Establishment of a method to expose and measure pollution in excised porcine skin with electron paramagnetic resonance spectroscopy.

Health problems associated with the amount of air pollutants are increasing worldwide. Pollution damages not only the lungs; it also has an impact on skin health and is co-responsible for the development of skin diseases. Anti-pollution products are on the rise in the cosmetic market but so far, there is no established method to directly assess the impact of pollution on the skin and to test the efficacy of anti-pollution products. To address this problem, two different chambers were developed for the reproducible exposure to realistic air pollutant concentrations. One chamber for the exclusive use of excised skin and hair samples, the second chamber for ex vivo and in vivo measurements. Measurements of nicotine next to the investigated skin area allow conclusions to be drawn on the particle concentration to which the skin is exposed. Electron paramagnetic resonance spectroscopy, which enables the detection of free radicals in different systems, was applied to assess the hazard potential of pollution in the skin. A direct proof of the formation of free radicals in the skin by the model pollutant cigarette smoke could be demonstrated. An additional application of UV irradiation even increased the formation of free radicals in the skin seven-fold (sum parameter). Depending on the question of interest, the use of different spin probes allows various assessments of the radical formation in skin: the amount of radicals but also the antioxidant status of the microenvironment can be estimated. Using two exposure chambers, the direct formation of oxidative stress by cigarette smoke on ex vivo skin, with and without additional UV exposure, could be reproducibly examined. This measurement method is promising for the assessment of anti-pollution products and could allow a direct causal connection between pollutant, effect on the skin and the protective function of skin care products.

Multidirectional activity of bakuchiol against cellular mechanisms of facial ageing - Experimental evidence for a holistic treatment approach.

OBJECTIVE: Skin ageing is a multifactorial process involving formation of reactive oxygen species, consecutive inflammation with reduced epidermal and dermal cell viability and resulting damage to the extracellular matrix. Effective dermocosmetic treatment modalities should ideally address these hallmarks in a holistic approach. Here, we determined the corresponding activity profile of bakuchiol, a plant-derived meroterpene, in an array of in vitro, ex vivo and in vivo studies and compared it to retinol, currently considered as gold standard in topical antiageing cosmetics. METHODS: The antioxidative capacity and power of bakuchiol and retinol were analysed by measuring 2,2'-diphenyl-1-picrylhydrazyl (DPPH) reduction via its absorption decay and electron spin resonance spectroscopy, respectively. Effects on prostaglandin E2 (PGE2), macrophage migration inhibitory factor (MIF), fibroblast growth factor 7 (FGF7), collagen type I and VII (COL1A1, COL7A1), fibronectin (FN) levels as well as the metabolization of water-soluble tetrazolium 1 (WST-1) were determined in human dermal fibroblasts. Epidermal regeneration was assessed utilizing an in vitro wound healing model. FN protein levels were analysed ex vivo after treatment with a formulation containing bakuchiol, retinol or vehicle using suction blister fluid. Skin condition improvement was determined in vivo in a split-face comparison study after application of bakuchiol or vehicle. RESULTS: In contrast to retinol, bakuchiol demonstrated high antioxidative efficacy. Levels of PGE2 and MIF were significantly decreased by both bakuchiol and retinol. Bakuchiol but not retinol significantly increased FGF7 protein levels. WST-1 metabolization levels were significantly augmented by bakuchiol and retinol. Bakuchiol and retinol application led to a significant augmentation of COL1A1, COL7A1 and FN protein levels. Wounds supplemented with bakuchiol but not retinol displayed a significant increase in epidermis regeneration. Clinically, areas treated with a bakuchiol-containing formulation showed a statistically significant increase in FN protein values after a 4-week application compared to untreated areas and areas treated with vehicle. CONCLUSION: These data provide evidence for the multidirectional efficacy of bakuchiol against cellular hallmarks of skin ageing. Its activity profile shares some common features with retinol but demonstrates several hitherto unknown biopositive effects in our studies, namely stimulation of the critical extracellular matrix component FN, and accelerated epidermal regeneration and wound healing.

