The 50 most-cited articles in Langmuir, 2016

We follow the history of nanobubbles from the earliest experiments pointing to their existence to recent years. We cover the effect of Laplace pressure on the thermodynamic stability of nanobubbles and why this implies that nanobubbles are thermodynamically never stable. Therefore, understanding bubble stability becomes a consideration of the rate of bubble dissolution, so the dominant approach to understanding this is discussed. Bulk nanobubbles (or fine bubbles) are treated separately from surface nanobubbles as this reflects their separate histories. For each class of nanobubbles, we look at the early evidence for their existence, methods for the production and characterization of nanobubbles, evidence that they are indeed gaseous, or otherwise, and theories for their stability. We also look at applications of both surface and bulk nanobubbles.

The renewability, biocompatibility, and mechanical properties of cellulose nanocrystals (CNCs) have made them an attractive material for numerous composite, biomedical, and rheological applications. However, for CNCs to shift from a laboratory curiosity to commercial applications, researchers must transition from CNCs extracted on the bench scale to material produced on an industrial scale. There are a number of companies currently producing kilogram to ton per day quantities of sulfuric acid-hydrolyzed CNCs as well as other nanocelluloses, as described herein. With the recent intensification of industrially produced CNCs and the variety of cellulose sources, hydrolysis methods, and purification procedures, the characterization of these materials becomes critical. This has further been justified by the past two decades of research that demonstrate that the CNC stability and behavior are highly dependent on the surface chemistry, surface charge density, and particle size. This work outlines key test methods that should be employed to characterize these properties to ensure a "known"…

We report on the development of ultrasmall core-shell silver nanoparticles synthesized by an upscaled modification of the polyol process. It is foreseen to use these thoroughly characterized particles as reference material to compare the catalytic and biological properties of functionalized silver nanoparticles. Small-angle X-ray scattering (SAXS) analysis reveals a narrow size distribution of the silver cores with a mean radius of Rc = 3.0 nm and a distribution width of 0.6 nm. Dynamic light scattering (DLS) provides a hydrodynamic radius of RH = 10.0 nm and a PDI of 0.09. The particles' surface is covered with poly(acrylic acid) (PAA) forming a shell with a thickness of 7.0 nm, which provides colloidal stability lasting for more than 6 months at ambient conditions. The PAA can be easily exchanged by biomolecules to modify the surface functionality. Replacements of PAA with glutathione (GSH) and bovine serum albumin (BSA) have been performed as examples. We demonstrate that the silver particles effectively catalyze the reduction of 4-nitrophenol to 4-aminophenol with sodium…

Liquid-liquid phase separation is responsible for formation of P granules, nucleoli, and other membraneless subcellular organelles composed of RNA and proteins. Efforts to understand the physical basis of liquid organelle formation have thus far focused on intrinsically disordered proteins (IDPs) as major components that dictate occurrence and properties. Here, we show that complex coacervates composed of low complexity RNA (polyuridylic acid, polyU) and short polyamines (spermine and spermidine) share many features of IDP-based coacervates. PolyU/polyamine coacervates compartmentalize biomolecules (peptides, oligonucleotides) in a sequence- and length-dependent manner. These solutes retain mobility within the coacervate droplets, as demonstrated by rapid recovery from photobleaching. Coacervation is reversible with changes in solution temperature due to changes in the polyU structure that impact its interactions with polyamines. We further demonstrate that lipid vesicles assemble at the droplet interface without impeding RNA entry/egress. These vesicles remain intact at the…

Lignin nanoparticles can serve as biodegradable carriers of biocidal actives with minimal environmental footprint. Here we describe the colloidal synthesis and interfacial design of nanoparticles with tunable surface properties using two different lignin precursors, Kraft (Indulin AT) lignin and Organosolv (high-purity lignin). The green synthesis process is based on flash precipitation of dissolved lignin polymer, which enabled the formation of nanoparticles in the size range of 45-250 nm. The size evolution of the two types of lignin particles is fitted on the basis of modified diffusive growth kinetics and mass balance dependencies. The surface properties of the nanoparticles are fine-tuned by coating them with a cationic polyelectrolyte, poly(diallyldimethylammonium chloride). We analyze how the colloidal stability and dispersion properties of these two types of nanoparticles vary as a function of pH and salinities. The data show that the properties of the nanoparticles are governed by the type of lignin used and the presence of polyelectrolyte surface coating. The coating…

The electrolysis of aqueous solutions produces solutions that are supersaturated in oxygen and hydrogen gas. This results in the formation of gas bubbles, including nanobubbles ∼100 nm in size that are stable for ∼24 h. These aqueous solutions containing bubbles have been evaluated for cleaning efficacy in the removal of model contaminants bovine serum albumin and lysozyme from surfaces and in the prevention of the fouling of surfaces by these same proteins. Hydrophilic and hydrophobic surfaces were investigated. It is shown that nanobubbles can prevent the fouling of surfaces and that they can also clean already fouled surfaces. It is also argued that in practical applications where cleaning is carried out rapidly using a high degree of mechanical agitation the role of cleaning agents is not primarily in assisting the removal of soil but in suspending the soil that is removed by mechanical action and preventing it from redepositing onto surfaces. This may also be the primary mode of action of nanobubbles during cleaning.

