Effects of Gas Layer Thickness on Capillary Interactions at Superhydrophobic Surfaces.

Strongly attractive forces act between superhydrophobic surfaces across water due to the formation of a bridging gas capillary. Upon separation, the attraction can range up to tens of micrometers as the gas capillary grows, while gas molecules accumulate in the capillary. We argue that most of these molecules come from the pre-existing gaseous layer found at and within the superhydrophobic coating. In this study, we investigate how the capillary size and the resulting capillary forces are affected by the thickness of the gaseous layer. To this end, we prepared superhydrophobic coatings with different thicknesses by utilizing different numbers of coating cycles of a liquid flame spraying technique. Laser scanning confocal microscopy confirmed an increase in gas layer thickness with an increasing number of coating cycles. Force measurements between such coatings and a hydrophobic colloidal probe revealed attractive forces caused by bridging gas capillaries, and both the capillary size and the range of attraction increased with increasing thickness of the pre-existing gas layer. Hence, our data suggest that the amount of available gas at and in the superhydrophobic coating determines the force range and capillary growth.

The dynamic nature of natural and fatty acid modified calcite surfaces.

Calcium carbonate, particularly in the form of calcite, is an abundant mineral widely used in both human-made products and biological systems. The calcite surface possesses a high surface energy, making it susceptible to the adsorption of organic contaminants. Moreover, the surface is also reactive towards a range of chemicals, including water. Consequently, studying and maintaining a clean and stable calcite surface is only possible under ultrahigh vacuum conditions and for limited amounts of time. When exposed to air or solution, the calcite surface undergoes rapid transformations, demanding a comprehensive understanding of the properties of calcite surfaces in different environments. Similarly, attention must also be directed towards the kinetics of changes, whether induced by fluctuating environments or at constant condition. All these aspects are encompassed in the expression "dynamic nature", and are of crucial importance in the context of the diverse applications of calcite. In many instances, the calcite surface is modified by adsorption of fatty acids to impart a desired nonpolar character. Although the binding between carboxylic acid groups and calcite surfaces is strong, the fatty acid layer used for surface modification undergoes significant alterations when exposed to water vapour and liquid water droplets. Therefore, it is also crucial to understand the dynamic nature of the adsorbed layer. This review article provides a comprehensive overview of the current understanding of both the dynamics of the calcite surface as well as when modified by fatty acid surface treatments.

Calcite Surfaces Modified with Carboxylic Acids (C2 to C18): Layer Organization, Wettability, Stability, and Molecular Structural Properties.

A fundamental understanding of the interactions between mineral surfaces and amphiphilic surface modification agents is needed for better control over the production and uses of mineral fillers. Here, we controlled the carboxylic acid layer formation conditions on calcite surfaces with high precision via vapor deposition. The properties of the resulting carboxylic acid layers were analyzed using surface-sensitive techniques, such as atomic force microscopy (AFM), contact angle measurements, angle resolved X-ray photoelectron spectroscopy (XPS), and vibrational sum-frequency spectroscopy. A low wettability was achieved with long hydrocarbon chain carboxylic acids such as stearic acid. The stearic acid layer formed by vapor deposition is initially patchy, but with increasing vapor exposure time, the patches grow and condense into a homogeneous layer with a thickness close to that expected for a monolayer as evaluated by AFM and XPS. The build-up process of the layer occurs more rapidly at higher temperatures due to the higher vapor pressure. The stability of the deposited fatty acid layer in the presence of a water droplet increases with the chain length and packing density in the adsorbed layer. Vibrational sum frequency spectroscopy data demonstrate that the stearic acid monolayers on calcite have their alkyl chains in an all-trans conformation and are anisotropically distributed on the plane of the surface, forming epitaxial monolayers. Vibrational spectra also show that the stearic acid molecules interact with the calcite surface through the carboxylic acid headgroup in both its protonated and deprotonated forms. The results presented provide new molecular insights into the properties of adsorbed carboxylic acid layers on calcite.

Effect of Gel Exposition on Calcium and Carbonate Ions Determines the Stm-l Effect on the Crystal Morphology of Calcium Carbonate.

