History-dependent attachment ofPseudomonas aeruginosato solid-liquid interfaces and the dependence of the bacterial surface density on the residence time distribution.

This study investigates how the recent history of bacteria affects their attachment to a solid-liquid interface. We compare the attachment from a flowing suspension of the bacterium,Pseudomonas aeruginosaPAO1, after one of two histories: (a) passage through a tube packed with glass beads or (b) passage through an empty tube. The glass beads were designed to increase the rate of bacterial interactions with solid-liquid surfaces prior to observation in a flow cell. Analysis of time-lapse microscopy of the bacteria in the flow cells shows that the residence time distribution and surface density of bacteria differ for these two histories. In particular, bacteria exiting the bead-filled tube, in contrast to those bacteria exiting the empty tube, are less likely to attach to the subsequent flow cell window and begin surface growth. In contrast, when we compared two histories defined by different lengths of tubing, there was no difference in either the mean residence time or the surface density. In order to provide a framework for understanding these results, we present a phenomenological model in which the rate of bacterial surface density growth,dN(t)/dt, depends on two terms. One term models the initial attachment of bacteria to a surface, and is proportional to the nonprocessive cumulative residence time distribution for bacteria that attach and detach from the surface without cell division. The second term for the rate is proportional to the bacterial surface density and models surface cell division. The model is in surprisingly good agreement with the data even though the surface growth process is a complex interplay between attachment/detachment at the solid-liquid interface and cell division on the surface.

Molecular Diffusion of Ions in Nanoscale Confinement.

We measured the diffusion of an anion, fluorescein, confined to a nanoscale (10-100 nm) aqueous film between two glass walls. The two glass walls were very slightly angled to form a crack. The diffusion of fluorescein was strongly influenced by the presence of an inert electrolyte, NaCl, in the film prior to the diffusion of charged fluorescein into the crack. The time to reach an equilibrium distribution of fluorescein was 10 times longer without the inert electrolyte than when the electrolyte was present. In applications where rapid diffusion of ions is important, it would therefore be advisable to not prewet a confined space with pure water. We attribute this phenomenon to the effect of the electrical potential of the confining walls. Unscreened surface potential in a thin film severely hinders the diffusion of the fluorescein ion. As salt diffuses into the thin film, the electrostatic double layer shrinks in thickness and further diffusion of ions is less hindered. On the other hand, diffusion of ions into the film is only weakly affected by the Debye length of the solution, provided that the surface potential inside a thin film is initially screened by even a low concentration of electrolyte inside the film. The time evolution of the concentration profile for different Debye lengths matches a diffusion model developed with the finite difference method (FDM).

The viability of SARS-CoV-2 on solid surfaces.

The COVID-19 pandemic had a major impact on life in 2020 and 2021. One method of transmission occurs when the causative virus, SARS-CoV-2, contaminates solids. Understanding and controlling the interaction with solids is thus potentially important for limiting the spread of the disease. We review work that describes the prevalence of the virus on common objects, the longevity of the virus on solids, and surface coatings that are designed to inactivate the virus. Engineered coatings have already succeeded in producing a large reduction in viral infectivity from surfaces. We also review work describing inactivation on facemasks and clothing and discuss probable mechanisms of inactivation of the virus at surfaces.

Removal of Bacteria from Solids by Bubbles: Effect of Solid Wettability, Interaction Geometry, and Liquid-Vapor Interface Velocity.

Air bubbles are a promising means of controlling fouling for a range of applications, particularly delaying fouling in marine environments. This work investigates the mechanism by which the collision of an air bubble with a solid removes adsorbed bacteria. A key feature of the work is that the numbers of bacteria were monitored via video microscopy throughout the collision; so, we were able to explore the mechanism of bacteria removal. When a bubble collides with a solid, an air-liquid interface crosses the solid twice, and we were able to distinguish the effects of the first and second air-liquid interfaces. The bacterium Pseudomonas aeruginosa was allowed to adhere to smooth poly(dimethylsiloxane) and then a collision with a bubble was investigated for one of three different approach geometries: perpendicular, parallel, and oscillating parallel to the solid surface. Other factors examined were the speed of the bubble, the duration of bacterial adhesion on the solid surface, and the wettability of the solid. Surface wettability was identified as the most significant factor. When the solid dewet, almost all bacteria were removed from hydrophobic surfaces upon the passage of the first air-liquid interface. In contrast, when a thin liquid film remained between the solid and the bubble (a hydrophilic solid), variable amounts of bacteria remained. Although almost all bacteria were initially removed from hydrophobic solids, many bacteria were redeposited on hydrophobic surfaces upon the passage of the second air-liquid interface, especially when the first and second air-liquid interfaces moved in opposite directions. As described previously, a lower velocity of the bubble allows more time for the thin liquid film to drain and improved removal efficiency on hydrophilic solids. A rougher solid (8 µm diameter hemispherical protrusions) decreased the detachment efficiency because bacteria and liquid were able to shelter in concavities.

