Effect of Non-Thermal Sulfur Hexafluoride Cold Plasma Modification on Surface Properties of Polyoxymethylene.

X-ray photoelectron spectroscopy was employed to reveal the differences in the chemical structure of the topmost layer after plasma modification. It was found out that changes in the surface properties of the polymer could be observed even after 20 seconds of treatment. The surface becomes hydrophobic or superhydrophobic, with the water contact angles up to 160 degrees. Morphological changes and increased roughness can be observed only in the nanoscale, whereas the structure seems to be unaffected in the microscale. As a result of plasma modification a permanent hydrophobic effect was obtained on the polyoxymethylene surface.

Hydrophobization of Cold Plasma Activated Glass Surfaces by Hexamethyldisilazane Treatment.

The objective of this study was to investigate the modification of glass surfaces by the synergistic combination of cold plasma and chemical surface modification techniques. Glass surface hydrophobicity was obtained as a result of various plasma and deposition operational conditions. The mechanisms governing the hydrophobization process were also studied. Glass plates were activated with plasma using different gases (oxygen and argon) at different treatment times, ranging from 30 to 1800 s. Then, the plasma-treated surfaces were exposed to hexamethyldisilazane vapors at different temperatures, i.e., 25, 60, and 100 °C. Complete characterization, including contact angle measurements, surface free energy calculations, 3D profilometry, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and scanning electron microscopy, was accomplished. It was found that the extent of the hydrophobicity effect depends on both the plasma pre-treatment and the specific conditions of the hexamethyldisilazane deposition process. Plasma activation led to the formation of active sites on the glass surface, which promoted the adsorption and reaction of hexamethyldisilazane species, thereby inducing surface chemical modification. Longer plasma pre-treatment resulted in stronger modification on the glass surface, resulting in changes in the surface roughness. The largest water contact angle of ≈100° was obtained for the surface activated by argon plasma for 1800 s and exposed to hexamethyldisilazane vapors at 25 °C. The changes in the surface properties were caused by the introduction of the hydrophobic trimethylsilyl groups onto the glass surface as well as roughness development.

Influence of Farming System and Forecrops of Spring Wheat on Protein Content in the Grain and the Physicochemical Properties of Unsonicated and Sonicated Gluten.

The potential for enhancing the spring wheat protein content by different cultivation strategies was explored. The influence of ultrasound on the surface and rheological properties of wheat-gluten was also studied. Spring wheat was cultivated over the period of 2018-2020 using two farming systems (conventional and organic) and five forecrops (sugar beet, spring barley, red clover, winter wheat, or oat). The obtained gluten was sonicated using the ultrasonic scrubber. For all organically grown wheat, the protein content was higher than for the conventional one. There was no correlation between the rheological properties of gluten and the protein content in the grain. Gluten derived from organically grown wheat was more elastic than those derived from the conventional one. Sonication enhanced the elasticity of gluten. The sonication effect was influenced by the forecrops. The most elastic gluten after sonication was found for organic barley and sugar beet. The lowest values of tan (delta) were noted for conventional wheat and conventional oat. Cultivation in the monoculture gave gluten with a smaller susceptibility to increase elasticity after sonic treatment. Sonication promoted the cross-linking of protein molecules and induced a more hydrophobic character, which was confirmed by an increment in contact angles (CAs). Most of the organically grown wheat samples showed a lower CA than the conventional ones, which indicated a less hydrophobic character. The gluten surface became rougher with the sonication, regardless of the farming system and applied forecrops. Sonication treatment of gluten proteins rearranged the intermolecular linkages, especially disulfide and hydrophobic bonds, leading to changes in their surface morphology.

Stability of Chlorophyll a Monomer Incorporated into Cremophor EL Nano-Micelles under Dark and Moderate Light Conditions.

