity when the Gaussian beam width increases.

Photocatalytic Degradation of 4,4'-Isopropylidenebis(2,6-dibromophenol) on Magnetite Catalysts vs. Ozonolysis Method: Process Efficiency and Toxicity Assessment of Disinfection By-Products.

Flame retardants have attracted growing environmental concern. Recently, an increasing number of studies have been conducted worldwide to investigate flame-retardant sources, environmental distribution, living organisms' exposure, and toxicity. The presented studies include the degradation of 4,4'-isopropylidenebis(2,6-dibromophenol) (TBBPA) by ozonolysis and photocatalysis. In the photocatalytic process, nano- and micro-magnetite (n-Fe3O4 and µ-Fe3O4) are used as a catalyst. Monitoring of TBBPA decay in the photocatalysis and ozonolysis showed photocatalysis to be more effective. Significant removal of TBBPA was achieved within 10 min in photocatalysis (ca. 90%), while for ozonation, a comparable effect was observed within 70 min. To determine the best method of TBBPA degradation concentration on COD and TOC, the removals were examined. The highest oxidation state was obtained for photocatalysis on µ-Fe3O4, whereas for n-Fe3O4 and ozonolysis, the COD/TOC ratio was lower. Acute toxicity results show noticeable differences in the toxicity of TBBPA and its degradation products to Artemia franciscana and Thamnocephalus platyurus. The EC50 values indicate that TBBPA degradation products were toxic to harmful, whereas the TBPPA and post-reaction mixtures were toxic to the invertebrate species tested. The best efficiency in the removal and degradation of TBBPA was in the photocatalysis process on µ-Fe3O4 (reaction system 1). The examined crustaceans can be used as a sensitive test for acute toxicity evaluation.

Photocatalytic Degradation of 4,4'-Isopropylidenebis(2,6-dibromophenol) on Sulfur-Doped Nano TiO2.

In present work, we examine the photocatalytic properties of S-doped TiO2 (S1, S2) compared to bare TiO2 (S0) in present work. The photocatalytic tests were performed in alkaline aqueous solutions (pH = 10) of three differently substituted phenols (phenol (I), 4,4'-isopropylidenebisphenol (II), and 4,4'-isopropylidenebis(2,6-dibromophenol) (III)). The activity of the catalysts was evaluated by monitoring I, II, III degradation in the reaction mixture. The physicochemical properties (particle size, ζ-potential, Ebg, Eu, E0cb, E0vb, σo, KL) of the catalysts were established, and we demonstrated their influence on degradation reaction kinetics. Substrate degradation rates are consistent with first-order kinetics. The apparent conversion constants of the tested compounds (kapp) in all cases reveal the sulfur-loaded catalyst S2 to show the best photocatalytic activity (for compound I and II S1 and S2 are similarly effective). The different efficiency of photocatalytic degradation I, II and III can be explained by the interactions between the catalyst and the substrate solution. The presence of bromine substituents in the benzene ring additionally allows reduction reactions. The yield of bromide ion release in the degradation reaction III corresponds to the Langmuir constant. The mixed oxidation-reduction degradation mechanism results in higher degradation efficiency. In general, the presence of sulfur atoms in the catalyst network improves the degradation efficiency, but too much sulfur is not desired for the reduction pathway.

Synthesis of Micro-Spikes and Herringbones Structures by Femtosecond Laser Pulses on a Titanium Plate-A New Material for Water Organic Pollutants Degradation.

(1) Background: The shrinkage of water resources, as well as the deterioration of its quality as a result of industrial human activities, requires a comprehensive approach relative to its protection. Advanced oxidation processes show high potential for the degradation of organic pollutants in water and wastewater. TiO2 is the most popular photocatalyst because of its oxidizing ability, chemical stability and low cost. The major drawback of using it in powdered form is the difficulty of separation from the reaction mixture. The solution to this problem may be immobilization on a support (glass beads, molecular sieves, etc.). In order to avoid these difficulties, the authors propose to prepare a catalyst as a titanium plate covered with an oxide layer obtained with laser treatment. (2) Methods: In the present work, we generated titanium oxide structures using a cheap and fast method based on femtosecond laser pulses. The structurized plates were tested in the reaction of methylene blue (MB) degradation under UVA irradiation (365 nm). The photocatalytic activity and kinetic properties for the degradation of MB are provided. (3) Results: Studies of X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirm a titanium oxide layer with laser-induced generated structures that are called "spikes" and "herringbones". The structurized plates were effective photocatalysts, and their activity depends on the structure of the oxide layer (spike and herringbone). (4) Conclusions: The immobilization of the catalyst on a solid support can be performed in a fast and reproducible manner by using the technique of laser ablation. The layers obtained with this method have been shown to have catalytic properties.

