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This study explores the impact of plasma treatment on Lavandin Grosso flowers and its influence on the extraction of essential oils (EOs) via hydrodistillation. Short plasma treatment times enhance the yield of EO extraction from 3.19% in untreated samples to 3.44%, corresponding to 1 min of plasma treatment, while longer treatment times (10 min) show diminishing returns to 3.07% of yield extraction. Chemical characterization (GC/MS and ATR-FTIR) indicates that plasma treatments do not significantly alter the chemical composition of the extracted EOs, preserving their aromatic qualities. Investigations into plasma-surface interactions reveal changes at the nanometer level, with XPS confirming alterations in the surface chemistry of Lavandin Grosso flowers by reducing surface carbon and increasing oxygen content, ultimately resulting in an increased presence of hydrophilic groups. The presence of hydrophilic groups enhances the interaction between the surface membrane of the glandular trichomes on Lavandin Grosso flowers and water vapor, consequently increasing the extraction of EOs. Furthermore, microscopic SEM examinations demonstrate that plasma treatments do not affect the morphology of glandular trichomes, emphasizing that surface modifications primarily occur at the nanoscale. This study underscores the potential of plasma technology as a tool to enhance EO yields from botanical sources while maintaining their chemical integrity.
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Óleos Voláteis , Óleos Voláteis/química , Cromatografia Gasosa-Espectrometria de Massas , Flores/química , Vapor , TecnologiaRESUMO
Until recently, superhydrophobicity was considered as a hint to predict surface icephobicity, an association of concepts that is by no means universal and that has been proven to depend on different experimental factors and material properties, including the actual morphology and chemical state of surfaces. This work presents a systematic study of the wetting and freezing properties of aluminum Al6061, a common material widely used in aviation, after being subjected to nanosecond pulsed IR laser treatments to modify its surface roughness and morphology. All treated samples, independent of their surface finishing state, presented initially an unstable hydrophilic wetting behavior that naturally evolved with time to reach hydrophobicity or even superhydrophobicity. To stabilize the surface state and to bestow the samples with a permanent and stable hydrophobic character, laser-treated surfaces were covered with a thin layer of CF x prepared by plasma-enhanced chemical vapor deposition. A systematic comparison between freezing delay (FD) and wetting properties of water droplets onto these plasma-/polymer-modified laser-treated surfaces that, under conditions where a heterogeneous nucleation mechanism prevails, surface morphology rather than the actual value of the surface roughness parameter the key feature for long FD times. In particular, it is found that surface morphologies rendering a Cassie-Baxter wetting regime longer FDs than those characterized by a Wenzel-like wetting state. It is that laser treatment, with or without additional coverage with thin CF x coatings, affects wetting and ice formation behaviors and might be an efficient procedure to mitigate icing problems on metal surfaces.
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Herein, we present the development of supported organic nanofabrics formed by a conformal polymer-like interconnection of small-molecule organic nanowires and nanotrees. These organic nanostructures are fabricated by a combination of vacuum and plasma-assisted deposition techniques to generate step by step, single-crystalline organic nanowires forming one-dimensional building blocks, organic nanotrees applied as three-dimensional templates, and the polymer-like shell that produces the final fabric. The complete procedure is carried out at low temperatures and is compatible with an ample variety of substrates (polymers, metal, ceramics; either planar or in the form of meshes) yielding flexible and low solid-fraction three-dimensional nanostructures. The systematic investigation of this progressively complex organic nanomaterial delivers key clues relating their wetting, nonwetting, and anti-icing properties with their specific morphology and outer surface composition. Water contact angles higher than 150° are attainable as a function of the nanofabric shell thickness with outstanding freezing-delay times (FDT) longer than 2 h at -5 °C. The role of the extremely low roughness of the shell surface is settled as a critical feature for such an achievement. In addition, the characteristic interconnected microstructure of the nanofabrics is demonstrated as ideal for the fabrication of slippery liquid-infused porous surfaces (SLIPS). We present the straightforward deposition of the nanofabric on laser patterns and the knowledge of how this approach provides SLIPS with FDTs longer than 5 h at -5 °C and 1 h at -15 °C.