Biomineralization of fish otoliths is regulated by macromolecules, such as proteins, whose presence is crucial for the functionality and properties of these mineralized structures. Special regulatory effects are exerted by intrinsically disordered proteins, such as the polyanionic Starmaker-like protein from medaka, a homolog of zebrafish Starmaker. In this study, we employed a set of bioinspired mineralization experiments with a single diffusion system to investigate the effect of the Starmaker-like protein on calcium carbonate biominerals with regards to the prior exposition of the protein to calcium or carbonate ions. Interestingly, the bioinspired minerals grown in the presence of the Starmaker-like protein in calcium- or carbonate-type experiments differ significantly in terms of morphology and protein distribution within the crystals. Our deeper analysis shows that the Starmaker-like protein action is a result of the environmental conditions to which it is exposed. These findings may be of special interest in the areas of biomineralization process pathways and biomaterial sciences.

Surface-Modified and Unmodified Calcite: Effects of Water and Saturated Aqueous Octanoic Acid Droplets on Stability and Saturated Fatty Acid Layer Organization.

A profound understanding of the properties of unmodified and saturated fatty acid-modified calcite surfaces is essential for elucidating their resistance and stability in the presence of water droplets. Additional insights can be obtained by also studying the effects of carboxylic acid-saturated aqueous solutions. We elucidate surface wettability, structure, and nanomechanical properties beneath and at the edge of a deposited droplet after its evaporation. When calcite was coated by a highly packed monolayer of stearic acid, a hydrophilic region was found at the three-phase contact line. In atomic force microscopy mapping, this region is characterized by low adhesion and a topographical hillock. The surface that previously was covered by the droplet demonstrated a patchy structure of about 6 nm height, implying stearic acid reorganization into a patchy bilayer-like structure. Our data suggest that during droplet reverse dispensing and droplet evaporation, pinning of the three-phase contact line leads to the transport of dissolved fatty carboxylic acid and possibly calcium bicarbonate Ca(HCO3)2 molecules to the contact line boundary. Compared to the surface of intrinsically hydrophobic materials, such as polystyrene, the changes in contact angle and base diameter during droplet evaporation on stearic acid-modified calcite are strikingly different. This difference is due to stearic acid reorganization on the surface and transport to the water-air interface of the droplet. An effect of the evaporating droplet is also observed on unmodified calcite due to dissolution and recrystallization of the calcite surface in the presence of water. In the case where a water droplet saturated with octanoic acid is used instead of water, the stearic acid-coated calcite remains considerably more stable. Our findings are discussed in terms of the coffee-ring effect.

Nanoscale Wear and Mechanical Properties of Calcite: Effects of Stearic Acid Modification and Water Vapor.

Understanding the wear of mineral fillers is crucial for controlling industrial processes, and in the present work, we examine the wear resistance and nanomechanical properties of bare calcite and stearic acid-modified calcite surfaces under dry and humid conditions at the nanoscale. Measurements under different loads allow us to probe the situation in the absence and presence of abrasive wear. The sliding motion is in general characterized by irregular stick-slip events that at higher loads lead to abrasion of the brittle calcite surface. Bare calcite is hydrophilic, and under humid conditions, a thin water layer is present on the surface. This water layer does not affect the friction force. However, it slightly decreases the wear depth and strongly influences the distribution of wear particles. In contrast, stearic acid-modified surfaces are hydrophobic. Nevertheless, humidity affects the wear characteristics by decreasing the binding strength of stearic acid at higher humidity. A complete monolayer coverage of calcite by stearic acid results in a significant reduction in wear but only a moderate reduction in friction forces at low humidity and no reduction at 75% relative humidity (RH). Thus, our data suggest that the wear reduction does not result from a lowering of the friction force but rather from an increased ductility of the surface region as offered by the stearic acid layer. An incomplete monolayer of stearic acid on the calcite surface provides no reduction in wear regardless of the RH investigated. Clearly, the wear properties of modified calcite surfaces depend crucially on the packing density of the surface modifier and also on the air humidity.

Wetting Transition on Liquid-Repellent Surfaces Probed by Surface Force Measurements and Confocal Imaging.

