Topological Avenue for Efficient Decontamination of Large Volumes of Fluids via UVC Irradiation of Packed Metamaterials.

Nowadays, metamaterials application enjoys notoriety in fluid decontamination and pathogen annihilation, which are frequently present in polluted fluids (e.g., water, blood, blood plasma, air or other gases). The depollution effect is largely enhanced by UVC irradiation. The novelty of this contribution comes from the significant increase by packing of the total surface of metamaterials in contact with contaminated fluids. Packed metamaterial samples are subjected to UVC irradiation, with expected advantages for implant sterilization and long-term prevention of nosocomial infections over large clinical areas. The novel aspect of the investigation consists of a combination of big and small elements of the metamaterial to optimize the above effects connected with fluids and irradiation. The big elements allow the radiation to penetrate deep inside the fluid, and the small elements optimally disperse this radiation toward deeper regions of the metamaterial. A packing scheme of smaller, in-between large metamaterial spheres and fibres is proposed for promoting enhanced depollution against pathogen agents. It is demonstrated that the total surface of metamaterials in contact with contaminated fluids/surface is significantly increased as a result of packing. This opens, in our opinion, new auspicious perspectives in the construction of novel equipment with high sensibility in the detection and decontamination of microorganisms.

Mathematical formalism of femtosecond laser-deoxyribonucleic acid interaction: thermal evolution.

A novel analytical formalism is proposed based upon Quantum heat transport equation in order to describe the femtoseconds/picoseconds laser pulses interaction with the Deoxyribonucleic acid (DNA). The formalism generates solutions based upon inputs as: voltage, laser beam intensity and laser - DNA interaction time. Thermal waves induced inside irradiated DNA are defined and accounted for. Analytical simulations show that the optimum regime of laser - DNA interaction was reached for a potential carrier generated at the interface equal to 3.5 × 10-3 eV. It has to be mentioned that the formalism breaks down if the potential carrier generated at the interface is inferior to 10-2 eV. Accordingly, for pulse duration inferior to 1 ps, the laser beam spatial-temporal distribution has an essential role in defining the shape and magnitude of the thermal distribution within the irradiated DNA strands.

UVC radiation intensity dependence of pathogen decontamination rate: semiclassical theory and experiment.

A semiclassical (light classical and molecule quantum) model describing the dependence of DNA/RNA dimerization rate as function of the ultraviolet C (UVC) radiation's intensity is proposed. Particularly, a nonlinear model is developed based on the Raman-like processes in quantum optics. The main result of the theory shows that the process of dimerization in the DNA/RNA depends strongly on the UVC light's intensity, thus proving a possible quantum microscopical mechanism of the interaction of UV light with the DNA. To corroborate the theoretical findings, we realize some experiments, by which want to investigate how the inactivation rate of the yeast colonies depends on the intensity of the UVC irradiation. The experimental results evidence a nonlinear decreasing of the residual yeast colonies as a function of the intensity in the irradiation process. The possibilities to optimize the intensity of UVC radiation in the considered decontamination equipment by using metamaterials are studied. The application of such equipment in disinfection of fluids (air, water, droplets, etc.), as well for the SARS-CoV-2-infected aerosols, is discussed.

Implant Surfaces Containing Bioglasses and Ciprofloxacin as Platforms for Bone Repair and Improved Resistance to Microbial Colonization.

Coatings are an attractive and challenging selection for improving the bioperformance of metallic devices. Composite materials based on bioglass/antibiotic/polymer are herein proposed as multifunctional thin films for hard tissue implants. We deposited a thin layer of the polymeric material by matrix-assisted pulsed laser evaporation-MAPLE onto Ti substrates. A second layer consisting of bioglass + antibiotic was applied by MAPLE onto the initial thin film. The antimicrobial activity of MAPLE-deposited thin films was evaluated on Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, and Pseudomonas aeruginosa standard strains. The biocompatibility of obtained thin films was assessed on mouse osteoblast-like cells. The results of our study revealed that the laser-deposited coatings are biocompatible and resistant to microbial colonization and biofilm formation. Accordingly, they can be considered viable candidates for biomedical devices and contact surfaces that would otherwise be amenable to contact transmission.