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One-dimensional (1D) nanostructured surfaces based on high-density arrays of nanowires and nanotubes of photoactive titanium dioxide (TiO2) present a tunable wetting behavior from superhydrophobic to superhydrophilic states. These situations are depicted in a reversible way by simply irradiating with ultraviolet light (superhydrophobic to superhydrophilic) and storage in dark. In this article, we combine in situ environmental scanning electron microscopy (ESEM) and near ambient pressure photoemission analysis (NAPP) to understand this transition. These experiments reveal complementary information at microscopic and atomic level reflecting the surface wettability and chemical state modifications experienced by these 1D surfaces upon irradiation. We pay special attention to the role of the water condensation mechanisms and try to elucidate the relationship between apparent water contact angles of sessile drops under ambient conditions at the macroscale with the formation of droplets by water condensation at low temperature and increasing humidity on the nanotubes' surfaces. Thus, for the as-grown nanotubes, we reveal a metastable and superhydrophobic Cassie state for sessile drops that tunes toward water dropwise condensation at the microscale compatible with a partial hydrophobic Wenzel state. For the UV-irradiated surfaces, a filmwise wetting behavior is observed for both condensed water and sessile droplets. NAPP analyses show a hydroxyl accumulation on the as-grown nanotubes surfaces during the exposure to water condensation conditions, whereas the water filmwise condensation on a previously hydroxyl enriched surface is proved for the superhydrophilic counterpart.
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The ability to control the porosity of thin oxide films is a key factor determining their properties. Despite the abundance of dry processes for synthesizing oxide porous layers, a high porosity range is typically achieved by spin-coating-based wet chemical methods. Besides, special techniques such as supercritical drying are required to replace the pore liquid with air while maintaining the porous network. In this study, we propose a new method for the fabrication of ultraporous titanium dioxide thin films at room or mild temperatures (T ≤ 120 °C) by a sequential process involving plasma deposition and etching. These films are conformal to the substrate topography even for high-aspect-ratio substrates and show percolated porosity values above 85% that are comparable to those of advanced aerogels. The films deposited at room temperature are amorphous. However, they become partly crystalline at slightly higher temperatures, presenting a distribution of anatase clusters embedded in the sponge-like open porous structure. Surprisingly, the porous structure remains after annealing the films at 450 °C in air, which increases the fraction of embedded anatase nanocrystals. The films are antireflective, omniphobic, and photoactive, becoming superhydrophilic when subjected to ultraviolet light irradiation. The supported, percolated, and nanoporous structure can be used as an electron-conducting electrode in perovskite solar cells. The properties of the cells depend on the aerogel-like film thickness, which reaches efficiencies close to those of commercial mesoporous anatase electrodes. This generic solvent-free synthesis is scalable and applicable to ultrahigh porous conformal oxides of different compositions, with potential applications in photonics, optoelectronics, energy storage, and controlled wetting.
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Numerous works have demonstrated that cold plasma treatments constitute an effective procedure to accelerate seed germination under nonstress conditions. Evidence also exists about a positive effect of plasmas for germination under environmental stress conditions. For barley seeds, this work studies the influence of cold plasma treatments on the germination rate and initial stages of plant growth in common stress environments, such as drought, salinity, and low-temperature conditions. As a general result, it has been found that the germination rate was higher for plasma-treated than for untreated seeds. Plasma also induced favorable changes in plant and radicle dimensions, which depended on the environment. The obtained results demonstrate that plasma affects the biochemical metabolic chains of seeds and plants, resulting in changes in the concentration of biochemical growing factors, a faster germination, and an initially more robust plant growth, even under stress conditions. These changes in phenotype are accompanied by differences in the concentration of biomarkers such as photosynthetic pigments (chlorophylls a and b and carotenoids), reactive oxygen species, and, particularly, the amino acid proline in the leaves of young plants, with changes that depend on environmental conditions and the application of a plasma treatment. This supports the idea that, rather than an increase in seed water imbibition capacity, there are clear beneficial effects on seedling of plasma treatments.
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Bone resorption and inadequate osseointegration are considered the main problems of titanium implants. In this investigation, the texture and surface roughness of porous titanium samples obtained by the space holder technique were modified with a femtosecond Yb-doped fiber laser. Different percentages of porosity (30, 40, 50, and 60 vol.%) and particle range size (100-200 and 355-500 µm) were compared with fully-dense samples obtained by conventional powder metallurgy. After femtosecond laser treatment the formation of a rough surface with micro-columns and micro-holes occurred for all the studied substrates. The surface was covered by ripples over the micro-metric structures. This work evaluates both the influence of the macro-pores inherent to the spacer particles, as well as the micro-columns and the texture generated with the laser, on the wettability of the surface, the cell behavior (adhesion and proliferation of osteoblasts), micro-hardness (instrumented micro-indentation test, P-h curves) and scratch resistance. The titanium sample with 30 vol.% and a pore range size of 100-200 µm was the best candidate for the replacement of small damaged cortical bone tissues, based on its better biomechanical (stiffness and yield strength) and biofunctional balance (bone in-growth and in vitro osseointegration).
