Heavy Metal Remediation by Dry Mycelium Membranes: Approaches to Sustainable Lead Remediation in Water.

Lead contamination poses significant and lasting health risks, particularly in children. This study explores the efficacy of dried mycelium membranes, distinct from live fungal biomass, for the remediation of lead (Pb(II)) in water. Dried mycelium offers unique advantages, including environmental resilience, ease of handling, biodegradability, and mechanical reliability. The study explores Pb(II) removal mechanisms through sorption and mineralization by dried mycelium hyphae in aqueous solutions. The sorption isotherm studies reveal a high Pb(II) removal efficiency, exceeding 95% for concentrations below 1000 ppm and ∼63% above 1500 ppm, primarily driven by electrostatic interactions. The measured infrared peak shifts and the pseudo-second-order kinetics for sorption suggests a correlation between sorption capacity and the density of interacting functional groups. The study also explores novel surface functionalization of the mycelium network with phosphate to enhance Pb(II) removal, which enables remediation efficiencies >95% for concentrations above 1500 ppm. Scanning electron microscopy images show a pH-dependent formation of Pb-based crystals uniformly deposited throughout the entire mycelium network. Continuous cross-flow filtration tests employing a dried mycelium membrane demonstrate its efficacy as a microporous membrane for Pb(II) removal, reaching remediation efficiency of 85-90% at the highest Pb(II) concentrations. These findings suggest that dried mycelium membranes can be a viable alternative to synthetic membranes in heavy metal remediation, with potential environmental and water treatment applications.

Gradient porous structures of mycelium: a quantitative structure-mechanical property analysis.

Gradient porous structures (GPS) are characterized by structural variations along a specific direction, leading to enhanced mechanical and functional properties compared to homogeneous structures. This study explores the potential of mycelium, the root part of a fungus, as a biomaterial for generating GPS. During the intentional growth of mycelium, the filamentous network undergoes structural changes as the hyphae grow away from the feed substrate. Through microstructural analysis of sections obtained from the mycelium tissue, systematic variations in fiber characteristics (such as fiber radii distribution, crosslink density, network density, segment length) and pore characteristics (including pore size, number, porosity) are observed. Furthermore, the mesoscale mechanical moduli of the mycelium networks exhibit a gradual variation in local elastic modulus, with a significant change of approximately 50% across a 30 mm thick mycelium tissue. The structure-property analysis reveals a direct correlation between the local mechanical moduli and the network crosslink density of the mycelium. This study presents the potential of controlling growth conditions to generate mycelium-based GPS with desired functional properties. This approach, which is both sustainable and economically viable, expands the applications of mycelium-based GPS to include filtration membranes, bio-scaffolds, tissue regeneration platforms, and more.

Adsorption behavior of long-chain perfluoroalkyl substances on hydrophobic surface: A combined molecular characterization and simulation study.

Hydrophobic interaction is a prevalent sorption mechanism of poly- and perfluoroalkyl substances (PFAS) in natural and engineered environments. In this study, we combined quartz crystal microbalance with dissipation (QCM-D), atomic force microscope (AFM) with force mapping, and molecular dynamics (MD) simulation to probe the molecular behavior of PFAS at the hydrophobic interface. On a CH3-terminated self-assembled monolayer (SAM), perfluorononanoic acid (PFNA) showed ∼2-fold higher adsorption than perfluorooctane sulfonate (PFOS) that has the same fluorocarbon tail length but a different head group. Kinetic modeling using the linearized Avrami model suggests that the PFNA/PFOS-surface interaction mechanisms can evolve over time. This is confirmed by AFM force-distance measurements, which shows that while the adsorbed PFNA/PFOS molecules mostly lay flat, a portion of them formed aggregates/hierarchical structures of 1-10 nm in size after lateral diffusion on surface. PFOS showed a higher affinity to aggregate than PFNA. Association with air nanobubbles is observed for PFOS but not PFNA. MD simulations further showed that PFNA has a greater tendency than PFOS to have its tail inserted into the hydrophobic SAM, which can enhance adsorption but limit lateral diffusion, consistent with the relative behavior of PFNA/PFOS in QCM and AFM experiments. This integrative QCM-AFM-MD study reveals that the interfacial behavior of PFAS molecules can be heterogeneous even on a relatively homogeneous surface.