OBJECTIF: le vieillissement de la peau est un processus multifactoriel impliquant la formation de dérivés réactifs de l'oxygène, une inflammation consécutive qui entraîne une viabilité réduite des cellules du derme et de l'épiderme, et endommage la matrice extracellulaire. Pour être efficaces, les traitements dermocosmétiques devraient dans l'idéal traiter ces caractéristiques selon une approche holistique. Ici, nous avons déterminé le profil d'activité correspondant du bakuchiol, un méroterpène d'origine végétale, dans une série d'études in vitro, ex vivo et in vivo, et l'avons comparé au rétinol, qui est aujourd'hui considéré comme la référence parmi les cosmétiques anti-âge topiques. MÉTHODES: la capacité antioxydante et la puissance du bakuchiol et du rétinol ont été analysées en mesurant la réduction du 2,2-diphényl-1-picrylhydrazyl (DPPH) selon sa décroissance par absorption et à l'aide d'une spectroscopie par résonance magnétique électronique, respectivement. Les effets sur la prostaglandine E2 (PGE2), le facteur inhibiteur de la migration (FIM) des macrophages, le facteur de croissance des fibroblastes 7 (FGF7), le collagène de type I et VII (COL1A1, COL7A1), les taux de fibronectine (FN), ainsi que la métabolisation du tétrazolium 1 soluble dans l'eau (WST-1) ont été déterminés dans des fibroblastes dermiques humains. La régénération épidermique a été évaluée à l'aide d'un modèle de cicatrisation des plaies in vitro. Les taux de fibronectine ont été analysés ex vivo après un traitement avec une formulation contenant du bakuchiol, du rétinol ou un excipient à l'aide d'un liquide d'aspiration sous forme de vésicules. L'amélioration de l'état de la peau a été déterminée in vivo dans une étude de comparaison en hémiface après l'application de bakuchiol ou d'un excipient. RÉSULTATS: Contrairement au rétinol, le bakuchiol s'est avéré présenter une efficacité antioxydante élevée. Les taux de PGE2 et de FIM ont significativement diminué avec le bakuchiol et le rétinol. L'application de bakuchiol s'est accompagnée d'une augmentation significative des taux de protéine FGF7, mais pas celle de rétinol. Les taux de métabolisation du WST-1 ont augmenté de façon significative avec le bakuchiol et le rétinol. L'application de bakuchiol et de rétinol a entraîné une augmentation significative des taux de protéines COL1A1, COL7A1 et fibronectine. Les plaies supplémentées en bakuchiol, mais pas en rétinol, ont montré une augmentation significative de la régénération épidermique. Sur le plan clinique, les zones traitées avec une formulation contenant du bakuchiol ont montré une augmentation statistiquement significative des taux de fibronectine après une application de 4 semaines par rapport aux zones non traitées et aux zones traitées avec un excipient. CONCLUSION: ces données fournissent des preuves de l'efficacité multidirectionnelle du bakuchiol contre les caractéristiques cellulaires du vieillissement de la peau. Son profil d'activité partage certaines caractéristiques communes avec le rétinol, mais démontre plusieurs effets biopositifs jusqu'alors inconnus dans nos études : la stimulation de la fibronectine, composante essentielle de la matrice extracellulaire, et une régénération épidermique et une cicatrisation accélérée des plaies.

Stress and Microstructure Evolution in Mo Thin Films without or with Cover Layers during Thermal-Cycling.

The intrinsic stress behavior and microstructure evolution of Molybdenum thin films were investigated to evaluate their applicability as a metallization in high temperature microelectronic devices. For this purpose, 100 nm thick Mo films were sputter-deposited without or with an AlN or SiO2 cover layer on thermally oxidized Si substrates. The samples were subjected to thermal cycling up to 900 °C in ultrahigh vacuum; meanwhile, the in-situ stress behavior was monitored by a laser based Multi-beam Optical Sensor (MOS) system. After preannealing at 900 °C for 24 h, the uncovered films showed a high residual stress at room temperature and a plastic behavior at high temperatures, while the covered Mo films showed an almost entirely elastic deformation during the thermal cycling between room temperature and 900 °C with hardly any plastic deformation, and a constant stress value during isothermal annealing without a notable creep. Furthermore, after thermal cycling, the Mo films without as well as with a cover layer showed low electrical resistivity (≤10 µΩ·cm).