Advances in Laser Additive Manufacturing of Cobalt-Chromium Alloy Multi-Layer Mesoscopic Analytical Modelling with Experimental Correlations: From Micro-Dendrite Grains to Bulk Objects.

This study presents two analytical models for the laser powder bed fusion (LPBF) process. To begin, the single layer's dimensions were measured using principal operating conditions, including laser power, laser scanning speed, powder layer thickness, and hatch distance. The single-layer printing dimensions were transformed into multi-layer printing using the hatch distance. The thermal history of the printed layers was used as an input to the Johnson-Mehl-Avrami-Kolmogorov model to estimate the average dendrite grain size. LPBF experiments were conducted for a Cobalt-chromium (Co-Cr) alloy to validate the developed model. The average dendrite grain size was estimated using a scanning electron microscope (SEM) combined with "Image J" software. The Vickers hardness test was performed to correlate the average dendrite grain size and operating conditions. A 10-15% mean absolute deviation was presented between experiments and simulation results. In all samples, a Co-based γ-FCC structure was identified. An inverse correlation was established between the laser power and smaller average dendrite grain, while a direct relationship has been determined between laser scanning speed and average dendrite grain size. A similar trend was identified between hatch distance and average dendrite grain size. A direct link has been determined between the average dendrite grain size and hardness value. Furthermore, a direct relationship has connected the laser volume energy density and hardness value. This study will help experimentalists to design operating conditions based on the required grain size and corresponding mechanical characteristics.

Laser Melting Deposition Additive Manufacturing of Ti6Al4V Biomedical Alloy: Mesoscopic In-Situ Flow Field Mapping via Computational Fluid Dynamics and Analytical Modelling with Empirical Testing.

Laser melting deposition (LMD) has recently gained attention from the industrial sectors due to producing near-net-shape parts and repairing worn-out components. However, LMD remained unexplored concerning the melt pool dynamics and fluid flow analysis. In this study, computational fluid dynamics (CFD) and analytical models have been developed. The concepts of the volume of fluid and discrete element modeling were used for computational fluid dynamics (CFD) simulations. Furthermore, a simplified mathematical model was devised for single-layer deposition with a laser beam attenuation ratio inherent to the LMD process. Both models were validated with the experimental results of Ti6Al4V alloy single track depositions on Ti6Al4V substrate. A close correlation has been found between experiments and modelling with a few deviations. In addition, a mechanism for tracking the melt flow and involved forces was devised. It was simulated that the LMD involves conduction-mode melt flow only due to the coaxial addition of powder particles. In front of the laser beam, the melt pool showed a clockwise vortex, while at the back of the laser spot location, it adopted an anti-clockwise vortex. During printing, a few partially melted particles tried to enter into the molten pool, causing splashing within the melt material. The melting regime, mushy area (solid + liquid mixture) and solidified region were determined after layer deposition. This research gives an in-depth insight into the melt flow dynamics in the context of LMD printing.

Non-Destructive X-ray Characterization of a Novel Joining Method Based on Laser-Melting Deposition for AISI 304 Stainless Steel.

In this study, an application of the laser-melting deposition additive manufacturing technique as a welding method has been studied for the laser welding (LW) of AISI 304 stainless steel, specifically 0.4 mm and 0.5 mm thick sheets. The welding was carried out without and with filler material. Inconel 718 powder particles were used as filler material in the second case. A series of experiments were designed by changing the process parameters to identify the effect of operating conditions on the weld width, depth, and height. The welds were examined through metallographic experiments performed at various cross-sections to identify the defects and pores. All the deposited welds were passed through a customized mini-focus X-ray system to analyze the weld uniformities. The optimal operating conditions were determined for 0.4 mm and 0.5 mm sheets for the LW with and without filler material. It was found that laser power, laser scanning speed, powder flow rate, and helium to argon gases mixture-control the weld bead dimensions and quality. X-ray analyses showed that the optimal operating conditions gave the least peak value of non-uniformity in the laser welds. This study opens a new window for laser welding via additive manufacturing with X-ray monitoring.

Keyhole Formation by Laser Drilling in Laser Powder Bed Fusion of Ti6Al4V Biomedical Alloy: Mesoscopic Computational Fluid Dynamics Simulation versus Mathematical Modelling Using Empirical Validation.