Surface Modifications of High-Performance Polymer Polyetheretherketone (PEEK) to Improve Its Biological Performance in Dentistry.

This comprehensive review focuses on polyetheretherketone (PEEK), a synthetic thermoplastic polymer, for applications in dentistry. As a high-performance polymer, PEEK is intrinsically robust yet biocompatible, making it an ideal substitute for titanium-the current gold standard in dentistry. PEEK, however, is also inert due to its low surface energy and brings challenges when employed in dentistry. Inert PEEK often falls short of achieving a few critical requirements of clinical dental materials, such as adhesiveness, osseoconductivity, antibacterial properties, and resistance to tribocorrosion. This study aims to review these properties and explore the various surface modification strategies that enhance the performance of PEEK. Literatures searches were conducted on Google Scholar, Research Gate, and PubMed databases using PEEK, polyetheretherketone, osseointegration of PEEK, PEEK in dentistry, tribology of PEEK, surface modifications, dental applications, bonding strength, surface topography, adhesive in dentistry, and dental implant as keywords. Literature on the topics of surface modification to increase adhesiveness, tribology, and osseointegration of PEEK were included in the review. The unavailability of full texts was considered when excluding literature. Surface modifications via chemical strategies (such as sulfonation, plasma treatment, UV treatment, surface coating, surface polymerization, etc.) and/or physical approaches (such as sandblasting, laser treatment, accelerated neutral atom beam, layer-by-layer assembly, particle leaching, etc.) discussed in the literature are summarized and compared. Further, approaches such as the incorporation of bioactive materials, e.g., osteogenic agents, antibacterial agents, etc., to enhance the abovementioned desired properties are explored. This review presents surface modification as a critical and essential approach to enhance the biological performance of PEEK in dentistry by retaining its mechanical robustness.

Comparative Degradation Kinetics Study of Polyamide Thin Films in Aqueous Solutions of Chlorine and Peracetic Acid Using Quartz Crystal Microbalance.

Polyamide thin film composite membranes are widely used in water reclamation. Peracetic acid (PAA) is an emerging wastewater disinfectant with a potential for membrane cleaning and disinfection; however, its interaction with polyamide remains poorly understood. This study employs quartz crystal microbalance with dissipation (QCM-D) to determine the PAA-induced degradation kinetics of polyamide thin films, in comparison with the conventional disinfectant-free chlorine (HOCl). Polyamide films showed a sorption phase followed by a degradation phase when exposed to PAA (1000 mg L-1) and HOCl (100 mg L-1) solutions. While the sorption phase in HOCl experiments was short (1.4-3.5 min) and followed a Boltzmann-sigmoidal model, it spanned over 3-33 h in PAA experiments and displayed a two-stage behavior. The latter kinetics are attributed to sequential processes of the physical sorption of PAA in polyamide films followed by PAA-induced polyamide oxidation. In the degradation phase, the HOCl-exposed films followed a rapid, two-step exponential decay reaching an equilibrium mass of ∼50% of the initial (wet) mass after ∼5 h of exposure. In contrast, the PAA-exposed films followed a Boltzmann-sigmoidal decay, with ∼80% of the initial (wet) mass remaining intact after >10 h of exposure. Fast force maps generated using atomic force microscopy showed a progressive increase in the morphological heterogeneity of the polyamide films in HOCl solution due to pitting, cracking, bulging, and eventual delamination under both flow and no-flow conditions. In contrast, PAA only formed small pits on the polyamide film under flow; in a stagnant PAA solution, the film had no visible changes even after ∼148 h of exposure. This is the first comparative study on the chemical and morphological changes in polyamide films induced by PAA and HOCl. The much higher compatibility of polyamide with PAA than with chlorine supports the potential of PAA being used as a halogen-free membrane cleaning/disinfecting agent.

