Surface Affinity Research Articles

Determination of seven phenoxy carboxylic acid herbicides in water using dispersive solid phase extraction coupled with ultra-high performance liquid chromatography-tandem mass spectrometry based on metal-organic framework composite aerogel

Phenoxy carboxylic acid herbicides (PCAs) are difficult to degrade and, thus, pose significant threats to the environment and human health. The limit for 2,4-dichlorophenoxyacetic acid is 30 μg/L in China's standards for drinking water quality, 70 μg/L in the United States' drinking water standards, and 30 μg/L in the World Health Organization's guidelines for drinking water quality. Therefore, the development of an effective detection method for trace PCAs in water is a crucial endeavor. Metal-organic frameworks (MOFs) are novel porous materials that possess advantages such as a large specific surface area, adjustable pore size, and abundant active sites. They exhibit excellent adsorption capability for various compounds. However, the applications of MOFs as adsorbents are limited. For example, the process of isolating powdered MOFs from aqueous solutions is laborious, and microporous MOFs exhibit limited surface affinity, which decreases their mass transfer efficiency in the liquid phase. MOF crystals can be embedded in a substrate to overcome these limitations. Aerogels are obtained by drying hydrogels, which are hydrophilic polymers with a three-dimensional crosslinked network structure. Spongy aerogel materials exhibit unique structural properties such as high porosity, large pore volume, ultralow density, and easy tailorability. When MOFs are combined with an aerogel, their efficient and selective adsorption properties are preserved. In addition, MOF aerogels exhibit a hierarchical porous structure, which enhances the affinity and mass transfer efficiency of the MOF for target molecules. At present, MOF aerogels are primarily prepared by freeze-drying or using supercritical carbon dioxide. These drying processes require significant amounts of energy and time. Hence, the development of greener and more efficient methods to prepare skeleton aerogels is urgently needed. In this study, we prepared an environment-friendly aerogel at ambient temperature and pressure without the use of specialized drying equipment. This ambient-dried MOF composite aerogel was then used for the dispersive solid phase extraction (DSPE) of seven PCAs from environmental water, followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The key parameters affecting the efficiency of DSPE, including the extraction conditions, ratio of MIL-101(Fe)-NH2 to sodium alginate, pH of the aqueous samples, extraction time, ionic strength (salinity), and elution conditions, such as the elution solvent ratio, elution time, and elution volume, were investigated to obtain optimal extraction efficiency. The adsorbent could adsorb the target contaminants within 12 min, and the analytes could be completely desorbed within 30 s by elution with 4 mL of 1.5% (v/v) formic acid in methanol solution. The water samples could be analyzed without pH adjustment. The main adsorption mechanisms were electrostatic interactions and π-π conjugation. Thus, a new method based on MOF aerogels coupled with UHPLC-MS/MS was developed for the determination of the seven PCA residues in water. The calibration curves for the seven PCAs showed good linearity (r2≥0.9986), with limits of detection (LODs) and quantification (LOQs) ranging from 0.30 to 1.52 ng/L and from 1.00 to 5.00 ng/L, respectively. Good intra- and inter-day precision values of 6.5%-17.1% and 7.4%-19.4%, respectively, were achieved under low (8 ng/L), medium (80 ng/L), and high (800 ng/L) spiking levels. The developed method was applied to the detection of PCAs in surface water, seawater, and waste leachate, and the detected mass concentrations ranged from 0.6 to 19.3 ng/L. Spiked recovery experiments were conducted at mass concentrations of 8, 80, and 800 ng/L, and the recoveries ranged from 61.7% to 120.3%. The proposed method demonstrates good sensitivity, precision, and accuracy, and has potential applications in the detection of trace PCAs in environmental water.

Contributions of Colloidal Forces to the Heterogeneous Separation of Stable Oil-In-Water Emulsions.