Dynamics of single-stranded DNA tethered to a solid.

Tethering is used to deliver specific biological and industrial functions. For example, single-stranded DNA (ssDNA) is tethered to polymerases and long sequences of double-stranded DNA (dsDNA) during replication, and to solids in DNA microarrays. However, tethering ssDNA to a large object limits not only the available ssDNA conformations, but also the range of time-scales over which the mechanical responses of ssDNA are important. In this work we examine the effect of tethering by measurement of the mechanical response of ssDNA that is tethered at each end to two separate atomic force microscope cantilevers in aqueous solution. Thermal motion of the cantilevers drives the ends of the ssDNA chain at frequencies near 2 kHz. The presence of a tethered molecule makes a large difference to the asymmetric cross-correlation of two cantilevers, which enables resolution of the mechanical properties in our experiments. By analysis of the correlated motion of the cantilevers we extract the friction and stiffness of the ssDNA. We find that the measured friction is much larger than the friction that is usually associated with the unencumbered motion of ssDNA. We also find that the measured relaxation time, ∼30 µs, is much greater than prior measurements of the free-molecule relaxation time. We attribute the difference to the loss of conformational possibilities as a result of constraining the ends of the ssDNA.

Direct measurement of field-induced polarization forces between particles in air.

We have measured the effect of DC and AC electric fields (up to 15 kV/m) on the force between two 15 µm radius BaTiO3 glass spheres in air in the separation range 0-6 µm. These fields cause attractive forces that are much greater than van der Waals forces and therefore can be used to control and separate particles in many applications. The attractive force has a static and dynamic component. The static forces are about 9000 times greater than the prediction by multiple-moment methods but otherwise follow the expected trends for polarization forces. For example, the force scales with the square of the field, is constant over a range of field frequencies, and has the same force-separation profile predicted by multipole-moment methods. In contrast to the point dipole approximation, which depends inversely on the fourth power of the distance between the centers of the spheres, the measured static force approximately follows a power law, F ∝ -s(-0.75), that depends on the separation, s, between the nearest points of the spheres. This power law is very similar to the prediction by multipole-moment method for separations less than 1/10th of the radius. The dynamic response force occurs at twice the frequency of the drive and has a similar amplitude to the static force. The electrical field also causes a large increase in adhesion.

Antimicrobial surfaces using covalently bound polyallylamine.

We investigated the antimicrobial properties of the cationic polymer polyallylamine (PA) when covalently bonded to glass. The objective was to obtain a robust attachment, yet still allow extension of the polymer chain into solution to enable interaction with the bacteria. The PA film displayed strong antimicrobial activity against Staphylococcus epidermidis , Staphylococcus aureus , and Pseudomonas aeruginosa , which includes both Gram-positive and Gram-negative bacteria. Glass surfaces were prepared by a straightforward two-step procedure of first functionalizing with epoxide groups using 3-glycidoxypropyltrimethoxy silane (GOPTS) and then exposing to PA so that the PA could bind via reaction of a fraction of its amine groups. The surfaces were characterized using X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy to verify the presence of the polymer on the surface, zeta potential measurements to estimate the surface charge of the films, and atomic force microscopy to determine the extension of the polymer chains into solution. Antimicrobial properties of these coatings were evaluated by spraying aqueous suspensions of bacteria on the functionalized glass slides, incubating them under agar, and counting the number of surviving cell colonies.

Time-Resolved Killing of Individual Bacterial Cells by a Polycationic Antimicrobial Polymer.