Superhydrophobic surfaces in the Cassie-Baxter wetting state retain an air layer at the surface which prevents liquid water from reaching into the porous surface structure. In this work we explore how addition of ethanol, which reduces the surface tension, influences the wetting properties of superhydrophobic and smooth hydrophobic surfaces. Wetting properties are measured by dynamic contact angles, and the air layer at the superhydrophobic surface is visualized by laser scanning confocal microscopy. Colloidal probe atomic force microscopy measurements between a hydrophobic microsphere and the macroscopic surfaces showed that the presence of ethanol strongly affects the interaction forces. When the macroscopic surface is superhydrophobic, attractive forces extending up to a few micrometers are observed on retraction in water and in 20 vol % ethanol, signifying the presence of a large and growing gas capillary. Submicrometer attractive forces are observed between the probe particle and a smooth hydrophobic surface, and in this case a smaller gas capillary is formed. Addition of ethanol results in markedly different effects between superhydrophobic and hydrophobic surfaces. In particular, we show that the receding contact angle on the superhydrophobic surface is of paramount importance for describing the interaction forces.

Stability investigation of FCC-based tablets for oral suspension with caffeine and oxantel pamoate as model drugs.

Tablets for oral suspension (TOS) present a convenient alternative dosage form to conventional tablets. Dispersed in a glass of water or on a spoon, such tablets can be easily administered, which can become beneficial for pediatric or geriatric patients. The novel excipient functionalized calcium carbonate (FCC), consisting of calcium carbonate and calcium phosphate, has already shown to be suitable to produce orally disintegrating placebo tablets. In this study, the influence of formulation composition on disintegration time in water and artificial saliva was investigated using caffeine and oxantel pamoate as model drugs, reflecting BCS class 1 and BCS class 4, respectively. The optimized formulation for each model drug underwent a stress test. The results show that the drug content in DTs was not influenced by FCC under stressed conditions, however the disintegration and dissolution performance was affected by temperature and humidity. It can be concluded that it was possible to produce TOS characterized by rapid disintegration complemented by high physical stability of the tablets and chemical stability of the drug.

Propofol adsorption at the air/water interface: a combined vibrational sum frequency spectroscopy, nuclear magnetic resonance and neutron reflectometry study.

Propofol is an amphiphilic small molecule that strongly influences the function of cell membranes, yet data regarding interfacial properties of propofol remain scarce. Here we consider propofol adsorption at the air/water interface as elucidated by means of vibrational sum frequency spectroscopy (VSFS), neutron reflectometry (NR), and surface tensiometry. VSFS data show that propofol adsorbed at the air/water interface interacts with water strongly in terms of hydrogen bonding and weakly in the proximity of the hydrocarbon parts of the molecule. In the concentration range studied there is almost no change in the orientation adopted at the interface. Data from NR show that propofol forms a dense monolayer with a thickness of 8.4 Å and a limiting area per molecule of 40 Å2, close to the value extracted from surface tensiometry. The possibility that islands or multilayers of propofol form at the air/water interface is therefore excluded as long as the solubility limit is not exceeded. Additionally, measurements of the 1H NMR chemical shifts demonstrate that propofol does not form dimers or multimers in bulk water up to the solubility limit.

Characterization of new functionalized calcium carbonate-polycaprolactone composite material for application in geometry-constrained drug release formulation development.

A new mineral-polymer composite (FCC-PCL) performance was assessed to produce complex geometries to aid in development of controlled release tablet formulations. The mechanical characteristics of a developed material such as compactibility, compressibility and elastoplastic deformation were measured. The results and comparative analysis versus other common excipients suggest efficient formation of a complex, stable and impermeable geometries for constrained drug release modifications under compression. The performance of the proposed composite material has been tested by compacting it into a geometrically altered tablet (Tablet-In-Cup, TIC) and the drug release was compared to commercially available product. The TIC device exhibited a uniform surface, showed high physical stability, and showed absence of friability. FCC-PCL composite had good binding properties and good compactibility. It was possible to reveal an enhanced plasticity characteristic of a new material which was not present in the individual components. The presented FCC-PCL composite mixture has the potential to become a successful tool to formulate controlled-release dosage solid forms.

