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Although many investigations of thermoresponsive microgels have been reported, their surface properties, which are crucial in colloid science, are still not fully understood. In this study, microgels with surface-localized charged groups were synthesized by precipitation polymerization, and their electrophoretic behaviors were analyzed using a modified version of Ohshima's equation to obtain two surface properties of the soft particles: the softness parameter and the surface charge density. This systematic evaluation allows us to discuss the thermoresponsiveness of the overall microgels and their surfaces separately. Furthermore, the validity of the surface properties obtained from electrophoresis was verified by comparing them with the results of seeded emulsion polymerization in the presence of the microgels and the force-indentation curves obtained via high-speed atomic force microscopy (HS-AFM).

International audience; An efficient superhydrophobic concentrator is developed using a hierarchical superhydrophobic surface on which the evaporation of a sessile droplet (6 mu L) drives the nonvolatile elements it contains on a predefined micrometric analytical surface (pedestal of 80 mu m diameter). This hierarchical silicon surface exhibits a surface texture made of etched nanopillars and consists of micropillars and guiding lines, arranged in radial symmetry around the central pedestal. The guiding lines ensure the overall convergence of the sessile droplet toward the central pedestal during evaporation. The nanopillar texturing induced a delay in the Cassie-Baxter to Wenzel regime transition, until the edge of the droplet reaches the periphery of the pedestal. Experiments performed with polymer microparticles suspended in ultrapure water or with DNA molecules solubilized in ultrapure water at sub-fM concentrations demonstrated that the totality of the nonvolatile elements in the liquid microvolume is delivered on or close to the pedestal area, in a very reproducible manner. The very high concentration capacity of the device enabled the discrimination of the degree of purity of ultrapure water samples from different origins. The concentrator also turned out to be functional for raw water samples, opening possible applications to environmental analysis.

Self-initiated photografting and photopolymerization (SI-PGP) uses UV illumination to graft polymers to surfaces without additional photoinitiators using the monomers as initiators, “inimers”. A wider use of this method is obstructed by a lack of understanding of the resulting, presumably heterogeneous, polymer structure and of the parallel degradation under continuous UV illumination. We have used neutron reflectometry to investigate the structure of hydrated SI-PGP-prepared poly(HEMA-co-PEG10MA) (poly(2-hydroxyethyl methacrylate-co-(ethylene glycol)10 methacrylate)) films and compared parabolic, sigmoidal, and Gaussian models for the polymer volume fraction distributions. Results from fitting these models to the data suggest that either model can be used to approximate the volume fraction profile to similar accuracy. In addition, a second layer of deuterated poly(methacrylic acid) (poly(dMAA)) was grafted over the existing poly(HEMA-co-PEG10MA) layer, and the resulting double-grafted films were also studied by neutron reflectometry to shed light on the UV-polymerization process and the inevitable UV-induced degradation which competes with the grafting.

Chemical and biological interfaces are of various types, which could be between two materials of the same and/or different states, two phases of the same material, biological substrates and the outer environment, surfactant or polymeric membranes and the bulk, and so forth. Small-molecule guests frequently interact with such interfaces that decide their functionalities. The structural and behavioral properties undergo considerable characteristic changes, which control their final course of action in the targeted application. This Perspective will discuss mainly the chemical interfaces constituted by the surfactants, polymers, lipids, and nucleic acids and their impacts on the dynamics of small-molecule guests. Some specific and interesting phenomena and future prospects will be elucidated in this Perspective.

Many biological surfaces with hierarchical structures exhibit super wetting properties, but a multiscale hierarchical metal surface with superhydrophilic performance is difficult to be fabricated using a simple method. In this work, we report a large area micro/nanotextured superhydrophilic silicon surface fabricated by a laser direct writing technique. The combination of a microscale column structure and randomization-distributed nano-bumps decorated on the column enhances the superhydrophilic properties, with the contact angle reduced substantially from about 46° to 0°, where the droplets are able to spread rapidly within 591 ms. The water wetting orientation can be regulated by controlling the shape of microcolumns on the surface. Moreover, our results show that the fabricated surface with the hierarchical structure has better droplet shape control performance and higher fog collection efficiency compared to a smooth surface. These surfaces have potential applications in heat exchangers, biosensors, cell adhesives, and self-cleaning solar cells.

