On Chip Sorting of Stem Cell-Derived ß Cell Clusters Using Traveling Surface Acoustic Waves.

There is a critical need for sorting complex materials, such as pancreatic islets of Langerhans, exocrine acinar tissues, and embryoid bodies. These materials are cell clusters, which have highly heterogeneous physical properties (such as size, shape, morphology, and deformability). Selecting such materials on the basis of specific properties can improve clinical outcomes and help advance biomedical research. In this work, we focused on sorting one such complex material, human stem cell-derived ß cell clusters (SC-ß cell clusters), by size. For this purpose, we developed a microfluidic device in which an image detection system was coupled to an actuation mechanism based on traveling surface acoustic waves (TSAWs). SC-ß cell clusters of varying size (∼100-500 µm in diameter) were passed through the sorting device. Inside the device, the size of each cluster was estimated from their bright-field images. After size identification, larger clusters, relative to the cutoff size for separation, were selectively actuated using TSAW pulses. As a result of this selective actuation, smaller and larger clusters exited the device from different outlets. At the current sample dilutions, the experimental sorting efficiency ranged between 78% and 90% for a separation cutoff size of 250 µm, yielding sorting throughputs of up to 0.2 SC-ß cell clusters/s using our proof-of-concept design. The biocompatibility of this sorting technique was also established, as no difference in SC-ß cell cluster viability due to TSAW pulse usage was found. We conclude the proof-of-concept sorting work by discussing a few ways to optimize sorting of SC-ß cell clusters for potentially higher sorting efficiency and throughput. This sorting technique can potentially help in achieving a better distribution of islets for clinical islet transplantation (a potential cure for type 1 diabetes). Additionally, the use of this technique for sorting islets can help in characterizing islet biophysical properties by size and selecting suitable islets for improved islet cryopreservation.

Rupture of thin liquid trilayer films with soluble surfactants: fundamentals and applications to droplet coalescence.

Understanding the stability of thin liquid trilayer films is of direct relevance to applications such as multilayer coatings and polymer processing. The stability of trilayer films can also be used to provide insights into emulsion dynamics, such as the rupture of the thin film formed between two droplets during coalescence. Often, emulsions are laden with surfactants and other additives, which can be present in one or both phases as well as at the interfaces between the liquids. In experimental studies, complicating factors such as variations in droplet sizes, curvatures, and collision processes make it difficult to specifically isolate the influence of surfactant transport on droplet coalescence and film rupture. The present work addresses this issue by systematic consideration of a model problem involving a thin liquid trilayer film. Surfactant is soluble in either the outer layers or the inner layer, corresponding to surfactant soluble in the droplets or the continuous phase. Rupture of the inner layer is driven by van der Waals forces. Lubrication theory is applied to derive coupled nonlinear evolution equations describing the perturbations to the interface positions and the surfactant concentrations. Our findings reveal that surfactant better stabilizes the film when soluble in the inner layer, and the stabilizing effect is more pronounced when the outer layers are thicker. These findings are consistent with experimental observations involving emulsions, where emulsions tend to be more stable when surfactant is in the continuous phase rather than in the droplets, with the distinction being more pronounced when droplets are larger.

A unified surface tension model for multi-component salt, organic, and surfactant solutions.

Despite the fact that the surface tension of liquid mixtures is of great importance in numerous fields and applications, there are no accurate models for calculating the surface tension of solutions containing water, salts, organic, and amphiphilic substances in a mixture. This study presents such a model and demonstrates its capabilities by modelling surface tension data from the literature. The presented equations not only allow to model solutions with ideal mixing behaviour but also non-idealities and synergistic effects can be identified and largely reproduced. In total, 22 ternary systems comprising 1842 data points could be modelled with an overall root mean squared error (RMSE) of 3.09 mN m-1. In addition, based on the modelling of ternary systems, the surface tension of two quaternary systems could be well predicted with RMSEs of 1.66 mN m-1 and 3.44 mN m-1. Besides its ability to accurately fit and predict multi-component surface tension data, the model also allows to analyze the nature and magnitude of bulk and surface non-idealities, helping to improve our understanding of the physicochemical mechanisms that influence surface tension.