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Polarizers are ubiquitous components in current optoelectronic devices as displays or photographic cameras. Yet, control over light polarization is an unsolved challenge, since the main drawback of the existing display technologies is the significant optical losses. In such a context, organometal halide perovskites (OMHP) can play a decisive role given their flexible synthesis with tunable optical properties such as bandgap and photoluminescence, and excellent light emission with a low non-radiative recombination rate. Therefore, along with their outstanding electrical properties have elevated hybrid perovskites as the material of choice in photovoltaics and optoelectronics. Among the different OMHP nanostructures, nanowires and nanorods have lately arisen as key players in the control of light polarization for lighting or detector applications. Herein, the fabrication of highly aligned and anisotropic methylammonium lead iodide perovskite nanowalls by glancing-angle deposition, which is compatible with most substrates, is presented. Their high alignment degree provides the samples with anisotropic optical properties such as light absorption and photoluminescence. Furthermore, their implementation in photovoltaic devices provides them with a polarization-sensitive response. This facile vacuum-based approach embodies a milestone in the development of last-generation polarization-sensitive perovskite-based optoelectronic devices such as lighting appliances or self-powered photodetectors.
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Switchable mechanically induced changes in the wetting behavior of surfaces are of paramount importance for advanced microfluidic, self-cleaning and biomedical applications. In this work we show that the well-known polydimethylsiloxane (PDMS) elastomer develops self-patterning when it is coated with nanostructured TiO2 films prepared by physical vapor deposition at glancing angles and subsequently subjected to a mechanical deformation. Thus, unlike the disordered wrinkled surfaces typically created by deformation of the bare elastomer, well-ordered and aligned micro-scaled grooves form on TiO2/PDMS after the first post-deposition bending or stretching event. These regularly patterned surfaces can be reversibly modified by mechanical deformation, thereby inducing a switchable and reversible wetting petal effect and the sliding of liquid droplets. When performed in a dynamic way, this mechanical actuation produces a unique capacity of liquid droplets (water and diiodomethane) transport and tweezing, this latter through their selective capture and release depending on their volume and chemical characteristics. Scanning electron and atomic force microscopy studies of the strained samples showed that a dual-scale roughness, a parallel alignment of patterned grooves and their reversible widening upon deformation, are critical factors controlling this singular sliding behavior and the possibility to tailor their response by the appropriate manufacturing of surface structures.
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In this work, we have developed a new kind of nanocolumnar birefringent Bragg microcavity (BBM) that, tailored by oblique angle deposition, behaves as a selective transducer of volatile organic compounds (VOCs). Unlike the atomic lattice origin of birefringence in anisotropic single crystals, in the BBM, it stems from an anisotropic self-organization at the nanoscale of the voids and structural elements of the layers. The optical adsorption isotherms recorded upon exposure of these nanostructured systems to water vapor and VOCs have revealed a rich yet unexplored phenomenology linked to their optical activity that provides both capacity for vapor identification and partial pressure determination. This photonic response has been reproduced with a theoretical model accounting for the evolution of the form birefringence of the individual layers upon vapor condensation in nanopores and internanocolumnar voids. BBMs that repel water vapor but are accessible to VOCs have been also developed through grafting of their internal surfaces with perfluorooctyltriethoxysilane molecules. These nanostructured photonic systems are proposed for the development of transducers that, operating under environmental conditions, may respond specifically to VOCs without any influence by the degree of humidity of the medium.
