Real-time application and modelling of the NOx-sorption reaction on a particulate calcium carbonate surface-flow filter exposed to combustion exhaust.

Of major interest, especially in city environments, and increasingly inside vehicles or industrial plants, is the drive to reduce human exposure to nitrogen oxides (NOx). This trend has drawn increasing attention to filtration, which has developed remarkably owing to the capabilities of recently developed mathematical models and novel filter concepts. This paper reports on the study of the kinetic modelling of adsorption of nitrogen dioxide (NO2), collected from the tailpipe of a diesel engine, reacting to calcium nitrate salt (Ca(NO3)2) on a surface flow filter consisting of a coating of fine ground limestone or marble (CaCO3) in combination with micro-nanofibrillated cellulose (MNFC) acting as binder and humectant applied onto a multiply recycled newsprint substrate. The coating and substrate are both porous, but on different pore size scales, with the coating having significantly lower permeability. To maximise gas-coating contact, therefore, the coating deposition is pixelated, achieved by pin coating. An axially dispersed gaseous plug flow model (dispersion model) was used to simulate the transport within the coating pore network structure, following earlier flow modelling studies, and a kinetic reaction model was used to examine NO2 to NO3- conversion in correlation with experimental results. Modelling results indicate a 60.38% conversion of exposed NO2 gas to Ca(NO3)2 under the specific conditions applied, with an absolute relative error between the predicted and experimentally estimated value being 0.81%. The model additionally enabled a prediction of effects of changing parameters over a limited perturbation range, thus assisting in predicting filter element consumption, with attention given to the active component CaCO3 surface as a function of particle size in relation to the gas contact exchange, promoting the reaction over time. It is intended that the Ca(NO3)2 formed from the reaction can go on to be used as a value-added fertiliser, thus contributing to circular economy.

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.

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.

Biodegradable Cellulose/Polycaprolactone/Keratin/Calcium Carbonate Mulch Films Prepared in Imidazolium-Based Ionic Liquid.

Ionic liquid 1-butyl-3-methylimidazolium chloride [BMIM][Cl] was used to prepare cellulose (CELL), cellulose/polycaprolactone (CELL/PCL), cellulose/polycaprolactone/keratin (CELL/PCL/KER), and cellulose/polycaprolactone/keratin/ground calcium carbonate (CELL/PCL/KER/GCC) biodegradable mulch films. Attenuated Total Reflectance Fourier-Transform Infrared (ATR-FTIR) spectroscopy, optical microscopy, and Field-Emission Scanning Electron Microscopy (FE-SEM) were used to verify the films' surface chemistry and morphology. Mulch film made of only cellulose regenerated from ionic liquid solution exhibited the highest tensile strength (75.3 ± 2.1 MPa) and modulus of elasticity of 944.4 ± 2.0 MPa. Among samples containing PCL, CELL/PCL/KER/GCC is characterized by the highest tensile strength (15.8 ± 0.4 MPa) and modulus of elasticity (687.5 ± 16.6 MPa). The film's breaking strain decreased for all samples containing PCL upon the addition of KER and KER/GCC. The melting temperature of pure PCL is 62.3 °C, whereas that of CELL/PCL film has a slight tendency for melting point depression (61.0 °C), which is a characteristic of partially miscible polymer blends. Furthermore, Differential Scanning Calorimetry (DSC) analysis revealed that the addition of KER or KER/GCC to CELL/PCL films resulted in an increment in melting temperature from 61.0 to 62.6 and 68.9 °C and an improvement in sample crystallinity by 2.2 and 3.0 times, respectively. The light transmittance of all studied samples was greater than 60%. The reported method for mulch film preparation is green and recyclable ([BMIM][Cl] can be recovered), and the inclusion of KER derived by extraction from waste chicken feathers enables conversion to organic biofertilizer. The findings of this study contribute to sustainable agriculture by providing nutrients that enhance the growth rate of plants, and hence food production, while reducing environmental pressure. The addition of GCC furthermore provides a source of Ca2+ for plant micronutrition and a supplementary control of soil pH.

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.

Micro Nanofibrillated Cellulose as Functional Additive Supporting Processability of Surface-Active Mineral Suspensions: Exemplified by Pixel Coating of an NOx-Sorbent Layer.