We theoretically predict the local density of nucleosomes on DNA brushes in a solution of molecules, which are necessary for transcription and the assembly of nucleosomes. Our theory predicts that in a confined space, DNA brushes show phase separation, where a region of relatively large nucleosomal occupancy coexists with a region of smaller nucleosomal occupancy. This phase separation is driven by an instability arising from the fact that the rate of transcription increases as the nucleosomal occupancy decreases due to the excluded volume interactions between nucleosomes and RNA polymerase during thermal diffusion and, in turn, nucleosomes are (in some cases) desorbed from DNA when RNA polymerase collides with nucleosomes during transcription. The miscibility phase diagram shows critical points, which are sensitive to the rate constants involved in transcription, the changes of interactions of DNA chain segments by assembling nucleosomes, and pressures that are applied to the brushes.

Exogenous reactive oxygen species (ROS) produced by nanobubble (NB) water offer a reasonable explanation for NBs’ physiological promotion and oxidation effects. To develop and exploit the NB technology, we have performed further research to identify the specific ROS produced by NBs. Using a fluorescent reagent APF, a Fenton reaction, a dismutation reaction of superoxide dismutase and DMSO, we distinguished four types of ROS (superoxide anion radical (O 2 · – ), hydrogen peroxide (H 2 O 2 ), hydroxyl radical (·OH), and singlet oxygen ( 1 O 2 )). ·OH was confirmed to be the specific ROS produced by NB water. The role of ·OH produced by NB water in physiological processes depends on its concentration. The amount of exogenous ·OH has a positive correlation with the NB number density in the water. Here, spinach and carrot seed germination tests were repeatedly performed with three seed groups submerged in distilled water, high-number density NB water, and low-number density NB water under similar dissolved oxygen concentrations. The final germination rates of spinach seeds in distilled…

Well known for the adhesive property, mussel-inspired polydopamine (PDA) has been shown to enhance performance in a wide range of adsorption-based applications. However, imparting porous nanostructures to PDA materials for enhanced loading capacities has not been demonstrated even when surfactants were present in the synthesis. Herein, we report on the preparation of mesoporous PDA particles (MPDA) based on the assembly of primary PDA particles and Pluronic F127 stabilized emulsion droplets on water/1,3,5-trimethylbenzene (TMB) interfaces. The key to the formation of this new type of the MPDA structure is the full utilization of the π–π stacking interactions between PDA structures and the π-electron-rich TMB molecules. Remarkably, this method presents a facile approach for MPDA particles with an average diameter of ∼90 nm, slit-like pores with a peak size of ∼5.0 nm as well as hollow cavities. When used as the adsorbent for a model dye RhB, the MPDA particles achieved an ultrahigh RhB adsorption capacity of 1100 μg mg –1, which is significantly higher than that for the PDA-reactive…

Interfacing DNA with two-dimensional (2D) materials has been intensely researched for various analytical and biomedical applications. Most of these studies have been performed on graphene oxide (GO) and two metal dichalcogenides, molybdenum disulfide (MoS 2 ) and tungsten disulfide (WS 2 ); all of them can all adsorb single-stranded DNA. However, they use different surface forces for adsorption based on their chemical structures. In this work, fluorescently labeled DNA oligonucleotides were used and their adsorption capacities and kinetics were studied as a function of ionic strength, DNA length, and sequence. Desorption of DNA from these surfaces was also measured. DNA is more easily desorbed from GO by various denaturing agents, whereas surfactants yield more desorption from MoS 2 and WS 2 . Our results are consistent with the fact that DNA can be adsorbed by GO via π–π stacking and hydrogen bonding, and MoS 2 and WS 2 mainly use van der Waals force for adsorption. Finally, fluorescent DNA probes were adsorbed by these 2D materials for detecting complementary DNA. For this assay,…

Since the development of simple, aqueous protocols for the synthesis of anisotropic metal nanoparticles, research into many promising, valuable applications of gold nanorods has grown considerably, but a number of challenges remain, including gold-particle yield, robustness to minor impurities, and precise control of gold nanorod surface chemistry. Herein we present the results of a composite fractional factorial series of experiments designed to screen seven additional potential avenues of control and to understand the seed-mediated silver-assisted synthesis of gold nanorods. These synthesis variables are the amount of sodium borohydride used and the rate of stirring when producing seed nanoparticles, the age of and the amount of seeds added, the reaction temperature, the amounts of silver nitrate and ascorbic acid added, and the age of the reduced growth solution before seed nanoparticles are added to initiate rod formation. This statistical experimental design and analysis method, besides determining which experimental variables are important and which are not when synthesizing…

Gold nanorods have garnered a great deal of scientific interest because of their unique optical properties, and they have the potential to greatly impact many areas of science and technology. Understanding the structure and chemical makeup of their surfaces as well as how to tailor them is of paramount importance in the development of their successful applications. This Feature Article reviews the current understanding of the surface chemistry of as-synthesized gold nanorods, methods of tailoring the surface chemistry of gold nanorods with various inorganic and organic coatings/ligands, and the techniques employed to characterize ligands on the surface of gold nanorods as well as the associated measurement challenges. Specifically, we address the challenges of determining how thick the ligand shell is, how many ligands per nanorod are present on the surface, and where the ligands are located in regiospecific and mixed-ligand systems. We conclude with an outlook on the development of the surface chemistry of gold nanorods leading to the development of a synthetic nanoparticle surface…

Droplet impact has been imaged on different rigid, smooth, and rough substrates for three liquids with different viscosity and surface tension, with special attention to the lower impact velocity range. Of all studied parameters, only surface tension and viscosity, thus the liquid properties, clearly play a role in terms of the attained maximum spreading ratio of the impacting droplet. Surface roughness and type of surface (steel, aluminum, and parafilm) slightly affect the dynamic wettability and maximum spreading at low impact velocity. The dynamic contact angle at maximum spreading has been identified to properly characterize this dynamic spreading process, especially at low impact velocity where dynamic wetting plays an important role. The dynamic contact angle is found to be generally higher than the equilibrium contact angle, showing that statically wetting surfaces can become less wetting or even nonwetting under dynamic droplet impact. An improved energy balance model for maximum spreading ratio is proposed based on a correct analytical modeling of the time at maximum…