Understanding the interfacial behaviors of biomolecules is crucial to applications in biomaterials and nanoparticle-based biosensing technologies. In this work, we utilized autoencoder-based graph clustering to analyze discontinuous molecular dynamics (DMD) simulations of lysozyme adsorption on a graphene surface. Our high-throughput DMD simulations integrated with a Go̅-like protein-surface interaction model makes it possible to explore protein adsorption at a large temporal scale with sufficient accuracy. The graph autoencoder extracts a low-dimensional feature vector from a contact map. The sequence of the extracted feature vectors is then clustered, and thus the evolution of the protein molecule structure in the absorption process is segmented into stages. Our study demonstrated that the residue-surface hydrophobic interactions and the π-π stacking interactions play key roles in the five-stage adsorption. Upon adsorption, the tertiary structure of lysozyme collapsed, and the secondary structure was also affected. The folding stages obtained by autoencoder-based graph clustering were consistent with detailed analyses of the protein structure. The combination of machine learning analysis and efficient DMD simulations developed in this work could be an important tool to study biomolecules' interfacial behaviors.

The formation of a protein nanobiofilm on the surface of degradable biomaterials such as magnesium (Mg) and its alloys influences metal ion release, cell adhesion/spreading, and biocompatibility. During the early stage of human body implantation, competition and interaction between inorganic species and protein molecules result in a complex film containing Mg oxide and a protein layer. This film affects the electrochemical properties of the metal surface, the protein conformational arrangement, and the electronic properties of the protein/Mg oxide interface. In this study, we discuss the impact of various simulated body fluids, including sodium chloride (NaCl), phosphate-buffered saline (PBS), and Hanks' solutions on protein adsorption, electrochemical interactions, and electrical surface potential (ESP) distribution at the adsorbed protein/Mg oxide interface. After 10 min of immersion in NaCl, atomic force microscopy (AFM) and scanning Kelvin probe force microscopy (SKPFM) showed a higher surface roughness related to enhanced degradation and lower ESP distribution on a Mg-based alloy than those in other solutions. Furthermore, adding bovine serum albumin (BSA) to all solutions caused a decline in the total surface roughness and ESP magnitude on the Mg alloy surface, particularly in the NaCl electrolyte. Using SKPFM surface analysis, we detected a protein nanobiofilm (∼10-20 nm) with an aggregated and/or fibrillary morphology only on the Mg surface exposed in Hanks' and PBS solutions; these surfaces had a lower ESP value than the oxide layer.

Cross-contamination during pharmaceutical drug manufacturing can result in expensive recalls. To counter that, companies spend significant time and resources to ensure equipment cleanliness, often relying on the compound solubility data in various solvents as the main indicator of cleaning success. The aim of this work is to provide an alternative way to analyze the fouling and cleaning of surfaces in pharmaceutical manufacturing processes by using the quartz crystal microbalance with dissipation (QCM-D) and Raman spectroscopy. In this study, we chose an active pharmaceutical ingredient (API), sitagliptin phosphate monohydrate (SIT), as the model drug compound and observed its adsorption and desorption on stainless steel (SS2343), borosilicate glass (glass), and polytetrafluoroethylene (PTFE) surfaces. SIT was selected as the model API since it is a product manufactured on a large scale and is part of the widely used dipeptidyl peptidase-IV inhibitor class of oral hypoglycemics used to treat type 2 diabetes mellitus, while the chosen surfaces mimic the wall materials of manufacturing equipment and components such as reactors, transfer lines, and valves. Both the QCM-D and Raman spectroscopy results show the highest physisorption on PTFE, followed by SS2343 and glass. Additionally, QCM-D revealed a harder removal of SIT from SS2343 compared to glass and PTFE. Raman analysis of the chemical interactions disclosed C-F and C═O bond interactions between SIT and the surfaces, and the lack of a peak shift suggested dipole-dipole interactions. Furthermore, contact angle measurements indicate that hydrophobic attraction contributed to SIT adhesion to the PTFE surface. Subsequently, SIT coverage upon deposition on a PTFE surface has a significantly smaller surface area than on SS2343 and glass due to surface hydrophobicity, hence resulting in a longer removal time. These results provide a practical use of QCM-D and Raman spectroscopy to enhance the understanding of fouling and improve the cleaning of complex small molecules on relevant surfaces during the pharmaceutical manufacturing process.