Aggregation Behavior of Inorganic 2D Nanomaterials Beyond Graphene: Insights from Molecular Modeling and Modified DLVO Theory.

We report the comparative aggregation behavior of three emerging inorganic 2D nanomaterials (NMs): MoS2, WS2, and h-BN in aquatic media. Their aqueous dispersions were subjected to aggregation under varying concentrations of monovalent (NaCl) and divalent (CaCl2) electrolytes. Moreover, Suwanee River Natural Organic Matter (SRNOM) has been used to analyze the effect of natural macromolecules on 2D NM aggregation. An increase in electrolyte concentration resulted in electrical double-layer compression of the negatively charged 2D NMs, thus displaying classical Derjaguin-Landau-Verwey-Overbeek (DLVO)-type interaction. The critical coagulation concentrations (CCC) have been estimated as 37, 60, and 19 mM NaCl and 3, 7.2, and 1.3 mM CaCl2 for MoS2, WS2, and h-BN, respectively. Theoretical predictions of CCC by modified DLVO theory have been found comparable to the experimental values when dimensionality of the materials is taken into account and a molecular modeling approach was used for calculating molecular level interaction energies between individual 2D NM nanosheets. Electrostatic repulsion has been found to govern colloidal stability of MoS2 and WS2 while the van der Waals attraction has been found to govern that of h-BN. SRNOM stabilizes the 2D NMs significantly possibly by electrosteric repulsion. The presence of SRNOM completely stabilized MoS2 and WS2 at both low and high ionic strengths. While h-BN still showed appreciable aggregation in the presence of SRNOM, the aggregation rates were decreased by 2.6- and 3.7-fold at low and high ionic strengths, respectively. Overall, h-BN nanosheets will have higher aggregation potential and thus limited mobility in the natural aquatic environment when compared to MoS2 and WS2. These results can also be used to mechanistically explain fate, transport, transformation, organismal uptake, and toxicity of inorganic 2D NMs in the natural ecosystems.

Assembly, Morphology, Diffusivity, and Indentation of Hydrogel-Supported Lipid Bilayers.

Recognizing the limitations of solid-supported lipid bilayers to reproduce the behavior of cell membranes, including bendability, transmembrane protein inclusion, and virus entry, this study describes a novel biomimetic system for cell membranes with the potential to overcome these and other limitations. The developed strategy utilizes a hydrogel with tunable mechanical behavior that resembles those of living cells as the soft support for the phospholipid bilayer, while a polyelectrolyte multilayer film serves as an intermediate layer to facilitate the self-assembly of the lipid bilayer on the soft cushion. Quartz crystal microbalance studies show that, upon coming into contact with the polyelectrolyte film, vesicles fuse and rupture to yield a robust lipid bilayer. Fluorescence recovery after photobleaching confirms the formation of a membrane, while atomic force microscopy shows a low adhesion between the indenting probe and the bilayer. More importantly, in comparison to the solid-supported lipid bilayer, the response of this biomimetic system to nanoindentation demonstrates its increased mechanical stability and bendability when assembled on a soft cushion. Hence, the developed hydrogel-supported lipid bilayers can mimic biomechanical properties of cell membranes, which will enable scientists to study and to understand biophysicochemical interactions between cell membranes and extracellular entities.

Competitive Adsorption of Polyelectrolytes onto and into Pellicle-Coated Hydroxyapatite Investigated by QCM-D and Force Spectroscopy.