In this paper, stability of chlorophyll a monomers encapsulated into the Cremophor EL nano-micelles was studied under dark and moderate light conditions, typical of a room with natural or artificial lighting, in the presence of oxygen. The pigment stability against visible light was determined using the dynamic light scattering and molecular spectroscopy (UV-Vis absorption and stationary fluorescence) methods. Chlorophyll a, at the molar concentration of 10-5 M, was dissolved in the 5 wt% Cremophor emulsion for comparison in the ethanolic solution. The stability of such a self-assembly pigment-detergent nano-system is important in the light of its application on the commercial-scale. The presented results indicate the high stability of the pigment monomeric molecular organization in the nano-emulsion. During the storage in the dark, the half-lifetime was calculated as about 7 months. Additionally, based on the shape of absorption and fluorescence emission spectra, chlorophyll aggregation in the Cremophor EL aqueous solution along with the time was excluded. Moreover, the average size of detergent micelles as chlorophyll carriers was not affected after 70 days of the nano-system storage. Pigment stability against the moderate white light (0.1 mW) did not differ significantly from storage conditions in the dark. The photooxidation products, detected by occurrence of new absorption and fluorescence emission bands, was estimated on the negligible level. The stability of such a self-assembly pigment-detergent nano-system would potentially broaden the field of chlorophyll a (chl a) application in the food industry, medicine or artificial photosynthesis models.

Co-gelation of gluten and gelatin as a novel functional material formation method.

Gelatin solution was added to the gluten dispersion to obtain 25% protein from gluten and 0, 0.3, 0.6 and 1.0% of gelatin. Heat-induced gels were formed. The gelatin was leached by immersing the gel straps in distilled water at 45 °C for 2 h. Incorporation of gelatin into the gluten gel matrix resulted in its strengthening. Increase in elastic properties with the increasing amount of gelatin was also found for the macerated gels. The tangent delta showed the minimum for the leached gel with the initial concentration of gelatin 0.6%, so probably at this concentration there was some reinforcement of gluten, or the structure of gluten matrix was formed with the best ability to include gelatin inside. FTIR (Fourier transform infrared spectroscopy) results showed, that at the 0.6% gelatin concentration more gelatin was present in the leached samples than in the 1% gelatin added samples. Gelatin gels can act as an active filler reinforcing the gluten microstructure. Leaching of gelatin from the mixed gel matrix resulted in the microstructure with visible phase separation. Generally gelatin addition gave a surface smoothing effect and lower surface roughness of the obtained gels. Pure gluten gels soaking in hot water resulted in the decreased roughness. Possibility of manipulation with gluten gels surface roughness by co-gelling with gelatin can have an influence on the application of such gels as matrices for active ingredients.

Quality and functional properties of bread containing the addition of probiotically fermented Cicer arietinum.

This study aimed to determine the impact of supplementation with probiotically fermented chickpea (Cicer arietinum L) seeds on the quality parameters and functional characteristics of wheat bread. The addition of chickpea seeds caused significant changes in the chemical composition of the control wheat bread. The legume-supplemented products exhibited higher values of a* and b* color parameters and higher hardness after 24 h of storage than the control. The application of fermented or unfermented chickpeas contributed to an increase in total polyphenol and flavonoid contents, iron chelating capacity, and antioxidant properties of the final product. The variant containing unfermented seeds had the highest riboflavin content (29.53 ± 1.11 µg/100 g d.w.), Trolox equivalent antioxidant capacity (227.02 ± 7.29 µmol·L-1 TX/100 g d.w.), and free radical scavenging activity (71.37 ± 1.30 % DPPH inhibition). The results of this preliminary research have practical importance in the production of innovative bakery products with potential properties of functional food.

Synthesis, characterization and biocompatibility of hybrid hydrogels based on alginate, κ-carrageenan, and chitosan filled with montmorillonite clay.

New hybrid hydrogel composites based on a mixture of natural polysaccharides (sodium alginate, κ-carrageenan, and chitosan) filled with the clay mineral of natural origin, montmorillonite (MMT), were studied. The structure of intercalated/flocculated MMT distribution in the interpenetrating network of polysaccharide matrix was characterized using FTIR, X-ray diffraction, and SEM techniques. Swelling kinetics was investigated using the weight analysis, whereas the phase transition of water in the composition of hybrid hydrogels, by DSC method. Their biosafety was estimated using the Nelyubov method, germination test on cress (L. sativum) seeds, and metabolic fingerprinting of microbial communities and dehydrogenase assay. The obtained results indicated promising water-retaining properties of the synthesized materials. The hydrogels had a good sorption affinity for cadmium (Cd) ions confining bioavailability of the selected toxic heavy metal. They were safe for soil microorganisms and did not generate metabolic stress for them. Moreover, they did not reduce the viability of pea seeds. Thus, the development of biosafe hybrid hydrogel composites with a comprehensive, good effect on the environment could be considered as successful.