We use theory to study the distribution of spherical emulsion oil droplets in water near a lipophilic surface as a guideline for designing membranes for oil/water phase separation. Heterogeneous phase separations are shown in our laboratory using hydrophilic and hydrophobic membrane designs, where the affinity of the membrane surface to one of the phases in the mixture locally increases its concentration. Considering a colloidal emulsion (nano- to microemulsions) of spherical and noncoalescing droplets, we assess the contribution of colloidal forces, i.e., van der Waals, electrical double layer, and hydrophobic interactions and the finite size of the droplets to the accumulation of spherical emulsion droplets near a surface. We use our theory to study an experiment-inspired case study and find that an isolated lipophilic membrane surface in contact with an oil-in-water emulsion supports the oil-enriched emulsion phase in a thin layer near the membrane surface, suggesting that a membrane pore size comparable to this thickness should support oil-enriched emulsion in the membrane pores and hence past the membrane.

Nonthermal Atmospheric Plasma Promotes Bonding Between Adhesive Monomers and Zirconia.

To investigate whether nonthermal atmospheric plasma (NTAP) can promote bonding between commonly used adhesive monomers and zirconia. The zirconia surface and monomers (HEMA, BisGMA, TEGDMA, and MDP) were treated with different NTAP approaches (10 w, 30 s), and the surface characteristics and chemical structures between the zirconia surface and monomers were verified by the contact angle, scanning electron microscopy (SEM), attenuated total reflectance Fourier transform infrared (ATR/FT-IR) spectroscopy, and x-ray photoelectron spectroscopy (XPS). Scotchbond Universal adhesive with two different resin cements, RelyX Ultimate and RelyX Unicem 2, was applied, followed by NTAP-aided clinical procedures, and then microtensile bond strength test (μTBS) and failure mode evaluation were tested for preliminary mechanical properties assessment. One-way ANOVA was employed for the statistical analysis. The contact angle analysis, SEM, and ATR-FTIR confirmed that NTAP can promote the polymerization of BisGMA, TEGDMA, and MDP on the zirconia surface, while XPS confirmed that NTAP can induce a chemical reaction between MDP and zirconia. Nonthermal atmospheric plasma can increase the affinity between selected monomers and zirconia and promote the chemical bonding strength between phosphate monomers and zirconia; besides, it can enhance the bonding strength of two different adhesive systems. The mechanism of how NTAP improved common adhesive monomers interacting with zirconia surfaces was revealed in this study. NTAP, as a relatively high energy-boosting method, could not only improve the surface affinity of zirconia and chemical bonding in-between monomers and zirconia but also enhance the polymerization of different monomers onto zirconia, resulting in improved bonding properties. Thus, further exploration of versatile bonding materials and/or onto different dental substrates could take this into account.

Spatial Variations in Hydrogen Bonding Interaction within Polymer Blends Revealed by Infrared Nanoimaging.

Hydrogen bonding plays a crucial role in enhancing the miscibility of polymer blends, allowing for the tailoring of their physicochemical properties to meet diverse application demands. However, nanoscale imaging of its impact on the phase-separation behavior of multicomponent polymeric materials remains largely unexplored. In this work, we introduce scattering-type scanning near-field optical microscopy (s-SNOM) equipped with a broadly tunable quantum cascade laser as a tool for investigating spatial variations in hydrogen-bonding interactions within blends of polyvinyl acetate (PVAc) and polyvinylphenol (PVPh), spin-coated from tetrahydrofuran solution. Our multiwavelength s-SNOM imaging approach reveals distinct features, namely, the hydrogen bonding mediated miscible PVAc/PVPh blend and the phase-separated PVAc domain. These results provide a more detailed understanding, indicating that hydrogen bonding may not lead to a completely uniform blend throughout the film, as previously believed, based on far-field spectroscopy. Furthermore, through comparisons between topography and near-field images, we find that the PVAc/PVPh hydrogen-bonded domain exhibits a strong affinity for the Si surface with its native oxide, while the free (non-hydrogen-bonded) PVAc film is vertically phase-separated atop the blend. Overall, our work demonstrates that s-SNOM is an effective and efficient tool for studying intermolecular interactions relevant to various chemical and biological phenomena.

Quantification of the Contribution of Heterogeneous Surface Processes to Pollutant Abatement during Heterogeneous Catalytic Ozonation.