Chitosan-based conventional and Pickering oil-in-water (O/W) emulsions with very fine droplet size (volume average diameter, dv, as low as 1.7 μm) and long-term stability (up to 5 months) were ultrasonically generated at different pH values without the addition of any surfactant or cross-linking agent. The ultrasonication treatment was found to break and disperse chitosan agglomerates effectively (particularly at pH ≥ 4.5) and also reduce the chitosan molecular weight, benefiting its emulsification properties. The emulsion stability and emulsion type could be controlled by chitosan solution pH. Increasing pH from 3.5 to 5.5 led to the formation of conventional emulsions with decreasing droplet size (dv from 14 to 2.1 μm) and increasing emulsion stability (from a few days to 2 months). These results can be explained by the increase of dynamic interfacial pressure, which results from the conformation transition of chitosan molecules from an extended state to a more flexible structure as pH increases. At pH = 6.5 (the acid dissociation constant (pKa) of chitosan), the chitosan…

Colloidal stability of graphene oxide (GO) is studied in aqueous and organic media accompanied by an improved aggregation model based on Derjaguin-Landau-Verwey- Overbeek (DLVO) theory for ultrathin colloidal flakes. It is found that both magnitude and scaling laws for the van der Waals forces are affected significantly by the two-dimensional (2D) nature of GO. Experimental critical coagulation concentrations (CCC) of GO in monovalent salt solutions concur with DLVO theory prediction. The surface charge density of GO is largely affected by pH. However, theoretical calculations and experimental observations show that the colloidal stability of the 2D colloids is less sensitive to the changes in the surface charge density compared to the classical picture of 3D colloids. The DLVO theory also quantitatively predicts the colloidal stability of reduced GO (rGO). The origin of lower stability of rGO compared to GO is rooted in the higher van der Waals forces among rGO sheets, and particularly, in the removal of negatively charged groups, and possibly formation of some cationic groups…

Injectable hydrogels have been widely used for a number of biomedical applications. Here, we report a new strategy to form an injectable and glucose-responsive hydrogel using the boronic acid-glucose complexation. The ratio of boronic acid and glucose functional groups is critical for hydrogel formation. In our system, polymers with 10-60% boronic acid, with the balance being glucose-modified, are favorable to form hydrogels. These hydrogels are shear-thinning and self-healing, recovering from shear-induced flow to a gel state within seconds. More importantly, these polymers displayed glucose-responsive release of an encapsulated model drug. The hydrogel reported here is an injectable and glucose-responsive hydrogel constructed from the complexation of boronic acid and glucose within a single component polymeric material.

A novel biopolymer-based aerogel was developed by freeze-drying a hydrogel, synthesized from cross-linking bifunctional hairy nanocrystalline cellulose and carboxymethylated chitosan through a Schiff base reaction. The nanocelluloses, bearing aldehyde and carboxylic acid groups, facilitated the cross-linking with chitosan through imine bond formation while providing negatively charged functional groups, and chitosan was modified to accommodate carboxylic acid. The potential of this bioaerogel in environmental remediation was examined in a model system comprising methylene blue, a cationic dye. Electrostatic complexation between acidic groups on the anionic aerogel with the dye resulted in time-dependent dye adsorption, with long-time equilibrium dye concentration fitting well to the Langmuir isotherm, yielding a maximum adsorption capacity of ∼785 mg g –1 and equilibrium constant K ∼ 0.0089 at room temperature. Dynamics of adsorption was modeled by numerically solving the unsteady-state diffusion–adsorption mass balance in a 1D spherical coordinate, which attested to a…

Injection of optimized chemistry water in enhanced oil recovery (EOR) has gained much interest in the past few years. Crude oil-water interfaces can have a viscoelastic character affected by the adsorption of amphiphilic molecules. The brine concentration as well as surfactants may strongly affect the fluid-fluid interfacial viscoelasticity. In this work we investigate interfacial viscoelasticity of two different oils in terms of brine concentration and a nonionic surfactant. We correlate these measurements with oil recovery in a glass-etched flow microchannel. Interfacial viscoelasticity develops relatively fast in both oils, stabilizing at about 48 h. The interfaces are found to be more elastic than viscous. The interfacial elastic (G') and viscous (G″) moduli increase as the salt concentration decreases until a maximum in viscoelasticity is observed around 0.01 wt % of salt. Monovalent (Na(+)) and divalent (Mg(2+)) cations are used to investigate the effect of ion type; no difference is observed at low salinity. The introduction of a small amount of a surfactant (100 ppm)…

Effects of substrate temperature, substrate wettability, and particle concentration are experimentally investigated for evaporation of a sessile water droplet containing colloidal particles. Time-varying droplet shapes and temperature of the liquid-gas interface are measured using high-speed visualization and infrared thermography, respectively. The motion of the particles inside the evaporating droplet is qualitatively visualized by an optical microscope and the profile of the final particle deposit is measured by an optical profilometer. On a nonheated hydrophilic substrate, a ring-like deposit forms after the evaporation, as reported extensively in the literature, while on a heated hydrophilic substrate, a thinner ring with an inner deposit is reported in the present work. The latter is attributed to Marangoni convection, and recorded motion of the particles as well as measured temperature gradient across the liquid-gas interface confirms this hypothesis. The thinning of the ring scales with the substrate temperature and is reasoned to stronger Marangoni convection at larger…