In the laser powder bed fusion (LPBF) process, the operating conditions are essential in determining laser-induced keyhole regimes based on the thermal distribution. These regimes, classified into shallow and deep keyholes, control the probability and defects formation intensity in the LPBF process. To study and control the keyhole in the LPBF process, mathematical and computational fluid dynamics (CFD) models are presented. For CFD, the volume of fluid method with the discrete element modeling technique was used, while a mathematical model was developed by including the laser beam absorption by the powder bed voids and surface. The dynamic melt pool behavior is explored in detail. Quantitative comparisons are made among experimental, CFD simulation and analytical computing results leading to a good correspondence. In LPBF, the temperature around the laser irradiation zone rises rapidly compared to the surroundings in the powder layer due to the high thermal resistance and the air between the powder particles, resulting in a slow travel of laser transverse heat waves. In LPBF, the keyhole can be classified into shallow and deep keyhole mode, controlled by the energy density. Increasing the energy density, the shallow keyhole mode transforms into the deep keyhole mode. The energy density in a deep keyhole is higher due to the multiple reflections and concentrations of secondary reflected beams within the keyhole, causing the material to vaporize quickly. Due to an elevated temperature distribution in deep keyhole mode, the probability of pores forming is much higher than in a shallow keyhole as the liquid material is close to the vaporization temperature. When the temperature increases rapidly, the material density drops quickly, thus, raising the fluid volume due to the specific heat and fusion latent heat. In return, this lowers the surface tension and affects the melt pool uniformity.

Composite Drug Delivery System Based on Amorphous Calcium Phosphate-Chitosan: An Efficient Antimicrobial Platform for Extended Release of Tetracycline.

One major warning emerging during the first worldwide combat against healthcare-associated infections concerns the key role of the surface in the storage and transfer of the virus. Our study is based on the laser coating of surfaces with an inorganic/organic composite mixture of amorphous calcium phosphate-chitosan-tetracycline that is able to fight against infectious agents, but also capable of preserving its activity for a prolonged time, up to several days. The extended release in simulated fluids of the composite mixture containing the drug (tetracycline) was demonstrated by mass loss and UV-VIS investigations. The drug release profile from our composite coatings proceeds via two stages: an initial burst release (during the first hours), followed by a slower evolution active for the next 72 h, and probably more. Optimized coatings strongly inhibit the growth of tested bacteria (Enterococcus faecalis and Escherichia coli), while the drug incorporation has no impact on the in vitro composite's cytotoxicity, the coatings proving an excellent biocompatibility sustaining the normal development of MG63 bone-like cells. One may, therefore, consider that the proposed coatings' composition can open the prospective of a new generation of antimicrobial coatings for implants, but also for nosocomial and other large area contamination prevention.

Thermal Nonlinear Klein-Gordon Equation for Nano-/Micro-Sized Metallic Particle-Attosecond Laser Pulse Interaction.

In this study, a rigorous analytical solution to the thermal nonlinear Klein-Gordon equation in the Kozlowski version is provided. The Klein-Gordon heat equation is solved via the Zhukovsky "state-of-the-art" mathematical techniques. Our study can be regarded as an initial approximation of attosecond laser-particle interaction when the prevalent phenomenon is photon-electron interaction. The electrons interact with the laser beam, which means that the nucleus does not play a significant role in temperature distribution. The particle is supposed to be homogenous with respect to thermophysical properties. This theoretical approach could prove useful for the study of metallic nano-/micro-particles interacting with attosecond laser pulses. Specific applications for Au "nano" particles with a 50 nm radius and "micro" particles with 110, 130, 150, and 1000 nm radii under 100 attosecond laser pulse irradiation are considered. First, the cross-section is supposed to be proportional to the area of the particle, which is assumed to be a perfect sphere of radius R or a rotation ellipsoid. Second, the absorption coefficient is calculated using a semiclassical approach, taking into account the number of atoms per unit volume, the classical electron radius, the laser wavelength, and the atomic scattering factor (10 in case of Au), which cover all the basic aspects for the interaction between the attosecond laser and a nanoparticle. The model is applicable within the 100-2000 nm range. The main conclusion of the model is that for a range inferior to 1000 nm, a competition between ballistic and thermal phenomena occurs. For values in excess of 1000 nm, our study suggests that the thermal phenomena are dominant. Contrastingly, during the irradiation with fs pulses, this value is of the order of 100 nm. This theoretical model's predictions could be soon confirmed with the new EU-ELI facilities in progress, which will generate pulses of 100 as at a 30 nm wavelength.