The Effect of Erythritol on the Physicochemical Properties of Reformulated, High-Protein, and Sugar-Free Macarons Produced from Whey Protein Isolate Intended for Diabetics, Athletes, and Physically Active People.

This study reports the possibility of obtaining sugar-free WPI-based macarons with erythritol addition. The whey protein isolate (WPI) solution (20%, w/v) was whipped, and erythritol was added to the foam at concentrations of 20, 40, and 60 g, with 125 g of almond flour. The rheological properties (τ, G', G″, and tan (δ)) and stability of the macaron batters before baking were evaluated. In order to produce the macarons, the batters were solidified at 147 °C for 12 min. The textural and surface properties (roughness and color), as well as the microstructures and water activities, were determined for the macarons. It was feasible to produce macarons over the entire range of the tested erythritol content. Even the smallest amount of erythritol (20 g) facilitated the preservation of the macaron structure. The medium erythritol concentration (40 g) improved the stability of the batters and their rheology and was the most effective for air pocket stabilization during baking; however, its largest addition (60 g) resulted in an increase in the final macaron volume. The increased erythritol addition improved mechanical properties and shelf life, producing a smoothing effect on the macaron surfaces and having a significant effect on their color co-ordinates.

Co-Gelation of Pumpkin-Seed Protein with Egg-White Protein.

The aim of this study was to investigate the gelation process of binary mixes of pumpkin-seed and egg-white proteins. The substitution of pumpkin-seed proteins with egg-white proteins improved the rheological properties of the obtained gels, i.e., a higher storage modulus, lower tangent delta, and larger ultrasound viscosity and hardness. Gels with a larger egg-white protein content were more elastic and more resistant to breaking structure. A higher concentration of pumpkin-seed protein changed the gel microstructure to a rougher and more particulate one. The microstructure was less homogenous, with a tendency to break at the pumpkin/egg-white protein gel interface. The decrease in the intensity of the amide II band with an increase in the pumpkin-seed protein concentration showed that the secondary structure of this protein evolved more toward a linear amino acid chain compared with the egg-white protein, which could have an impact on the microstructure. The supplementation of pumpkin-seed proteins with egg-white proteins caused a decrease in water activity from 0.985 to 0.928, which had important implications for the microbiological stability of the obtained gels. Strong correlations were found between the water activity and rheological properties of the gels; an improvement of their rheological properties resulted in a decrease in water activity. The supplementation of pumpkin-seed proteins with egg-white proteins resulted in more homogenous gels with a stronger microstructure and better water binding.

Physicochemical, Nutritional, Microstructural, Surface and Sensory Properties of a Model High-Protein Bars Intended for Athletes Depending on the Type of Protein and Syrup Used.

The main objective of this study was to investigate the possibility of using a combination of vegetable proteins from soybean (SOY), rice (RPC), and pea (PEA) with liquid syrups: tapioca fiber (TF), oligofructose (OF), and maltitol (ML) in the application of high-protein bars to determine the ability of these ingredients to modify the textural, physicochemical, nutritional, surface properties, microstructure, sensory parameters, and technological suitability. Ten variants of the samples were made, including the control sample made of whey protein concentrate (WPC) in combination with glucose syrup (GS). All combinations used had a positive effect on the hardness reduction of the bars after the storage period. Microstructure and the contact angle showed a large influence on the proteins and syrups used on the features of the manufactured products, primarily on the increased hydrophobicity of the surface of samples made of RPC + ML, SOY + OF, and RPC + TF. The combination of proteins and syrups used significantly reduced the sugar content of the product. Water activity (<0.7), dynamic viscosity (<27 mPas∙g/cm3), and sensory analysis (the highest final ratings) showed that bars made of RPC + OF, SOY + OF, and SOY + ML are characterized by a high potential for use in this type of products.