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AIM: Titanium implants are commonly used as replacement therapy for lost teeth and much current research is focusing on the improvement of the chemical and physical properties of their surfaces in order to improve the osseointegration process. TiO2, when it is deposited in the form of pillar array nanometric structures, has photocatalytic properties and wet surface control, which, together with UV irradiation, provide it with superhydrophilic surfaces, which may be of interest for improving cell adhesion on the peri-implant surface. In this article, we address the influence of this type of surface treatment on type IV and type V titanium discs on their surface energy and cell growth on them. MATERIALS AND METHODS: Samples from titanium rods used for making dental implants were used. There were two types of samples: grade IV and grade V. In turn, within each grade, two types of samples were differentiated: untreated and treated with sand blasting and subjected to double acid etching. Synthesis of the film consisting of titanium oxide pillar array structures was carried out using plasma-enhanced chemical vapor deposition equipment. The plasma was generated in a quartz vessel by an external SLAN-1 microwave source with a frequency of 2.45 GHz. Five specimens from each group were used (40 discs in total). On the surfaces to be studied, the following determinations were carried out: (a) X-ray photoelectron spectroscopy, (b) scanning electron microscopy, (c) energy dispersive X-ray spectroscopy, (d) profilometry, (e) contact angle measurement or surface wettability, (f) progression of contact angle on applying ultraviolet irradiation, and (g) a biocompatibility test and cytotoxicity with cell cultures. RESULTS: The application of ultraviolet light decreased the hydrophobicity of all the surfaces studied, although it did so to a greater extent on the surfaces with the studied modification applied, this being more evident in samples manufactured in grade V titanium. In samples made in grade IV titanium, this difference was less evident, and even in the sample manufactured with grade IV and SLA treatment, the application of the nanometric modification of the surface made the surface optically less active. Regarding cell growth, all the surfaces studied, grouped in relation to the presence or not of the nanometric treatment, showed similar growth. CONCLUSIONS: Treatment of titanium oxide surfaces with ultraviolet irradiation made them change temporarily into superhydrophilic ones, which confirms that their biocompatibility could be improved in this way, or at least be maintained.
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Plasma treatments had emerged as a useful technique to improve seed germination. In this work we investigate the influence of different irrigation conditions and plasma treatments on the germination of nasturtium seeds. During plasma treatment, seeds experience a progressive weight loss as a function of treatment time that has been associated to water release, a process that is more pronounced after longer plasma treatment times. Seeds treated for short times (<30 s) are able to germinate more efficiently than untreated specimen under hydric stress (drought conditions), while plasma treatments for longer times (up to 300 s) impaired germination independently on irrigation conditions. Characterization analysis of plasma treated seeds by FTIR-ATR, SEM/EDX and XPS showed that plasma treatment affected the chemical state of pericarp while, simultaneously, induced a considerable increase in the seeds water uptake capacity. The decrease in germination efficiency found after plasma treatment for long times, or for short times under optimum irrigation conditions, has been attributed to that the excess of water accumulated in the pericarp hampers the diffusion up to the embryo of other agents like oxygen which are deemed essential for germination.
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Irrigação Agrícola , Germinação , Nasturtium/crescimento & desenvolvimento , Gases em Plasma/farmacologia , Sementes/crescimento & desenvolvimento , Temperatura , Nasturtium/efeitos dos fármacos , Sementes/efeitos dos fármacos , ÁguaRESUMO
(1) Background: The use of physical barriers to prevent the invasion of gingival and connective tissue cells into bone cavities during the healing process is called guided bone regeneration. The objective of this in-vitro study was to compare the growth of human osteoblasts on Poly(Lacticâ»coâ»Glycolic) (PLGA) membranes modified with oxygen plasma and Hydroxyapatite (HA), silicon dioxide (SiO2), and titanium dioxide (TiO2) composite nanoparticles, respectively. (2) Methods: All the membranes received a common treatment with oxygen plasma and were subsequently treated with HA nanostructured coatings (n = 10), SiO2 (n = 10) and TiO2 (n = 10), respectively and a PLGA control membrane (n = 10). The assays were performed using the human osteoblast line MG-63 acquired from the Center for Scientific Instrumentation (CIC) from the University of Granada. The cell adhesion and the viability of the osteoblasts were analyzed by means of light-field microphotographs of each condition with the inverted microscope Axio Observer A1 (Carl Zeiss). For the determination of the mitochondrial energy balance, the MitoProbe™ JC-1 Assay Kit was employed. For the determination of cell growth and the morphology of adherent osteoblasts, two techniques were employed: staining with phalloidin-TRITC and staining with DAPI. (3) Results: The modified membranes that show osteoblasts with a morphology more similar to the control osteoblasts follow the order: PLGA/PO2/HA > PLGA/PO2/SiO2 > PLGA/PO2/TiO2 > PLGA (p < 0.05). When analysing the cell viability, a higher percentage of viable cells bound to the membranes was observed as follows: PLGA/PO2/SiO2 > PLGA/PO2/HA > PLGA/PO2/TiO2 > PLGA (p < 0.05), with a better energy balance of the cells adhered to the membranes PLGA/PO2/HA and PLGA/PO2/SiO2. (4) Conclusion: The membrane in which osteoblasts show characteristics more similar to the control osteoblasts is the PLGA/PO2/HA, followed by the PLGA/PO2/SiO2.
