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In spite of its superior chemical sensitivity, XPS depth profiling is rarely used because of the alteration introduced by the sputter removal process and the resulting inhomogeneous in-depth concentration distribution. Moreover, the application of XPS becomes increasingly challenging in the case of the analysis of thin layers, if the thickness is in the range of 2-3 inelastic mean free paths (IMFP) of the photoelectrons. In this paper we will show that even in these unfavorable cases the XPS depth profiling is applicable. Herein the XPS depth profiling of a model system tungsten-carbide-rich nano-layer of high hardness and corrosion resistance is presented. We will show that the problems arising because of the relatively high IMFP can be corrected by introducing a layer model for the calculation of the observed XPS intensities, while the alteration, e.g. ion mixing, compound formation and similar artefact, introduced by the sputter removal process can be handled by TRIDYN simulation. The method presented here overcomes the limitation of XPS depth profiling.
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Thin (ca. 340 nm) chitosan coatings were deposited onto glass substrates via dip-coating, then modified with the methanol solution of decanoic anhydride (0.17-56 mM). NMR, FTIR and XPS measurements confirmed that the acylation degree increased from 18 % to 45 %, and at the highest degree, the whole layer was acylated homogeneously by the reagent molecules. The coating thickness increased (up to 60 %), and the refractive index decreased (from 1.541 to 1.532) due to the acylation, that was determined by UV-visible spectroscopy. The AFM did not reveal morphological changes, but wetting tests showed that the acylation rendered the coating hydrophobic (water contact angle increased from ca. 75° to 100°). The contact angle, however, decreased to 85° due to the development of a second molecular layer of the decanoic acid by-product at the highest (over 25 mM) reagent concentrations. XRD studies showed a self-assembling structuring of the alkyl-chains in the bulk phase, which occurred in the case of the highest degree of acylation. This also manifested itself in a significant decrease of the layer hygroscopicity: the swelling degree decreased from 40 % to 8 % in a saturated water atmosphere monitored by spectroscopic ellipsometry.
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Hydrophobic coatings from chitosan-surfactant composites (ca. 400 nm thick by UV-Vis spectroscopy) for possible corrosion protection were developed on glass and zinc substrates. The surfactants (sodium dodecyl sulfate, SDS or sodium dodecylbenzenesulfonate, and SDBS) were added to the chitosan by two methods: mixing the surfactants with the aqueous chitosan solutions before film deposition or impregnating the deposited chitosan films with surfactants from their aqueous solutions. For the mixed coatings, it was found that the lower surface tension of solutions (40-45 mN/m) corresponded to more hydrophobic (80-90°) coatings in every case. The hydrophobicity of the impregnated coatings was especially significant (88° for SDS and 100° for SDBS). Atomic force microscopy studies revealed a slight increase in roughness (max 1.005) for the most hydrophobic coatings. The accumulation of surfactants in the layer was only significant (0.8-1.0 sulfur atomic %) in the impregnated samples according to X-ray photoelectron spectroscopy. Polarization and electron impedance spectroscopy tests confirmed better barrier properties for these samples (40-50% pseudo-porosity instead of 94%). The degree of swelling in a water vapor atmosphere was significantly lower in the case of the impregnated coatings (ca. 25%) than that of the native ones (ca. 75%), measured by spectroscopic ellipsometry. Accordingly, good barrier layer properties require advantageous bulk properties in addition to surface hydrophobicity.
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A novel nanolayer is formed by means of ion irradiation applicable as protective coating. Tungsten carbide (WC)-rich nanolayers were produced at room temperature by applying ion beam mixing of various carbon/tungsten (C/W) multilayer structures using argon and xenon ions with energy in the range of 40-120 keV and fluences between 0.25 and 3 × 1016 ions/cm2. The hardness of the nanolayers was estimated by means of standard scratch test applying an atomic force microscope equipped with a diamond-coated tip (radius < 10 nm); the applied load was 2 µN. The irradiation-induced hardness of the nanolayers correlated with the areal density of the WC; with the increasing amount of WC, the hardness of the nanolayer increased. The produced layers had an order of magnitude better corrosion resistance than a commercially available WC cermet circular saw. If the WC amount was high enough, the hardness of the layer became higher than that of the investigated WC cermet. These findings allow us to tune and design the mechanical and chemical properties of the WC protective coatings.
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Nanostructured photoactive systems are promising for applications such as air and water purification, including self-cleaning coatings. In this study, mesoporous TiO2 sol-gel coatings with different pore structures were prepared and modified with silver by two methods: the "mixing" method by adding AgNO3 to the precursor sol, and the "impregnation" method by immersing the samples in AgNO3 solution (0.03 and 1 M) followed by heat treatment. Our aim was to investigate the effects that silver modification has on the functional properties (e.g., those that are important for self-cleaning coatings). Transmittance, band gap energy, refractive index, porosity and thickness values were determined from UV-Vis spectroscopy measurements. Silver content and structure of the silver modified samples were characterized by X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, High-resolution transmission electron microscopy and Energy Dispersive X-ray Spectrometry elemental mapping measurements. Wettability properties, including photoinduced wettability conversion behavior were investigated by water contact angle measurements. Photoactivity was studied under both UV and visible light with rhodamine 6G and methylene blue dye molecules, at the liquid-solid and air-solid interfaces modeling the operating conditions of self-cleaning coatings. Samples made with "impregnation" method showed better functional properties, in spite of their significantly lower silver content. The pore structure influenced the Ag content achieved by the "impregnation" method, and consequently affected their photoactivity.