Polycationic polymers are widely studied antiseptics, and their efficacy is usually quantified by the solution concentration required to kill a fraction of a population of cells (e.g., by Minimum Bactericidal Concentration (MBC)). Here we describe how the response to a polycationic antimicrobial varies greatly among members of even a monoclonal population of bacteria bathed in a single common antimicrobial concentration. We use fluorescence microscopy to measure the adsorption of a labeled cationic polymer, polydiallyldimethylammmonium chloride (PDADMAC, Mw ≈ 4 × 105 g mol-1) and the time course of cell response via a cell permeability indicator for each member of an ensemble of either Escherichia coli, Staphylococcus aureus, or Pseudomonas aeruginosa cells. This is a departure from traditional methods of evaluating synthetic antimicrobials, which typically measure the overall response of a collection of cells at a particular time and therefore do not assess the diversity within a population. Cells typically die after they reach a threshold adsorption of PDADMAC, but not always. There is a substantial time lag of about 5-10 min between adsorption and death, and the time to die of an individual cell is well correlated with the rate of adsorption. The amount adsorbed and the time-to-die differ among species but follow a trend of more adsorption on more negatively charged species, as expected for a cationic polymer. The study of individual cells via time-lapse microscopy reveals additional details that are lost when measuring ensemble properties at a particular time.

In Situ control of gas flow by modification of gas-solid interactions.

The boundary condition for gas flow at the solid-gas interface can be altered by in situ control of the state of a thin film adsorbed to the solid. A monolayer of ocatadecyltrichlorosilane (OTS) reversibly undergoes a meltinglike transition. When the temperature of an OTS-coated particle and plate is moved through the range of OTS "melting" temperatures, there is a change in the lubrication force between the particle and plate in 1 atm of nitrogen gas. This change is interpreted in terms of a change in the flow of gas mediated by the slip length and tangential momentum accommodation coefficient (TMAC). There is a minimum in slip length (290 nm) at 18 °C, which corresponds to a maximum in TMAC (0.44). The slip length increases to 590 nm at 40 °C which corresponds to a TMAC of 0.25. We attribute the decrease in TMAC with increasing temperature to a decrease in roughness of the monolayer on melting, which allows a higher fraction of specular gas reflections, thereby conserving tangential gas momentum. The importance of this work is that it demonstrates the ability to control gas flow simply by altering the interface for fixed geometry and gas properties.

Effect of grafted oligopeptides on friction.

Frictional and normal forces in aqueous solution at 25 °C were measured between a glass particle and oligopeptide films grafted from a glass plate. Homopeptide molecules consisting of 11 monomers of either glutamine, leucine, glutamic acid, lysine, or phenylalanine and one heteropolymer were each "grafted from" an oxidized silicon wafer using microwave-assisted solid-phase peptide synthesis. The peptide films were characterized using X-ray photoelectron spectroscopy and secondary ion mass spectrometry. Frictional force measurements showed that the oligopeptides increased the magnitude of friction compared to that on a bare hydrophilic silicon wafer but that the friction was a strong function of the nature of the monomer unit. Overall we find that the friction is lower for more hydrophilic films. For example, the most hydrophobic monomer, leucine, exhibited the highest friction whereas the hydrophilic monomer, polyglutamic acid, exhibited the lowest friction at zero load. When the two surfaces had opposite charges, there was a strong attraction, adhesion, and high friction between the surfaces. Friction for all polymers was lower in phosphate-buffered saline than in pure water, which was attributed to lubrication via hydrated salt ions.

Decreasing the Energy of Evaporation Using Interfacial Water: Is This Useful for Solar Evaporation Efficiency?

Evaporation of water using solar power is an economical and environmentally friendly method for purification of aqueous solutions. It has been suggested that intermediate states can be used to lower the enthalpy of evaporation of water and therefore to increase the efficiency of evaporation that uses absorption of sunlight. However, the relevant quantity is the enthalpy of evaporation from bulk water to bulk vapor, which is fixed for a given temperature and pressure. The formation of an intermediate state does not alter the enthalpy of the overall process.

Super-enhanced evaporation of droplets from porous coatings.

HYPOTHESIS: The addition of a thin, hydrophilic, porous, coating to an impermeable solid will lead to more rapid evaporation of liquid droplets that impinge on the solid. The droplet will imbibe quickly, but the progress normal to the interface will be limited to the thickness of the coating, and therefore the liquid will spread laterally into a broad disk to expose a large liquid-vapor interface for evaporation. EXPERIMENTS: Liquid droplets of volume 2.5-25 µL were placed on solids and then both the mass and area of each droplet were monitored over time. We compared data for smooth, impermeable hydrophilic glass to the same glass that was coated in thin (35-109 µm) porous, hydrophilic-glass layer fabricated from glass beads. FINDINGS: The droplet was imbibed (wicked) into the coating within seconds, and the liquid spread laterally to form a thin, broad, disk. Critically, evaporation of a droplet was enhanced by a factor of 7-8 on the thin coating. The evaporation rate was not proportional to the reciprocal thickness of the coating. The ability to enhance evaporation of small droplets on a solid may have practical applications, for example, in speeding the death of microbes.