Fish Bone Derived Bi-Phasic Calcium Phosphate Coatings Fabricated by Pulsed Laser Deposition for Biomedical Applications.

We report on new biomaterials with promising bone and cartilage regeneration potential, from sustainable, cheap resources of fish origin. Thin films were fabricated from fish bone-derived bi-phasic calcium phosphate targets via pulsed laser deposition with a KrF * excimer laser source (λ = 248 nm, τFWHM ≤ 25 ns). Targets and deposited nanostructures were characterized by SEM and XRD, as well as by Energy Dispersive X-ray (EDX) and FTIR spectroscopy. Films were next assessed in vitro by dedicated cytocompatibility and antimicrobial assays. Films were Ca-deficient and contained a significant fraction of ß-tricalcium phosphate apart from hydroxyapatite, which could contribute to an increased solubility and an improved biocompatibility for bone regeneration applications. The deposited structures were biocompatible as confirmed by the lack of cytotoxicity on human gingival fibroblast cells, making them promising for fast osseointegration implants. Pulsed laser deposition (PLD) coatings inhibited the microbial adhesion and/or the subsequent biofilm development. A persistent protection against bacterial colonization (Escherichia coli) was demonstrated for at least 72 h, probably due to the release of the native trace elements (i.e., Na, Mg, Si, and/or S) from fish bones. Progress is therefore expected in the realm of multifunctional thin film biomaterials, combining antimicrobial, anti-inflammatory, and regenerative properties for advanced implant coatings and nosocomial infections prevention applications.

An Analytical Multiple-Temperature Model for Flash Laser Irradiation on Single-Layer Graphene.

A Multiple-Temperature Model is proposed to describe the flash laser irradiation of a single layer of graphene. Zhukovsky's mathematical approach is applied to solve the Fourier heat equations based upon quantum concepts, including heat operators. Easy solutions were inferred with respect to classical mathematics. Thus, simple equations were set for the electrons and phonon temperatures in the case of flash laser treatment of a single layer of graphene. Our method avoids the difficulties and extensive time-consuming nonequilibrium green function method or quantum field theories when applied in a condensed matter. Simple expressions were deduced that could prove useful for researchers.

Metal Matrix Composites Synthesized by Laser-Melting Deposition: A Review.

Metal matrix composites (MMCs) present extraordinary characteristics, including high wear resistance, excellent operational properties at elevated temperature, and better chemical inertness as compared to traditional alloys. These properties make them prospective candidates in the fields of aerospace, automotive, heavy goods vehicles, electrical, and biomedical industries. MMCs are challenging to process via traditional manufacturing techniques, requiring high cost and energy. The laser-melting deposition (LMD) has recently been used to manufacture MMCs via rapid prototyping, thus, solving these drawbacks. Besides the benefits mentioned above, the issues such as lower ultimate tensile strength, yield strength, weak bonding between matrix and reinforcements, and cracking are still prevalent in parts produced by LMD. In this article, a detailed analysis is made on the MMCs manufactured via LMD. An illustration is presented on the LMD working principle, its classification, and dependent and independent process parameters. Moreover, a brief comparison between the wire and powder-based LMDs has been summarized. Ex- and in-situ MMCs and their preparation techniques are discussed. Besides this, various matrices available for MMCs manufacturing, properties of MMCs after printing, possible complications and future research directions are reviewed and summarized.

Functional Bioglass-Biopolymer Double Nanostructure for Natural Antimicrobial Drug Extracts Delivery.

Aseptic loosening and periprosthetic infections are the main causes of implant failure. Strategies to mitigate this drawback are therefore mandatory to avoid primary and revision replacement surgeries. A functional bioapatite-biopolymer double nanostructure fabricated by matrix-assisted pulsed laser evaporation to prevent infection of orthopedic and dental implants could promote osseointegration and ensure controlled delivery of natural antimicrobial drugs. The synthesized nanostructure consists of two overlapping layers, the lower from a biocompatible polymer for anticorrosive protection, and the upper of bioactive glass incorporating antimicrobial plant extract, acting as a potential drug delivery system. Morphology, composition, adherence, ability for drug delivery and biological properties (cytotoxicity and antimicrobial effect) were studied. Structures proved compact and stable, conserving a remarkable drug delivery ability for more than 21 days, i.e., enough to ensure long-term microbes' eradication.