Phase Formation and High-Temperature Stability of Very Thin Co-Sputtered Ti-Al and Multilayered Ti/Al Films on Thermally Oxidized Si Substrates.

Ti-Al thin films with a thickness of 200 nm were prepared either by co-sputtering from elemental Ti and Al targets or as Ti/Al multilayers with 10 and 20 nm individual layer thickness on thermally oxidized Si substrates. Some of the films were covered with a 20-nm-thick SiO 2 layer, which was used as an oxidation protection against the ambient atmosphere. The films were annealed at up to 800 ∘ C in high vacuum for 10 h, and the phase formation as well as the film architecture was analyzed by X-ray diffraction, cross section, and transmission electron microscopy, as well as Auger electron and X-ray photoelectron spectroscopy. The results reveal that the co-sputtered films remained amorphous after annealing at 600 ∘ C independent on the presence of the SiO 2 cover layer. In contrast to this, the γ -TiAl phase was formed in the multilayer films at this temperature. After annealing at 800 ∘ C, all films were degraded completely despite the presence of the cover layer. In addition, a strong chemical reaction between the Ti and SiO 2 of the cover layer and the substrate took place, resulting in the formation of Ti silicide. In the multilayer samples, this reaction already started at 600 ∘ C.

High Temperature Behavior of RuAl Thin Films on Piezoelectric CTGS and LGS Substrates.

This paper reports on a significant further improvement of the high temperature stability of RuAl thin films (110 nm) on the piezoelectric Ca 3 TaGa 3 Si 2 O 14 (CTGS) and La 3 Ga 5 SiO 14 (LGS) substrates. RuAl thin films with AlN or SiO 2 cover layers and barriers to the substrate (each 20 nm), as well as a combination of both were prepared on thermally oxidized Si substrates, which serve as a reference for fundamental studies, and the piezoelectric CTGS, as well as LGS substrates. In some films, additional Al layers were added. To study their high temperature stability, the samples were annealed in air and in high vacuum up to 900 °C, and subsequently their cross-sections, phase formation, film chemistry, and electrical resistivity were analyzed. It was shown that on thermally oxidized Si substrates, all films were stable after annealing in air up to 800 °C and in high vacuum up to 900 °C. The high temperature stability of RuAl thin films on CTGS substrates was improved up to 900 °C in high vacuum by the application of a combined AlN/SiO 2 barrier layer and up to 800 °C in air using a SiO 2 barrier. On LGS, the films were only stable up to 600 °C in air; however, a single SiO 2 barrier layer was sufficient to prevent oxidation during annealing at 900 °C in high vacuum.

An extraordinary chiral exchange-bias phenomenon: engineering the sign of the bias field in orthogonal bilayers by a magnetically switchable response mechanism.

Isothermal tuning of both the magnitude and the sign of the bias field has been achieved by exploiting a new phenomenon in a system consisting of two orthogonally coupled films: SmCo5 (out-of-plane anisotropy)-CoFeB (in-plane anisotropy). This has been achieved by using the large dipolar magnetic field of the SmCo5 layer resulting in the pinning of one of the branches of the hysteresis loop (either the ascending or the descending branch) at a fixed field value while the second one is modulated along the field axis by varying the orientation of an externally applied magnetic field. This means the possibility of controlling the sign of the bias field in a manner not reported to date. Moreover, modulation of the bias field strength is possible by varying the thickness of a spacer between the SmCo5 and CoFeB layers. This study shows that the observed phenomena find their origin in the competition between the artificially induced anisotropies in both layers, resulting in a reversible chiral bias effect that allows the selection of the initial sign of the bias field by switching (upwards/downwards) the magnetization in the SmCo5 film.