Instability and rupture of surfactant-laden bilayer thin liquid films.

The stability of surfactant-laden bilayer thin films, where the top layer is subject to van der Waals driven breakup, is of particular relevance to applications where one thin liquid layer is spread on another, such as film-forming firefighting foams and multilayer coatings. Although there has been much prior modeling work on the stability of thin liquid bilayers, additional physical effects and assumptions were incorporated in those studies, making it difficult to isolate the influence of surfactant on the rupture of the top layer. The present work addresses this issue through application of the lubrication approximation to derive a coupled system of nonlinear evolution equations describing the perturbations to the liquid-liquid and liquid-air interfaces and the surfactant interfacial concentrations. The surfactant is assumed to be insoluble and can be present at each interface. Linear stability analysis suggests, and nonlinear simulations confirm, that by using surfactant that adsorbs to both interfaces, the rupture time can be increased by an order of magnitude relative to the surfactant-free case. However, we find it crucial to have the right amount of surfactant to generate strongly stabilizing Marangoni stresses without reducing the interfacial tension too much. Nonlinear simulations and linear stability analysis provide insight into the mechanisms of the delayed rupture and show how the direction and strength of the Marangoni stresses strongly depend on the viscosity ratio of the layers. These results can help guide the choice and design of surfactants to achieve more effective firefighting foams and more stable liquid coatings.

Dispersion and mixing dynamics of complex oil-in-water emulsions in Taylor-Couette flows.

The seminal study by G. I. Taylor (1923) has inspired generations of work in exploring and characterizing Taylor-Couette (TC) flow instabilities and laid the foundation for research of complex fluid systems requiring a controlled hydrodynamic environment. Here, TC flow with radial fluid injection is used to study the mixing dynamics of complex oil-in-water emulsions. Concentrated emulsion simulating oily bilgewater is radially injected into the annulus between rotating inner and outer cylinders, and the emulsion is allowed to disperse through the flow field. The resultant mixing dynamics are investigated, and effective intermixing coefficients are calculated through measured changes in the intensity of light reflected by the emulsion droplets in fresh and salty water. The impacts of the flow field and mixing conditions on the emulsion stability are tracked via changes in droplet size distribution (DSD), and the use of emulsified droplets as tracer particles is discussed in terms of changes in the dispersive Péclet, Capillary and Weber numbers. For oily wastewater systems, the formation of larger droplets is known to yield better separation during a water treatment process, and the final DSD observed here is found to be tunable based on salt concentration, observation time and mixing flow state in the TC cell. This article is part of the theme issue 'Taylor-Couette and related flows on the centennial of Taylor's seminal Philosophical Transactions paper (Part 2)'.

Droplet Interfacial Tensions and Phase Transitions Measured in Microfluidic Channels.

Measurements of droplet phase and interfacial tension (IFT) are important in the fields of atmospheric aerosols and emulsion science. Bulk macroscale property measurements with similar constituents cannot capture the effect of microscopic length scales and highly curved surfaces on the transport characteristics and heterogeneous chemistry typical in these applications. Instead, microscale droplet measurements ensure properties are measured at the relevant length scale. With recent advances in microfluidics, customized multiphase fluid flows can be created in channels for the manipulation and observation of microscale droplets in an enclosed setting without the need for large and expensive control systems. In this review, we discuss the applications of different physical principles at the microscale and corresponding microfluidic approaches for the measurement of droplet phase state, viscosity, and IFT.

Ionic strength and polyelectrolyte molecular weight effects on floc formation and growth in Taylor-Couette flows.