Heterogeneous surface processes such as adsorption and oxidation with surface-adsorbed reactive oxygen species (ROSad, e.g., adsorbed oxygen atom (*Oad) and hydroxyl radicals (•OHad)) have been suggested to play an important role in pollutant abatement during heterogeneous catalytic ozonation (HCO). However, to date, there is no reliable method to quantitatively evaluate the contribution of heterogeneous surface processes to pollutant abatement (fS) during HCO. In this study, we developed a method by combining probe compound-based experiments with kinetic modeling to distinguish heterogeneous surface processes from homogeneous bulk reactions with aqueous O3 and ROS (•OH and superoxide radicals (O2•-) in the abatement of various pollutants (e.g., atrazine, ibuprofen, tetrachloroethylene, and perfluorooctanoic acid) during HCO with reduced graphene oxide. The results show that the pollutants that have a low affinity for the rGO surface (e.g., ibuprofen and tetrachloroethylene) were essentially abated by homogeneous bulk reactions, while the contribution of heterogeneous surface processes was negligible (fS < 5%). In contrast, heterogeneous surface processes played an important or even dominant role in the abatement of pollutants that have a high surface affinity (e.g., fS = 32-82% for atrazine and perfluorooctanoic acid). This study is a critical first step in quantitatively evaluating the role of heterogeneous surface processes for pollutant abatement during HCO, which is crucial to understanding the mechanism of HCO and designing catalysts for effective pollutant abatement.

Roles of kaolinite-oil-gas molecular interactions in hydrogen storage within depleted reservoirs

Hydrogen is a clean alternative to fossil fuels, emitting only water vapor during combustion. In a future hydrogen economy, large-scale storage will be an important component of the supply chain. Due to its low volumetric density, conventional surface storage methods are inadequate. Underground hydrogen storage (UHS) offers a viable solution, enabling the storage of millions of cubic meters. Among potential geological sites, including salt caverns, aquifers, and depleted gas reservoirs, depleted oil reservoirs show promise. Studying hydrogen interactions with residual oil and reservoir minerals is vital for understanding the properties of hydrogen and the reservoir post-injection. In this study, we employed molecular dynamics simulations to gain molecular-level insights into these interactions. We investigated hydrogen dissolution in oil, adsorption at kaolinite/oil interfaces, the role of CO2 as a cushion gas, and the influence of kaolinite’s hydrophobicity on H2 behavior. The main findings include: (1) hydrogen dissolves more in oil than in water, (2) the introduction of CO2 suppresses hydrogen dissolution in oil and reduces the interfacial tension (IFT) between oil and gas, (3) CO2 decreases H2 partitioning near kaolinite surfaces due to its strong affinity for the hydrophilic gibbsite surface of kaolinite, and (4) CO2 is more effective than H2 in reducing IFT between kaolinite and the oil–gas mixture. These findings emphasize the effectiveness of CO2 as a cushion gas and the important role of clay hydrophobicity in UHS, providing insights that are challenging to obtain experimentally.

Effects of Cosolvent on the Intermolecular Interactions between an Analyte and a Gold Nanostar Surface Studied Using SERS.

For surface-enhanced Raman scattering (SERS), reproducible solution-phase results are typically obtained using nanoparticles functionalized with surface-stabilizing molecules that can prevent the adsorption of analyte molecules with surface affinities lower than those of the stabilizing agent. Herein, we investigate the effects of intermolecular interactions between a nonthiolated analyte and cosolvent to facilitate and modulate analyte adsorption to gold nanostars. SERS, extinction spectroscopy, transmission electron microscopy (TEM), and density functional theory (DFT) calculations are employed in this regard. Tetrahydrofuran (THF) is utilized as a cosolvent in water to facilitate the detection of acetylsalicylic acid (aspirin) on anisotropic gold nanoparticles. Intermolecular interactions between the analyte, solvent, and surface are modulated by changing the solution composition to understand how THF facilitates the SERS detection of aspirin in THF-water cosolvents. SERS signals for 5 mM aspirin arise only in the presence of THF at and above 60 mM, while no signal with or without THF below 60 mM is observed. SERS detection of aspirin is hypothesized to depend on THF forming a hydrogen-bonded complex with aspirin that reduces aspirin hydrophobicity, thus stabilizing the acid form of the molecule and allowing it to weakly interact with the gold nanoparticles. The aspirin-THF complex adsorbs to the gold surface through π-orbital overlap between the aromatic ring and gold, where additional THF weakens orbital overlap. Understanding the mechanism by which organic cosolvents facilitate the SERS detection of nonthiolated analytes such as aspirin, in aqueous media, allows other cosolvents, nonthiolated analytes, and other surfaces to obtain a SERS signal in a variety of systems.