Mo-La2O3 Multilayer Metallization Systems for High Temperature Surface Acoustic Wave Sensor Devices.

Developing advanced thin film materials is the key challenge in high-temperature applications of surface acoustic wave sensor devices. One hundred nanometer thick (Mo-La 2 O 3 ) multilayer systems were fabricated at room temperature on thermally oxidized (100) Si substrates (SiO 2 /Si) to study the effect of lanthanum oxide on the electrical resistivity of molybdenum thin films and their high-temperature stability. The multilayer systems were deposited by the magnetron sputter deposition of extremely thin (≤1 nm) La interlayers in between adjacent Mo layers. After deposition of each La layer the process was interrupted for 25 to 60 min to oxidize the La using the residual oxygen in the high vacuum of the deposition chamber. The samples were annealed at 800 ∘ C in high vacuum for up to 120 h. In case of a 1 nm thick La interlayer in-between the Mo a continuous layer of La 2 O 3 is formed. For thinner La layers an interlayer between adjacent Mo layers is observed consisting of a (La 2 O 3 -Mo) mixed structure of molybdenum and nm-sized lanthanum oxide particles. Measurements show that the (Mo-La 2 O 3 ) multilayer systems on SiO 2 /Si substrates are stable at least up to 800 ∘ C for 120 h in high vacuum conditions.

Electroless-Deposited Platinum Antennas for Wireless Surface Acoustic Wave Sensors.

In an effort to develop a cost-efficient technology for wireless high-temperature surface acoustic wave sensors, this study presents an evaluation of a combined method that integrates physical vapor deposition with electroless deposition for the fabrication of platinum-based planar antennas. The proposed manufacturing process becomes attractive for narrow, thick, and sparse metallizations for antennas in the MHz to GHz frequency range. In detail, narrow platinum-based lines of a width down to 40 µm were electroless-deposited on γ-Al 2O 3 substrates using different seed layers. At first, the electrolyte chemistry was optimized to obtain the highest deposition rate. Films with various thickness were prepared and the electrical resistivity, microstructure, and chemical composition in the as-prepared state and after annealing at temperatures up to 1100 ∘C were evaluated. Using these material parameters, the antenna was simulated with an electromagnetic full-wave simulation tool and then fabricated. The electrical parameters, including the S-parameters of the antenna, were measured. The agreement between the simulated and the realized antenna is then discussed.

Evaluation of Surface Cleaning Procedures for CTGS Substrates for SAW Technology with XPS.

A highly efficient and reproducible cleaning procedure of piezoelectric substrates is essential in surface acoustic waves (SAW) technology to fabricate high-quality SAW devices, especially for new applications such SAW sensors wherein new materials for piezoelectric substrates and interdigital transducers are used. Therefore, the development and critical evaluation of cleaning procedures for each material system that is under consideration becomes crucial. Contaminants like particles or the presence of organic/inorganic material on the substrate can dramatically influence and alter the properties of the thin film substrate composite, such as wettability, film adhesion, film texture, and so on. In this article, focus is given to different cleaning processes like SC-1 and SC-2, UV-ozone treatment, as well as cleaning by first-contact polymer Opticlean, which are applied for removal of contaminants from the piezoelectric substrate Ca 3 TaGa 3 Si 2 O 14 . By means of X-ray photoelectron spectroscopy, the presence of the most critical contaminants such as carbon, sodium, and iron removed through different cleaning procedures were studied and significant differences were observed between the outcomes of these procedures. Based on these results, a two-step cleaning process, combining SC-1 at a reduced temperature at 30 ∘ C instead of 80 ∘ C and a subsequent UV-ozone cleaning directly prior to deposition of the metallization, is suggested to achieve the lowest residual contamination level.

Capability Study of Ti, Cr, W, Ta and Pt as Seed Layers for Electrodeposited Platinum Films on γ-Al2O3 for High Temperature and Harsh Environment Applications.