Competitive coadsorption of water is a major problem in the deployment of adsorption-based CO 2 capture. Water molecules may compete for adsorption sites, reducing the capacity of the material, and dehumidification prior to separating CO 2 from N 2 increases process complexity and cost. The development of adsorbent materials that can selectively adsorb CO 2 in the presence of water would be a major step forward in the deployment of CO 2 capture materials in practice. In this study, large-scale computational screening was carried out to search for metal–organic frameworks (MOFs) with high selectivity toward CO 2 over H 2 O. Calculating framework charges for thousands of MOFs is a significant challenge, so initial screening used a fast, but approximate, charge calculation method. On the basis of the initial screening, 15 MOFs were selected, and Monte Carlo simulations were carried out to compute the adsorption isotherms for these MOFs using more accurate framework charges calculated by density functional theory. A detailed investigation was performed on the effect of using different…

Cellulose nanocrystals (CNCs) are negatively charged nanorods that present challenges for characterization of particle size distribution and surface area-two of the common parameters for characterizing nanomaterials. CNC size distributions have been measured by two microscopy methods: atomic force microscopy (AFM) and transmission electron microscopy (TEM). The agreement between the two methods is good for length measurements, after taking into consideration tip-convolution effects for AFM. However, TEM widths are almost twice as large as AFM heights-an effect that we hypothesize is due to counting of a larger fraction of laterally associated CNCs in the TEM images. Overall, the difficulty of selecting individual particles for analysis and possible bias due to selection of a specific particle size during sample deposition are the main limitations associated with the microscopy measurements. The microscopy results were compared to Z-average data from dynamic light scattering, which is a useful method for routine analysis and for examining trends in size as a function of sample…

The dynamic equilibrium model for a bulk nanobubble partly covered with hydrophobic material in water is theoretically and numerically studied. The gas diffusion into a bubble near the peripheral edge of the hydrophobic material on the bubble surface balances that out of the bubble from the other part of the uncovered bubble surface. In the present model, gas diffusion in quiescent liquid is assumed and there is no liquid flow. The total changes of energy and entropy are both zero as it is a kind of equilibrium state. The main origin of the dynamic equilibrium state is the gradient of chemical potential of gas near the peripheral edge of the hydrophobic material. It is caused by the permanent attractive potential of a hydrophobic material to gas molecules dissolved in liquid water as there is permanent repulsion of a hydrophobic material against liquid water. Thus, the gas supply will not terminate. It is numerically shown that stable nanobubble could be present when the fraction of surface coverage by hydrophobic material is from about 0.5 to 1. The stable size of a nanobubble…

Liquid marbles are nonstick droplets wrapped by micro- or nanometrically scaled colloidal particles, representing a platform for a variety of chemical, biological, and microfluidics applications. Liquid marbles demonstrate elastic properties and do not coalesce when bounced or pressed. The effective surface tension and Young modulus of liquid marbles are discussed. Physical sources of the elasticity of liquid marbles are considered. Liquids and powders used for the fabrication of liquid marbles are surveyed. This feature article reviews properties and applications of liquid marbles. Liquid marbles demonstrate potential as microreactors, microcontainers for growing micro-organisms and cells, and microfluidics devices. The Marangoni-flow-driven self-propulsion of marbles supported by liquids is addressed.

Understanding the fundamental mechanisms governing vapor condensation on nonwetting surfaces is crucial to a wide range of energy and water applications. In this paper, we reconcile classical droplet growth modeling barriers by utilizing two-dimensional axisymmetric numerical simulations to study individual droplet heat transfer on nonwetting surfaces (90° < θa < 170°). Incorporation of an appropriate convective boundary condition at the liquid-vapor interface reveals that the majority of heat transfer occurs at the three phase contact line, where the local heat flux can be up to 4 orders of magnitude higher than at the droplet top. Droplet distribution theory is incorporated to show that previous modeling approaches underpredict the overall heat transfer by as much as 300% for dropwise and jumping-droplet condensation. To verify our simulation results, we study condensed water droplet growth using optical and environmental scanning electron microscopy on biphilic samples consisting of hydrophobic and nanostructured superhydrophobic regions, showing excellent agreement with the…

The zeta potential (ZP) is an oft-reported measure of the macroscopic charge state of solid surfaces and colloidal particles in contact with solvents. However, the origin of this readily measurable parameter has remained divorced from the molecular-level processes governing the underlying electrokinetic phenomena, which limits its usefulness. Here, we connect the macroscopic measure to the microscopic realm through nonequilibrium molecular dynamics simulations of electroosmotic flow between parallel slabs of the hydroxylated (110) rutile (TiO 2 ) surface. These simulations provided streaming mobilities, which were converted to ZP via the commonly used Helmholtz-Smoluchowski equation. A range of rutile surface charge densities (0.1 to −0.4 C/m 2 ), corresponding to pH values between about 2.8 and 9.4, in RbCl, NaCl, and SrCl 2 aqueous solutions, were modeled and compared to experimental ZPs for TiO 2 particle suspensions. Simulated ZPs qualitatively agree with experiment and show that “anomalous” ZP values and inequalities between the point of zero charge derived from electrokinetic…