Interfacial properties of polymeric materials are significantly influenced by their architectural structures and spatial features, while such a study of topologically interesting macromolecules is rarely reported. In this work, we reported, for the first time, the interfacial behavior of catenated poly(l-lactide) (C-PLA) at the air-water interface and compared it with its linear analogue (L-PLA). The isotherms of surface pressure-area per repeating unit showed significant interfacial behavioral differences between the two polymers with different topologies. Isobaric creep experiments and compression-expansion cycles also showed that C-PLA demonstrated higher stability at the air-water interface. Interestingly, when the films at different surface pressures were transferred via the Langmuir-Blodgett method, successive atomic force microscopy imaging displayed distinct nanomorphologies, in which the surface of C-PLA exhibited nanofibrous structures, while that of the L-PLA revealed a smoother topology with less fiber-like structures.

While roughening the surface of neural implants has been shown to significantly improve their performance, the mechanism for this improvement is not understood, preventing systematic optimization of surfaces. Specifically, prior work has shown that the cellular response to a surface can be significantly enhanced by coating the implant surface with inorganic nano-particles and neuroadhesion protein L1, and this improvement occurs even when the surface chemistry is identical between the nanoparticle-coated and uncoated electrodes, suggesting the critical importance of surface topography. Here, we use transmission electron microscopy to characterize the topography of bare and nanoparticle-coated implants across 7 orders of magnitude in size, from the device scale to the atomic scale. The results reveal multiscale roughness, which cannot be adequately described using conventional roughness parameters. Indeed, the topography is nearly identical between the two samples at the smallest scales and also at the largest scales but vastly different in the intermediate scales, especially in the range of 5–100 nm. Using a multiscale topography analysis, we show that the coating causes a 76% increase in the available surface area for contact and an order-of-magnitude increase in local surface curvature at characteristic sizes corresponding to specific biological structures. These are correlated with a 75% increase in bound proteins on the surface and a 134% increase in neurite outgrowth. The present investigation presents a framework for analyzing the scale-dependent topography of medical device-relevant surfaces, and suggests the most critical size scales that determine the biological response to implanted materials.

Long-term and green marine antifouling coatings are an important means to prolong the service life of ships and other marine instruments and equipment. To accomplish this, we prepared three new green and high-efficiency antifouling coatings containing phthalimide derivatives inspired by capsaicin (PDIC-AC) by using a collaborative strategy that incorporates self-polishing, fouling repelling, and antifouling properties. Static simulation tests confirmed that the zinc acrylate resin of the PDIC-AC has excellent self-polishing properties due to changes in the roughness, surface free energy, and mass loss. Antifouling tests demonstrated that both PDIC and PDIC-AC possess efficient antibacterial and anti-algal effects. Moreover, marine field tests showed that the PDIC-AC are highly antifouling for at least 9 months, and their antifouling effect is similar to that of an antifouling coating with chlorothalonil (CT-AC). The collaborative strategy in this study can be used to research and develop long-term environmentally friendly antifouling coatings.