In silico and in vitro methods to optimize the performance of experimental gastroretentive floating mini-tablets.

CONTEXT: Development of floating drug delivery systems (FDDS) is challenging. To facilitate this task, an evaluation method was proposed, which allows for a combined investigation of drug release and flotation. OBJECTIVE: It was the aim of the study to use functionalized calcium carbonate (FCC)-based lipophilic mini-tablet formulations as a model system to design FDDS with a floating behavior characterized by no floating lag time, prolonged flotation and loss of floating capability after complete drug release. MATERIALS AND METHODS: Release of the model drug caffeine from the mini-tablets was assessed in vitro by a custom-built stomach model. A cellular automata-based model was used to simulate tablet dissolution. Based on the in silico data, floating forces were calculated and analyzed as a function of caffeine release. RESULTS AND DISCUSSION: Two floating behaviors were identified for mini-tablets: linear decrease of the floating force and maintaining of the floating capability until complete caffeine release. An optimal mini-tablet formulation with desired drug release time and floating behavior was developed and tested. CONCLUSION: A classification system for a range of varied floating behavior of FDDS was proposed. The FCC-based mini-tablets had an ideal floating behavior: duration of flotation is defined and floating capability decreases after completion of drug release.

Frictional forces between hydrophilic and hydrophobic particle coated nanostructured surfaces.

Friction forces have long been associated with the famous Amontons' rule that states that the friction force is linearly dependent on the applied normal load, with the proportionality constant being known as the friction coefficient. Amontons' rule is however purely phenomenological and does not in itself provide any information on why the friction coefficient is different for different material combinations. In this study, friction forces between a colloidal probe and nanostructured particle coated surfaces in an aqueous environment exhibiting different roughness length scales were measured by utilizing the atomic force microscope (AFM). The chemistry of the surfaces and the probe was varied between hydrophilic silica and hydrophobized silica. For hydrophilic silica surfaces, the friction coefficient was significantly higher for the particle coated surfaces than on the flat reference surface. All the particle coated surfaces exhibited similar friction coefficients, from which it may be concluded that the surface geometry, and not the roughness amplitude per se, influenced the measured friction. During measurements with hydrophobic surfaces, strong adhesive forces related to the formation of a bridging air cavity were evident from both normal force and friction force measurements. In contrast to the frictional forces between the hydrophilic surfaces, the friction coefficient for hydrophobic surfaces was found to depend on the surface structure and we believe that this dependence is related to the restricted movement of the three-phase line of the bridging air cavity. For measurements using a hydrophobic surface and a hydrophilic probe, the friction coefficient was significantly smaller compared to the two homogeneous systems. A layer of air or air bubbles on the hydrophobic surface working as a lubricating layer is a possible mechanism behind this observation.

The processes behind drug loading and release in porous drug delivery systems.

Porous materials are ubiquitous and exhibit properties suitable for depositing therapeutic compounds. Drug loading in porous materials can protect the drug, control its release rate, and improve its solubility. However, to achieve such outcomes from porous delivery systems, effective incorporation of the drug in the internal porosity of the carrier must be guaranteed. Mechanistic knowledge of the factors influencing drug loading and release from porous carriers allows rational design of formulations by selecting a suitable carrier for each application. Much of this knowledge exists in research areas other than drug delivery. Thus, a comprehensive overview of this topic from the drug delivery aspect is warranted. This review aims to identify the loading processes and carrier characteristics influencing the drug delivery outcome with porous materials. Additionally, the kinetics of drug release from porous materials are elucidated, and the common approaches to mathematical modeling of these processes are outlined.

Mineral Particles in Foliar Fertilizer Formulations Can Improve the Rate of Foliar Uptake.