Non-damaged preparation and energy band structure modulation of silicon-based nitrogen-terminated diamond films

The surface terminal structure of diamond film determines its surface physical properties. In this paper, the surface of silicon-based polycrystalline diamond film was nitrided by radio frequency (RF) plasma, and the evolution of the diamond surface termination structure under different nitridation temperatures and times was investigated. In-situ X-ray photoelectron spectroscopy (XPS) analysis showed that nitridation at 600 °C is beneficial for the more effective formation of nitrogen terminal diamond (N-diamond) structure dominated by CN bonds on the diamond surface. In-situ ultraviolet photoelectron spectroscopy (UPS) indicated that the electron affinity of diamond surface can gradually change from negative to positive with prolonged nitridation time. The increased positive electron affinity (PEA) of surface terminations made it more difficult for electrons to escape from the diamond surface, resulting in a significant decrease in the intensity of the secondary electron peak. Furthermore, AFM and Raman measurements indicated that nitridation treatment does not significantly improve the surface roughness of diamond or form graphite phase, which realized the preparation of non-damaged N-diamond.

Laser Direct Writing of Setaria Virids-Inspired Hierarchical Surface with TiO2 Coating for Anti-Sticking of Soft Tissue.

In minimally invasive surgery, the tendency for human tissue to adhere to the electrosurgical scalpel can complicate procedures and elevate the risk of medical accidents. Consequently, the development of an electrosurgical scalpel with an anti-sticking coating is critically important. Drawing inspiration from nature, we identified that the leaves of Setaria Virids exhibit exceptional non-stick properties. Utilizing this natural surface texture as a model, we designed and fabricated a specialized anti-sticking surface for electrosurgical scalpels. Employing nanosecond laser direct writing ablation technology, we created a micro-nano textured surface on the high-frequency electrosurgical scalpel that mimics the structure found on Setaria Virids leaves. Subsequently, a TiO2 coating was deposited onto the ablated scalpel surface via magnetron sputtering, followed by plasma-induced hydrophobic modification and treatment with octadecyltrichlorosilane (OTS) to enhance the surface's affinity for silicone oil, thereby constructing a self-lubricating and anti-sticking surface. The spreading behavior of deionized water, absolute ethanol, and dimethyl silicone oil on this textured surface is investigated to confirm the effectiveness of the self-lubrication mechanism. Furthermore, the sticking force and quality are compared between the anti-sticking electrosurgical scalpel and a standard high-frequency electrosurgical scalpel to demonstrate the efficacy of the nanosecond laser-ablated micro-nano texture in preventing sticking. The findings indicate that the self-lubricating anti-sticking surface fabricated using this texture exhibits superior anti-sticking properties.

3D Co-doped carbon nanosheets as high-performance electrodes for Li-S batteries

3D petal-shaped Cobalt-doped carbon nanosheets (PCoCNS) were synthesized as excellent sulfur hosts for lithium-sulfur (Li-S) batteries. Co doping enhanced the affinity of the carbon surface for lithium polysulfides (LiPSs), inhibiting the shuttle effect. The electrocatalytic effect of the PCoCNS electrode exhibited enhanced polysulfide conversion kinetics, thereby promoting Li2S formation. Owing to the above advantages, the PCoCNS cathode exhibited satisfactory reversibility of 841 mAh/g with a high capacity retention of 91 %. Additionally, it displayed high coulombic efficiency (CE) values exceeding 97 % over 100 cycles at a current rate of 0.5C. Furthermore, the electrode demonstrated low polarization and exhibited an excellent rate performance, delivering a capacity of 575 mAh/g at the high rate of 3C. This study synthesized a promising sulfur cathode for enhancing the electrochemical performance of Li-S batteries.