A current effort in preventive dentistry is to inhibit surface attachment of bacteria using antibacterial polymer coatings on the tooth surface. For the antibacterial coatings, the physisorption of anionic and cationic polymers directly onto hydroxyapatite (HA) and saliva-treated HA surfaces was studied using quartz crystal microbalance, force spectroscopy, and atomic force microscopy. First, single species adsorption is shown to be stronger on HA surfaces than on silicon oxide surfaces for all polymers (i.e., Gantrez, sodium hyaluronate (NaHa), and poly(allylamine-co-allylguanidinium) (PAA-G75)). It is observed through pH dependence of Gantrez, NaHa, and PAA-G75 adsorption on HA surfaces that anionic polymers swell at high pH and collapse at low pH, whereas cationic polymers behave in the opposite fashion. Thicknesses of Gantrez, NaHa, and PAA-G75 are 52 nm (46 nm), 35 nm (11 nm), and 6 nm (54 nm) at pH 7 (3.5), respectively. Second, absorption of charged polymer is followed by absorption of the oppositely charged polymer. Upon exposure of the anionic polymer layers, Gantrez and NaHa, to the cationic polymer, PAA-G75, films collapse from 52 to 8 nm and 35 to 11 nm, respectively. This decrease in film thickness is attributed to the electrostatic cross-linking between anionic and cationic polymers. Third, for HA surfaces pretreated with artificial saliva (AS), the total thickness decreases from 25 to 16 nm upon exposure to PAA-G75. Force spectroscopy is used to further investigate the PAA-G75/AS coating. The results show that the interaction between a negatively charged colloidal bead and the AS surface is strongly repulsive, whereas PAA-G75/AS is attractive but varies across the surface. Additionally, AFM studies show that AS/HA is smooth with a RMS roughness of 1.7 nm, and PAA-G75-treated AS/HA is rough (RMS roughness of 5.4 nm) with patches of polymer distributed across the surface with an underlying coating. The high roughness of PAA-G75 treated AS/HA is attributed to the strong adsorption of the relatively small PAA-G75 onto the heterogeneously distributed negatively charged AS surface. In addition, uptake of PAA-G75 by pellicle layer (saliva-treated HA surface) is observed, and the adsorbed amount of PAA-G75 on/into pellicle layer is ∼2 times more than that on/into AS layer. These studies show that polymer adsorption onto HA and saliva-coated HA depends strongly on the polymer type and size and that there is an electrostatic interaction between polymer and saliva and/or oppositely charged polymers that stabilizes the coatings on HA. Lastly, assessing the viability of the adherent bacteria collected from the PAA-G75-coated surfaces showed a significant reduction (∼93%) in bacterial viability when compared to bacteria collected from untreated and Gantrez-coated HA. These results suggest the potential antimicrobial activity of PAA-G75.

Nanomechanics of pH-Responsive, Drug-Loaded, Bilayered Polymer Grafts.

Stimuli-responsive polymer films play an important role in the development of smart antibacterial coatings. In this study, we consider complementary architectures of polyelectrolyte films, including a thin chitosan layer (CH), poly(acrylic acid) (PAA) brushes, and a bilayer structure of CH grafted to PAA brushes (CH/PAA) as possible candidates for targeted drug delivery platforms. Atomic force microscopy (AFM) was employed to study the structure-mechanical property relationship for these mono- and bi-layered polymer grafts at pH 7.4 and 4.0, corresponding to physiological and biofilm formation conditions, respectively. Herein, the surface interactions between polymer grafts and the negatively charged silica colloid attached to an AFM lever are considered as representative interactions between the antibacterial coating and a bacteria/biofilm. The bilayered structure of CH/PAA showed significantly reduced adhesive interactions in comparison to pure CH but slightly higher interactions in comparison to PAA films. Among PAA and CH/PAA films, upon grafting CH over the PAA brushes, the normal stiffness increased by 10-fold at pH 7.4 and 20-fold at pH 4.0. Notably, the study also showed that the addition of an antibiotic drug such as multicationic Tobramycin (TOB) impacts the mechanical properties of the antibacterial coatings. Competition between TOB and water molecules for the PAA chains is shown to determine the structural properties of PAA and CH/PAA films loaded with TOB. At high pH (7.4), the TOB molecules, which remain multicationic, strongly interact with polyanionic PAA, thereby reducing the film's compressibility. On the contrary, at low pH (4.0), the water molecules preferentially interact with TOB in comparison to uncharged PAA chains and, upon TOB release, results in a stronger film collapse together with an increase in adhesive interactions between the probe, the surface, and the elastic modulus of the film. The bacterial proliferation on these platforms when compared to the measured mechanical properties shows a direct correlation; hence, understanding nanomechanical properties can provide insights into designing new antibacterial polymer coatings.