Artificial Neural Network Algorithms for 3D Printing.

Additive manufacturing with an emphasis on 3D printing has recently become popular due to its exceptional advantages over conventional manufacturing processes. However, 3D printing process parameters are challenging to optimize, as they influence the properties and usage time of printed parts. Therefore, it is a complex task to develop a correlation between process parameters and printed parts' properties via traditional optimization methods. A machine-learning technique was recently validated to carry out intricate pattern identification and develop a deterministic relationship, eliminating the need to develop and solve physical models. In machine learning, artificial neural network (ANN) is the most widely utilized model, owing to its capability to solve large datasets and strong computational supremacy. This study compiles the advancement of ANN in several aspects of 3D printing. Challenges while applying ANN in 3D printing and their potential solutions are indicated. Finally, upcoming trends for the application of ANN in 3D printing are projected.

Synthesis and Modification of Nanostructured Thin Films.

The idea of nanomaterials, nanoscience, and nanotechnologies was formulated by Richard Feynman in 1959 in his famous lecture "There's Plenty of Room at the Bottom" [...].

Pulsed Laser Fabrication of TiO2 Buffer Layers for Dye Sensitized Solar Cells.

We report on the fabrication of dye-sensitized solar cells with a TiO2 buffer layer between the transparent conductive oxide substrate and the mesoporous TiO2 film, in order to improve the photovoltaic conversion efficiency of the device. The buffer layer was fabricated by pulsed laser deposition whereas the mesoporous film by the doctor blade method, using TiO2 paste obtained by the sol-gel technique. The buffer layer was deposited in either oxygen (10 Pa and 50 Pa) or argon (10 Pa and 50 Pa) onto transparent conducting oxide glass kept at room temperature. The cross-section scanning electron microscopy image showed differences in layer morphology and thickness, depending on the deposition conditions. Transmission electron microscopy studies of the TiO2 buffer layers indicated that films consisted of grains with typical diameters of 10 nm to 30 nm. We found that the photovoltaic conversion efficiencies, determined under standard air mass 1.5 global (AM 1.5G) conditions, of the solar cells with a buffer layer are more than two times larger than those of the standard cells. The best performance was reached for buffer layers deposited at 10 Pa O2. We discuss the processes that take place in the device and emphasize the role of the brush-like buffer layer in the performance increase.

Gradient coatings of strontium hydroxyapatite/zinc ß-tricalcium phosphate as a tool to modulate osteoblast/osteoclast response.

The chemistry, structure and morphology of the implant surface have a great influence on the integration of an implant material with bone tissue. In this work, we applied Combinatorial Matrix-Assisted Pulsed Laser Evaporation (C-MAPLE) to deposit gradient thin films with variable compositions of Sr-substituted hydroxyapatite (SrHA) and Zn-substituted ß-tricalcium phosphate (ZnTCP) on Titanium substrates. Five samples with different SrHA/ZnTCP composition ratios were fabricated by a single step laser procedure. SrHA was synthesized in aqueous medium, whereas ZnTCP was obtained by reaction at high temperature. Both powders were separately suspended in deionized water, frozen at liquid nitrogen temperature and used as targets for C-MAPLE experiments, which proceed via simultaneous laser vaporization of two distinct material targets. X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy analyses confirmed that the coatings contain the same crystalline phases as the as-prepared powder samples, with a homogeneous distribution of the two phosphates along deposited thin films. Human osteoclast precursor 2T-110 and human osteoblast-like cells MG63 were co-cultured on the coatings. The results indicate that osteoblast viability and production of osteocalcin were promoted by the presence of ZnTCP. On the other hand, SrHA inhibited osteoclastogenesis and osteoclast differentiation, as demonstrated by the observed increase of the osteoprotegerin/RANKL ratio and decrease of the number of TRAP-positive multinucleated cells when increasing SrHA amount in the coatings. The results indicate that the possibility to tailor the composition of the coatings provides materials able to modulate bone growth and bone resorption.