Hydrophobins, a new class of potential protein emulsifiers, have been extensively employed in the food, pharmaceutical, and chemical industries. However, the knowledge of the underlying molecular mechanism of protein adsorption at the oil-water interface remains elusive. In this study, all-atom molecular dynamics simulations were performed to probe the adsorption orientation and conformation change of class II hydrophobin HFBI at the cyclohexane-water interface. It was proposed that a hydrophobic dipole of the protein could be used to quantitatively predict the orientation of the adsorbed HFBI. Simulation results revealed that HFBI adsorbed at the interface with the patch-up orientation toward the oil phase, regardless of its initial orientations. HFBI's secondary structure was maintained to be intact in the course of simulations despite relatively significant variations in the tertiary structure observed, which could well preserve the bioactivity of HFBI. From the energy analysis, the driving force for interface adsorption was primarily determined by van der Waals interactions between HFBI and cyclohexane. Further analysis indicated that the adsorption orientation and conformation of HFBI at the oil-water interface were typically regulated by the hydrophobic patch and some key residues. This study provides some insights into the orientation, conformation, and adsorption mechanism of proteins at the oil-water interface and theoretical guidelines for the design and development of novel biological emulsifiers involved in the food, pharmaceutical, and chemical industries.

The interaction of amorphous silica nanoparticles with phospholipid monolayers and bilayers has received a great deal of interest in recent years and is of importance for assessing potential cellular toxicity of such species, whether natural or synthesized for the purpose of nanomedical drug delivery and other applications. This present communication studies the rate of silica nanoparticle adsorption on to phospholipid monolayers in order to extract a heterogeneous rate constant from the data. This rate constant relates to the initial rate of growth of an adsorbed layer of nanoparticles as SiO2 on a unit area of the monolayer surface from unit concentration in dispersion. Experiments were carried out using the system of dioleoyl phosphatidylcholine (DOPC) monolayers deposited on Pt/Hg electrodes in a flow cell. Additional studies were carried out on the interaction of soluble silica with these layers. Results show that the rate constant is effectively constant with respect to silica nanoparticle size. This is interpreted as indicating that the interaction of hydrated SiO2 molecular species with phospholipid polar groups is the molecular initiating event (MIE) defined as the initial interaction of the silica particle surface with the phospholipid layer surface promoting the adsorption of silica nanoparticles on DOPC. The conclusion is consistent with the observed significant interaction of soluble SiO2 with the DOPC layer and the established properties of the silica–water interface., We acknowledge EU for supporting ENNSATOX GA No. 229244, HISENTS GA No. 685817, and SABYDOMA GA No 862296.

In orthopedics, developing functionalized biomaterials to enhance osteogenesis and bacterial resistance is crucial. Although poly(ether ether ketone) (PEEK) is regarded as an important engineering plastic for biomedical material with excellent mechanical properties and biocompatibility, its biological inertness has greatly compromised its application in biomedical engineering. Inspired by the catecholamine chemistry of mussels, we propose a universal and versatile approach for enhancing the osteogenesis and antibacterial performances of PEEK based on surface functionalization of polydopamine-modified nanohydroxyapatite and lysozyme simultaneously. The characterizations of surface morphology and elemental composition revealed that the composite coating was successfully added to the PEEK surface. Additionally, the

Rapid shedding of microdroplets enhances the performance of self-cleaning, anti-icing, water-harvesting, and condensation heat-transfer surfaces. Coalescence-induced droplet jumping represents one of the most efficient microdroplet shedding approaches and is fundamentally limited by weak fluid-substrate dynamics, resulting in a departure velocity smaller than 0.3

Phospholipid monolayers formed at oil-water interfaces are used for various biological applications. However, monolayer structures are not well understood. Herein, we investigated hydrocarbon partitioning in 1-palmitoyl-2-oleoyl

