Interfacial Rheological Investigation of Modified Silica Nanoparticles with Different Alkyl Chain Lengths at the n-Octane/Water Interface.

The interfacial dilational rheology of silica nanoparticles (NPs) directly reflects the relationship between surface structure and interfacial behaviors in NPs, which has attracted significant attention in various industrial fields. In this work, modified silica nanoparticles (MNPs) with various alkyl chain lengths were synthesized and systematically characterized using Fourier transform infrared spectra, Zeta potential, and water contact angle measurements. It was found that the MNPs were successfully fabricated with similar degrees of modification. Subsequently, the interfacial behaviors of the MNPs in an n-octane/water system were investigated through interfacial dilational rheological experiments. The length of the modified alkyl chain dominated the hydrophilic-lipophile balance and the interfacial activity of the MNPs, evaluated by the equilibrium interfacial tension (IFT) variation and dilational elasticity modulus. In the large amplitude compression experiment, the balance between the electrostatic repulsion and interfacial activity in the MNPs was responsible for their ordered interfacial arrangement. The MNPs with the hexyl alkyl chain (M6C) presented the optimal amphipathy and could partly overcome the repulsion, causing a dramatic change in surface pressure. This was further confirmed by the variations in IFT and dilational elasticity during the compression path. The study provides novel insights into the interfacial rheology and interactions of functionally modified NPs.

Effect of a harmonic surface pressure on wave propagation over a beach.

The objective is to study the harmonic forced wave motion over a beach by a finite Fourier transform technique. The constructed approximate solution has a logarithmic singularity at the shoreline. It accounts for reflexion and local perturbations. Trapping of waves may take place for particular choices of the applied surface pressure excess. The case of a wave incident against a cliff with horizontal bottom is solved exactly. The method deals invariably with a variety of bottom shapes, including the case where there is an additional corrugation of the bottom on a finite interval. Other bottom boundary conditions than impermeability can be treated as well. The results may be of interest in several practical applications, in particular the evaluation of the reflected wave. Numerical applications for a plane sloping beach, a parabolic-type beach and a shelf-type beach are presented and the systems of streamlines have been drawn over and in the proximity of the beach.

Effect of Trough Incidence Angle on the Aerodynamic Characteristics of a Biomimetic Leading-Edge Protuberanced (LEP) Wing at Various Turbulence Intensities.

A series of wind tunnel tests were performed to investigate the effect of turbulent inflows on the aerodynamic characteristics of variously modified trough incident leading-edge-protuberanced (LEP) wing configurations at various turbulence intensities. A self-developed passive grid made of parallel arrays of round bars was placed at different locations of the wind tunnel to generate desired turbulence intensity. The aerodynamic forces acting over the trough incidence LEP wing configuration where obtained from surface pressure measurements made over the wing at different turbulence intensities using an MPS4264 Scanivalve simultaneous pressure scanner corresponding to a sampling frequency of 700 Hz. All the test models were tested at a wide range of angles of attack ranging between 0°≤α≤90° at turbulence intensities varying between 5.90% ≤ TI ≤ 10.54%. Results revealed that the time-averaged mean coefficient of lift (CL) increased with the increase in the turbulence intensity associated with smooth stall characteristics rendering the modified LEP test models advantageous. Furthermore, based on the surface pressure coefficients, the underlying dynamics behind the stall delay tendency were discussed. Additionally, attempts were made to statistically quantify the aerodynamic forces using standard deviation at both the pre-stall and the post-stall angles.

Impact of chlorogenic acid on surface and phase properties of cholesterol-enriched phosphatidylcholine membranes.

This study analyses the insertion of Chlorogenic acid (CGA) in phosphatidylcholine (PC) membranes enriched with cholesterol (Chol). While cholesterol decreases the area per lipid and increases the dipole potential, CGA increases and decreases these values, respectively. When CGA is inserted into cholesterol-containing DMPC membranes, these effects cancel out, resulting in values that overlap with those of DMPC monolayers without Chol and CGA. The presence of CGA also compensates the increase of dipole potential produced by Chol which can be explain as a consequence of the orientation of CGA molecule at the interphase opposing the cholesterol dipole moieties and water dipoles. This compensatory effect is less effective when lipids lack carbonyl groups (CO). When monolayers are composed by unsaturated PCs the Chol compensation is found at higher concentrations of CGA due to the direct interaction between CGA and Chol. These results suggest that cholesterol modulates the interaction and distribution of CGA in the lipid membrane, which may have implications for its biological activity.