Insights in the wettability of hard chromium coated steel for cold rolling applications

The use of toxic Cr (VI) in the chrome plating process poses significant health risks, highlighting the urgent need to find sustainable alternatives for many applications such as cold rolling. Understanding key properties of functional chrome coating in lubricated industrial processes, especially its wetting properties that can support lubrication, low friction, and durability, is essential for the development of safer coating processes. However, the wetting properties of hard chromium coating are not fully understood. This study investigates the wetting characteristics of chromium coatings in comparison to uncoated steel. The study explores the dynamic wetting behavior by conducting contact angle measurements with water and lubricant oil, determining surface free energy using the sessile drop method, and characterizing the surface through X-ray photoelectron spectroscopy analysis. The findings reveal that a standard hard chrome coating exhibits superior wettability by both water and oil and higher surface energy compared to uncoated steel. The research, supported by theoretical modelling, highlights that factors are not limited to chromium alone, but rather involve a multilayer system that includes chromium oxide and organic contaminations, which have a substantial impact on surface properties and wettability. Increased levels of organic contamination on the chrome-coated surface, are shown to result in weaker intermolecular interactions with the contacting fluid, leading to reduced surface affinity to water and consequently result in higher contact angles. Our findings provide critical insights into the intricate nature of chromium coatings and lay foundations for developing sustainable alternatives.

Green synthesis of magnesium oxide nanoparticles using Hyphaene thebaica extract and their photocatalytic activities

Magnesium oxide nanoparticles (MgO NPs) represent an interesting inorganic material widely utilized across various fields including sensing, antimicrobial applications, optical coatings, water purification, fuel additives, absorbents, and catalysis, owing to their exceptional broad energy band gap, surface affinity, and strong chemical and thermal durability. In this investigation, MgO NPs were successfully synthesized through a green approach employing fruit extract from the gingerbread tree (Hyphaene thebaica). Analysis via scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirmed their agglomerated quasi-spherical shape with a size range of 20–60 nm. The X-ray diffraction (XRD) pattern exhibited prominent peaks at planes (200) and (220), indicating the high crystallinity of MgO NPs with a crystallite size of 32.6 ± 5 nm while Energy-dispersive X-ray spectroscopy (EDS) analysis highlighted the composition comprises 40.47% Magnesium and 48.64% Oxygen by weight. Fourier transform infrared spectroscopy (FT-IR) revealed characteristic Mg-O bonds through peaks at 560 cm−1 and 866 cm−1, while Raman spectroscopy affirmed the cubic structure of MgO. Subsequently, the photocatalytic performance of MgO NPs under visible light irradiation was evaluated. Remarkably, the addition of 1 g/L of MgO nano-catalyst resulted in a degradation efficiency of 98% after 110 min on methylene blue dye, showcasing the high catalytic activity of MgO NPs. This remarkable photocatalytic efficiency emphasizes the potential of MgO NPs in environmental remediation.

A negatively charged cluster in the disordered acidic domain of GPIHBP1 provides selectivity in the interaction with lipoprotein lipase

GPIHBP1 is a membrane protein of endothelial cells that transports lipoprotein lipase (LPL), the key enzyme in plasma triglyceride metabolism, from the interstitial space to its site of action on the capillary lumen. An intrinsically disordered highly negatively charged N-terminal domain of GPIHBP1 contributes to the interaction with LPL. In this work, we investigated whether the plethora of heparin-binding proteins with positively charged regions found in human plasma affect this interaction. We also wanted to know whether the role of the N-terminal domain is purely non-specific and supportive for the interaction between LPL and full-length GPIHBP1, or whether it participates in the specific recognition mechanism. Using surface plasmon resonance, affinity chromatography, and FRET, we were unable to identify any plasma component, besides LPL, that bound the N-terminus with detectable affinity or affected its interaction with LPL. By examining different synthetic peptides, we show that the high affinity of the LPL/N-terminal domain interaction is ensured by at least ten negatively charged residues, among which at least six must sequentially arranged. We conclude that the association of LPL with the N-terminal domain of GPIHBP1 is highly specific and human plasma does not contain components that significantly affect this complex.