Diffraction of a Gaussian Beam with Limited cross Section by a Volume Phase Grating under Waveguide Mode Resonance.

In this work, the diffraction of a Gaussian beam on a volume phase grating was researched theoretically and numerically. The proposed method is based on rigorous coupled-wave analysis (RCWA) and Fourier transform. The Gaussian beam is decomposed into plane waves using the Fourier transform. The number of plane waves is determined using the sampling theorem. The complex reflected and transmitted amplitudes are calculated for each RCWA plane wave. The distribution of the fields along the grating for the reflected and transmitted waves is determined using inverse Fourier transform. The powers of the reflected and transmitted waves are determined based on these distributions. Our method shows that the energy conservation law is satisfied for the phase grating. That is, the power of the incident Gaussian beam is equal to the sum of the powers of the reflected and transmitted beams. It is demonstration of our approach correctness. The numerous studies have shown that the spatial shapes of the reflected and transmitted beams differ from the Gaussian beam under resonance. In additional, the waveguide mode appears also in the grating. The spatial forms of the reflected and transmitted beams are Gaussian in the absence of resonance. It was found that the width of the resonance curves is wider for the Gaussian beam than for the plane wave. However, the spectral and angular sensitivities are the same as for the plane wave. The resonant wavelengths are slightly different for the plane wave and the Gaussian beam. Numerical calculations for four refractive index modulation coefficients of the grating medium were carried out by the proposed method. The widths of the resonance curves decrease with the increasing in the refractive index modulation. Moreover, the reflection coefficient also increases.

Functionalization of Polycaprolactone Electrospun Osteoplastic Scaffolds with Fluorapatite and Hydroxyapatite Nanoparticles: Biocompatibility Comparison of Human Versus Mouse Mesenchymal Stem Cells.

A capability for effective tissue reparation is a living requirement for all multicellular organisms. Bone exits as a precisely orchestrated balance of bioactivities of bone forming osteoblasts and bone resorbing osteoclasts. The main feature of osteoblasts is their capability to produce massive extracellular matrix enriched with calcium phosphate minerals. Hydroxyapatite and its composites represent the most common form of bone mineral providing mechanical strength and significant osteoinductive properties. Herein, hydroxyapatite and fluorapatite functionalized composite scaffolds based on electrospun polycaprolactone have been successfully fabricated. Physicochemical properties, biocompatibility and osteoinductivity of generated matrices have been validated. Both the hydroxyapatite and fluorapatite containing polycaprolactone composite scaffolds demonstrated good biocompatibility towards mesenchymal stem cells. Moreover, the presence of both hydroxyapatite and fluorapatite nanoparticles increased scaffolds' wettability. Furthermore, incorporation of fluorapatite nanoparticles enhanced the ability of the composite scaffolds to interact and support the mesenchymal stem cells attachment to their surfaces as compared to hydroxyapatite enriched composite scaffolds. The study of osteoinductive properties showed the capacity of fluorapatite and hydroxyapatite containing composite scaffolds to potentiate the stimulation of early stages of mesenchymal stem cells' osteoblast differentiation. Therefore, polycaprolactone based composite scaffolds functionalized with fluorapatite nanoparticles generates a promising platform for future bone tissue engineering applications.

Features of the Resonance in a Rectangular Dielectric Surace-Relief Gratings Illuminated with a Limited Cross Section Gaussian Beam.

In this work the features of the resonance in a rectangular dielectric surface-relief gratings, illuminated with a limited cross-section Gaussian beam, have been studied. The rigorous coupled wave method and beam decomposition into the plane waves by the Fourier transform have been used. It is shown that there is a resonant wavelength for each thickness of the dielectric grating. The value of resonant wavelength depends on the beam angle of incidence on the gratings. Moreover, the two types of resonances can occur in the grating at certain grating parameters. The power reflection coefficient is practically equal to unity for the first type of resonance and is much smaller than unity, for the second one. The obtained results extend the knowledge regarding the nature of the waveguide resonance in the dielectric grating, considering the limited cross section beam, and they can increase its use in many applications.

Relation between Resonance Parameters of Surface Plasmon-Polariton Waves with Properties of the Dielectric-Metal Film-Dielectric Waveguide.

The resonant excitation of the surface plasmon-polariton waves by the prism structure, where a thin silver film was coated on the prism, was studied. New analytical relations between the angular and spectral sensitivities on the change of the medium refractive index, adjacent to the metal film, were obtained. In addition, the analytical relation between the full width at the half maximum of the spectral and angular resonance dependencies were found.

Efficient NIR energy conversion of plasmonic silver nanostructures fabricated with the laser-assisted synthetic approach for endodontic applications.