Phase separation of aqueous solutions containing polyelectrolytes can lead to formation of dense, solute-rich liquid droplets referred to as coacervates, surrounded by a dilute continuous phase of much larger volume. This type of liquid-liquid phase separation is thought to help explain the appearance of polyelectrolyte-rich intracellular droplets in the cytoplasm and nucleoplasm of extant biological cells and may be relevant to protocellular compartmentalization of nucleic acids on the early Earth. Here we describe complex coacervates formed upon mixing the polycation poly(allylamine) (PAH, 15 kDa) with the anionic nucleotides adenosine 5'-mono-, di-, and triphosphate (AMP, ADP, and ATP). Droplet formation was observed over a wide range of pH and MgCl2 concentrations. The nucleotides themselves as well as Mg(2+) and RNA oligonucleotides were all extremely concentrated within the coacervates. Nucleotides present at just 2.5 mM in bulk solution had concentrations greater than 1 M inside the coacervate droplets. A solution with a total Mg(2+) concentration of 10 mM had 1-5 M Mg(2+) in…

Silica has been frequently studied using infrared and Raman spectroscopy due to its importance in many practical contexts where its surface chemistry plays a vital role. The majority of these studies have utilized chemical-vapor-deposited films in vacuo after high-temperature calcination. However, room-temperature hydration and dehydration of thin silica particle films has not been well characterized in spite of the importance of such films as substrates for polymer and surfactant adsorption. The present study has utilized ATR-IR spectroscopy and thin silica particle films exposed to varying humidity to clearly show reversible conversion between surface siloxanes and hydrogen-bonded silanols without the need for semiempirical peak deconvolution. The IR spectra from corresponding hydration experiments on deuterated silica films has confirmed the vibrational mode assignments. The variation of humidity over silica films formed from silica suspensions of differing pH gave IR spectra consistent with the change in the relative populations of siloxide to silanol surface groups. In…

In this paper, the pinning and depinning mechanism of the contact line during droplet evaporation on chemically stripe-patterned surfaces is numerically investigated using a thermal multiphase lattice Boltzmann (LB) model with liquid-vapor phase change. A local force balance in the context of diffuse interfaces is introduced to explain the equilibrium states of droplets on chemically patterned surfaces. It is shown that when the contact line is pinned on a hydrophobic-hydrophilic boundary, different contact angles can be interpreted as the variation of the length of the contact line occupied by each component. The stick-slip-jump behavior of evaporating droplets on chemically patterned surfaces is well captured by the LB simulations. Particularly, a slow movement of the contact line is clearly observed during the stick (pinning) mode, which shows that the pinning of the contact line during droplet evaporation on chemically stripe-patterned surfaces is actually a dynamic pinning process and the dynamic equilibrium is achieved by the self-adjustment of the contact lines occupied by…

When soy glycinin (11S) is heated for a prolonged time at pH 2 (20 h at 85 °C), a mixture is formed consisting of long semiflexible 11S fibrils and small peptides. The surface and foaming properties of this mixture were investigated at different pHs, and compared to the behavior of pure fibrils and pure peptides, to determine the individual contributions of these two factions to the behavior of the mixture. The adsorption of these three systems at air-water interfaces and the resulting surface rheological properties were studied by combining drop shape analysis tensiometry, ellipsometry, and surface large amplitude oscillatory dilatational (LAOD) rheology. Lissajous plots of surface pressure versus deformation were used to analyze the surface rheological response in terms of interfacial microstructure. Our results show that the adsorption kinetics, dilatational rheological properties, and the foaming behavior of the mixture were mainly dominated by the small peptides in the fibril system. Compared to pH 2, the fibril mixture at pH 5 and 7 provides much better foam stability and…

Emulsions with interface-active components at the oil/water interface have long been of fundamental and practical interest in many fields. In this work, the interaction forces between two oil droplets in water in the absence/presence of asphaltenes were directly measured using droplet probe atomic force microscopy (AFM) and analyzed using a theoretical model based on Reynolds lubrication theory and the augmented Young-Laplace equation by including the effects of disjoining pressure. It was revealed that the interaction forces measured between two pristine oil droplets (i.e., toluene) could be well described by the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, while an additional steric interaction should be included in the presence of asphaltenes in the oil. The surface interaction and the stability of oil droplets in aqueous solution were demonstrated to be significantly influenced by the asphaltenes concentration in oil, salt concentration, pH, and presence of divalent ions (Ca(2+)) in water. Adsorbed asphaltenes at the oil/water interface led to more negative surface…

Interdroplet vapor pressure gradients are the driving mechanism for several phase-change phenomena such as condensation dry zones, interdroplet ice bridging, dry zones around ice, and frost halos. Despite the fundamental nature of the underlying pressure gradients, the majority of studies on these emerging phenomena have been primarily empirical. Using classical nucleation theory and Becker-Döring embryo formation kinetics, here we calculate the pressure field for all possible modes of condensation and desublimation in order to gain fundamental insight into how pressure gradients govern the behavior of dry zones, condensation frosting, and frost halos. Our findings reveal that in a variety of phase-change systems the thermodynamically favorable mode of nucleation can switch between condensation and desublimation depending upon the temperature and wettability of the surface. The calculated pressure field is used to model the length of a dry zone around liquid or ice droplets over a broad parameter space. The long-standing question of whether the vapor pressure at the interface of…

The workability of fresh Portland cement (PC) concrete critically depends on the reaction of the cubic tricalcium aluminate (C 3 A) phase in Ca- and S-rich pH >12 aqueous solution, yet its rate-controlling mechanism is poorly understood. In this article, the role of adsorption phenomena in C 3 A dissolution in aqueous Ca-, S-, and polynaphthalene sulfonate (PNS)-containing solutions is analyzed. The zeta potential and pH results are consistent with the isoelectric point of C 3 A occurring at pH ∼12 and do not show an inversion of its electric double layer potential as a function of S or Ca concentration, and PNS adsorbs onto C 3 A, reducing its zeta potential to negative values at pH >12. The S and Ca K -edge X-ray absorption spectroscopy (XAS) data obtained do not indicate the structural incorporation or specific adsorption of SO 4 2– on the partially dissolved C 3 A solids analyzed. Together with supporting X-ray ptychography and scanning electron microscopy results, a model for C 3 A dissolution inhibition in hydrated PC systems is proposed whereby the formation of an Al-rich…