Effect of Various Surface Treatments on Wettability and Morphological Properties of Titanium Oxide Thin Films.

The effect of three popular surface activation methods for a titanium oxide (titania) surface was thoroughly investigated to identify the most effective protocol for the enhancement of hydrophilicity. All the methods, namely H2O2 activation, UV irradiation and oxygen plasma treatment resulted in an enhanced hydrophilic titania surface, which was evidenced by the reduced contact angle values. To study in detail the chemical and morphological features responsible for the increased hydrophilicity, the treated surfaces were submitted to inspection with atomic force microscopy and X-ray photoelectron spectroscopy. The correlation between the treatment and titania surface hydroxylation as well as hydrophilic behavior have been discussed.

Enhanced uranium removal from acidic wastewater by phosphonate-functionalized ordered mesoporous silica: Surface chemistry matters the most.

The removal of uranium species from aqueous phases using non-hazardous chemicals is still an open challenge, and remediation by adsorption is a prosperous strategy. Among the most crucial concerns regarding the design of an efficient material as adsorbent are, except the cost and the green character, the feasibility to be stable and effective under acidic pH, and to selectively adsorb the desired metal ion (e.g. uranium). Herein, we present a phosphonate functionalized ordered mesoporous silica (OMS-P), prepared by a one-step co-condensation synthesis. The physicochemical features of the material were determined by HR-TEM, XPS, EDX, N2 sorption, and solid NMR, while the surface zeta potential was also measured. The removal efficiency was evaluated at two different temperatures (20 and 50 °C) in acidic environment to avoid interferences like solid phase formation or carbonate complexation and the adsorption isotherms, including data fitting with Langmuir and Freundlich models and thermodynamic parameters are presented and discussed. The high and homogeneous dispersion of the phosphonate groups within the entire silica's structure led to the greatest reported up-todays capacity (345 mg/g) at pH = 4, which was achieved in less than 10 min. Additionally, OMS-P showed that the co-presence of other polyvalent cation like Eu(III) did not affect the efficiency of adsorption, which occurs via inner-sphere complex formation. The comparison to the non-functionalized silica (OMS) revealed that the key feature towards an efficient, stable, and selective removal of the U(VI) species is the specific surface chemistry rather than the textural and structural features. Based on all the results and spectroscopic validations of surface adsorbed U(VI), the main interactions responsible for the elevated uranium removal were proposed.

The effect of pH and ageing on the fate of CuO and ZnO nanoparticles in soils.

The objective of this study was to evaluate the fractionation of ZnO and CuO engineered nanoparticles (ENPs) in soils with a pH adjusted to 4.0, 6.5, and 9.0 after 1 day and 30 days of incubation. Based on the multi-stage extraction, 5 fractions of metals were determined. Moreover, the effect of ENPs on the activity of acid, neutral and alkaline phosphatase was determined. The results of the study revealed that pH had a dominant effect on the metal participation in soils. The levels of those fractions of metals differed between nano-ZnO and nano-CuO, which could have resulted from differences in the dissolution of the ENPs. After 1 day, the concentration of Zn2+ (0.02-7.4 mg L-1) was 10 times higher than that of Cu2+. The metal fractionation in soil treated with ENPs and metal salts may also confirm the role of ENP dissolution. The concentration of potentially bioavailable fraction of Zn increased with a drop in pH. At a 4 pH concentration of Zn in the treatment with nano-ZnO and ZnCl2 was at a similar level (42.1-45 mg kg-1), whereas the addition of nano-CuO resulted in a lower content of Cu (24.7 mg kg-1) than CuCl2 (36.5 mg kg-1). On the other hand, the concentration of fraction exchangeable of both metals in the alkaline soil did not exceed the level of 5.0 mg kg-1. Sample incubation time was especially important for metal participation in samples with a pH of 6.5. The greatest differentiation of metal fractionation between the soils was also noted at a pH of 6.5, which could also have been a result of other properties of the soils. The strong effect of pH on the lability of ENPs in soils confirmed a need to trace the fate of ENPs in extreme soil conditions as well as in changing environment.