Nano-rheology of hydrogels using direct drive force modulation atomic force microscopy.

We present a magnetic force-based direct drive modulation method to measure local nano-rheological properties of soft materials across a broad frequency range (10 Hz to 2 kHz) using colloid-attached atomic force microscope (AFM) probes in liquid. The direct drive method enables artefact-free measurements over several decades of excitation frequency, and avoids the need to evaluate medium-induced hydrodynamic drag effects. The method was applied to measure the local mechanical properties of polyacrylamide hydrogels. The frequency-dependent storage stiffness, loss stiffness, and loss tangent (tan δ) were quantified for hydrogels having high and low crosslinking densities by measuring the amplitude and the phase response of the cantilever while the colloid was in contact with the hydrogel. The frequency bandwidth was further expanded to lower effective frequencies (0.1 Hz to 10 Hz) by obtaining force-displacement (FD) curves. Slow FD measurements showed a recoverable but highly hysteretic response, with the contact mechanical behaviour dependent on the loading direction: approach curves showed Hertzian behaviour while retraction curves fit the JKR contact mechanics model well into the adhesive regime, after which multiple detachment instabilities occurred. Using small amplitude dynamic modulation to explore faster rates, the load dependence of the storage stiffness transitioned from Hertzian to a dynamic punch-type (constant contact area) model, indicating significant influence of material dissipation coupled with adhesion. Using the appropriate contact model across the full frequency range measured, the storage moduli were found to remain nearly constant until an increase began near ∼100 Hz. The softer gels' storage modulus increased from 7.9 ± 0.4 to 14.5 ± 2.1 kPa (∼85%), and the stiffer gels' storage modulus increased from 16.3 ± 1.1 to 31.7 ± 5.0 kPa (∼95%). This increase at high frequencies may be attributed to a contribution from solvent confinement in the hydrogel (poroelasticity). The storage moduli measured by both macro-rheometry and AFM FD curves were comparable to those measured using the modulation method at their overlapping frequencies (10-25 Hz). In all cases, care was taken to ensure the contact mechanics models were applied within the important limit of small relative deformations. This study thus highlights possible transitions in the probe-material contact mechanical behaviour for soft matter, especially when the applied strain rates and the material relaxation rates become comparable. In particular, at low frequencies, the modulus follows Hertzian contact mechanics, while at high frequencies adhesive contact is well represented by punch-like behaviour. More generally, use of the Hertz model on hydrogels at high loading rates, at high strains, or during the retraction portion of FD curves, leads to significant errors in the calculated moduli.

Adhesion and friction properties of polymer brushes on rough surfaces: a gradient approach.

The effect of nanoscale surface roughness on the lubrication properties of a polymer brush in a good solvent has been investigated. Friction and adhesion forces were measured by means of polyethylene colloidal-probe AFM across a 12 nm silica particle gradient before and after the adsorption of a poly(L-lysine)-g-poly(ethylene glycol) (PLL-g-PEG) polymer brush. The adsorption and conformation of the polymer chains were studied with multiple transmission and reflection infrared (MTR-IR) spectroscopy. The results show that prior to the adsorption of PLL-g-PEG on the gradient surface, the friction is high at the smooth end of the gradient while it decreases toward the rough end. Moreover, there is a direct correlation between friction and adhesion. Upon adsorption of the brushes, adhesion vanishes. In this case, a higher frictional force between the PEG-coated particle gradient substrate and the polyethylene sphere is observed at the rough end of the gradient in comparison to the smooth end. In spite of the increased adsorbed mass of PLL-g-PEG at the rough end of the gradient, theory and simulations show that the high curvature of the nanoparticles leads to a less swollen PEG brush in comparison to PEG brushes adsorbed on a planar surface, resulting in a lower repulsion, which can explain the observed increase in friction with particle density.

