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Nafion/oxide composite membranes were produced by pulsed laser ablation method using UV laser pulses generated by a COMPEXPro 205 KrF* excimer laser source λ = 248 nm and τFWHM ≈ 25 ns. We selected TiO2 material and distributed it uniformly over the surface of Nafion 112 membrane using 100 and 250 laser pulses and an incident laser fluence set at 5 J cm–2 were applied to improve the water retention property and corresponding proton conductivity under high temperature operating conditions. TGA and DSC methods were used to characterize the thermal stability of the membranes. Furthermore, UV-Vis spectroscopy experiments showed incorporation of the inorganic phase in the polymer matrix. Water uptake and proton conductivity characterizations of the Nafion composite membranes were carried out, and the results demonstrated that there was higher water uptake and an increased proton conductivity at 120 °C temperature, compared with Nafion 112 membrane. [ABSTRACT FROM AUTHOR]

Abstract: The extension of pulsed laser deposition to the synthesis on Ti substrates of β-tricalcium phosphate (β-TCP) coatings doped with manganese is reported. Targets sintered from two crystalline Mn-doped β-TCP powders (with the composition Ca2.9Mn0.1(PO4)2 and Ca2.8Mn0.2(PO4)2) were ablated with an UV KrF* (λ =248nm, τ ∼7ns) laser source. X-ray diffraction and energy dispersive X-ray spectroscopy investigations showed that the films, while prevalently amorphous, had a Ca/P ratio of about 1.50–1.52. Scanning electron microscopy analyses revealed a rather homogeneous aspect of the coatings which were molded to the relief of the chemically etched Ti substrate. Fluorescence microscopy was applied to test the proliferation of mesenchymal stem cells grown on the obtained biostructures. Our investigations found that, even 14 days after cultivation, the synthesized films were not cytotoxic. On the contrary, they showed excellent bioactivity, as demonstrated by the neat spread of the cells over the entire surface of Mn-doped β-TCP. When tested in osteoprogenitor cell culture, the Ca2.8Mn0.2(PO4)2 samples revealed a higher potential for proliferation and better viability compared with Ca2.9Mn0.1(PO4)2. [Copyright &y& Elsevier]

Abstract: Anatase phase titanium dioxide (TiO2) thin films were grown by pulsed laser deposition on 〈001〉 SiO2 substrates. An UV KrF* (λ =248nm, τ FWHM ≅20ns, ν =2Hz) excimer laser was used for the irradiation of the TiO2 targets. The substrates were kept at room temperature or heated during the film deposition at values within the 100–500°C range. The crystalline quality of the films and their chemical composition were investigated by X-ray diffractometry and energy dispersive X-ray spectroscopy. The optical properties were studied by a double beam spectrophotometer in the spectral range of 400–1200nm. At substrate temperatures higher than 300°C, the structure of the deposited thin films changes from poorly to well crystallised, corresponding to the tetragonal TiO2 anatase phase. The average optical transmittance in the visible-infrared spectral range of the films is higher than 85% which makes them suitable for sensor applications. [Copyright &y& Elsevier]

We report the film deposition of Poly(D,L-lactide-co-glycolide) (PLGA) particle systems by matrix assisted pulsed laser evaporation (MAPLE) technique. PLGA+polyvinyl alcohol (PVA), PLGA+PVA+ bovine serum albumin (BSA) and PLGA+PVA+chitosan (CH) nanoparticles were prepared by an oil-in-water emulsion-diffusion-evaporation method. The average diameter of PLGA particles was between 180-250 nm. The coatings were obtained by laser evaporation of frozen targets prepared by mixing appropriate PLGA aqueous suspensions and dimethyl sulfoxide (DMSO) in three ratios. Depending on the DMSO content, we deposited PLGA particles embedded into polymeric layer mainly obtained due to the entirely or partially dissolving of nanoparticles into the initial solution. In vitro results showed that the distribution and morphology of osteoblast-like SaOs-2 cells on some PLGA particle coatings were similar with that of the positive control. The purpose of this study was to develop layers of PLGA particles for local controlled drug delivery. [ABSTRACT FROM AUTHOR]

Indium Zinc Oxide compositional libraries were fabricated by combinatorial pulsed laser deposition technique on glass substrate at room temperature. Two pairs of targets with In atomic concentrations, In/(In+Zn), of 28 at.% and 56 at.% or 42 at.% and 70 at.% were employed. A high transparency was observed for all the coatings with transmittance values better than 95%. The maximum thicknesses of the samples, inferred by spectroscopic ellipsometry, were within the 174-310 nm range for the simple PLD films, whereas in case of combinatorial PLD coatings were 341 or 467 nm. Energy dispersive X-ray spectroscopy revealed that In content in the combinatorial films was in the 27-52 at. % range. From atomic force microscopy histograms we evidenced a decrease of the RMS roughness down to 1 nm with the increase of the In content. As a result of the compositional library studies two minimum values of the electrical resistivity were identified at 2.3×10-3 Ω·cm and 8.6 ×10-4 Ω·cm, which correspond to 28.8-29.5 at.% and 44-49 at% range of Indium content. [ABSTRACT FROM AUTHOR]