Microalgal biofilm, a stable community of many algal cells attached to a solid substrate, plays a significant role in the efficient accumulation of renewable energy feedstocks, wastewater treatment, and carbon reduction. The adhesion tendency of microalgal cells on solid substrates is the basis for controlling the formation and development of microalgal biofilm. To promote the adhesion of microalgal cells on solid substrates, it is necessary to clarify which surface properties have to be changed in the most critical factors affecting the adhesion. However, there have been few systematic discussions on what surface properties influence the adhesion tendency of algal cells on solid substrates. In this study, the essential principle of microalgal cell adhesion onto solid substrates was explored from the perspective of the interaction energy between microalgal cells and solid substrates. The influence of surface properties between microalgal cells and solid substrates on interaction energies was discussed via extended Derjaguin-Landau-Verwey-Overbeek (eDLVO) theory and a sensitivity analysis. The results showed that surface properties, including surface potential (ξ) and surface free energy components, significantly affect the adhesion tendency of microalgal cells on different solid substrates. When the solid surface possesses positive charges (ξ0), reducing ξ or the electron donor components of the solid substrate (γ

Sporopollenin shells isolated from natural pollen grains have received attention in translational and applied research in diverse fields of drug delivery, vaccine delivery, and wastewater remediation. However, little is known about the sporopollenin shell's potential as an adsorbent. Herein, we have isolated sporopollenin shells from four structurally diverse pollen species, black walnut, marsh elder, mugwort, and silver birch, to study protein adsorption onto sporopollenin shells. We investigated three major interfacial properties, surface area, surface functional groups, and surface charge, to elucidate the mechanism of protein adsorption onto sporopollenin shells. We showed that sporopollenin shells have a moderate specific surface area (12 m

Nature shows various approaches to create superhydrophobicity, such as the lotus leaf, where the superhydrophobic (SHPB) surface arising from its hierarchical surface consists of random microscale bumps with superimposed nanoscale hairs. Some natural systems, such as the hydrophilic silk of some spider's webs, even allow the passive transport of water droplets from one part of a surface to another by creating gradients in surface tension and Laplace pressure. We look to combine both ideas and replicate the superb water repellence of the lotus leaf and the surface tension gradient-driven motion of the spider silk to form an all-metal, coating-less surface that promotes spontaneous droplet motion. We present the design, fabrication, and investigation of such superhydrophobic gradient surfaces on aluminum, which are aimed at spontaneous water droplet movement for improved surface water management. One surface demonstrates a droplet travel distance of almost 2 mm for a 11 μL droplet volume. We also present surfaces that map the theoretical ranges of the surface tension gradient surfaces tested here.

Elucidation of protein adsorption beyond simple polymer surfaces to those presenting greater chemical complexity and nanoscopic features is critical to developing well-controlled nanobiomaterials and nanobiosensors. In this study, we repeatedly and faithfully track individual proteins on the same nanodomain areas of a block copolymer (BCP) surface and monitor the adsorption and assembly behavior of a model protein, immunoglobulin G (IgG), over time into a tight surface-packed structure. With discrete protein adsorption events unambiguously visualized at the biomolecular level, the detailed assembly and packing states of IgG on the BCP nanodomain surface are subsequently correlated to various regimes of IgG adsorption kinetic plots. Intriguing features, entirely different from those observed from macroscopic homopolymer templates, are identified from the IgG adsorption isotherms on the nanoscale, chemically varying BCP surface. They include the presence of two Langmuir-like adsorption segments and a nonmonotonic regime in the adsorption plot. Via correlation to time-corresponding topographic data, the unique isotherm features are explained with single biomolecule level details of the IgG adsorption pathway on the BCP. This work not only provides much needed, direct experimental evidence for time-resolved, single protein level, adsorption events on nanoscale polymer surfaces but also signifies mutual linking between specific topographic states of protein adsorption and assembly to particular segments of adsorption isotherms. From the fundamental research viewpoint, the correlative ability to examine the nanoscopic surface organizations of individual proteins and their local as well as global adsorption kinetic profiles will be highly valuable for accurately determining protein assembly mechanisms and interpreting protein adsorption kinetics on nanoscale surfaces. Application-wise, such knowledge will also be important for fundamentally guiding the design and development of biomaterials and biomedical devices that exploit nanoscale polymer architectures.

