Wettability, Adsorption and Adhesion in Polymer (PMMA)-Commercially Available Mouthrinse System.

The study concerns the evaluation of the physicochemical and thermo-adsorptive surface properties of six commercially available mouthrinses, particularly surface tension, surface activity, partitioning coefficient, critical micellar concentration, Gibbs excesses at interfaces, surface entropy, and enthalpy. The aim was to quantify their effect on the adhesion and wettability of a model poly(methyl methacrylate) (PMMA) polymer. The adsorptive and thermal surface characteristics were derived from surface tension (γLV) vs. concentration and temperature dependences. Polymer surface wettability was characterized by the contact angle hysteresis (CAH) formalism, using the measurable advancing ΘA and receding ΘR dynamic contact angles and γLV as the input data. Further, wettability parameters: Young static angle (Θ), film pressure (Π), surface free energy (γSV) with its dispersive and polar components, work of adhesion (WA), and adhesional tension (γLV cosΘA) were considered as interfacial interaction indicators. The mouthrinse effect demonstrated the parameter's evolution in reference to the PMMA/pure water case: Θ, ΘA and ΘR↓, CAH↑, Π↓, WA↓, γSV↓, and γLVcosΘA↑. Furthermore, the variations of the surface excess ratio pointed to the formation of multilayered structures of surfactants composing the mouthrinse mixtures considered. The contact angle data allowed for the penetration coefficient and the Marangoni temperature gradient-driven liquid flow speed to be estimated.

Micron-Scale Biogeography of Seawater Biofilm Colonies at Submersed Solid Substrata Affected by Organic Matter and Microbiome Transformation in the Baltic Sea.

The aim of this research was to determine temporal and spatial evolution of biofilm architecture formed at model solid substrata submersed in Baltic sea coastal waters in relation to organic matter transformation along a one-year period. Several materials (metals, glass, plastics) were deployed for a certain time, and the collected biofilm-covered samples were studied with a confocal microscopy technique using the advanced programs of image analysis. The geometric and structural biofilm characteristics: biovolume, coverage fraction, mean thickness, spatial heterogeneity, roughness, aggregation coefficient, etc., turned out to evolve in relation to organic matter transformation trends, trophic water status, microbiome evolution, and biofilm micro-colony transition from the heterotrophic community (mostly bacteria) to autotrophic (diatom-dominated) systems. The biofilm morphology parameters allowed the substratum roughness, surface wettability, chromatic organisms colony adaptation to substrata, and quorum sensing or cell to cell signaling effects to be quantitatively evaluated. In addition to the previous work, the structural biofilm parameters could become further novel trophic state indicators.

Nonconventional 1,8-Diazafluoren-9-One Aggregates for Green Light Enhancement in Hybrid Biocompatible Media.

Organic aggregates currently play a prominent role, mainly for their unique optoelectronic properties in the aggregated state. Such properties can be related to the aggregates' structure and the molecular packing mode. In the literature, we have well-established models of H and J aggregates defined based on the molecular exciton model. However, unconventional aggregates, the most unrecognized forms, have been generating interest among researchers recently. Within unconventional aggregation, aggregation-induced emission systems (AIE) are considered. In the present work, we discuss the effect of the forming of unconventional aggregation together with the change in dye concentration on the surface energy characteristics of the materials. All materials were prepared as hybrid biocompatible thin films where the matrix is TiO2 or TiO2/carbon nanowalls (CNWs) with the incorporated dye in the form of 1,8-diazafluoren-9-one (DFO). Using the time-resolved emission spectra and the determination of surface parameters from contact angle measurements, we indicated the correlation between the changes in such parameters and the concentration of DFO dye in two types of TiO2 and TiO2/CNW structures. To examine the propensity of DFO for aggregation, the internal energy of the dye was assessed in several aggregate structures using Quantum chemistry calculations. The results emphasize that DFO is an attractive structure in the design of new fluorophores due to its low molecular weight, the presence of a nitrogen atom that provides good coordination properties, and the ability to form hydrogen bonds. Our studies show that when using suitable matrices, i.e., rigid media, it forms the preferred forms of aggregates in the excited state, characterized by high emission efficiency in the band maximum of around 550 nm.

Wettability of Metal Surfaces Affected by Paint Layer Covering.

The aim of the work was to quantify the surface wettability of metallic (Fe, Al, Cu, brass) surfaces covered with sprayed paints. Wettability was determined using the contact angle hysteresis approach, where dynamic contact angles (advancing ΘA and receding ΘR) were identified with the inclined plate method. The equilibrium, ΘY, contact angle hysteresis, CAH = ΘA − ΘR, film pressure, Π, surface free energy, γSV, works of adhesion, WA, and spreading, WS, were considered. Hydrophobic water/solid interactions were exhibited for the treated surfaces with the dispersive term contribution to γSV equal to (0.66−0.69). The registered 3D surface roughness profiles allowed the surface roughness and surface heterogeneity effect on wettability to be discussed. The clean metallic surfaces turned out to be of a hydrophilic nature (ΘY < 90°) with high γSV, heterogeneous, and rough with a large CAH. The surface covering demonstrated the parameters' evolution, ΘA↑, ΘR↑, γSV↓, WA↓, and WS↓, corresponding to the surface hydrophobization and exhibiting base substratum-specific signatures. The dimensionless roughness fluctuation coefficient, η, was linearly correlated to CAH. The CAH methodology based on the three measurable quantities, ΘA, ΘR, and liquid surface tension, γLV, can be a useful tool in surface-mediated process studies, such as lubrication, liquid coating, and thermoflow.