Radiation delivery at ultrahigh dose rates (UHDRs) has potential for use as a new anticancer therapeutic strategy. The FLASH effect induced by UHDR irradiation has been shown to maintain antitumour efficacy with a reduction in normal tissue toxicity; however, the FLASH effect has been difficult to demonstrate in vitro. The objective to demonstrate the FLASH effect in vitro is challenging, aiming to reveal a differential response between cancer and normal cells to further identify cell molecular mechanisms. New high-intensity petawatt laser-driven accelerators can deliver very high-energy electrons (VHEEs) at dose rates as high as 10 13  Gy/s in very short pulses (10 -13  s). Here, we present the first in vitro experiments carried out on cancer cells and normal non-transformed cells concurrently exposed to laser-plasma accelerated (LPA) electrons. Specifically, melanoma cancer cells and normal melanocyte co-cultures grown on chamber slides were simultaneously irradiated with LPA electrons. A non-uniform dose distribution on the cell cultures was revealed by Gafchromic films placed behind the chamber slide supporting the cells. In parallel experiments, cell co-cultures were exposed to pulsed X-ray irradiation, which served as positive controls for radiation-induced nuclear DNA double-strand breaks. By measuring the impact on discrete areas of the cell monolayers, the greatest proportion of the damaged DNA-containing nuclei was attained by the LPA electrons at a cumulative dose one order of magnitude lower than the dose obtained by pulsed X-ray irradiation. Interestingly, in certain discrete areas, we observed that LPA electron exposure had a different effect on the DNA damage in healthy normal human epidermal melanocyte (NHEM) cells than in A375 melanoma cells; here, the normal cells were less affected by the LPA exposure than cancer cells. This result is the first in vitro demonstration of a differential response of tumour and normal cells exposed to FLASH irradiation and may contribute to the development of new cell culture strategies to explore fundamental understanding of FLASH-induced cell effect., (© 2024. The Author(s).)

Foturan glass is a photosensitive transparent material which has attracted much interest for microfluidic applications due to possibility of volume processing by ultrafast lasers. In this work, we have investigated the effect of picosecond laser on volume processing in Foturan glass when varying the beam diameter incident on a lens. To this end, specific laser focusing configurations have been designed using raytracing models and an analysis protocol has been developed in the lens focusing region in order to describe the focal point displacement occurring at the variation of the incident laser beam diameter. The numerically simulated results were explained in association with Rayleigh length and found to be in good agreement with the experimental data obtained at well-defined conditions. Specifically, it was found that the hollow microstructures developed by thermal treatment and chemical etching after laser irradiation were significantly displaced along the propagation direction when the incident beam diameter varied in the range of 1-3.5 times. This approach aims to bring an essential contribution to the field of ultrashort pulse lasers micro- and nanoprocessing in transparent materials proving that the laser beam focus position and its size can be precisely controlled with high precision by automated optics for the variation of incident laser beam diameter in predefined conditions. This approach has the potential for laser multi-beam processing at various volume depths using the same optics setup and may even be applicable to two-photon excitation microscopy. On the other hand, the processing protocol in Foturan glass may allow understanding transparent material modification by tailoring laser beam characteristics.

Self-absorption of spectral lines is known to lower the performance of analytical measurements via calibration-free laser-induced breakdown spectroscopy. However, the error growth due to this effect is not clearly assessed. Here we propose a method to quantify the measurement error due to self-absorption based on the calculation of the spectral radiance of a plasma in local thermodynamic equilibrium. Validated through spectroscopic measurements for a binary alloy thin film of compositional gradient, the method evidences that measurement performance lowering due to self-absorption depends on the spectral shape of the analytical transition and on the intensity measurement method. Thus, line-integrated intensity measurements of Stark broadened lines enable accurate analysis, even at large optical thickness, if line width and plasma size are precisely known. The error growth due to self-absorption is significantly larger for line shapes dominated by Doppler broadening and for line-center intensity measurements. The findings present a significant advance in compositional measurements via calibration-free laser-induced breakdown spectroscopy, as they enable straightforward selection of most appropriate analytical lines., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Lab-on-a-chip (LOC) and organ-on-a-chip (OOC) devices are highly versatile platforms that enable miniaturization and advanced controlled laboratory functions (i.e., microfluidics, advanced optical or electrical recordings, high-throughput screening). The manufacturing advancements of LOCs/OOCs for biomedical applications and their current limitations are briefly discussed. Multiple studies have exploited the advantages of mimicking organs or tissues on a chip. Among these, we focused our attention on the brain-on-a-chip, blood-brain barrier (BBB)-on-a-chip, and neurovascular unit (NVU)-on-a-chip applications. Mainly, we review the latest developments of brain-on-a-chip, BBB-on-a-chip, and NVU-on-a-chip devices and their use as testing platforms for high-throughput pharmacological screening. In particular, we analyze the most important contributions of these studies in the field of neurodegenerative diseases and their relevance in translational personalized medicine.

