Chitosan nanocoatings N-acylated with decanoic anhydride: Hydrophobic, hygroscopic and structural properties.

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.

Bubble ascent and rupture in mud volcanoes.

Large gas bubbles can reach the surface of pools of mud and lava where they burst, often through the formation and expansion of circular holes. Bursting bubbles release volatiles and generate spatter, and hence play a key role in volcanic degassing and volcanic edifice construction. Here, we study the ascent and rupture of bubbles using a combination of field observations at Pâclele Mici (Romania), laboratory experiments with mud from the Imperial Valley (California, USA), numerical simulations and theoretical models. Numerical simulations predict that bubbles ascend through the mud as elliptical caps that develop a dimple at the apex as they impinge on the free surface. We documented the rupture of bubbles in nature and under laboratory conditions using high-speed video. The bursting of mud bubbles starts with the nucleation of multiple holes, which form at a near-constant rate and in quick succession. The quasi-circular holes rapidly grow and coalesce, and the sheet evolves towards a filamentous structure that finally falls back into the mud pool, sometimes breaking up into droplets. The rate of expansion of holes in the sheet can be explained by a generalization of the Taylor-Culick theory, which is shown to hold independent of the fluid rheology.

Chitosan-Surfactant Composite Nanocoatings on Glass and Zinc Surfaces Prepared from Aqueous Solutions.

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.

Quantitative examination of factors influencing the colour reproduction ability of lithium disilicate glass-ceramics.

BACKGROUND: Effects of ceramic translucency, layer thickness, and substrate colour on the shade of lithium disilicate glass-ceramic restorations proved to be significant in several studies, however, quantitative, numerical results on the relationship between the colour difference and these parameters are still lacking. The purpose of this in vitro study was to quantitatively determine how the colour reproduction ability of a lithium disilicate glass-ceramic is affected by its translucency, layer thickness, and substrate colour. METHODS: Ceramic samples were prepared from A2 shade IPS e.max CAD blocks with high and low translucencies (HT and LT) in a thickness range of 0.5-2.5 mm (+/- 0.05 mm). Layered samples were acquired utilizing composite substrates in 9 shades; transparent try-in paste was used. The spectral reflectance of the specimens was assessed under D65 standard illumination with a Konica Minolta CM-3720d spectrophotometer. The CIEDE2000 colour difference (ΔE00) between two samples was analysed using perceptibility and acceptability thresholds set at 50:50%. Statistical analysis involved linear regression analysis and the Kruskal-Wallis test. RESULTS: An increase in the thickness of 0.5 mm reduced the ΔE00 of the HT samples to 72.8%, and that of the T samples to 71.1% (p < 0.0001). 7 substrates with HT and LT specimens had significantly different results from the mean (p < 0.05). A thickness of 0.5 mm is not sufficient to achieve an acceptable result at any level of translucency, while the low translucency ceramic at a thickness of 1.5 mm gave acceptable results, except for severely discoloured substrates (ND8 and ND9). CONCLUSIONS: The colour reproduction ability of lithium disilicate glass-ceramics is significantly affected by their translucency, layer thickness, and 7 substrates out of 9 substrates examined.

Ranking the dietary interventions by their effectiveness in the management of polycystic ovary syndrome: a systematic review and network meta-analysis.

INTRODUCTION: Polycystic ovary syndrome (PCOS) is a common condition in women, characterised by reproductive and metabolic dysfunction. While dietary approaches have been evaluated as a first-line treatment for patients with PCOS, there is limited evidence to support preference for a specific dietary composition. This systematic review and network meta-analysis was performed with the objective of comparing different dietary interventions in terms of positive impact. Metformin, the currently preferred treatment, was also compared. METHODS: The latest systematic search was performed on the 20th of March, 2023. Eligible randomised controlled trials (RCTs) included patients with PCOS and compared the dietary approach with another intervention or a standard diet. Outcomes were expressed via anthropometric measurements and hormonal, glycemic, and lipid levels. The Bayesian method was used to perform a network meta-analysis and to calculate the surface under the cumulative ranking curve (SUCRA) values in order to rank the dietary interventions. The overall quality of the evidence was assessed using the Grading of Recommendations Assessment, Development, and Evaluation system. RESULTS: 19 RCTs were identified, comprising data from 727 patients who were variously treated with 10 types of dietary interventions and metformin. The Dietary Approaches to Stop Hypertension (DASH) diet was the most effective in reducing Homeostatic Model Assessment of Insulin Resistance (SUCRA 92.33%), fasting blood glucose (SUCRA 85.92%), fasting insulin level (SUCRA 79.73%) and triglyceride level (SUCRA 82.07%). For body mass index (BMI), the most effective intervention was the low-calorie diet (SUCRA 84.59%). For weight loss, the low-calorie diet with metformin (SUCRA 74.38%) was the most effective intervention. Metformin produced the greatest reductions in low-density lipoprotein cholesterol (SUCRA 78.08%) and total testosterone levels (SUCRA 71.28%). The low-carb diet was the most effective intervention for reducing cholesterol levels (SUCRA 69.68%), while the normal diet (SUCRA 65.69%) ranked first for increasing high-density lipoprotein cholesterol levels. CONCLUSION: Dietary interventions vary in their effects on metabolic parameters in women with PCOS. Based on our results, the DASH diet is the most effective dietary intervention for treating PCOS. Registration PROSPERO ID CRD42021282984.