Snowpack-stored atmospheric surface-active contaminants traced with snowmelt water surface film rheology.

The aim of the study was to quantify the adsorptive and thermo-elastic properties of snowmelt water surface films and their spatial-temporal evolution with snowpack structure characteristics and the entrapped surface-active organic composition. Surface pressure-area (π-A)T isotherms, surface pressure-temperature (π-T)A isochors, and stress-relaxation (π-t) measurements were performed using a Langmuir trough system on snowmelt water samples collected in a large-scale field studies performed at several industrialized and rural Tricity (Gdansk, Poland) areas at various environmental conditions and subsequent stages of the snowpack melting progress. Since the snow-melted water composition and concentrations of surface active organic matter fractions therein are largely undetermined, the force-area isotherm scaling formalisms (2D virial equation and 2D film scaling theory of polymeric films) were adapted to the complex mixture of surfactants. The surface film parameters and their spatial and temporal evolution turned out to be unequivocally related to principal signatures of the film-forming materials: surfactant concentrations (π, Alim), surface activity (Eisoth, |E|), film material solubility (R), surface material miscibility and 2D architecture complexity (y, ßs), molecular thermal mobility (πk), and a timescale of the relaxation processes within the film (τi, |E|). Moreover, the parameters appeared to be correlated with snowpack structure characteristics (snow density ρ, specific snow area SSA, snow cover thickness), sample age time, and anthropogenic atmospheric contamination pressure source locations. In particular, Eisoth was found to be related to ρ and SSA, while R correlated with the solubility of film-forming organics which turned out to be long-chain fatty acids; similarly, spatial profiles of Eisoth revealed the peak values next to the areas being under a severe anthropogenic air pollution pressure. Snowmelt water films stand for a structurally heterogeneous (y > 10) interfacial system where several transition processes of differentiated time-scales (relaxation times from 7 to 63 s) took place leading to the apparent surface viscoelasticity. To sum up, the established surface rheological parameters could serve as novel indicators, based solely on physical attributes, allowing to follow the snowpack evolution, and its melting polymorphism in order to test or improve the existing snow-entrapped organics release models based on chemical analyses. The cross-correlation functional dependences of practical value remain to be established on the larger data set.

Evolution of natural sea surface films: a new quantification formalism based on multidimensional space vector.

Spatial and temporal variability of natural surfactant sea surface film structural parameters were evaluated from force-area isotherms, film pressure-temperature isochors, dynamic surface tension-time relations performed on samples collected in Baltic Sea shallow coastal waters. The film structure state was postulated as a 10-D dimensionless vector created from the normalized thermodynamic, adsorptive, and viscoelastic film parameters. The normalization procedure is based on the concept of self-corresponding states known in thermodynamics. The values taken by all the reduced parameters indicated a significant deviation from the reference ideal-2D gas behavior. The exhibited deviations of the surface parameters from the background values of the same thermodynamic state of each film were independent on the film-collecting procedure, sample solvent treatment, and temperature. The structural similarity was expressed quantitatively as a (Cartesian, street, and Czebyszew) distance between two vectors of the analyzed film and the standard one from the database, and appeared to be related to environmental conditions, surface-active organic matter production, and migration in the studied coastal sea region. The most distinctive parameters differing the films were y, M w and E isoth, as established from Czebyszew function application. The proposed formalism is of universal concern and could be applied to any natural water surfactant system (seawater, inland water, rain water, and snowmelt water).

Physicochemical signatures of natural sea films from Middle Adriatic stations.

Monolayer studies and a force-area quantification approach, in combination with electrochemical methods, are applied for physicochemical characterization of surface active substances (SAS) of the sea surface microlayers (MLs) from Middle Adriatic stations. Higher primary production during late spring-early autumn was reflected in the presence of MLs of higher surfactant activity containing on average molecules of lower molecular masses (M(w) = 0.65 ± 0.27 kDa) and higher miscibility (y = 6.46 ± 1.33) and elasticity (E(isoth) = 18.33 ± 2.02 mN m(-1)) modulus in comparison to structural parameters (average M(w) = 2.15 ± 1.58 kDa; y = 3.51 ± 1.46; E(isoth) = 6.41 ± 1.97 mN m(-1)) obtained for MLs from a period of lower production. A higher inhibition effect on the reduction process of Cd(2+) was observed for SAS abundant MLs from a more productive period. This kind of distribution is explained as the consequence of competitive adsorption of hydrophobic lipid-like substances of lower M(w) that act as end-members, highly influencing the surface structural properties of the natural air-water interface forming there segregated surface films during more productive period.