This work investigates the structure-activity properties of CuOx-decorated CeO2 nanocubes with a meticulous scrutiny on the role of the CuOx/CeO2 nanointerface in the catalytic oxidation of diesel soot, a critical environmental problem all over the world. For this, a systematic characterization of the materials has been undertaken using transmission electron microscopy (TEM), transmission electron microscopy-energy-dispersive X-ray spectroscopy (TEM-EDS), high-angle annular dark-field-scanning transmission electron microscopy (HAADF-STEM), scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS), X-ray diffraction (XRD), Raman, N2 adsorption-desorption, and X-ray photoelectron spectroscopy (XPS) techniques. The TEM images show the formation of nanosized CeO2 cubes (∼25 nm) and CuOx nanoparticles (∼8.5 nm). The TEM-EDS elemental mapping images reveal the uniform decoration of CuOx nanoparticles on CeO2 nanocubes. The XPS and Raman studies show that the decoration of CuOx on CeO2 nanocubes leads to improved structural defects, such as higher…

Nanogels (or nanohydrogels) have been extensively investigated as one of the most promising nanoparticulate biomedical platforms owing to their advantageous properties that combine the characteristics of hydrogel systems with nanoparticles. Among them, smart nanogels that have the ability to respond to external stimuli, such as pH, redox, temperature, enzymes, light, magnetic field and so forth, are most attractive in the area of drug delivery. Besides, numerous multifunctionalized nanogels with high sensitivity and specificity were designed for diagnostic applications. In this feature article, we have reviewed and discussed the recent progress of biodegradable nanogels as smart nanocarriers of anticancer drugs and biomedical diagnostic agents for cancer.

Mechanical rigidity of the liposome membrane is often defined by the membrane bending modulus and is one of the determinants of liposome stability, but the quantitative experimental data are still limited to a few kinds of liposomes. Here, we used atomic force microscopy to investigate the membrane bending moduli of liposomes by immobilizing them on bovine serum albumin-coated glass in aqueous medium. The following lipids were used for liposome preparation: egg yolk phosphatidylcholine, dioleoylphosphatidylcholine, hydrogenated soybean phosphatidylcholine, dipalmitoylphosphatidylcholine, 1,2-dioleoyl-3-trimethylammonium-propane, cholesterol, and N-(carbonylmethoxypoly(ethylene glycol) 2000)-1,2-distearoyl-sn-glycero-3-phosphoethanolamine. By using liposomes of various compositions, we showed that the thermodynamic phase state of the membrane rather than the electric potential or liposome surface modification with poly(ethylene glycol) is the predominant determinant of the bending modulus, which decreased in the following order: solid ordered > liquid ordered > liquid disordered. By…

Antireflective coatings (ARCs) are applied to reduce surface reflections. We review coatings that reduce the reflection of the surface of the transparent substrates float glass, polyethylene terephthalate, poly(methyl methacrylate), and polycarbonate. Three main coating concepts exist to lower the reflection at the interface of a transparent substrate and air: multilayer interference coatings, graded index coatings, and quarter-wave coatings. We introduce and discuss these three concepts, and zoom in on porous quarter-wave coatings comprising colloidal particles. We extensively discuss the four routes for introducing porosity in quarter-wave coatings through the use of colloidal particles, which have the highest potential for application: (1) packing of dense nanospheres, (2) integration of voids through hollow nanospheres, (3) integration of voids through sacrificial particle templates, and (4) packing of nonspherical nanoparticles. Finally, we address the remaining challenges in the field of ARCs, and elaborate on potential strategies for future research in this area.

Self-assembly of metal nanoparticles has attracted considerable attention because of its unique applications in technologies such as plasmonics, surface-enhanced optics, sensors, and catalysts. However, fabrication of ordered nanoparticle structures remains a significant challenge. Thus, developing an efficient approach for the assembly of large-scale Au nanoparticles films for theoretical studies and for various applications is highly desired. In this paper, a facial approach for fabricating a monolayer film of Au nanoparticles was developed successfully. Using the surfactant polyvinylpyrrolidone (PVP), a large-scale monolayer film of well-ordered, uniform-sized Au nanoparticles was fabricated at the air/water interface. The film exhibited a two-dimensional (2D) hexagonal close-packed (HCP) structure having interparticle gaps smaller than 2 nm. These gaps generated numerous uniform "hot spots" for surface-enhanced Raman scattering (SERS) activity. The as-prepared monolayer film could be transferred to a solid substrate for use as a suitable SERS substrate with high activity, high…

The formation of bacterial biofilms on indwelling medical devices generally causes high risks for adverse complications such as catheter-associated urinary tract infections. In this work, a strategy for synthesizing innovative coatings of poly(dimethylsiloxane) (PDMS) catheter material, using layer-by-layer assembly with three novel functional polymeric building blocks, is reported, i.e., an antifouling copolymer with zwitterionic and quaternary ammonium side groups, a contact biocidal derivative of that polymer with octyl groups, and the antibacterial hydrogen peroxide (H2O2) producing enzyme cellobiose dehydrogenase (CDH). CDH oxidizes oligosaccharides by transferring electrons to oxygen, resulting in the production of H2O2. The design and synthesis of random copolymers which combine segments that have antifouling properties by zwitterionic groups and can be used for electrostatically driven layer-by-layer (LbL) assembly at the same time were based on the atom-transfer radical polymerization of dimethylaminoethyl methacrylate and subsequent partial sulfobetainization with…