Joint Stress Analysis of the Navicular Bone of the Horse and Its Implications for Navicular Disease.

The horse's navicular bone is located inside the hoof between the deep flexor tendon (DDFT) and the middle and end phalanges. The aim of this study was to calculate the stress distribution across the articular surface of the navicular bone and to investigate how morphological variations of the navicular bone affect the joint forces and stress distribution. Joint forces normalised to the DDFT force were calculated from force and moment equilibria from morphological parameters determined on mediolateral radiographs. The stress distribution on the articular surface was determined from the moment equilibrium of the stress vectors around the centre of pressure. The ratio of the proximal to the distal moment arms of the DDFT, as well as the proximo-distal position and extent of the navicular bone, individually or in combination, have a decisive influence on the position and magnitude of the joint force and the stress distribution. If the moment arms are equal and the bone is more proximal, the joint force vector originates from the centre of the joint surface and the joint load is evenly distributed. However, in a more distal position with a longer distal moment arm, the joint force is close to the distal edge, where the joint stress reaches its peak. Degenerative navicular disease, which causes lameness and pathological changes in the distal portion of the bone in sport horses, is likely to be more severe in horses with wedge-shaped navicular bones than in horses with square bones.

Dynamic properties of the layers of cupin-1.1 aggregates at the air/water interface.

Spread layers of amorphous aggregates of the structural domain of plant protein vicilin, cupin-1.1, at the water - air interface were studied by the surface tensiometry, dilational surface rheology, Brewster angle and atomic force microscopy. The layer properties differed strongly from the results for the layers of previously studied proteins. The dependency of the dynamic elasticity of the layer on surface pressure had two local maxima with the second peak being four times higher than the first one. In the region of the first maximum the obtained results are similar to those for dispersions of polymer microgels with a hairy corona. At the beginning of surface compression separate threads of the corona are stretched along the surface and the surface elasticity increases. The further compression results in the formation of loops and tails leading to a decrease of the elasticity. The second local maximum of the dynamic surface elasticity is presumably caused by the interactions of the rigid cores of the aggregates leading finally to the formation of multilayer structures at high surface pressures. In this case, the surface elasticity starts to decrease as a result of the segment exchange between different layers at the interface.

Interaction of sakuranetin with unsaturated lipids forming Langmuir monolayers at the air-water interface: A biomembrane model.

This study investigates the interaction between sakuranetin, a versatile pharmaceutical flavonoid, and monolayers composed of unsaturated phospholipids, serving as a surrogate for cell membranes. The phospholipids were 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE). We conducted a series of experiments to comprehensively investigate this interaction, including surface pressure assessments, Brewster angle microscopy (BAM), and polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS). Our findings unequivocally demonstrate that sakuranetin interacts with these phospholipids, expanding the monomolecular films. Notably, regarding POPC, the presence of sakuranetin led to a reduction in stability and a decline in surface elasticity, which can likely be attributed to intricate molecular rearrangements at the interface. The visual evidence of aggregations in BAM images reinforces the interactions substantiated by PM-IRRAS, highlighting sakuranetin's interaction with the polar and nonpolar regions of POPC. However, it is worth noting that these aggregations do not appear to contribute significantly to the viscosity of the mixed film, and our investigations did not reveal any substantial hysteresis. In contrast, when examining POPE, we observed a minor reduction in thermodynamic stability, indicative of fewer rearrangements within the monolayer. This notion was further reinforced by the limited presence of aggregations in the BAM images. Sakuranetin also increased the rigidity of the lipid monolayer; nevertheless, the monolayer remained predominantly elastic, facilitating easy re-spreading on the surface, especially for the first lipid. PM-IRRAS analysis unveiled interactions between sakuranetin and POPE's polar and nonpolar segments, compellingly explaining the observed monolayer expansion. Taken together, our data suggest that sakuranetin was more effectively incorporated into the monomolecular layer of POPE, indicating that membranes comprised of POPC might exhibit a greater degree of interaction in the presence of this pharmacologically active compound.