Since Graphene discovery, their associated derivate nanomaterials, Graphene Oxide (GO) and reduced-GO were in the forefront of continuous developments in bio-nano-technology due to unique physical-chemical properties. Although GO nano-colloids (GON) were proposed as drug release matrix for targeting cancer cells, there is still a concern regarding its cytotoxicity issues. In this study, we report on the fabrication of functional GON bio-coatings by Matrix-Assisted Pulsed Laser Evaporation (MAPLE) to be used as drug carriers for targeting melanoma cells. We first performed a thorough in vitro cytotoxicity assay for comparison between GON and protein functionalized GON coatings. As functionalization protein, Bovine Serum Albumin (BSA) was non-covalently conjugated to GO surface. Safe concentration windows were identified in cytotoxicity tests by live/dead staining and MTS assays for five different human melanoma cell lines as well as for non-transformed melanocytes and human dermal fibroblasts. Hybrid GON-BSA nano-scaled thin coatings incorporating Dabrafenib (DAB) and Trichostatin A (TSA) inhibitors for cells bearing BRAF V600E pathway activating mutation were assembled on solid substrates by MAPLE technique. We further demonstrated the successful immobilization for each drug-containing GON-BSA assembling systems by evaluating cellular BRAF activity inhibition and histone deacetylases activity blocking, respectively. DAB activity was proven by the decreased ERK phosphorylation in primary melanoma cells (SKmel28 BRAF V600E cell line), while TSA effect was evidenced by acetylated histones accumulation in cell's nuclei (SKmel23 BRAF WT cell line). In addition, melanoma cells exposed to GON-BSA coatings with compositional gradient of inhibitors evidenced a dose-dependent effect on target activity. Such functional bio-platforms could present high potential for cell-biomaterial interface engineering to be applied in personalized cancer therapy studies., (Copyright © 2020 Sima, Chiritoiu, Negut, Grumezescu, Orobeti, Munteanu, Sima and Axente.)

There is permanent progress with the fabrication of smart bioactive surfaces that could govern tissue regeneration. Thin coatings of two or more materials with compositional gradient allow the construction of arrays with different chemical and physical features on a solid substrate. With such intelligent bio-platforms, cells can be exposed to a tissue-like biomimetic micro-environment with precise characteristics that directs cells fate towards specific phenotypes. We have introduced combinatorial matrix-assisted pulsed laser evaporation (C-MAPLE) as an alternative approach for the fabrication in a single-step process of either organic or inorganic thin and nanostructured coatings with variable composition. A continuous reciprocal gradient of two biomolecules can be achieved by C-MAPLE with discrete areas exhibiting physicochemical specificity that modulates intracellular signaling events. Herein, we present a review of the current combinatorial laser strategies and methods for fabricating thin organic and inorganic films with compositional gradient with emphasis on the surface influence on cell responsiveness. In particular, the specific biological potential of surface functionalization with thin coatings of biopolymers, proteins and drugs will be discussed. Laser deposition combinatorial processes are considered an emerging unconventional technology that can be widely applied to produce composite multilayers and micro-patterns for faster cell colonization and tissue engineering., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Elemental analyses of thin films with complex composition are challenging as the standard analytical techniques based on measurement calibration are difficult to apply. We show that calibration-free laser-induced breakdown spectroscopy (LIBS) presents a powerful solution, enabling quantitative analyses of multielemental thin films with analytical performances better than those obtained with other techniques. The demonstration is given for a nickel-chromium-molybdenum alloy film of 150 nm thickness that was produced by pulsed laser deposition. The LIBS spectra were recorded under experimental conditions that enable simple and accurate modeling of plasma emission. Thus, a calibration-free approach based on the calculation of the spectral radiance of a uniform plasma in local thermodynamic equilibrium was applied to deduce the elemental composition. Supported by analyses via Rutherford backscattering spectrometry and energy-dispersive X-ray spectroscopy, the LIBS measurements evidence nonstoichiometric mass transfer of the alloy during the thin-film deposition process. This technique could be used even for thinner films, provided that the film-composing elements are not present in the substrate.