Wetting and swelling behaviour of N-acetylated thin chitosan coatings in aqueous media.

Chitosan nanocoatings (thickness range of 120-540 nm) were produced on glass, zinc and silicon substrates with dip-coating and spin coating techniques to study their pH-dependent wetting and swelling behaviour. The coatings were N-acetylated with the methanolic solution of acetic anhydride to increase the degree of acetylation from 36 % to 100 % (according to ATR-FTIR studies). The measured contact angles of Britton-Robinson (BR) buffer solutions (pH 6.0, 7.4 and 9.0) were lower on the acetylated surfaces (ca. 50°), than that of their native counterparts (ca. 70°) and does not depend on the pH. Contrary, contact angles on the native coating deteriorated 10°-15° with increasing the pH. In addition, for native coatings, the decrease of the contact angles over time also showed a pH dependence: at pH 9.0 the contact angle decreased by 7° in 10 min, while at pH 6.0 it decreased by 13° and at a much faster rate. The constraint swelling of the coatings in BR puffer solutions was studied in situ by scanning angle reflectometry. The swelling degree of the native coatings increased significantly with decreasing pH (from 250 % to 500 %) due to the increased number of protonated amino groups, while the swelling degree of acetylated coatings was ca. 160 % regardless of the pH. The barrier properties of the coatings were studied by electrochemical tests on zinc substrates. The analysis of polarization curves showed the more permeable character of the acetylated coatings despite the non-polar character of the bulk coating matrix. It can be concluded that in the case of native coatings, 49 % of the absorbed water is in bound form, which does not assist ion transport, while in the case of acetylated coatings, this value is only 33 %.

Effect of thickness, translucency, and substrates on the masking ability of a polymer-infiltrated ceramic-network material.

OBJECTIVE: The aim of this in vitro study is to evaluate the masking ability of polymer-infiltrated ceramic-network materials (PICN) with different translucencies and thicknesses on multiple types of substrates. MATERIALS AND METHODS: Ceramic samples were prepared of VITA ENAMIC blocks in two different translucencies (2M2-T, 2M2-HT) in a thickness range of 0.5-2.5 mm (±0.05 mm). Layered specimens were obtained using composite substrates in nine shades and transparent try-in paste. Spectral reflectance of specimens was measured using a Konica Minolta CM-3720d spectrophotometer and D65 standard illumination. CIEDE2000 color difference (ΔE00 ) between two samples was evaluated using 50%:50% perceptibility and acceptability thresholds. Specular component of the reflection was examined with Specular Component Excluded (SCE) and Included (SCI) settings. Statistical evaluation was performed by linear regression analysis, Kruskal-Wallis test, and multiplicative effect analysis. RESULTS: An increase in thickness of 0.5 mm reduces ΔE00 of HT samples to 73.5%, of T samples to 60.5% (p < 0.0001). Five substrates with HT specimens, and three substrates with T specimens had significantly different results from average (p < 0.05). There is a significant difference between SCE and SCI data depending on the wavelength (p < 0.0001). CONCLUSIONS: Masking ability of PICN materials is influenced by the thickness and translucency of the ceramic, and by the substrate. Reflection of the examined PICN material is characterized by both diffuse and specular reflection. CLINICAL SIGNIFICANCE: Although PICN materials have been available on the market for 10 years now, there is a lack of information regarding their masking ability. Acquiring in-depth data and thereby practical experience of the factors affecting the esthetics of PICN materials is essential for creating perfectly lifelike restorations.

Surface Affinity of Tetramethylammonium Iodide in Aqueous Solutions: A Combined Experimental and Computer Simulation Study.