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BACKGROUND: Although it is known that some corneal diseases and degenerations have a significant heritable background, heritability on corneal endothelial cell density (ECD) has never been clearly determined. Our aim was to determine the heritability of corneal ECD. MATERIAL AND METHODS: Corneal ECD of 114 eyes (66 eyes of 33 monozygotic and 48 eyes of 24 dizygotic pairs; mean age 49.0 ± 15.5 years) was investigated by Konan Noncon Robo NSP-9900 specular microscopy. Structural equation modeling (ACE model) was applied. RESULTS: Endothelial corneal cell density was highly heritable (82.0%, 95%CI, 70.0-92.0%), whereas the unique environmental contribution was 18.0% (95%CI, 8.0-29.0%). Shared environmental factors had no influence on the endothelial corneal cell density. DISCUSSION: In this twin study, we established first that the density of the corneal endothelial cells is strongly heritable, which should stimulate future genetic studies to identify genes and pathways that are involved in determining ECD which might in turn lead to future treatments to prevent EC loss.
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Endotélio Corneano/citologia , Gêmeos Dizigóticos/genética , Gêmeos Monozigóticos/genética , Adulto , Idoso , Contagem de Células , Feminino , Humanos , Masculino , Microscopia/instrumentação , Pessoa de Meia-IdadeRESUMO
BACKGROUND: Few, and inconsistent, studies have showed high heritability of some parameters of the anterior segment of the eye; however, no heritability of anterior chamber volume (ACV) has been reported, and no study has been performed to investigate the correlation between the ACV and central corneal thickness (CCT). METHODS: Anterior segment measurements (Pentacam, Oculus) were obtained from 220 eyes of 110 adult Hungarian twins (41 monozygotic and 14 same-sex dizygotic pairs; 80% women; age 48.6 ± 15.5 years) obtained from the Hungarian Twin Registry. RESULTS: Age- and sex-adjusted heritability of ACV was 85% (bootstrapped 95% confidence interval; CI: 69% to 93%), and 88% for CCT (CI: 79% to 95%). Common environmental effects had no influence, and unshared environmental factors were responsible for 12% and 15% of the variance, respectively. The correlation between ACV and CCT was negative and significant (r ph = -0.35, p < .05), and genetic factors accounted for the covariance significantly (0.934; CI: 0.418, 1.061) based on the bivariate Cholesky decomposition model. CONCLUSION: These findings support the high heritability of ACV and central corneal thickness, and a strong genetic covariance between them, which underscores the importance of identification of the specific genetic factors and the family risk-based screening of disorders related to these variables, such as open-angle and also angle closure glaucoma and corneal endothelial alterations.
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Câmara Anterior/patologia , Córnea/patologia , Glaucoma de Ângulo Fechado , Glaucoma de Ângulo Aberto , Gêmeos Dizigóticos/genética , Gêmeos Monozigóticos/genética , Adolescente , Adulto , Feminino , Glaucoma de Ângulo Fechado/genética , Glaucoma de Ângulo Fechado/patologia , Glaucoma de Ângulo Aberto/genética , Glaucoma de Ângulo Aberto/patologia , Humanos , Hungria , Masculino , Pessoa de Meia-Idade , Tamanho do Órgão/genéticaRESUMO
OBJECTIVE: Central blood pressure and aortic stiffness have been consistently reported as strong cardiovascular risk factors. Twin studies by comparing identical with nonidentical twins produce information on the relative contribution of genes and environment. METHODS: One hundred and fifty-four monozygotic (MZ) and 42 dizygotic (DZ) twin pairs (age 43 ± 17 years) from Hungary and the United States underwent brachial and central augmentation index (AIx), brachial and central pressure, and aortic pulse wave velocity (PWV) measurements with the invasively validated Arteriograph device. Bivariate Cholesky decomposition models were applied. RESULTS: Age-adjusted, sex-adjusted and country-adjusted heritability was 60.0% for central SBP [95% confidence interval (CI), 44.8-69.6%], 50.1% for aortic PWV (95%CI, 26.0-66.8%), 48.7% for aortic AIx (95%CI, 1.7-74.0%), 46.8% for brachial AIx (95%CI, 1.1-73.8%), 46.7% for central pulse pressure (PP) (95%CI, 12.4-61.4%), and 30.0% for brachial PP (95%CI, 0.0-53.4%). Central SBP and PP had strong bivariate correlations with brachial (r = 0.461 and 0.425) and central AIx (r = 0.457 and 0.419), as well as with aortic PWV (r = 0.341 and 0.292, all P < 0.001). Brachial PP had a weak correlation with brachial AIx (r = -0.118, P < 0.05), central AIx (r = -0.122, P < 0.05), and none with aortic PWV (r = 0.08, P = n.s.). Genetic factors explained a moderate phenotypic correlation between central PP, SBP, brachial SBP and aortic PWV. CONCLUSIONS: Central systolic and PPs, brachial PP, AIx, aortic PWV are moderately heritable. A moderate genetic covariance among aortic PWV and central PP, central SBP and brachial SBP was found.