Preparation of Thin Films Containing Modified Hydroxyapatite Particles and Phospholipids (DPPC) for Improved Properties of Biomaterials.

The main aims of thin biofilm synthesis are to either achieve a new form to promote the transport of drugs in oral delivery systems or as a coating to improve the biocompatibility of the implant's surface. In this study, the Langmuir monolayer technique was employed to obtain films containing Mg-doped hydroxyapatite with 0.5%, 1.0%, and 1.5% Mg(II). The obtained modified HA particles were analysed via the FT-IR, XRD, DLS, and SEM methods. It was shown that the modified hydroxyapatite particles were able to form thin films at the air/water interface. BAM microscopy was employed to characterized the morphology of these films. In the next step, the mixed films were prepared using phospholipid (DPPC) molecules and modified hydroxyapatite particles (HA-Mg(II)). We expected that the presence of phospholipids (DPPC) in thin films improved the biocompatibility of the preparing films, while adding HA-Mg(II) particles will promote antibacterial properties and enhance osteogenesis processes. The films were prepared in two ways: (1) by mixing DPPC and HA-Mg (II) and spreading this solution onto the subphase, or (2) by forming DPPC films, dropping the HA-Mg (II) dispersion onto the phospholipid monolayer. Based on the obtained π-A isotherms, the surface parameters of the achieved thin films were estimated. It was observed that the HA-Mg(II) films can be stabilized with phospholipid molecules, and a more stable structure was obtained from films synthesied via method (2).

Dynamic Surface Properties of α-Lactalbumin Fibril Dispersions.

The dynamic surface properties of aqueous dispersions of α-lactalbumin (ALA) amyloid fibrils differ noticeably from the properties of the fibril dispersions of other globular proteins. As a result, the protocol of the application of ALA fibrils to form stable foams and emulsions has to be deviate from that of other protein fibrils. Unlike the fibrils of ß-lactoglobulin and lysozyme, ALA fibrils can be easily purified from hydrolyzed peptides and native protein molecules. The application of the oscillating barrier method shows that the dynamic surface elasticity of ALA fibril dispersions exceeds the surface elasticity of native protein solutions at pH 2. ALA fibrils proved to be stable at this pH, but the stability breaks at higher pH levels when the fibrils start to release small peptides of high surface activity. As a result, the dynamic surface properties of ALA coincide with those of native protein solutions. The ionic strength strongly influences the adsorption kinetics of both fibril dispersions and native protein solutions but have almost no impact on the structure of the adsorption layers.

Effect of Calcium Foliar Spray Technique on Mechanical Properties of Strawberries.

The calcium fertilization of strawberry plants (Fragaria × ananassa Duchesne) was evaluated using two types of nozzles, with two liquid pressure levels and two driving speeds. The calcium content of the leaves and fruit were analyzed via flame photometry. Higher leaf calcium content was found in plots sprayed with standard nozzles, while higher fruit calcium content was observed for those sprayed with air induction nozzles. The fruit quality was assessed by determining the basic physical and mechanical properties, using uniaxial compression tests integrated with surface pressure measurements. Different spraying techniques influenced the mechanical resistance of the fruit. A spraying speed of 5 km/h and an operating pressure of 0.4 MPa significantly increased the firmness of the fruit by ~66%, the critical load level by 36%, and the maximum surface pressure by up to 38%, but did not increase the geometrical parameters of the strawberries. Regular foliar feeding during harvest could improve the mechanical strength of strawberries. An appropriate spraying technique with a calcium agent could effectively improve the mechanical properties of the delicate fruit, which is particularly important for limiting losses during harvesting, transportation, and storage.

Modulation of Membrane Trafficking of AQP5 in the Lens in Response to Changes in Zonular Tension Is Mediated by the Mechanosensitive Channel TRPV1.