Glass is an alternative solution to polymer for the fabrication of three-dimensional (3D) microfluidic biochips. Femtosecond (fs) lasers are nowadays the most promising tools for transparent glass processing. Specifically, the multiphoton process induced by fs pulses enables fabrication of embedded 3D channels with high precision. The subtractive fabrication process creating 3D hollow structures in glass, known as fs laser-assisted etching (FLAE), is based on selective removal of the laser-modified regions by successive chemical etching in diluted hydrofluoric acid solutions. In this work we demonstrate the possibility to generate embedded hollow channels in photosensitive Foturan glass volume by high repetition rate picosecond (ps) laser-assisted etching (PLAE). In particular, the influence of the critical irradiation doses and etching rates are discussed in comparison of two different wavelengths of ultraviolet (355 nm) and visible (532 nm) ranges. Fast and controlled fabrication of a basic structure composed of an embedded micro-channel connected with two open reservoirs, commonly used in the biochip design, are achieved inside glass. Distinct advantages such as good aspect-ratio, reduced processing time for large areas, and lower fabrication cost are evidenced.

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 β-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., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Laboratory plasmas inherently exhibit temperature and density gradients leading to complex investigations. We show that plasmas generated by laser ablation can constitute a robust exception to this. Supported by emission features not observed with other sources, we achieve plasmas of various compositions which are both uniform and in local thermodynamic equilibrium. These properties characterize an ideal radiation source opening multiple perspectives in plasma spectroscopy. The finding also constitutes a breakthrough in the analytical field as fast analyses of complex materials become possible.

Both strontium and zoledronate (ZOL) are known to be useful for the treatment of bone diseases associated to the loss of bone substance. In this work, we applied an innovative technique, Combinatorial Matrix-Assisted Pulsed Laser Evaporation (C-MAPLE), to deposit gradient thin films with variable compositions of Sr-substituted hydroxyapatite (SrHA) and ZOL modified hydroxyapatite (ZOLHA) on Titanium substrates. Compositional gradients were obtained by simultaneous laser vaporization of the two distinct material targets. The coatings display good crystallinity and granular morphology, which do not vary with composition. Osteoblast-like MG63 cells and human osteoclasts were co-cultured on the thin films up to 21 days. The results show that Sr counteracts the negative effect of relatively high concentration of ZOL on osteoblast viability, whereas both Sr and ZOL enhance extracellular matrix deposition. In particular, ZOL promotes type I collagen production, whereas Sr increases the production of alkaline phosphatase. Moreover, ZOL exerts a greater effect than Sr on osteoprotegerin/RANKL ratio and, as a consequence, on the reduction of osteoclast proliferation and activity. The deposition method allows to modulate the composition of the thin films and hence the promotion of bone growth and the inhibition of bone resorption., (Copyright © 2015 Elsevier Inc. All rights reserved.)

There is increased interest in smart bioactive materials to control tissue regeneration for the engineering of cell instructive scaffolds. We introduced combinatorial matrix-assisted pulsed laser evaporation (C-MAPLE) as a new method for the fabrication of organic thin films with a compositional gradient. Synchronized C-MAPLE of levan and oxidized levan was employed to assemble a two-compound biopolymer film structure. The gradient of the film composition was validated by fluorescence microscopy. In this study, we investigated the cell response induced by the compositional gradient using imaging of early osteoblast attachment and analysis of signalling phosphoprotein expression. Cells attached along the gradient in direct proportion to oxidized levan concentration. During this process distinct areas of the binary gradient have been shown to modulate the osteoblasts' extracellular signal-regulated kinase signalling with different propensity. The proposed fabrication method results in the preparation of a new bioactive material, which could control the cell signalling response. This approach can be extended to screen new bioactive interfaces for tissue regeneration.

The sheltered transfer and immobilization of rabbit anti-human antiserum immunoglobulin G (IgG) by matrix-assisted pulsed laser evaporation (MAPLE) are reported. The iced targets submitted to laser irradiation consisted of 0.2-2 mg/mL IgG blended or not with lipid (L-α-phosphatidylcholine dipalmitoyl) dissolved in distilled water-based saline buffer. Thin IgG coatings were obtained at room temperature onto glass, fused silica, or silicon substrates. Ten thousand subsequent laser pulses of 0.33, 0.5, or 0.67 J/cm(2) fluence were applied for the synthesis of each sample. Morphology and composition of the thin films were studied by optical, scanning, and atomic force microscopy and Fourier transformed infrared spectrometry. Optical labeling methods such as spectrofluorimetry and fluorescence microscopy were selected to verify the biosensor transduction principle because of their high sensitivity for detecting low amounts of antigen (IgG). Protein immobilization to the substrate surface was demonstrated for all obtained structures after immersion in the donkey anti-rabbit secondary antibody solution. The IgG transfer and immobilization onto substrates were improved by addition of lipid to MAPLE solutions., (2010 Wiley Periodicals, Inc.)