Silver nanoparticles were synthesized with the laser-assisted wet chemical approach at room temperature. The effect of light exposure on the silver nanoparticles' spatial parameters shaping the localized surface plasmon resonance has been evaluated. The optical, structural and morphological characterizations of the Ag nanostructures were conducted with UV-VIS-NIR spectrophotometry, DLS and TEM techniques. The ability of the light-modified Ag nanostructures for energy conversion under the influence of 445 and 880 nm laser radiation is estimated. We have found that the most efficient heat generation can be achieved using triangular Ag nanostructures under the NIR irradiation (880 nm). The temperature effect on the Ag nanostructures' antibacterial properties has been evaluated against the Staphylococcus aureus population. The prospects of triangular Ag nanostructures' application on modern endodontics for the rapid nano-laser disinfection of the root canal system of the human tooth have been demonstrated.

Correction: Efficient NIR energy conversion of plasmonic silver nanostructures fabricated with the laser-assisted synthetic approach for endodontic applications.

[This corrects the article DOI: 10.1039/D0RA06614A.].

Alternative Approach for Fighting Bacteria and Fungi: Use of Modified Fluorapatite.

The recent studies on fluorapatite and hydroxyapatite, in the context of their medical applications, have shown that the former has relatively higher thermal stability and better mechanical properties than the latter. Moreover, the presence of fluoride ions is relevant for protection of teeth from dental caries since they stimulate processes of mineralization and crystallization. In this report, a silver modified fluorapatite (FAP/Ag), considered as a novel biomedical compound, was tested for its bactericidal, fungicidal and cytotoxicity activity. All these features were compared to the impact of pure FAP and were evaluated against the bacteria and fungi strains, which constitute main pathogenic species among orthopedic clinical isolates of implant-associated infections. Generally, considerable increase in the antimicrobial activity was observed when silver modified fluorapatite was compared to the pure material. This was manifested among others by disturbance of cell growth pattern and various deformations in the final cell shape as revealed using atomic force microscopy (AFM). Regarding toxicity nowadays as a major issue in implantation, we additionally examined whether the Ag+ ions have an impact on human keratinocytes and mouse fibroblasts using a cytotoxicity assay. To conclude, owing to a great bactericidal potential without collateral cytotoxicity effect the fluorapatite doped with silver ions may be considered a promising biocomponent useful in medical and healthcare applications.

Experimental Investigation of Electrical Conductivity and Permittivity of SC-TiO 2 -EG Nanofluids.

The paper presents experimental studies of dielectric properties of nanofluids based on ethylene glycol and SC-TiO2 nanoparticles with average size of 15-40 nm with various mass concentrations. The dielectric permittivity both real part and imaginary part as a function of temperature and frequency were measured. Also, dependence ac conductivity on frequency, temperature, and mass concentration were investigated. Based on the curves of ac conductivity, dc conductivity was calculated, and 400 % enhancement in dc conductivity was exposed.

Annealing Effects on Structure and Optical Properties of Diamond-Like Carbon Films Containing Silver.

In the present study, diamond-like carbon films with embedded Ag nanoparticles (DLC:Ag) were deposited by reactive magnetron sputtering. Structure of the films was investigated by Raman scattering spectroscopy. Atomic force microscopy was used to define thickness of DLC:Ag films as well as to study the surface morphology and size distribution of Ag nanoparticles. Optical absorbance and reflectance spectra of the films were studied in the 180-1100-nm range. Air annealing effects on structure and optical properties of the DLC:Ag were investigated. Annealing temperatures were varied in the 180-400 °C range. Changes of size and shape of the Ag nanoclusters took place due to agglomeration. It was found that air annealing of DLC:Ag films can result in graphitization following destruction of the DLC matrix. Additional activation of surface-enhanced Raman scattering (SERS) effect in DLC:Ag films can be achieved by properly selecting annealing conditions. Annealing resulted in blueshift as well as significant narrowing of the plasmonic absorbance and reflectance peaks. Moreover, quadrupole surface plasmon resonance peaks appeared. Modeling of absorption spectra of the nanoclusters depending on the shape and surrounding media has been carried out.

Spectroellipsometric characterization and modeling of plasmonic diamond-like carbon nanocomposite films with embedded Ag nanoparticles.

Diamond-like carbon nanocomposite films with embedded silver nanoparticles are considered experimentally (spectroellipsometric characterization) and theoretically (modeling of optical properties). Metallic nanocomposite films were synthesized by reactive magnetron sputtering and were studied by transmission electron microscope (TEM) and atomic force microscope (AFM). The optical constants of the films were determined from spectroscopic ellipsometry measurements and were modeled using the Maxwell-Garnett approximations. Comparison between the extended and renormalized Maxwell-Garnett theory was conducted. Surface plasmon resonance peak have been found to be strongly dependent on the shape of nanoparticles and interaction between them.