In mice, the contraction of the ciliary muscle via the administration of pilocarpine reduces the zonular tension applied to the lens and activates the TRPV1-mediated arm of a dual feedback system that regulates the lens' hydrostatic pressure gradient. In the rat lens, this pilocarpine-induced reduction in zonular tension also causes the water channel AQP5 to be removed from the membranes of fiber cells located in the anterior influx and equatorial efflux zones. Here, we determined whether this pilocarpine-induced membrane trafficking of AQP5 is also regulated by the activation of TRPV1. Using microelectrode-based methods to measure surface pressure, we found that pilocarpine also increased pressure in the rat lenses via the activation of TRPV1, while pilocarpine-induced removal of AQP5 from the membrane observed using immunolabelling was abolished by pre-incubation of the lenses with a TRPV1 inhibitor. In contrast, mimicking the actions of pilocarpine by blocking TRPV4 and then activating TRPV1 resulted in sustained increase in pressure and the removal of AQP5 from the anterior influx and equatorial efflux zones. These results show that the removal of AQP5 in response to a decrease in zonular tension is mediated by TRPV1 and suggest that regional changes to PH2O contribute to lens hydrostatic pressure gradient regulation.

Effect of Fluoxetine on the Surface Behavior of the Lipid Monolayers at Different Surface Pressures.

Fluoxetine (FLX), used in the clinic to treat depression, is a well-known cationic amphiphilic antidepressant. However, there is a lack of research on the effect of FLX on the surface behavior of lipid monolayers under different surface pressures. In this study, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine/CHOL (DPPC/POPC/CHOL) monolayers were prepared via the Langmuir method, and FLX was added to these monolayers under various surface pressures. The effect of FLX on the surface behavior of DPPC/POPC/CHOL monolayers under various surface pressures was studied using a combination of surface pressure-area isotherms, compressibility modulus-surface pressure curves, and atomic force microscope (AFM). The results showed that the effect of FLX on the lipid monolayers was different under different surface pressures. The interaction between FLX and lipid molecules was weak under low surface pressures, and FLX could easily intercalate between the lipid molecules to inhibit monolayer phase transition. The interaction between FLX and lipid molecules was enhanced and FLX tended to self-aggregate to reduce the monolayer stability when the surface pressure was high. This study lays the foundation for further studies on the interaction between FLX and lipid monolayers.

Structural analysis of the peptides temporin-Ra and temporin-Rb and interactions with model membranes.

The skin of amphibians is widely exploited as rich sources of membrane active peptides that differ in chain size, polypeptide net charge, secondary structure, target selectivity and toxicity. In this study, two small antimicrobial peptides, temporin-Ra and temporin-Rb, originally isolated from the skin of the European marsh frog (Rana ridibunda), described as active against pathogen bacteria and presenting low toxicity to eukaryotic cells were synthesized and had their physicochemical properties and mechanism of action investigated. The temporin peptides were examined in aqueous solution and in the presence of membrane models (lipid monolayers, micelles, lipid bilayers and vesicles). A combined approach of bioinformatics analyses, biological activity assays, surface pressure measurements, synchrotron radiation circular dichroism spectroscopy, and oriented circular dichroism spectroscopy were employed. Both peptides were able to adsorb at a lipid-air interface with a negative surface charge density, and efficiently disturb the lipid surface packing. A disorder-to-helix transition was observed on the secondary structure of both peptides when either in a non-polar environment or interacting with model membranes containing a negative net charge density. The binding of both temporin-Ra and temporin-Rb to membrane models is modulated by the presence of negatively charged lipids in the membrane. The amphipathic helix induced in temporin-Ra is oriented parallel to the membrane surface in negatively charged or in zwitterionic lipid bilayers, with no tendency for realignment after binding. Temporin-Rb, instead, assumes a ß-sheet conformation when deposited into oriented stacked lipid bilayers. Due to their short size and simple composition, both peptides are quite attractive for the development of new classes of peptide-based anti-infective drugs.

PFAS fluidize synthetic and bacterial lipid monolayers based on hydrophobicity and lipid charge.