Enhanced absorption of TiO2 nanotubes by N-doping and CdS quantum dots sensitization: insight into the structure.

Anodization of titanium film sputtered on fluorine doped tin oxide (FTO) glass was performed to obtain highly ordered ∼2 µm long and ∼60 nm wide TiO2 nanotubes. The titania films were annealed in ammonia atmosphere to enable the doping with N. The annealing did not affect the nanotubular morphology and the porosity remained open which is a very important requirement for further deposition of CdS quantum dots. The analysis done by transmission electron microscopy (TEM) has shown that the N-doped nanotubes have a smaller interplanar distance as compared to the undoped ones, whose interplanar distance corresponded to anatase phase. This difference was attributed to the N doping and the Sn migration from the substrate, as demonstrated by energy dispersive spectroscopy (EDS) combined with electron energy loss spectroscopy (EELS). The near edge X-ray absorption fine structure (NEXAFS) analysis clearly demonstrated that also the doped TiO2 film has anatase phase. Regarding the chemical composition of the studied samples, the X-ray photoelectron spectroscopy (XPS) and synchrotron radiation photoelectron spectroscopy (SRPES) analyses have shown that N is incorporated both interstitially and substitutionally in the TiO2 lattice, with a decreased contribution of the interstitial after ionic sputtering. The shift of the valence band maximum (VBM) position for the doped TiO2 vs. the undoped TiO2 proved the narrowing of the band gap. The CdS/TiO2 films show bigger VBM shifting that can be attributed to CdS deposit. Comparing the absorption spectra of the bare undoped and doped TiO2 samples, it was noticed that the doping causes a red shift from 397 to 465 nm. Furthermore, the CdS deposition additionally enhances the absorption in the visible range (575 nm for undoped TiO2/CdS and 560 nm for doped TiO2/CdS films).

Synergistic effects of BMP-2, BMP-6 or BMP-7 with human plasma fibronectin onto hydroxyapatite coatings: A comparative study.

Design of new osteoinductive biomaterials to reproduce an optimized physiological environment capable of recruiting stem cells and instructing their fate towards the osteoblastic lineage has become a priority in orthopaedic surgery. This work aims at evaluating the bioactivity of BMP combined with human plasma fibronectin (FN/BMP) delivered in solution or coated onto titanium-hydroxyapatite (TiHA) surfaces. Herein, we focus on the comparison of in vitro osteogenic efficacy in mouse C2C12 pre-osteoblasts of three BMP members, namely: BMP-2, BMP-6 and BMP-7. In parallel, we evaluated the molecular binding strength between each BMP with FN using the Surface Plasmon Resonance (SPR) technology. The affinity of BMPs for FN was found totally different and dependent on BMP type. Indeed, the combination of FN with BMP-2 on TiHA surfaces potentiates the burst of gene-mediated osteogenic induction, while it prolongs the osteogenic activity of BMP-6 and surprisingly annihilates the BMP-7 one. These results correlate with FN/BMP affinity for TiHA, since BMP-6>BMP-2>BMP-7. In addition, by analyzing the osteogenic activity in the peri-implant environment, we showed that osteoinductive paracrine effects were significantly decreased upon (FN/BMP-6), as opposed to (FN/BMP-2) coatings. Altogether, our results support the use of FN/BMP-6 to develop a biomimetic microenvironment capable to induce osteogenic activity under physiological conditions, with minimum paracrine signalization. STATEMENT OF SIGNIFICANCE: The originality of our paper relies on the first direct comparison of the in vitro osteogenic potential of three osteogenic BMPs (BMP-2, -6 and -7) combined with native human plasma fibronectin delivered in solution or coated by laser transfer onto titanium hydroxyapatite surfaces. We confirm that BMP association with fibronectin enhances the osteogenic activity of BMP-2, -6 and -7, but with essential discrepancies, depending on the BMP member, and in agreement with the affinity of BMPs for fibronectin. Moreover, we bring elements to explain the origin of the BMP-2 medical life-threatening side-effects by analyzing in vitro paracrine effects. Finally, this work supports the alternative use of FN/BMP-6 to induce osteogenic activity under physiological conditions, with minimum side effects.