High temperature surface acoustic wave sensors based on radio frequency identification technology require adequate antennas of high efficiency and thermal stability for the signal transmission. Platinum is well known and frequently used as a material of choice for high temperature and harsh environment applications because of the high melting point and its chemical stability. Therefore, one way to realize high temperature stable antennas is the combination of a Pt metallization on an Al 2 O 3 substrate. As a cost-effective technique, the Pt film is deposited via electrochemical deposition. For this growth procedure, a pre-deposited metallization on the Al 2 O 3 layer is required. This paper analyzes the influence of various seed layers (Ta, Ti, W, Cr, Pt) on the morphology, stability and electrical properties of the electrochemically-grown Pt thick film after heat treatments up to 1000 ∘ C in air. We find an oxidation of all adhesion layers except for Pt, for which the best electrical properties were measured. Although significant areas of the films delaminate from the substrate, individual anchor structures retain a stable connection between the Pt layer and the rough Al 2 O 3 substrate.

The Influence of the Composition of Ru100-xAlx (x = 50, 55, 60, 67) Thin Films on Their Thermal Stability.

RuAl thin films possess a high potential as a high temperature stable metallization for surface acoustic wave devices. During the annealing process of the Ru-Al films, Al 2 O 3 is formed at the surface of the films even under high vacuum conditions, so that the composition of a deposited Ru 50 Al 50 film is shifted to a Ru-rich alloy. To compensate for this effect, the Al content is systematically increased during the deposition of the Ru-Al films. Three Al-rich alloys-Ru 45 Al 55 , Ru 40 Al 60 and Ru 33 Al 67 -were analyzed concerning their behavior after high temperature treatment under high vacuum and air conditions in comparison to the initial Ru 50 Al 50 sample. Although the films' cross sections show a more homogeneous structure in the case of the Al-rich films, the RuAl phase formation is reduced with increasing Al content.

Tungsten as a Chemically-Stable Electrode Material on Ga-Containing Piezoelectric Substrates Langasite and Catangasite for High-Temperature SAW Devices.

Thin films of tungsten on piezoelectric substrates La3Ga5SiO14 (LGS) and Ca3TaGa3Si2O14 (CTGS) have been investigated as a potential new electrode material for interdigital transducers for surface acoustic wave-based sensor devices operating at high temperatures up to 800 °C under vacuum conditions. Although LGS is considered to be suitable for high-temperature applications, it undergoes chemical and structural transformation upon vacuum annealing due to diffusion of gallium and oxygen. This can alter the device properties depending on the electrode nature, the annealing temperature, and the duration of the application. Our studies present evidence for the chemical stability of W on these substrates against the diffusion of Ga/O from the substrate into the film, even upon annealing up to 800 °C under vacuum conditions using Auger electron spectroscopy and energy-dispersive X-ray spectroscopy, along with local studies using transmission electron microscopy. Additionally, the use of CTGS as a more stable substrate for such applications is indicated.

Surface Effects and Challenges for Application of Piezoelectric Langasite Substrates in Surface Acoustic Wave Devices Caused by High Temperature Annealing under High Vacuum.

Substrate materials that are high-temperature stable are essential for sensor devices which are applied at high temperatures. Although langasite is suggested as such a material, severe O and Ga diffusion into an O-affine deposited film was observed during annealing at high temperatures under vacuum conditions, leading to a damage of the metallization as well as a change of the properties of the substrate and finally to a failure of the device. Therefore, annealing of bare LGS (La 3 Ga 5 SiO 14 ) substrates at 800 ∘ C under high vacuum conditions is performed to analyze whether this pretreatment improves the suitability and stability of this material for high temperature applications in vacuum. To reveal the influence of the pretreatment on the subsequently deposited metallization, RuAl thin films are used as they are known to oxidize on LGS at high temperatures. A local study of the pretreated and metallized substrates using transmission electron microscopy reveals strong modification of the substrate surface. Micro cracks are visible. The composition of the substrate is strongly altered at those regions. Severe challenges for the application of LGS substrates under high-temperature vacuum conditions arise from these substrate damages, revealing that the pretreatment does not improve the applicability.