Fluorescently labeled DNA adsorbed on graphene oxide (GO) is a well-established sensing platform for detecting a diverse range of analytes. GO is a loosely defined material and its oxygen content may vary depending on the condition of preparation. Sometimes, a further reduction step is intentionally performed to decrease the oxygen content, and the resulting material is called reduced GO (rGO). In this study, DNA adsorption and desorption from GO and rGO is systematically compared. Under the same salt concentration, DNA adsorbs slightly faster with a 2.6-fold higher capacity on rGO. At the same time, DNA adsorbed on rGO is more resistant to desorption induced by temperature, pH, urea, and organic solvents. Various lengths and sequences of DNA probes have been tested. When its complementary DNA is added as a model target analyte, the rGO sample has a higher signal-to-background and signal-to-noise ratio, whereas the GO sample has a slightly higher absolute signal increase and faster signaling kinetics. DNAs adsorbed on GO or rGO are still susceptible to nonspecific displacement by…

All surfaces in water experience at short separations hydration repulsion or hydrophobic attraction, depending on the surface polarity. These interactions dominate the more long-ranged electrostatic and van der Waals interactions and are ubiquitous in biological and colloidal systems. Despite their importance in all scenarios where the surface separation is in the nanometer range, the origin of these hydration interactions is still unclear. Using atomistic solvent-explicit molecular dynamics simulations, we analyze the interaction free energies of charge-neutral model surfaces with different elastic and water-binding properties. The surface polarity is shown to be the most important parameter that not only determines the hydration properties and thereby the water contact angle of a single surface but also the surface-surface interaction and whether two surfaces attract or repel. Elastic properties of the surfaces are less important. On the basis of surface contact angles and surface-surface binding affinities, we construct a universal interaction diagram featuring three different…

For the successful development and application of lubricants, a full understanding of the nanoscale behavior of complex tribological systems is required, but this is difficult to obtain experimentally. In this study, we use nonequilibrium molecular dynamics (NEMD) simulations to examine the atomistic structure and friction properties of commercially relevant organic friction modifier (OFM) monolayers adsorbed on iron oxide surfaces and lubricated by a thin, separating layer of hexadecane. Specifically, acid, amide, and glyceride OFMs, with saturated and Z-unsaturated hydrocarbon tail groups, are simulated at various surface coverages and sliding velocities. At low and medium coverage, the OFMs form liquidlike and amorphous monolayers, respectively, which are significantly interdigitated with the hexadecane lubricant, resulting in relatively high friction coefficients. At high coverage, solidlike monolayers are formed for all of the OFMs, which, during sliding, results in slip planes between well-defined OFM and hexadecane layers, yielding a marked reduction in the friction…

Cellulose nanocrystals (CNCs) are emerging nanomaterials that form chiral nematic liquid crystals above a critical concentration (C*) and additionally orient within electromagnetic fields. The control over CNC alignment is significant for materials processing and end use; to date, magnetic alignment has been demonstrated using only strong fields over extended or arbitrary time scales. This work investigates the effects of comparatively weak magnetic fields (0-1.2 T) and CNC concentration (1.65-8.25 wt %) on the kinetics and degree of CNC ordering using small-angle X-ray scattering. Interparticle spacing, correlation length, and orientation order parameters (η and S) increased with time and field strength following a sigmoidal profile. In a 1.2 T magnetic field for CNC suspensions above C*, partial alignment occurred in under 2 min followed by slower cooperative ordering to achieve nearly perfect alignment in under 200 min (S = -0.499 where S = -0.5 indicates perfect antialignment). At 0.56 T, nearly perfect alignment was also achieved, yet the ordering was 36% slower. Outside of a…

Carbon quantum dots (CQDs) induced ultrasmall BiOI nanosheets with assembled hollow microsphere structures were prepared via ionic liquids 1-butyl-3-methylimidazolium iodine ([Bmim]I)-assisted synthesis method at room temperature condition. The composition, structure, morphology, and photoelectrochemical properties were investigated by multiple techniques. The CQDs/BiOI hollow microspheres structure displayed improved photocatalytic activities than pure BiOI for the degradation of three different kinds of pollutants, such as antibacterial agent tetracycline (TC), endocrine disrupting chemical bisphenol A (BPA), and phenol rhodamine B (RhB) under visible light, light above 580 nm, or light above 700 nm irradiation, which showed the broad spectrum photocatalytic activity. The key role of CQDs for the improvement of photocatalytic activity was explored. The introduction of CQDs could induce the formation of ultrasmall BiOI nanosheets with assembled hollow microsphere structure, strengthen the light absorption within full spectrum, increase the specific surface areas and improve the…

The Cassie-state stability plays a vital role in the applications of metallic superhydrophobic surfaces. Although a large number of papers have reported the superhydrophobic performance of various surface micro/nanostructures, the knowledge of which kind of micro/nanostructure contributes significantly to the Cassie-state stability especially under low temperature and pressure is still very limited. In this article, we fabricated six kinds of typical micro/nanostructures with different topography features on metal surfaces by a femtosecond laser, and these surfaces were modified by fluoroalkylsilane to generate superhydrophobicity. We then systematically studied the Cassie-state stability of these surfaces by means of condensation and evaporation experiments. The results show that some superhydrophobic surfaces, even with high contact angles and low sliding angles under normal conditions, are unstable under low temperature or external pressure. The Cassie state readily transits to a metastable state or even a Wenzel state under these conditions, which deteriorates their…