Unlike established coating formulations, functional particulate coatings often demand the omission of polymer dispersant so as to retain surface functionality. This results in heterogeneous complex rheology. We take an example from a novel development for an NOx mitigation surface flow filter system, in which ground calcium carbonate (GCC), applied in a coating, reacts with NO2 releasing CO2. Inclusion of mesoporous ancillary mineral acts to capture the CO2. The coating is applied as droplets to maximize gas-contact dynamic by forming a pixelated 2D array using a coating device consisting of protruding pins, which are loaded by submersion in the aqueous coating color such that the adhering droplets are transferred onto the substrate. The flow is driven by surface meniscus wetting causing lateral spread and bulk pore permeation. Filamentation occurs during the retraction of the pins. Stress-related viscoelastic and induced dilatancy in the suspension containing the ancillary mesoporous mineral disrupts processability. Adopting shear, oscillation and extensional rheometric methods, we show that the inclusion of an ancillary mineral that alone absorbs water, e.g., perlite (a naturally occurring porous volcanic glass), is rheologically preferable to one that in addition to absorbing water also immobilizes it on the mineral surface, e.g., sepiolite. When including micro-nanofibrillated cellulose (MNFC), critical for maintaining moisture to support NO2 sorption, it is observed that it acts also as a flow modifier, enabling uniform coating transfer to be achieved, thus eliminating any possible detrimental effect on mineral surface activity by avoiding the use of soluble polymeric dispersant.

Modification of CaCO3 and CaCO3 pin-coated cellulose paper under supercritical carbon dioxide-ethanol mixture for enhanced NO2 capture.

In this work, we examine two modifications of fine-ground calcium carbonate material (GCC) in order to enhanced sorption of NO2 and subsequent reaction properties toward NO2-/NO3- formation by firstly exposing the GCC to supercritical (sc) CO2 in order to increase particle surface area, a choice specifically made to avoid altering the surface chemistry, and secondly considering the potential advantage of using a surface coupling agent toward NO2. The modification by the coupling agent amino silane (AMEO silane) was applied in a supercritical CO2-ethanol mixture. The samples were characterised before and after modification by field emission scanning electron microscopy (FESEM), specific surface area determination (BET nitrogen adsorption), ATR-FTIR spectroscopy and ion chromatography to reveal the effects of the surface modification(s) on the morphology, surface textural properties and sorption versus reaction properties with NO2. The performance of the treated sorbents for NO2 capture was evaluated at room temperature. Results show that reactivity of NO2 with GCC was observed to increase as a function of increased surface area resulting from scCO2 exposure, but that the presence of AMEO silane on the surface, while enhancing initial adsorption of NO2 was seen subsequently to act to block reactivity. Thus, judicious use of coupling agent can provide desired rapid initial adsorption of the gas, but the goal of long-term CaCO3-consuming reactivity, so as to prolong the uptake of NO2 beyond surface saturation alone, is achieved by increasing surface area while retaining chemical-free exposed CaCO3 surface.

Bicomponent Cellulose Fibrils and Minerals Afford Wicking Channels Stencil-Printed on Paper for Rapid and Reliable Fluidic Platforms.

Flexible and easy-to-use microfluidic systems are suitable options for point-of-care diagnostics. Here, we investigate liquid transport in fluidic channels produced by stencil printing on flexible substrates as a reproducible and scalable option for diagnostics and paper-based sensing. Optimal printability and flow profiles were obtained by combining minerals with cellulose fibrils of two different characteristic dimensions, in the nano- and microscales, forming channels with ideal wettability. Biomolecular ligands were easily added by inkjet printing on the channels, which were tested for the simultaneous detection of glucose and proteins. Accurate determination of clinically relevant concentrations was possible from linear calibration, confirming the potential of the introduced paper-based diagnostics. The results indicate the promise of simple but reliable fluidic channels for drug and chemical analyses, chromatographic separation, and quality control.

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.

Iso- and Anisotropic Etching of Micro Nanofibrillated Cellulose Films by Sequential Oxygen and Nitrogen Gas Plasma Exposure for Tunable Wettability on Crystalline and Amorphous Regions.