What Is the Value of Water Contact Angle on Silicon?

Silicon is a widely applied material and the wetting of silicon surface is an important phenomenon. However, contradictions in the literature appear considering the value of the water contact angle (WCA). The purpose of this study is to present a holistic experimental and theoretical approach to the WCA determination. To do this, we checked the chemical composition of the silicon (1,0,0) surface by using the X-ray photoelectron spectroscopy (XPS) method, and next this surface was purified using different cleaning methods. As it was proved that airborne hydrocarbons change a solid wetting properties the WCA values were measured in hydrocarbons atmosphere. Next, molecular dynamics (MD) simulations were performed to determine the mechanism of wetting in this atmosphere and to propose the force field parameters for silica wetting simulation. It is concluded that the best method of surface cleaning is the solvent-reinforced de Gennes method, and the WCA value of silicon covered by SiO2 layer is equal to 20.7° (at room temperature). MD simulation results show that the mechanism of pure silicon wetting is similar to that reported for graphene, and the mechanism of silicon covered by SiO2 layer wetting is similar to this observed recently for a MOF.

Investigations of chromium(III) oxide removal from the aqueous suspension using the mixed flocculant composed of anionic and cationic polyacrylamides.

The main purpose of experiments was determination of the adsorption mechanism of two forms of ionic polyacrylamide (PAM) on the surface of chromium(III) oxide dispersed in the aqueous medium. This was performed in relation to anionic polyacrylamide (AN PAM) and cationic one (CT PAM) in the simple systems (containing only one selected polymer) and in the mixed systems (containing both ionic forms of PAM). The turbidimetry was applied to determine the stability of examined suspensions. To explain the obtained changes in suspension stability after the polymer addition, polyacrylamide adsorbed amount, surface charge density and zeta potential of solid particles were determined. It was found that the solution pH, order of both adsorbates addition as well as the time interval between the AN and CT PAM addition have considerable influence on the structure of polymeric adsorption layer formed on the Cr2O3 surface. It was also proved that changes in the PAM adsorbed amount in the systems containing mixed adsorbates result from formation of AN PAM - CT PAM complexes. They are bounded at the interface in the formed multilayer. As a result, the dual-polymer flocculation occurs more effectively than the destabilization process in the suspensions containing only one type of adsorbate.

Cremophor EL Nano-Emulsion Monomerizes Chlorophyll a in Water Medium.

In this paper, the application of a non-ionic detergent Cremophor EL for monomerization of chlorophyll a in an aqueous medium is studied. The spectrophotometric properties of chlorophyll a encapsulated into the Cremophor EL nano-emulsion system were characterized by electronic absorption, steady-state and time-resolved fluorescence as well as circular dichroism spectroscopy. The results have shown that chlorophyll a dissolves more efficiently in the aqueous medium containing low-level Cremophor (5 wt%) than at an ethanolic solution even in the concentration of 10-4 M. The molecular organization of the chlorophyll a in the Cremophor EL nano-micelles was also investigated by means of Raman spectroscopy. The spectral changes in the frequency of the C=O stretching group were used to distinguish the aggregation state of chlorophyll. It was revealed that chlorophyll a exists dominantly in the monomeric form in the Cremophor EL aqueous solution. The promising aspect of the use of Cremophor EL nano-emulsion as a delivery system is to maintain stable chlorophyll monomer in an aqueous medium. It would open the potential for a new, practical application of chlorophyll a in medicine, as a dietary supplement or studies on molecular organization of chlorophyll a in the well-defined artificial system.

Surface free energy of sulfur--revisited I. Yellow and orange samples solidified against glass surface.