Antimicrobial mechanism of cuprous oxide (Cu2O) coatings.

Some very effective antimicrobial coatings exploit copper or cuprous oxide (Cu2O) as the active agent. The aim of this study is to determine which species is the active antimicrobial - dissolved ions, the Cu2O solid, or reactive oxygen species. Copper ions were leached from Cu2O into various solutions and the leachate tested for both dissolved copper and the efficacy in killing Pseudomonas aeruginosa. The concentration of copper species leached from Cu2O into aqueous solution varied greatly with the composition of the aqueous solution. For a range of solution buffers, killing of P. aeruginosa was highly correlated with the concentration of copper in the leachate. Further, 10 µL bacterial suspension droplets were placed on Cu2O coatings, with or without a polymer barrier layer, and tested for bacterial kill. Killing occurred without contact between bacterium and solid, demonstrating that contact with Cu2O is not necessary. We therefore conclude that soluble copper species are the antimicrobial agent, and that the most potent species is Cu+. The solid quickly raises and sustains the concentration of soluble copper species near the bacterium. Killing via soluble copper ions rather than contact should allow copper coatings to kill bacteria even when fouled, which is an important practical consideration.

Facile Implementation of Antimicrobial Coatings through Adhesive Films (Wraps) Demonstrated with Cuprous Oxide Coatings.

Antimicrobial coatings have a finite lifetime because of wear, depletion of the active ingredient, or surface contamination that produces a barrier between the pathogen and the active ingredient. The limited lifetime means that facile replacement is important. Here, we describe a generic method for rapidly applying and reapplying antimicrobial coatings to common-touch surfaces. The method is to deposit an antimicrobial coating on a generic adhesive film (wrap), and then to attach that modified wrap to the common-touch surface. In this scenario, the adhesion of the wrap and antimicrobial efficacy are separated and can be optimized independently. We demonstrate the fabrication of two antimicrobial wraps, both using cuprous oxide (Cu2O) as the active ingredient. The first uses polyurethane (PU) as the polymeric binder and the second uses polydopamine (PDA). Our antimicrobial PU/Cu2O and PDA/Cu2O wraps, respectively, kill >99.98% and >99.82% of the human pathogen, P. aeruginosa, in only 10 min, and each of them kill >99.99% of the bacterium in 20 min. These antimicrobial wraps can be removed and replaced on the same object in <1 min with no tools. Wraps are already frequently used by consumers to coat drawers or cars for aesthetic or protective purposes.

Porous Antimicrobial Coatings for Killing Microbes within Minutes.

Antimicrobial coatings can be used to reduce the transmission of infectious agents that are spread by contact. An effective coating should kill microbes in the time between users, which is sometimes minutes or less. Fast killing requires fast transport, and our proposed method of fast transport is a porous coating where the contaminated liquid imbibes (infiltrates) into the pores to achieve rapid contact with active material inside the pores. We test the hypothesis that a porous antimicrobial coating will enable faster inactivation of microorganisms than a planar coating of the same material. We use hydrophilic pores with dimensions of 5-100 µm such that liquid droplets imbibe in seconds, and from there transport distances and times are short, defined by the pore size rather than the droplet size. Our coating has two levels of structure: (A) a porous scaffold and (B) an antimicrobial coating within the pore structure containing the active ingredient. Two scaffolds are studied: stainless steel and poly(methyl methacrylate) (PMMA). The active ingredient is electrolessly deposited copper. To enhance adhesion and growth of copper, a layer of polydopamine (PDA) is deposited on the scaffold prior to deposition of the copper. This porous copper coating kills 99.84% of Pseudomonas aeruginosa within 3 min, which is equivalent to a half-life of 27 s. In contrast, the same layer of PDA/copper on a nonporous coating kills 79.65% in the same time frame, consistent with the hypothesis that the killing rate is increased by the addition of porosity. Using the porous PMMA scaffold, the porous antimicrobial coating kills >99.99% P. aeruginosa in 5 min, which is equivalent to a half-life of 21 s. The higher rate of kill on the porous antimicrobial solid is appropriate for hindering the spread of infectious agents on common-use objects.