The surface of cellulose films, obtained from micro nanofibrillated cellulose produced with different enzymatic pretreatment digestion times of refined pulp, was exposed to gas plasma, resulting in a range of surface chemical and morphological changes affecting the mechanical and surface interactional properties. The action of separate and dual exposure to oxygen and nitrogen cold dielectric barrier discharge plasma was studied with respect to the generation of roughness (confocal laser and atomic force microscopy), nanostructural and chemical changes on the cellulose film surface, and their combined effect on wettability. Elemental analysis showed that with longer enzymatic pretreatment time the wetting response was sensitive to the chemical and morphological changes induced by both plasma gases, but distinctly oxygen plasma was seen to induce much greater morphological change while nitrogen plasma contributed more to chemical modification of the film surface. In this novel study, it is shown that exposure to oxygen plasma, subsequently followed by exposure to nitrogen plasma, leads first to an increase in wetting, and second to more hydrophobic behaviour, thus improving, for example, suitability for printing using polar functional inks or providing film barrier properties, respectively.

Coupled Effects of Fibril Width, Residual and Mechanically Liberated Lignin on the Flow, Viscoelasticity, and Dewatering of Cellulosic Nanomaterials.

The rheological behavior of aqueous suspensions of lignocellulose nanofibrils (LCNFs) is investigated systematically by considering the coupled effect of residual lignin and LCNF morphology. The LCNF was obtained by high-energy fluidization of TEMPO-oxidized mechanical fibers, followed by size fractionation (fibril widths of ∼5, ∼9, and ∼18 nm). The nanofibril width and the corresponding fibril-fibril interactions are strongly influenced by the presence and distribution of lignin in the respective fractions, either retained on the fibril surface or as free structures present in the finest size fraction. All samples containing lignin display dilatancy, typifying gel suspensions with aggregated hydrophobic particles. Fine fractionated samples display strong gel behavior. The coarse fractionated sample, by contrast, shows a greater tendency to flocculate via entanglement and displays less gel-like characteristics; hence, it dewaters more freely.

Influence of the Surface Modification of Calcium Carbonate on Polyamide 12 Composites.

In previous investigations, it was found that the thermal properties of a polyamide 12 compound can be manipulated, using a designed filler, to improve the melting as well as crystallization behavior, determined for selective laser sintering. A common downside of the introduction of a non-flexing mineral filler is the reduction of the mechanical properties, such as ductility. This paper investigates the influence of content and surface modification of limestone on the mechanical properties. The aim is to understand the effect of an optimized coupling agent on the properties of a compound, containing polyamide 12 filled with 10 wt % of surface modified calcium carbonate. A range of four mineral filler modifications was chosen to investigate their coupling effect, namely 6-amino hexanoic acid, ε-caprolactam, l-arginine or glutamic acid. The in advance surface modified fillers were then each used in combination with the polyamide 12 in a twin-screw extrusion process. With an optimized surface modifying agent, the tensile strength as well as elongation at break can be improved in comparison with uncoated filler implementation, such that up to 60% of the loss of ductility and toughness of a final part when using an untreated filler could be regained using an optimized surface modifier at a correct amount. With the tested filler grade and the specific tested filler amount, the optimized amount of 6-amino hexanoic acid was approx. 2.5 mmol of treatment agent per 100 m2 of CaCO3. These found improvements in a twin-screw extruded polyamide 12 compound show the possible usage of modified calcium carbonate as a functional filler in additive manufacturing and can potentially be transferred in a subsequent investigation in the selective laser sintering process.

Simultaneous investigation of the liquid transport and swelling performance during tablet disintegration.

Fast disintegrating tablets have commonly been used for fast oral drug delivery to patients with swallowing difficulties. The different characteristics of the pore structure of such formulations influence the liquid transport through the tablet and hence affect the disintegration time and the release of the drug in the body. In this work, terahertz time-domain spectroscopy and terahertz pulsed imaging were used as promising analytical techniques to quantitatively analyse the impact of the structural properties on the liquid uptake and swelling rates upon contact with the dissolution medium. Both the impact of porosity and formulation were investigated for theophylline and paracetamol based tablets. The drug substances were either formulated with functionalised calcium carbonate (FCC) with porosities of 45% and 60% or with microcrystalline cellulose (MCC) with porosities of 10% and 25%. The terahertz results reveal that the rate of liquid uptake is clearly influenced by the porosity of the tablets with a faster liquid transport observed for tablets with higher porosity, indicating that the samples exhibit structural similarity in respect to pore connectivity and pore size distribution characteristics in respect to permeability. The swelling of the FCC based tablets is fully controlled by the amount of disintegrant, whereas the liquid uptake is driven by the FCC material and the interparticle pores created during compaction. The MCC based formulations are more complex as the MCC significantly contributes to the overall tablet swelling. An increase in swelling with increasing porosity is observed in these tablets, which indicates that such formulations are performance-limited by their ability to take up liquid. Investigating the effect of the microstructure characteristics on the liquid transport and swelling kinetics is of great importance for reaching the next level of understanding of the drug delivery, and, depending on the surface nature of the pore carrier function, in turn controlling the performance of the drug mainly in respect to dissolution in the body.