Polydopamine (pDA) coatings afford tremendous versatility due to their capabilities to provide substrate-independent functionalization with a wide range of amine- and thiol-containing molecules. In this work, we developed a new and facile conjugation approach to the formation of β-amino carbonyl linkages between pDA and acrylate/acrylamide molecules via the aza-Michael reaction. Sulfobetaine acrylamide (SBAA), sulfobetaine methacrylate (SBMA), and poly(ethylene glycol) methacrylate (PEGMA) were employed to graft onto pDA films, giving rise to formation of antifouling coatings. Because of the universal adhesive property of pDA, the coating strategy was applied to different substrates, including TiO2, gold, SiO2, Nitinol alloy, polystyrene, and poly(dimethylsiloxane). The variation of surface chemistry and surface wettability upon pDA modification and subsequent conjugation was monitored with X-ray photoelectron spectroscopy (XPS) and water contact angle measurements. Antifouling properties of coatings were challenged by three common Gram-negative and Gram-positive bacteria.…

The protein-functionalized reduced graphene oxide (rGO) nanosheet is of great interest in stimuli-responsive drug delivery and controlled release applications. We developed doxorubicin (DOX)-loaded bovine serum albumin (BSA)-functionalized rGO (DOX-BSA-rGO) nanosheets. To investigate the reduction of BSA-functionalized GO nanosheets and drug loading efficiency, we used X-ray photoelectron spectroscopy (XPS) and UV-visible spectrophotometer analysis. DOX-BSA-rGO nanosheets exhibited dose-dependent cellular uptake without any cytotoxic effect. We also demonstrated near-infrared (NIR)-induced chemo-photothermal therapy of brain tumor cells treated with DOX-BSA-rGO nanosheets. Therefore, this DOX-BSA-rGO nanosheet could be a powerful tool for chemo-photothermal therapy applications.

Biomedical magnetic colloids commonly used in magnetic hyperthermia experiments often display a bidisperse structure, i.e., are composed of stable nanoclusters coexisting with well-dispersed nanoparticles. However, the influence of nanoclusters in the optimization of colloids for heat dissipation is usually excluded. In this work, bidisperse colloids are used to analyze the effect of nanoclustering and long-range magnetic dipolar interaction on the magnetic hyperthermia efficiency. Two kinds of colloids, composed of magnetite cores with mean sizes of around 10 and 18 nm, coated with oleic acid and dispersed in hexane, and coated with meso-2,3-dimercaptosuccinic acid and dispersed in water, were analyzed. Small-angle X-ray scattering was applied to thoroughly characterize nanoparticle structuring. We proved that the magnetic hyperthermia performances of nanoclusters and single nanoparticles are distinctive. Nanoclustering acts to reduce the specific heating efficiency whereas a peak against concentration appears for the well-dispersed component. Our experiments show that the heating…

The number of antibiotic-resistant bacteria is increasing worldwide, and the demand for novel antimicrobials is constantly growing. Antimicrobial peptides (AMPs) could be an important part of future treatment strategies of various bacterial infection diseases. However, AMPs have relatively low stability, because of proteolytic and chemical degradation. As a consequence, carrier systems protecting the AMPs are greatly needed, to achieve efficient treatments. In addition, the carrier system also must administrate the peptide in a controlled manner to match the therapeutic dose window. In this work, lyotropic liquid crystalline (LC) structures consisting of cubic glycerol monooleate/water and hexagonal glycerol monooleate/oleic acid/water have been examined as carriers for AMPs. These LC structures have the capability of solubilizing both hydrophilic and hydrophobic substances, as well as being biocompatible and biodegradable. Both bulk gels and discrete dispersed structures (i.e., cubosomes and hexosomes) have been studied. Three AMPs have been investigated with respect to phase…

The maximum spreading of an impinging droplet on a rigid surface is studied for low to high impact velocity, until the droplet starts splashing. We investigate experimentally and numerically the role of liquid properties, such as surface tension and viscosity, on drop impact using three liquids. It is found that the use of the experimental dynamic contact angle at maximum spreading in the Kistler model, which is used as a boundary condition for the CFD-VOF calculation, gives good agreement between experimental and numerical results. Analytical models commonly used to predict the boundary layer thickness and time at maximum spreading are found to be less correct, meaning that energy balance models relying on these relations have to be considered with care. The time of maximum spreading is found to depend on both the impact velocity and surface tension, and neither dependency is predicted correctly in common analytical models. The relative proportion of the viscous dissipation in the total energy budget increases with impact velocity with respect to surface energy. At high impact…

The efficient separation of gases has industrial, economic, and environmental importance. Here, the gas separation performance of a metal organic framework (MOF) is enhanced by ionic liquid (IL) incorporation. One of the most commonly used ILs, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), was incorporated into a commercially available MOF, CuBTC. Detailed characterization by combining spectroscopy with diffraction, electron microscopy, and thermal analysis confirmed that the structures were intact after incorporation. Adsorption isotherms of CH4, H2, N2, and CO2 in IL-incorporated CuBTC were experimentally measured and compared with those of pristine CuBTC. Consequently, ideal selectivities for CO2/CH4, CO2/N2, CO2/H2, CH4/N2, CH4/H2, and N2/H2 separations were calculated. The results showed that the CH4 selectivity of CuBTC over CO2, H2, and N2 gases becomes at least 1.5 times higher than that of pristine CuBTC upon the incorporation of IL. For example, the CH4/H2 selectivity of CuBTC increased from 26 to 56 at 0.2 bar when the IL loading was 30 wt %. These results…