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The novelty of this study is the addition of an ultrathin layer of nanostructured hydroxyapatite (HA) on oxygen plasma modified poly(lacticâ»coâ»glycolic) (PLGA) membranes (PO2) in order to evaluate the efficiency of this novel material in bone regeneration. METHODS: Two groups of regenerative membranes were prepared: PLGA (control) and PLGA/PO2/HA (experimental). These membranes were subjected to cell cultures and then used to cover bone defects prepared on the skulls of eight experimental rabbits. RESULTS: Cell morphology and adhesion of the osteoblasts to the membranes showed that the osteoblasts bound to PLGA were smaller and with a lower number of adhered cells than the osteoblasts bound to the PLGA/PO2/HA membrane (p < 0.05). The PLGA/PO2/HA membrane had a higher percentage of viable cells bound than the control membrane (p < 0.05). Both micro-CT and histological evaluation confirmed that PLGA/PO2/HA membranes enhance bone regeneration. A statistically significant difference in the percentage of osteoid area in relation to the total area between both groups was found. CONCLUSIONS: The incorporation of nanometric layers of nanostructured HA into PLGA membranes modified with PO2 might be considered for the regeneration of bone defects. PLGA/PO2/HA membranes promote higher osteosynthetic activity, new bone formation, and mineralisation than the PLGA control group.
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ITO thin films have been prepared by electron beam evaporation at oblique angles (OA), directly and while assisting their growth with a downstream plasma. The films microstructure, characterized by scanning electron microscopy, atomic force microscopy, and glancing incidence small-angle X-ray scattering, consisted of tilted and separated nanostructures. In the plasma assisted films, the tilting angle decreased and the nanocolumns became associated in the form of bundles along the direction perpendicular to the flux of evaporated material. The annealed films presented different in-depth and sheet resistivity as confirmed by scanning conductivity measurements taken for the individual nanocolumns. In addition, for the plasma-assisted thin films, two different sheet resistance values were determined by measuring along the nanocolumn bundles or the perpendicular to it. This in-plane anisotropy induces the electrochemical deposition of elongated gold nanostructures. The obtained Au-ITO composite thin films were characterized by anisotropic plasmon resonance absorption and a dichroic behavior when examined with linearly polarized light.
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Surface properties play an important role in the functioning of a biomaterial in the biological environment. This work describes the influence of the changes that occurred on diamond-like carbon (DLC) and polymeric substrata by different nitrogen and ammonia plasmas treatments and its effects on the cell proliferation on these materials. All substrata were additionally subjected to the effect of neutral beams of nitrogen atoms and NH species for comparison purposes. Results about the proliferation, viability, and morphology of fibroblasts were correlated with surface chemical composition, surface tension, and topography. It was found that the presence of amine groups on the surface and the surface tension are beneficial factors for the cell growth. Surface roughness in DLC also plays a positive role in favoring cell adhesion and proliferation, but it can be detrimental for some of the treated polymers because of the accumulation of low molecular weight fragments formed as a result of the plasma treatments. Analysis of the overall results for each type of material allowed to define a unique parameter called 'factor of merit' accounting for the influence of the different surface characteristics on the cell deployment, which can be used to predict qualitatively the efficiency for cell growth.
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Materiais Revestidos Biocompatíveis/química , Fibroblastos/citologia , Carbono/química , Adesão Celular , Proliferação de Células , Células Cultivadas , Materiais Revestidos Biocompatíveis/toxicidade , Diamante/química , Humanos , Teste de Materiais , Polietileno/química , Polietilenotereftalatos/química , Polímeros/química , Propriedades de SuperfícieRESUMO
Polyethylene terephthalate (PET) plates have been exposed to different nitrogen containing plasmas with the purpose of incorporating nitrogen functional groups on its surface. Results with a dielectric barrier discharge (DBD) at atmospheric pressure and a microwave discharge (MW) at reduced pressure and those using an atom source working under ultrahigh vacuum conditions have been compared for N(2) and mixtures Ar + NH(3) as plasma gases. The functional groups have been monitored by X-ray Photoemission Spectroscopy (XPS). Nondestructive oxygen and carbon depth profiles for the plasma treated and one month aged samples have been determined by means of the nondestructive Tougaard's method of XPS background analysis. The surface topography of the treated samples has been examined by Atomic Force Microscopy (AFM), while the surface tension has been determined by measuring the static contact angles of water and iodomethane. It has been found that the DBD with a mixture of Ar+NH(3) is the most efficient treatment for nitrogen and amine group functionalization as determined by derivatization by reaction with chlorobenzaldehyde. It is also realized that the nitrogen functional groups do not contribute significantly to the observed increase in surface tension of plasma treated PET.