Dopamine is an important amine-based chemical neurotransmitter whose protonated state plays a crucial role in the recognition process. Understanding the structure and protonated state of dopamine at the aqueous interface is desired as the diffusion as well as binding of dopamine with the receptors take place frequently in the aqueous interface region. Vibrational sum frequency generation (VSFG) study of the OH stretch of water at the air/water interface in the presence of dopamine is performed and compared with its analog, phenylethylamine, and catechol. The VSFG data suggest that, unlike the bulk case, the population of the deprotonated amine group of dopamine is higher at the aqueous interface. This study suggests that the structure of dopamine at the aqueous interface is different from the bulk which may be useful in understanding the recognition process of dopamine in the interfacial region.

The balance between hydration and Derjaguin-Landau-Verwey-Overbeek (DLVO) forces at solid-liquid interfaces controls many processes, such as colloidal stability, wetting, electrochemistry, biomolecular self-assembly, and ion adsorption. Yet, the origin of molecular scale hydration forces and their relation to the surface charge density that controls the continuum scale electrostatic forces is poorly understood. We argue that these two types of forces are largely independent of each other. To support this hypothesis, we performed atomic force microscopy experiments using intermediate-sized tips that enable the simultaneous detection of DLVO and molecular scale oscillatory hydration forces at the interface between composite gibbsite:silica-aqueous electrolyte interfaces. We extract surface charge densities from forces measured at tip-sample separations of 1.5 nm and beyond using DLVO theory in combination with charge regulation boundary conditions for various pH values and salt concentrations. We simultaneously observe both colloidal scale DLVO forces and oscillatory hydration forces for an individual crystalline gibbsite particle and the underlying amorphous silica substrate for all fluid compositions investigated. While the diffuse layer charge varies with pH as expected, the oscillatory hydration forces are found to be largely independent of pH and salt concentration, supporting our hypothesis that both forces indeed have a very different origin. Oscillatory hydration forces are found to be distinctly more pronounced on gibbsite than on silica. We rationalize this observation based on the distribution of hydroxyl groups available for H bonding on the two distinct surfaces.

We investigated a viscous protein layer formed on self-assembled monolayers (SAMs) in crowded biological environments. The results were obtained through force spectroscopic measurements using colloidal probes and substantiated by exhaustive analysis using a quartz crystal microbalance with an energy dissipation technique. A hydrophobic SAM of

Azide-oligo(ethylene glycol)-terminated self-assembled monolayers (N

Silicon rubber has been widely used in the biomedical field due to its excellent mechanical properties and physiological inertia. However, the hydrophobic properties of silicon rubber surfaces limit their further application. Therefore, constructing a silicon rubber coating with hydrophilic and low-friction surface properties would be highly significant. Existing methods to achieve such coatings, including grafting polymer brushes and the deposition of hydrophilic materials, suffer from several deficiencies such as complicated coating processes and insufficient coating firmness. In this paper, we report a hydrophilic polymer poly(hydroxyethyl methacrylate) (PHEMA) coating that can easily coat the surface of silicon rubber to provide low-friction performance. Sample silicon rubber was treated with benzophenone and hydroxyethyl methacrylate monomer solution in turn. The as-prepared coating was characterized by infrared spectroscopy, X-ray photoelectron spectroscopy, white light interference, and MFT-5000 wear test. The results indicated that the PHEMA coating had excellent hydrophilic properties (with a low contact angle of 9.39°) compared to uncoated silicon rubber. As the concentration of glycerol in the monomer solution was increased, the thickness and surface roughness of the as-prepared coating gradually decreased. The coating was firmly adsorbed on the substrate, and it had a zero-class bonding strength. In addition, the as-prepared coating demonstrated good friction-reduced properties, with the coefficient of friction being reduced by 98.0% compared with the uncoated silicon rubber in simulated blood. In summary, a hydrophilic and low-friction coating was successfully prepared using a simple method, and the results reported herein provide valuable insight into the surface design of similar soft materials.