Poly- and Perfluoroalkyl substances (PFASs) are pollutants of emerging concern that persist in nature and pose environmental health and safety risks. PFAS disrupt biological membranes resulting in cellular inhibition, but the mechanism of disruption and the role of lipid composition remain unclear. We examine the role of phospholipid saturation and headgroup charge on the interactions between PFASs and phospholipid monolayers comprised of synthetic phosphocholine (PC) and phosphoglycerol (PG) lipids and prepared from bacteria membrane extracts rich in PG lipids from an environmentally relevant marine bacterium Alcanivorax borkumensis. When deposited on a buffered subphase containing PFAS, PFAS mixed within and fluidized zwitterionic and net-anionic monolayers leading to increases in monolayer compressibility that were driven by a combination of PFAS hydrophobicity and monolayer charge density. Differences in the monolayer response using saturated or unsaturated lipids are attributed to the ability of the unsaturated lipids to accommodate PFAS within 'void space' arising from the bent lipid tails. Similar fluidization and compressibility behavior were also observed in A. borkumensis lipid monolayers. This work provides new insight into PFAS partitioning into bacterial membranes and the effect PFAS have on the physicomechanical properties of zwitterionic and charged lipid monolayers.

The lung surfactant activity probed with molecular dynamics simulations.

The surface of pulmonary alveolar subphase is covered with a mixture of lipids and proteins. This lung surfactant plays a crucial role in lung functioning. It shows a complex phase behavior which can be altered by the interaction with third molecules such as drugs or pollutants. For studying multicomponent biological systems, it is of interest to couple experimental approach with computational modelling yielding atomic-scale information. Simple two, three, or four-component model systems showed to be useful for getting more insight in the interaction between lipids, lipids and proteins or lipids and proteins with drugs and impurities. These systems were studied theoretically using molecular dynamic simulations and experimentally by means of the Langmuir technique. A better understanding of the structure and behavior of lung surfactants obtained from this research is relevant for developing new synthetic surfactants for efficient therapies, and may contribute to public health protection.

Complexation of DNA with Thermoresponsive Charged Microgels: Role of Swelling State and Electrostatics.

Micro- and nanogels are being increasingly used to encapsulate bioactive compounds. Their soft structure allows large loading capacity while their stimuli responsiveness makes them extremely versatile. In this work, the complexation of DNA with thermoresponsive microgels is presented. To this end, PEGylated charged microgels based on poly-N-isopropylacrylamide have been synthesized, allowing one to explore the electrostatics of the complexation. Cationic microgels complexate spontaneously by electrostatic attraction to oppositely charged DNA as demonstrated by electrophoretic mobility of the complexes. Then, Langmuir monolayers reveal an increased interaction of DNA with swollen microgels (20 °C). Anionic microgels require the presence of multivalent cations (Ca2+) to promote the complexation, overcoming the electrostatic repulsion with negatively charged DNA. Then again, Langmuir monolayers evidence their complexation at the surface. However, the presence of Ca2+ seems to induce profound changes in the interaction and surface conformation of anionic microgels. These alterations are further explored by measuring adsorbed films with the pendant drop technique. Conformational changes induced by Ca2+ on the structure of the microgel can ultimately affect the complexation with DNA and should be considered in the design. The combination of microstructural and surface properties for microgels offers a new perspective into complexation of DNA with soft particles with biomedical applications.

Surface mechanical behavior of water-spread poly(styrene)-poly(ethylene glycol) (PS-PEG) micelles at the air-water interface: Effect of micelle size and polymer end/linking group chemistry.

HYPOTHESIS: The surface mechanical properties of poly(styrene)-poly(ethylene glycol) (PS-PEG) micelles are influenced by the PEG corona structure. Changes in micelle aggregation number as well as changes in the PEG end group and linking group chemistry of the PS-PEG block copolymer are expected to alter PEG corona characteristics and therefore affect surface mechanical properties of the resulting micelle film. EXPERIMENTS: Different sized micelles comprised of PS-PEG block copolymer chains were formulated by equilibrating micelles in different ratios of acetone/water mixtures and subsequently removing acetone using dialysis. Additionally, micelles of a similar size and PS-PEG molecular weight but slightly different chemistry were formulated. The micelles were characterized using dynamic light scattering (DLS), transmission electron microscopy (TEM), 1H NMR, surface pressure-area isotherms and Brewster angle microscopy (BAM). FINDINGS: The reduction in micelle aggregation number results in the subsequent monolayer having higher compressibility moduli and bending stiffnesses and collapsing at lower surface pressures. Micelle hydrophobicity was shown to improve readsorption of micelles to interface after collapse. Analysis of Brewster angle microscopy images of out-of-plane wrinkle structures which formed upon monolayer collapse indicates the presence of continuous 1 nm thick PEG layer which allows micelle monolayers to bend under high compression.