Surface free energy of two different samples of solidified sulfur (yellow and orange) was investigated, using several approaches for its determination. It was found that values determined about two decades ago for surface free energy of sulfur were overestimated. From current studies the apparent value of this energy ranges between 30 and 60 mJ/m(2), depending on the kind and age of the sulfur samples (up to 1 year old) and/or the probe liquid used for the advancing and receding contact angle measurements. The energy has been calculated from van Oss et al.'s approach (Lifshitz-van der Walls, electron-donor, and electron-acceptor components), the contact angle hysteresis approach proposed by Chibowski, the equation of Owens and Wendt (dispersion and polar components), and Neumann et al.'s equation of state, as well as from equilibrium contact angle using Tadmor's procedure. The lowest values of the energy for 3-day- and 3-month-old samples of sulfur were calculated from the equation of state; they were below the range mentioned above.

Surface free energy of sulfur--revisited II. Samples solidified against different solid surfaces.

The apparent surface free energy of yellow and orange samples of sulfur crystallized at the surface of gold, silicon, and Teflon and in air was evaluated from the advancing and receding contact angles of water. The samples were prepared by casting melted rhombic mineralogical specimen sulfur onto the surface of the above-noted solids. Yellow samples were obtained when just melted sulfur (ca. 120 degrees C) was cast onto the surfaces, and the orange ones, when the melted sulfur was heated longer to a higher temperature (ca. 160 degrees C) and then cast onto the surfaces. The obtained results show that the apparent surface free energy depends on which surface it crystallized. The greatest value is for the sample crystallized at the gold surface, which is 35% higher than that crystallized in air. Generally, the surface free energy of orange samples is slightly higher than that of yellow ones. It is believed that the differences in the energy result from changes in the packing and structural orientation of sulfur atoms on the surfaces.

Effect of polyols on the DMPC lipid monolayers and bilayers.

In this study, the effect of polyols, erythritol, xylitol, mannitol, on a model membrane systems composed of DMPC was investigated using differential scanning calorimetry and Fourier transform infrared spectroscopy. Generally, it is considered that polyols possess strong hydrophilic properties, and either does not interact with the hydrophobic environment at all, or these interactions are very weak. To better understand the mutual interactions between polyols and the lipid system, the Langmuir technique was used to examine the molecular organization of monolayers and to calculate their thickness in the presence of polyols at the subphase. The detailed description of the interactions between polyols and DMPC molecules was complemented by the analysis of the morphology of monolayers with the application of Brewster angle microscopy. From ATR FTIR, the significant spectral shift is observed only for the PO2- stretching band, which correlates strongly with the polyol chain-length. The longer the polyol chain, the weaker the observed interactions with lipid molecules. The most important findings, obtained from thickness measurements, reveal that short-chain polyols may prevent the formation of bilayers by the DMPC molecules under high surface pressure. The changes in the organization of DMPC monolayers on the surface, as visualized by Brewster angle microscopy, showed that the domains observed for phospholipid film spread on pure water differ substantially from those containing polyols in the subphase.

Nanooxide/Polymer Composites with Silica@PDMS and Ceria-Zirconia-Silica@PDMS: Textural, Morphological, and Hydrophilic/Hydrophobic Features.

SiO2@PDMS and CeO2-ZrO2-SiO2@PDMS nanocomposites were prepared and studied using nitrogen adsorption-desorption, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), measurements of advancing and receding contact angles with water, and microcalorimetry. The pore size distributions indicate that the textural characteristics change after oxide modification by poly(dimethylsiloxane) (PDMS). Composites are characterized by mainly mesoporosity and macroporosity of aggregates of oxide nanoparticles or oxide@PDMS nanoparticles and their agglomerates. The FT-IR spectra show that PDMS molecules cover well the oxide surface, since the intensity of the band of free silanols at 3748 cm-1 decreases with increasing PDMS concentration and it is absent in the IR spectrum at C PDMS ≥ 20 wt% that occurs due to the hydrogen bonding of the PDMS molecules to the surface hydroxyls. SEM images reveal that the inter-particle voids are gradually filled and aggregates are re-arranged and increase from 20 to 200 nm in size with the increasing polymer concentration. The highest hydrophobicity (contact angle θ = 140° at C PDMS = 20-40 wt%) is obtained for the CeO2-ZrO2-SiO2@PDMS nanocomposites. The heat of composite immersion in water shows a tendency to decrease with increasing PDMS concentration.