The application of foliar sprays of suspensions of relatively insoluble essential element salts is gradually becoming common, chiefly with the introduction of nano-technology approaches in agriculture. However, there is controversy about the effectiveness of such sparingly soluble nutrient sources as foliar fertilizers. In this work, we focussed on analysing the effect of adding Ca-carbonate (calcite, CaCO3) micro- and nano-particles as model sparingly soluble mineral compounds to foliar fertilizer formulations in terms of increasing the rate of foliar absorption. For these purposes, we carried out short-term foliar application experiments by treating leaves of species with variable surface features and wettability rates. The leaf absorption efficacy of foliar formulations containing a surfactant and model soluble nutrient sources, namely Ca-chloride (CaCl2), magnesium sulphate (MgSO4), potassium nitrate (KNO3), or zinc sulphate (ZnSO4), was evaluated alone or after addition of calcite particles. In general, the combination of the Ca-carbonate particles with an essential element salt had a synergistic effect and improved the absorption of Ca and the nutrient element provided. In light of the positive effects of using calcite particles as foliar formulation adjuvants, dolomite nano- and micro-particles were also tested as foliar formulation additives, and the results were also positive in terms of increasing foliar uptake. The observed nutrient element foliar absorption efficacy can be partially explained by geochemical modelling, which enabled us to predict how these formulations will perform at least in chemical terms. Our results show the major potential of adding mineral particles as foliar formulation additives, but the associated mechanisms of action and possible additional benefits to plants should be characterised in future investigations.

Effects of liquid surface tension on gas capillaries and capillary forces at superamphiphobic surfaces.

The formation of a bridging gas capillary between superhydrophobic surfaces in water gives rise to strongly attractive interactions ranging up to several micrometers on separation. However, most liquids used in materials research are oil-based or contain surfactants. Superamphiphobic surfaces repel both water and low-surface-tension liquids. To control the interactions between a superamphiphobic surface and a particle, it needs to be resolved whether and how gas capillaries form in non-polar and low-surface-tension liquids. Such insight will aid advanced functional materials development. Here, we combine laser scanning confocal imaging and colloidal probe atomic force microscopy to elucidate the interaction between a superamphiphobic surface and a hydrophobic microparticle in three liquids with different surface tensions: water (73 mN m-1), ethylene glycol (48 mN m-1) and hexadecane (27 mN m-1). We show that bridging gas capillaries are formed in all three liquids. Force-distance curves between the superamphiphobic surface and the particle reveal strong attractive interactions, where the range and magnitude decrease with liquid surface tension. Comparison of free energy calculations based on the capillary menisci shapes and the force measurements suggest that under our dynamic measurements the gas pressure in the capillary is slightly below ambient.

Influence of surface topography on the interactions between nanostructured hydrophobic surfaces.

Nanostructured particle coated surfaces, with hydrophobized particles arranged in close to hexagonal order and of specific diameters ranging from 30 nm up to 800 nm, were prepared by Langmuir-Blodgett deposition followed by silanization. These surfaces have been used to study interactions between hydrophobic surfaces and a hydrophobic probe using the AFM colloidal probe technique. The different particle coated surfaces exhibit similar water contact angles, independent of particle size, which facilitates studies of how the roughness length scale affects capillary forces (previously often referred to as "hydrophobic interactions") in aqueous solutions. For surfaces with smaller particles (diameter < 200 nm), an increase in roughness length scale is accompanied by a decrease in adhesion force and bubble rupture distance. It is suggested that this is caused by energy barriers that prevent the motion of the three-phase (vapor/liquid/solid) line over the surface features, which counteracts capillary growth. Some of the measured force curves display extremely long-range interaction behavior with rupture distances of several micrometers and capillary growth with an increase in volume during retraction. This is thought to be a consequence of nanobubbles resting on top of the surface features and an influx of air from the crevices between the particles on the surface.

Effect of surface depressions on wetting and interactions between hydrophobic pore array surfaces.

The surface structure is known to significantly affect the long-range capillary forces between hydrophobic surfaces in aqueous solutions. It is, however, not clear how small depressions in the surface will affect the interaction. To clarify this, we have used the AFM colloidal probe technique to measure interactions between hydrophobic microstructured pore array surfaces and a hydrophobic colloidal probe. The pore array surfaces were designed to display two different pore spacings, 1.4 and 4.0 µm, each with four different pore depths ranging from 0.2 to 12.0 µm. Water contact angles measured on the pore array surfaces are lower than expected from the Cassie-Baxter and Wenzel models and not affected by the pore depth. This suggests that the position of the three-phase contact line, and not the interactions underneath the droplet, determines the contact angle. Confocal Raman microscopy was used to investigate whether water penetrates into the pores. This is of importance for capillary forces where both the movement of the three-phase contact line and the situation at the solid/liquid interface influence the stability of bridging cavities. By analyzing the shape of the force curves, we distinguish whether the cavity between the probe and the surfaces was formed on a flat part of the surface or in close proximity to a pore. The pore depth and pore spacing were both found to statistically influence the distance at which cavities form as surfaces approach each other and the distance at which cavities rupture during retraction.