Dual-mode electrochemical and SERS detection of PFAS using functional porous substrate

Human activity is the cause of the continuous and gradual grooving of environmental contaminants, where some released toxic and dangerous compounds cannot be degraded under natural conditions, resulting in a serious safety issue. Among them are the widely occurring water-soluble perfluoroalkyl and polyfluoroalkyl substances (PFAS), sometimes called “forever chemicals” because of the impossibility of their natural degradation. Hence, a reliable, expressive, and simple method should be developed to monitor and eliminate the risks associated with these compounds. In this study, we propose a simple, express, and portable detection method for water-soluble fluoro-alkyl compounds (PFOA and GenX) using mutually complementary methods: electrochemical impedance spectroscopy (EIS) and surface-enhanced Raman spectroscopy (SERS). To implement our method, we developed special substrates based on porous silicon with a top-deposited plasmon-active Au layer by subsequently grafting –C6H4-NH2 chemical moieties to provide surface affinity toward negatively charged water-soluble PFAS. Subsequent EIS utilization allows us to perform semiquantitative detection of PFOA and GenX up to 10−10 M concentration because surface entrapping of PFAS leads to a significant increase in the electrode–electrolyte charge-transfer resistance. However, distinguishing by EIS whether even PFAS were entrapped was impossible, and thus the substrates were subsequently subjected to SERS measurements (allowed by surface plasmon activity due to the presence of a porous Au layer), clearly indicating the appearance of characteristic C–F vibration bands.

Carbon black dispersing agents based on fully hydrophilic poly(N‐vinylamide): Surface adsorption via selective interactions

AbstractInterface‐stabilizing polymers are frequently used in commercial applications to provide long‐lasting dispersions of colloids in liquid media. Dispersing high concentrations of pigments in aqueous solution can be particularly challenging. Here, we present a novel, fully hydrophilic dispersing agent system for carbon black (CB) pigments based on partially hydrolyzed poly(N‐vinylamides). These highly water‐soluble polymers adsorb onto CB through specific interactions between the polymer and surface‐bound moieties, rather than the hydrophobic effect. They participate in hydrogen bonding, ion–dipole interactions and can be partially positively charged to engage in ion pair formation, providing strong surface affinity. Dispersants are synthesized using free radical copolymerization of N‐vinylform‐ and ‐acetamide, acidic hydrolysis, and subsequent PEGylation. Molecular water solubility of the synthesized polymers is confirmed by using fluorescence spectroscopy. Highly concentrated CB dispersions are prepared in acidic, neutral, and basic media, which we identify to strongly affect the interactions between polymer and CB. The stability of CB dispersions is analyzed using ultracentrifugation and thermogravimetric analysis. The presented polymers are able to provide significantly more stable dispersions than a commercial reference product, showcasing the suitability of poly(N‐vinylamines) as potent CB dispersing agents.

Competitive Effects of Anions on Protein Solvation by Aqueous Ionic Liquids.

The present study utilizes molecular dynamics simulations to examine how different anions compete for protein solvation in aqueous solutions of ionic liquids (ILs). Ubiquitin is used as model protein and studied in IL mixtures sharing the same cation, 1-ethyl-3-methylimidazolium (EMIM), and two different anions in the same solution, from combinations of dicyanamide (DCA), chloride (Cl), nitrate (NO3), and tetrafluoroborate (BF4). Our findings reveal that specific interactions between anions and the protein are paramount in IL solvation, but that combinations of anions are not additive. For example, DCA exhibits a remarkable ability to form hydrogen bonds with the protein, resulting in a significantly stronger preferential binding to the protein than other anions. However, the combination of DCA with NO3, which also forms hydrogen bonds with the protein, results in a smaller preferential solvation of the protein than the combination of DCA with chloride ions, which are weaker binders. Thus, combining anions with varying affinities for the protein surface modulates the overall ion accumulation through nonadditive mechanisms, highlighting the importance of the understanding of competition for specific interaction sites, cooperative binding, bulk-solution affinity, and overall charge compensations, on the overall solvation capacity of the solution. Such knowledge may allow for the design of novel IL-based processes in biotechnology and material science, where fine-tuning protein solvation is crucial for optimizing performance and functionality.

Engineered intrinsically fluorescent galectin-8 variants with altered valency, ligand recognition and biological activity

Galectin-8 is a small soluble lectin with two carbohydrate recognition domains (CRDs). N- and C-terminal CRDs of Gal-8 differ in their specificity for glycan ligands. Here, we wanted to find out whether oligomerization of individual CRDs of galectin-8 affects its biological activity. Using green fluorescent protein polygons (GFPp) as an oligomerization scaffold, we generated intrinsically fluorescent CRDs with altered valency. We show that oligomers of C-CRD are characterized by significant cell surface affinity. Furthermore, the multivalency of the resulting variants has an impact on cellular activities such as cell signaling, heparin binding and proliferation. Our data indicates that tunable valence is a useful tool for modifying the biological activity of CRDs of galectins.