Robust and Transparent Silver Oxide Coating Fabricated at Room Temperature Kills Clostridioides difficile Spores, MRSA, and Pseudomonas aeruginosa.

Antimicrobial coatings can inhibit the transmission of infectious diseases when they provide a quick kill that is achieved long after the coating application. Here, we describe the fabrication and testing of a glass coating containing Ag2O microparticles that was prepared from sodium silicate at room temperature. The half-lives of both methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa on this coating are only 2-4 min. The half-life of Clostridioides difficile spores is about 9-12 min, which is extremely short for a spore. Additional tests on MRSA demonstrate that the coating retains its antimicrobial activity after abrasion and that an increased loading of Ag2O leads to a shorter half-life. This coating combines the properties of optical transparency, robustness, fast kill, and room temperature preparation that are highly desirable for an antimicrobial coating.

Forces between hydrophobic solids in concentrated aqueous salt solution.

Much research has focused on the discovery and description of long-ranged forces between hydrophobic solids immersed in water. Here we show that the force between high contact-angle solids in concentrated salt solution (1 M KCl) agrees very well with van der Waals forces calculated from Lifshitz theory for separations greater than 5 nm. The hydrophobic solids are octadecyltrichlorosilane-coated glass, with an advancing contact angle of 108°. Thus, in 1 M salt solution, it is unnecessary to invoke the presence of a hydrophobic force at separations greater than 5 nm. Through measurement in salt solution, we avoid the necessity of accounting for large electrostatic forces that frequently occur in pure water and may obscure resolution of other forces.

A deliberation on nanobubbles at surfaces and in bulk.

Surface and bulk nanobubbles are two types of nanoscopic gaseous domain that have recently been discovered in interfacial physics. Both are expected to be unstable to dissolution because of the high internal pressure driving diffusion and the surface tension which squeezes the gas out, but there is a rapidly growing body of experimental evidence that demonstrates both bubble types to be stable. However, the two types of bubbles also differ in many respects: surface nanobubble stability is most probably assisted by the nearby wall, which can repel the water (in the case of hydrophobicity), accept physisorbed gas molecules, and reduce the surface area through which outfluxing can occur; bulk nanobubbles, on the other hand, must stabilise themselves. This is perhaps through ionic shielding, perhaps through diffusive shielding, or perhaps through both. Herein, the features of both bubble types are described individually, their common and disparate features are discussed, and emerging applications are examined.

Selective adsorption to particular crystal faces of ZnO.

We examine the hypothesis that selective adsorption to a particular face of ZnO is responsible for the ability of small organic molecules to control the aspect ratio of ZnO crystals during hydrothermal synthesis. Large, single crystals of ZnO were prepared such that the vast majority of a surface consisted of a single crystal plane, as shown by atomic force microscopy, and the adsorption to a single crystal plane was determined by attenuated total reflectance spectroscopy. The results show that citrate strongly and selectively adsorbs to the (0001) face. Similarly, results show that ethylenediamine selectively adsorbs to the (1010) face. Each of these results separately shows a correlation between selective adsorption to and growth of large areas of a particular face, and thus, each result is consistent with the proposed hypothesis.

Mechanism and Efficacy of Cu2O-Treated Fabric.

Pathogenic bacteria can remain viable on fabrics for several days and therefore are a source of infection. Antimicrobial fabrics are a potential method of reducing such infections, and advances in antimicrobial fabrics can be enhanced by knowledge of how the fabric kills bacteria. Metal oxides have been considered and used as antimicrobial ingredients in self-sanitizing surfaces, including in clinical settings. In this work, we examine how the addition of cuprous oxide (Cu2O) particles to polypropylene fibers kills bacteria. First, we show that the addition of the Cu2O particles reduces the viability of common hospital pathogens, Staphylococcus aureus, Pseudomonas aeruginosa, and Streptococcus pneumoniae, by 99.9% after 30 min of contact with the treated polypropylene. Then, we demonstrate that the main killing effect is due to the drying of the bacteria onto the cuprous oxide particles. There is also a weaker effect due to free Cu+ ions that dissolve into the liquid. Other dissolved species were unimportant. Chelation of these Cu+ ions in soluble form or precipitation removes their antimicrobial activity.