Porous Coatings to Control Release Rates of Essential Oils to Generate an Atmosphere with Botanical Actives.

Essential oils have been used in diverse areas such as packaging, agriculture and cosmetics, for their antimicrobial and pesticide activity. The organic volatile compounds of the essential oils are involved in its activity. Controlling their release helps to prolong their functionality. In this study, a functionalized calcium carbonate porous coating was employed to control the release of thyme and rosemary oil in a confined space. The release rate was evaluated at 7 °C and 23 °C, gravimetrically. It was shown that the capillary effect of the porous coating slowed down the release of the volatiles into the headspace compared to the bulk essential oil. A linear drive force model was used to fit the obtained data from both essential oils. The model showed that rosemary reached the asymptotic mass loss equilibrium faster than thyme. This result can be explained by the diverse composition and concentration of monoterpenoids between the two essential oils. Temperature and degree of loading also played important roles in the desorption of the essential oils. It was observed that at high degrees of loading and temperatures the desorption of essential oils was higher. The above-described technology could be used for applications related to food preservation, pest control among others.

Robust hydrophobic surfaces displaying different surface roughness scales while maintaining the same wettability.

A range of surfaces coated with spherical silica particles, covering the size range from nanometer to micrometer, have been produced using Langmuir-Blodgett (LB) deposition. The particles were characterized both in suspension and in the Langmuir trough to optimize the surface preparation procedure. By limiting the particle aggregation and surface layer failures during the preparation steps, well-defined monolayers with a close-packed structure have been obtained for all particle sizes. Thus, this procedure led to structured surfaces with a characteristic variation in the amplitude and spatial roughness parameters. In order to obtain robust surfaces, a sintering protocol and an AFM-based wear test to determine the stability of the deposited surface layer were employed. Hydrophobization of the LB films followed by water contact angle measurements showed, for all tested particle sizes, the same increase in contact angle compared to the contact angle of a flat hydrophobic surface. This indicates nearly hexagonal packing and gives evidence for nearly complete surface wetting of the surface features.

Evaluation of the Potential of Modified Calcium Carbonate as a Carrier for Unsaturated Fatty Acids in Oxygen Scavenging Applications.

Modified calcium carbonates (MCC) are inorganic mineral-based particles with a large surface area, which is enlarged by their porous internal structure consisting of hydroxyapatite and calcium carbonate crystal structures. Such materials have high potential for use as carriers for active substances such as oxygen scavenging agents. Oxygen scavengers are applied to packaging to preserve the quality of oxygen-sensitive products. This study investigated the potential of MCC as a novel carrier system for unsaturated fatty acids (UFAs), with the intention of developing an oxygen scavenger. Linoleic acid (LA) and oleic acid (OA) were loaded on MCC powder, and the loaded MCC particles were characterized and studied for their oxygen scavenging activity. For both LA and OA, amounts of 20 wt% loading on MCC were found to provide optimal surface area/volume ratios. Spreading UFAs over large surface areas of 31.6 and 49 m2 g-1 MCC enabled oxygen exposure and action on a multitude of molecular sites, resulting in oxygen scavenging rates of 12.2 ± 0.6 and 1.7 ± 0.2 mL O2 d-1 g-1, and maximum oxygen absorption capacities of >195.6 ± 13.5 and >165.0 ± 2.0 mL g-1, respectively. Oxygen scavenging activity decreased with increasing humidity (37-100% RH) and increased with rising temperatures (5-30 °C). Overall, highly porous MCC was concluded to be a suitable UFA carrier for oxygen scavenging applications in food packaging.