Mixing behaviour and sources of Ag, Pd, and other trace elements in the Estuary and Gulf of St. Lawrence under winter conditions

The marine chemistry of platinum group elements is poorly documented despite robust evidence of their widespread emissions and deposition around the globe. Here, we report the concentrations and discuss the geochemical behaviours of Ag, Pd and other trace and ultra-trace elements in the Estuary and Gulf of St. Lawrence (EGSL). We highlight the contrasting mixing behaviours of these elements, i.e., conservative (Cd, Re) vs. non-conservative (Ag, Pd), in samples collected during the winter and under ice-covered conditions. We ascribe the contrasting geochemical behaviour of these elements to their differential affinity for reactive surfaces carried into the estuary from the frozen watersheds. We also report an increase of the concentrations of Ag (up to 40 pmol L−1), Pd (up to 10 pmol L−1) and Pt (up to 0.4 pmol L−1) in the bottom and oxygen-depleted waters of the Gulf of St. Lawrence (GSL). A strong correlation between dissolved Pt concentrations and the stable carbon isotopic composition of the dissolved inorganic carbon (δ13C-DIC) suggests that the increased mobility of Pt may result from the aerobic mineralization of organic carbon or the oxidation of Pt-bearing organic complexes. Molar Pt/Pd ratios in the three water masses that compose the water column in the EGSL highlight a potential influence of anthropogenic sources near urban centers. The signature of continental end-members will be required to confirm the impacts of road traffic on the estuarine geochemistry of these elements.

Water sorption modeling and monolayer of biological and food materials

Despite water molecules are strongly hydrogen bonding to hydrophilic solids, the Brunauer-Emmet-Teller (BET) and Guggenheim-Anderson-de Boer (GAB) surface adsorption models have been widely accepted to describe water sorption properties of biological and food materials. These mathematically quite similar models use parameters which include a theoretical ‘monolayer’ value and one or two other parameters which describe ‘surface affinity’ in thermodynamic terms as heat of sorption. A high surface affinity indicates a strong surface binding of water molecules and preferential monolayer adsorption prior to multilayer sorption. Conversely, biological materials are water plasticized and suffer physicochemical changes at various stages of water sorption. Dynamic water sorption measurements often show regions where time-dependent changes in material characteristics, such as viscous flow and crystallization, may occur as a result of the glass transition. The two or three parameters of the BET and GAB models, respectively, are useful in the analysis of water sorption characteristics of individual substances, although the existence of a monolayer particularly in multicomponent materials may not be justified. Fitting the models to experimental data may occur rather for empirical than theoretical reasons.

Enhanced removal of nano-oil droplets utilizing polysilicate aluminum ferric (PSAF): Leveraging bridging and non-polar surface advantages.

Hydraulic oil leaks during mechanical maintenance, resulting in flushing wastewater contaminated with dispersed nano-oil droplets. In this study, 75 mg L-1 of polysilicate aluminum ferric (PSAF) was stirred at 350 rpm and the optimal chemical oxygen demand (COD) removal was 71%. The increase of PSAF led to more hydrolysis of Fe, and 1,175 cm-1 hydroxyl bridged with negative oil droplets. At the same molar concentration, PSAF hydrolyzes cationic metals more rapidly than polymeric aluminum chloride (PAC). PSAF forms flocs of smaller complex structures with greater bridging. The Al-O and Si-O peaks occurred at 611 and 1,138 cm-1, indicating the formation of Si-O-Fe and Si-O-Al bonds on the flocs surface. Higher stirring speeds did not change the free energy of the flocs surface γTot, mainly because the decrease in the van der Waals force (γLW) offset the increase of Lewis acid-base force (γAB). Preserving the non-polar surface, in summary, owing to its bridging abilities and affinity for non-polar surfaces, PSAF demonstrates superior efficiency over PAC in capturing and removing oil droplets.