The surface modification of soft zwitterionic polymer brushes with antifouling properties represents a facile approach to enhancing the performance of bioelectronics. Ionic strength and applied potentials play a crucial role in controlling polymer brushes' conformation and hydration states. In this study, we quantitatively investigated and compared poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) and poly(sulfobetaine methacrylate) (PSBMA) brushes at different salt concentrations and applied surface potentials. Initiator-containing poly(3,4-ethylenedioxythiophene) films (poly(EDOT-Br)) were prepared by electropolymerization. After the conducting polymer was deposited, polymer brushes grew from the electrode surface through surface-initiated atom-transfer radical polymerization (SI-ATRP). Polymer brushes were carefully characterized for their surface morphologies using an atomic force microscope (AFM). The force volume method measured using AFM enabled the analysis of the Young's modulus of the two polymer brushes. Hydration states and protein binding behaviors of polymer brushes were examined using quartz crystal microbalance with dissipation (QCM-D). We further integrated a potentiostat with the QCM-D to conduct an electrochemical QCM-D study. The energy dissipation and frequency changes corresponded to the ion adsorption on the film surface under different ionic strengths. The results of both hydration states and nonspecific protein binding behavior indicate that PMPC brushes have greater ionic strength independency, implying the conformation of the unchanged PMPC brushes. Moreover, we illustrated how the surface potential influences nonspecific and specific binding behavior on PMPC brushes on PEDOT films compared with electrified poly(EDOT-PC) electrodes. We concluded that PMPC brushes exhibit unique behaviors that are barely affected by ion concentration, and that the brushes' modification results in less influence by surface potential due to the finite Debye length influencing the electrode surface to outer environment in an NaCl aqueous solution.

Nanoparticle carriers show promise for drug delivery, including by inhalation, where the first barrier for uptake in the lungs is the monolayer pulmonary surfactant membrane that coats the air/alveoli interface and is critical to breathing. It is imperative to establish the fate of potential nanocarriers and their effects on the biophysical properties of the pulmonary surfactant. To this end, the impact of the nanoparticle surface charge on the lateral organization, thickness, and recompressibility of Langmuir monolayers of model phospholipid-only and phospholipid-protein mixtures was investigated using native and modified forms of nanophytoglycogen, a carbohydrate-based dendritic polymer extracted from corn as monodisperse nanoparticles. We show that the native (quasi-neutral) and anionic nanophytoglycogens have little impact on the phase behavior and film properties. By contrast, cationic nanophytoglycogen alters the film morphology and increases the hysteresis associated with the work of breathing due to its electrostatic interaction with the anionic phospholipids in the model systems. These findings specifically highlight the importance of surface charge as a selection criterion for inhaled nanoformulations.

Carbamylation of blood proteins is a common post-translational modification that occurs upon kidney dysfunction that is strongly associated with deleterious outcomes for patients treated using hemodialysis. In this study, we focused on the removal of two representative carbamylated plasma proteins, carbamylated albumin (cHSA) and fibrinogen (cFgn), through adsorption onto a surface functionalized with a specific peptide (cH2p1). Surfaces modified with poly(hydroxyethyl methacrylate) (p(HEMA)) were prepared using surface-initiated atom transfer radical polymerization (SI-ATRP) techniques and functionalized with cH2p1. cH2p1-functionalized surfaces showed selective binding toward cHSA and cFgn, compared to their native protein form, with NH-cH2p1 of superior selectivity than CO-cH2p1. The adsorption capacity of carbamylated protein on NH-cH2p1 was maintained in diluted plasma, and ultralow adsorption of native Fgn was observed. Similar to unmodified p(HEMA) surfaces, NH-cH2p1 showed a low platelet adhesion and activation, suggesting that the designed surface does not adversely affect platelets.