Inverse electron-demand diels-alder reactions of tetrazine and norbornene at the air-water interface.

The surface chemistry of the inverse electron-demand Diels-Alder (IEDDA) reaction at the air-water interface is elucidated. Tetrazine (C18-Tz) and norbornene derivatives (C16-NCA) were used as the reactants. Langmuir monolayers of C18-Tz, C16-NCA, and their binary mixtures were prepared on aqueous substrates. The surface properties were analyzed using the surface pressure (π)-molecular area (A) and surface potential (ΔV)-A isotherms, as well as fluorescence microscopy to monitor the progress of the reaction. First, to provide comparison data to evaluate the reaction on the surface, the two components were mixed in stock solutions of organic solvents for the IEDDA reaction. The Langmuir monolayer spread from the reaction solution was characterized as a function of the reaction time. In the subsequent experiments, the Langmuir monolayers were deposited onto the surface of the substrate solutions by spreading from separate stock solutions of C18-Tz and C16-NCA. The variation of the surface behavior of the monolayers with the molecular area, surface composition of the two components, compression speed of the monolayers, and the temperature was studied. We discuss the effects of the air phase in the reaction field on the reaction efficiency by comparing the results obtained from the two methods.

Evaluating the Impact of Hydrophobic Silicon Dioxide in the Interfacial Properties of Lung Surfactant Films.

The interaction of hydrophobic silicon dioxide particles (fumed silicon dioxide), as model air pollutants, and Langmuir monolayers of a porcine lung surfactant extract has been studied in order to try to shed light on the physicochemical bases underlying the potential adverse effects associated with pollutant inhalation. The surface pressure-area isotherms of lung surfactant (LS) films including increasing amounts of particles revealed that particle incorporation into LS monolayers modifies the organization of the molecules at the water/vapor interface, which alters the mechanical resistance of the interfacial films, hindering the ability of LS layers for reducing the surface tension, and reestablishing the interface upon compression. This influences the normal physiological function of LS as is inferred from the analysis of the response of the Langmuir films upon the incorporation of particles against harmonic changes of the interfacial area (successive compression-expansion cycles). These experiments evidenced that particles alter the relaxation mechanisms of LS films, which may be correlated to a modification of the transport of material within the interface and between the interface and the adjacent fluid during the respiratory cycle.

Evaluating the Combined Impact of Temperature and Application of Interfacial Dilatational Stresses on Surface-mediated Protein Particle Formation in Monoclonal Antibody Formulations.

Formation of submicron and subvisible protein particles (0.1-100 µm) present a major obstacle during processing and storage of therapeutic proteins. While protein aggregation resulting in particle formation is well-understood in bulk solution, the mechanisms of aggregation due to interfacial stresses is less understood. Particularly, in this study, we focus on understanding the combined effect of temperature and application of interfacial dilatational stresses, on interface-induced protein particle formation, using two industrially relevant monoclonal antibodies (mAbs). The surface activity of Molecule C (MC) and Molecule B (MB) were measured at room temperature (RT) and 4 °C in the absence and presence of interfacial dilatation stress using a Langmuir trough. These results were correlated with Micro-flow imaging (MFI) to characterize formation of subvisible protein particles at the interface and in the bulk solution. Our results show that the surface activity for both proteins is temperature dependent. However, the extent of the impact of temperature on the mechanical properties of the monomolecular protein films when subjected to dilatational stresses is protein dependent. Protein particle analysis provided evidence that protein particles formed in bulk solution originate at the interface and are dependent on both application of thermal stresses and interfacial dilatational stresses. In the absence of any interfacial stresses, more and larger protein particles were formed at the interface at RT than at 4 °C. When mAb formulations are subjected to interfacial dilatational stresses, protein particle formation in bulk solution was found to be temperature dependent. Together our results validate that mAb solutions maintained at 4 °C can lower the surface activity of proteins and reduce their tendency to form interface-induced protein particles both in the absence and presence of interfacial dilatational stresses.