The surface affinity of tetramethylammonium iodide (TMAI) in aqueous solutions is investigated by surface tension measurements and molecular dynamics computer simulations. Experiments, performed in the entire composition range of solubility using the pendant drop method with two different setups, clearly reveal that TMAI is a weakly capillary active salt. Computer simulations performed with the AMBER force field reproduce the experimental data very well, while two other major force fields (i.e., CHARMM and OPLS) can still reproduce the experimental trend qualitatively; however, even qualitative reproduction of the experimental trend requires scaling down the ion charges according to the Leontyev-Stuchebrukhov correction. On the other hand, the GROMOS force field fails in reproducing the experimentally confirmed capillary activity of TMAI. Molecular dynamics simulation results show that, among the two ions, iodide has a clearly larger surface affinity than tetramethylammonium (TMA+). Further, the adsorption of the I- anions is strictly limited to the first molecular layer beneath the liquid-vapor interface, which is followed by several layers of their depletion. On the other hand, the net negative charge of the surface layer, caused by the excess amount of I- with respect to TMA+, is compensated by a diffuse layer of adsorbed TMA+ cations, extending to or beyond the fourth molecular layer beneath the liquid surface.

Barrier behaviour of partially N-acetylated chitosan layers in aqueous media.

Chitosan coatings of 353 ± 12 nm thickness were prepared on glass and zinc substrates by dip-coating method to study their barrier-behaviour. The coatings were chemically modified to increase their degree of acetylation (DA) from ca. 44 % up to ca. 98 % resulting a quasi-chitin coating. The effect of the acetylation reaction was studied by infrared spectroscopy, and the structural changes of the native and acetylated coatings were investigated by UV-Vis spectrophotometry and X-ray diffraction. The surface properties of the coated samples were characterized by wettability measurements - advancing water contact angle decreased from ca. 80° (native) to ca. 43° (fully acetylated) - and microscopic (SEM, AFM) studies. The barrier behaviour of the chitosan layer depending on the DA was evaluated by electrochemical impedance spectroscopy studies and with a special mesoporous silica - chitosan bilayer system by measuring the amount of dye (Rhodamine 6G) accumulated in the silica through the chitosan coating during an impregnation step. These methods showed significant decrease in the barrier-effect of the coatings with increasing DA (accumulation of approximately six times more dye and a reduction of charge transfer resistance by an order of magnitude), due to the structural and ionization changes in the coatings.

Epidemiology of firesetting in adolescents: mental health and substance use correlates.

OBJECTIVE: Despite high rates of firesetting among community adolescents, little is known about its correlates. This study identifies the mental health and substance use correlates of four firesetting levels in an epidemiological sample of adolescents. METHODS: Three thousand, nine hundred and sixty-five (3,965) students in grades 7 to 12 were surveyed. Multinomial analyses were used to compare non-firesetters; desisters (lifetime, but no past-year firesetting); low frequency firesetters (once or twice in the past 12 months); and high frequency firesetters (3 + times) on measures of mental health and substance use. RESULTS: Twenty-seven percent of youth reported firesetting during the past year. Of these, 13.7% reported one or two episodes, and 13.5% reported 3 or more episodes. Firesetting was more prevalent among males and among those in high school. Youth who began firesetting before age 10 were more likely to report frequent firesetting during the past year. Compared to non-firesetters, the firesetting groups had elevated risk profiles. Desisters and low frequency firesetters were more likely to report psychological distress, binge drinking, frequent cannabis use, and sensation seeking. Low frequency firesetters also reported higher rates of delinquent behavior, suicidal intent, and low parental monitoring than non-firesetters. High frequency firesetters reported elevated risk ratios for all of these risk indicators plus other illicit drug use. The cumulative number of risk indicators was positively associated with firesetting severity. CONCLUSIONS: Firesetting is associated with psychopathology and substance use during adolescence. Findings highlight the need for programs to address the mental health and substance use problems that co-occur with firesetting.

Fire interest and antisociality as risk factors in the severity and persistence of juvenile firesetting.

OBJECTIVE: In the DSM-IV-TR, firesetting is included as a criterion for the diagnoses of conduct disorder and pyromania. The link between firesetting and antisocial behavior is well established in the empirical literature. Although theoretical models of firesetting often include fire interest as a putative risk factor, there is little research on the role of fire interest in firesetting or on the construct of pyromania. METHOD: The present study evaluated a sample of children and adolescents referred to an outpatient specialty program for juvenile firesetters with firesetting as the primary presenting problem. By assessing fire interest and antisocial behavior concurrently, the contribution of fire interest to firesetting after controlling for the role of conduct problems was evaluated. RESULTS: Results revealed that fire interest and antisocial behavior were significantly and positively correlated. Moreover, variations in fire interest added to the prediction of firesetting severity at assessment and firesetting recidivism at 18-month follow-up above and beyond what was predicted by antisociality alone. CONCLUSIONS: These findings have implications for an empirically derived taxonomy of pathological firesetting.