Willow Bark for Sustainable Energy Storage Systems.

Willow bark is a byproduct from forestry and is obtained at an industrial scale. We upcycled this byproduct in a two-step procedure into sustainable electrode materials for symmetrical supercapacitors using organic electrolytes. The procedure employed precarbonization followed by carbonization using different types of KOH activation protocols. The obtained electrode materials had a hierarchically organized pore structure and featured a high specific surface area (>2500 m2 g-1) and pore volume (up to 1.48 cm3 g-1). The assembled supercapacitors exhibited capacitances up to 147 F g-1 in organic electrolytes concomitant with excellent cycling performance over 10,000 cycles at 0.6 A g-1 using coin cells. The best materials exhibited a capacity retention of 75% when changing scan rates from 2 to 100 mV s-1.

Highly Porous Willow Wood-Derived Activated Carbon for High-Performance Supercapacitor Electrodes.

In this study, we present willow wood as a new low-cost, renewable, and sustainable biomass source for the production of a highly porous activated carbon for application in energy storage devices. The obtained activated carbon showed favorable features required for excellent electrochemical performance such as high surface area (∼2 800 m2 g-1) and pore volume (1.45 cm3 g-1), with coexistence of micropores and mesopores. This carbon material was tested as an electrode for supercapacitor application and showed a high specific capacitance of 394 F g-1 at a current density of 1 A g-1 and good cycling stability, retaining ∼94% capacitance after 5 000 cycles (at a current density of 5 A g-1) in 6 M KOH electrolyte. The prepared carbon material also showed an excellent rate performance in a symmetrical two-electrode full cell configuration using 1 M Na2SO4 electrolyte, in a high working voltage of 1.8 V. The maximum energy density and power density of the fabricated symmetric cell reach 23 W h kg-1 and 10 000 W kg-1, respectively. These results demonstrate that willow wood can serve as a low-cost carbon feedstock for production of high-performance electrode material for supercapacitors.

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.

Direct Observation of Gas Meniscus Formation on a Superhydrophobic Surface.

The formation of a bridging gas meniscus via cavitation or nanobubbles is considered the most likely origin of the submicrometer long-range attractive forces measured between hydrophobic surfaces in aqueous solution. However, the dynamics of the formation and evolution of the gas meniscus is still under debate, in particular, in the presence of a thin air layer on a superhydrophobic surface. On superhydrophobic surfaces the range can even exceed 10 µm. Here, we report microscopic images of the formation and growth of a gas meniscus during force measurements between a superhydrophobic surface and a hydrophobic microsphere immersed in water. This is achieved by combining laser scanning confocal microscopy and colloidal probe atomic force microscopy. The configuration allows determination of the volume and shape of the meniscus, together with direct calculation of the Young-Laplace capillary pressure. The long-range attractive interactions acting on separation are due to meniscus formation and volume growth as air is transported from the surface layer.

Iceland spar calcite: Humidity and time effects on surface properties and their reversibility.

Understanding the complex and dynamic nature of calcite surfaces under ambient conditions is important for optimizing industrial applications. It is essential to identify processes, their reversibility, and the relevant properties of CaCO3 solid-liquid and solid-gas interfaces under different environmental conditions, such as at increased relative humidity (RH). This work elucidates changes in surface properties on freshly cleaved calcite (topography, wettability and surface forces) as a function of time (≤28 h) at controlled humidity (≤3-95 %RH) and temperature (25.5 °C), evaluated with atomic force microscopy (AFM) and contact angle techniques. In the presence of humidity, the wettability decreased, liquid water capillary forces dominated over van der Waals forces, and surface domains, such as hillocks, height about 7.0 Å, and trenches, depth about -3.5 Å, appeared and grew primarily in lateral dimensions. Hillocks demonstrated lower adhesion and higher deformation in AFM experiments. We propose that the growing surface domains were formed by ion dissolution and diffusion followed by formation of hydrated salt of CaCO3. Upon drying, the height of the hillocks decreased by about 50% suggesting their alteration into dehydrated or less hydrated CaCO3. However, the process was not entirely reversible and crystallization of new domains continued at a reduced rate.

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.