The COVID-19 pandemic has claimed millions of lives worldwide, sickened many more, and has resulted in severe socioeconomic consequences. As society returns to normal, understanding the spread and persistence of SARS CoV-2 on commonplace surfaces can help to mitigate future outbreaks of coronaviruses and other pathogens. We hypothesize that such an understanding can be aided by studying the binding and interaction of viral proteins with nonbiological surfaces. Here, we propose a methodology for investigating the adhesion of the SARS CoV-2 spike glycoprotein on common inorganic surfaces such as aluminum, copper, iron, silica, and ceria oxides as well as metallic gold. Quantitative adhesion was obtained from the analysis of measured forces at the nanoscale using an atomic force microscope operated under ambient conditions. Without imposing further constraints on the measurement conditions, our preliminary findings suggest that spike glycoproteins interact with similar adhesion forces across the majority of the metal oxides tested with the exception to gold, for which attraction forces ∼10 times stronger than all other materials studied were observed. Ferritin, which was used as a reference protein, was found to exhibit similar adhesion forces as SARS CoV-2 spike protein. This study results show that glycoprotein adhesion forces for similar ambient humidity, tip shape, and contact surface are nonspecific to the properties of metal oxide surfaces, which are expected to be covered by a thin water film. The findings suggest that under ambient conditions, glycoprotein adhesion to metal oxides is primarily controlled by the water capillary forces, and they depend on the surface tension of the liquid water. We discuss further strategies warranted to decipher the intricate nanoscale forces for improved quantification of the adhesion.

In the present study, we investigated the effect of permodified 2,3,6-tri-O-trimethylsilyl β- and γ-cyclodextrin (TMS·β-CD, TMS·γ-CD) encapsulation on the optical, electrochemical, morphological, and supramolecular arrangements of a poly[2,7'-(9,9-dioctylfluorene-alt-2',7-fluorene)] PF copolymer. For this purpose, the photophysical properties and Langmuir monolayer formation of PF·TMS·β-CD and PF·TMS·γ-CD polyrotaxanes were investigated and compared with those of the reference PF. Surface pressure-area isotherms and Brewster angle microscopy studies indicated the capability of both polyrotaxanes to organize into larger and homogeneous 2D supramolecular assemblies at the air-water interface. The obtained results suggest that the presence of the surrounding TMS·β-CD and TMS·γ-CD macrocycles on the PF backbones leads to changes in the conformation and hydrophobicity of the film surfaces. Our investigation offers a method to assess the impact of TMS-CD encapsulation on the control of 2D monolayer formation, with particular attention on the generation of stable PF monolayers for organic electronic devices.

Inorganic materials used for biomedical applications such as implants generally induce the adsorption of proteins on their surface. To control this phenomenon, the bioinspired peptidomimetic polymer 1 (PMP1), which aims to reproduce the adhesion of mussel foot proteins, is commonly used to graft specific proteins on various surfaces and to regulate the interfacial mechanism. To date and despite its wide application, the elucidation at the atomic scale of the PMP1 mechanism of adsorption on surfaces is still unknown. The purpose of the present work was thus to unravel this process through experimental and computational investigations of adsorption of PMP1 on gold, TiO2, and SiO2 surfaces. A common mechanism of adsorption is identified for the adsorption of PMP1 which emphasizes the role of electrostatics to approach the peptide onto the surface followed by a full adhesion process where the entropic desolvation step plays a key role. Besides, according to the fact that mussel naturally controls the oxidation states of its proteins, further investigations were performed for two distinct redox states of PMP1, and we conclude that even if both states are able to allow interaction of PMP1 with the surfaces, the oxidation of PMP1 leads to a stronger interaction.