Exploring lubrication regimes at the nanoscale: nanotribological characterization of silica and polymer brushes in viscous solvents.

Nanotribological properties of silica surfaces, with and without adsorbed, brushlike copolymers of poly(L-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG) and poly(L-lysine)-graft-dextran (PLL-g-dextran) have been investigated in aqueous viscous solvent mixtures by means of colloid-probe lateral force microscopy. Lateral forces for PEG/dextran brushes have been measured as a function of shear velocity in aqueous mixtures of glycerol and ethylene glycol (EG), which are highly miscible with water, but are poor solvents for hydrophilic PEG and dextran chains. Prior to the friction measurements on polymer brushes, a nanoscale Stribeck curve was obtained on a bare silica surface in the selected aqueous cosolvent mixtures. The Stribeck curve for bare surfaces indicates the existence of a surface-solvating thin film due to the adsorption of hydrated ions, preventing direct silica-silica contact in the boundary-lubrication regime. A clear transition to the hydrodynamic regime is seen at high speeds for solvents with higher viscosities. The polymer brushes, however, show a shear-thinning effect with increasing shear speed and a combined influence of polymer film and solvent viscosity on the measured friction forces. The formation of an interfacial fluid-film is shown to shift the hydrodynamic regime of hydrated brushes to a lower value of Uη. The correlation between the structural configuration and the corresponding frictional properties of the polymer brushes upon changing solvent quality is discussed.

Study of adhesion and friction properties on a nanoparticle gradient surface: transition from JKR to DMT contact mechanics.

We have previously investigated the dependence of adhesion on nanometer-scale surface roughness by employing a roughness gradient. In this study, we correlate the obtained adhesion forces on nanometer-scale rough surfaces to their frictional properties. A roughness gradient with varying silica particle (diameter ≈ 12 nm) density was prepared, and adhesion and frictional forces were measured across the gradient surface in perfluorodecalin by means of atomic force microscopy with a polyethylene colloidal probe. Similarly to the pull-off measurements, the frictional forces initially showed a reduction with decreasing particle density and later an abrupt increase as the colloidal sphere began to touch the flat substrate beneath, at very low particle densities. The friction-load relation is found to depend on the real contact area (A(real)) between the colloid probe and the underlying particles. At high particle density, the colloidal sphere undergoes large deformations over several nanoparticles, and the contact adhesion (JKR type) dominates the frictional response. However, at low particle density (before the colloidal probe is in contact with the underlying surface), the colloidal sphere is suspended by a few particles only, resulting in local deformations of the colloid sphere, with the frictional response to the applied load being dominated by long-range, noncontact (DMT-type) interactions with the substrate beneath.

Impact of hydrophilic/hydrophobic surface chemistry on hydration forces in the absence of confinement.

The oscillatory force profile, observed in liquids due to molecular ordering at interfaces, has been extensively investigated by means of atomic force microscopy, but it remains unclear whether molecular ordering is present at the tip apex. Using a displacement-sensitive, low-noise atomic force microscope (AFM) operated in dynamic mode, with a tip of radius < 1 nm, we have investigated the force profile between two approaching surfaces of the same or different hydrophilic and hydrophobic character. By directly comparing different surface chemistry interactions, we have been able to elucidate whether an oscillatory force profile is due to structured water layers adjacent to the surface, the tip, or a combination of the two. We have found that an oscillatory force profile is observed when the surface is hydrophilic in nature, irrespective of whether the tip is hydrophilic or hydrophobic. When the surface is hydrophobic, an oscillatory force profile is not measured, but rather a monotonic repulsive or a short-range attractive force is observed for interactions with a hydrophilic or a hydrophobic tip, respectively. Thus, we attribute the measurement of an oscillatory force profile, in the absence of lateral confinement effects, solely to water layers adjacent to a hydrophilic surface rather than the structuring of water at the tip apex. This is the first direct evidence that solvation forces occur solely as a result of water layers adjacent to the substrate.