Polyelectrolyte-driven flocculation of suspended particulate in solution is an important process in a variety of industrial processes such as drinking water treatment and composite material synthesis. Flocculation depends on a wide variety of physicochemical and hydrodynamic properties, which affect floc size, growth rate, and floc morphology. Floc formation and growth behavior is explored here using two different molecular weights of a cationic polyacrylamide flocculant and anisotropic Na-bentonite clay particles under a variety of solution ionic strengths. A Taylor-Couette cell with radial injection capabilities was used to study the effects of solution ionic strength and polyelectrolyte molecular weight on floc size, growth rate, and floc morphology during the flocculation process with a constant global velocity gradient. The floc size generally decreased with increasing ionic strength whereas the floc growth rate initially increased then decreased. This likely occurred due to charge screening effects, where increased bentonite aggregate size and a less expanded polyelectrolyte conformation at higher ionic strengths results in a decreased ability for the polyelectrolyte to bridge multiple bentonite aggregates. The densification of bentonite aggregates at higher ionic strengths resulted in floc morphologies that were more resistant to shear-induced breakage. With the exceptions of optimal dose concentration and dispersion coefficients, there were no clear differences in the floc growth rate behaviors for the two molecular weights studied. This work contributes to an improved understanding of the physicochemical complexities of polyelectrolyte-driven flocculation that can inform dosing requirements for more efficient industrial operations.

Dilatational rheology of water-in-diesel fuel interfaces: effect of surfactant concentration and bulk-to-interface exchange.

Micrometer-sized water droplets dispersed in diesel fuel are stabilized by the fuel's surface-active additives, such as mono-olein and poly(isobutylene)succinimide (PIBSI), making the droplets challenging for coalescing filters to separate. Dynamic material properties found from interfacial rheology are known to influence the behavior of microscale droplets in coalescing filters. In this work, we study the interfacial dilatational properties of water-in-fuel interfaces laden with mono-olein and PIBSI, with a fuel phase of clay-treated ultra-low sulphur diesel (CT ULSD). First, the dynamic interfacial tension (IFT) is measured using pendant drop tensiometry, and a curvature-dependent form of the Ward and Tordai diffusion equation is applied for extracting the diffusivity of the surfactants. Additionally, Langmuir kinetics are applied to the dynamic IFT results to obtain the maximum surface concentration (Γ∞) and ratio of adsorption to desorption rate constants (κ). We then use a capillary pressure microtensiometer to measure the interfacial dilatational modulus, and further extract the characteristic frequency of surfactant exchange (ω0) by fitting a model assuming diffusive exchange between the interface and bulk. In this measurement, 50-100 µm diameter water droplets are pinned at the tip of a glass capillary in contact with the surfactant-containing fuel phase, and small amplitude capillary pressure oscillations over a range of frequencies from 0.45-20 rad s-1 are applied to the interface, inducing changes in interfacial tension and area to yield the dilatational modulus, E*(ω). Over the range of concentrations studied, the dilatational modulus of CT ULSD with either mono-olein or PIBSI increases with a decrease in bulk concentration and plateaus at the lowest concentrations of mono-olein. Characteristic frequency (ω0) values extracted from the fit are compared with those calculated using equilibrium surfactant parameters (κ and Γ∞) derived from pendant drop tensiometry, and good agreement is found between these values. Importantly, the results imply that diffusive exchange models based on the equilibrium relationships between surfactant concentration and interfacial tension can be used to infer the dynamic dilatational behavior of complex surfactant systems, such as the water-in-diesel fuel interfaces in this study.

Concentration Depth Profile-Based Multilayer Sorption Surface Tension Model for Aqueous Solutions.

Surface tension of chemically complex aqueous droplets is significant to atmospheric aerosol particle dynamics and fate. Isotherm-based predictive surface tension models are available which consider one layer of solute molecules sorbed at the liquid-vapor interface. However, the concentration depth profile (CDP) of solute molecules near the surface is continuous, making the single monolayer assumption inappropriate. Here, this work extends the isotherm framework by dividing the surface region into multiple layers to capture the continuity of the spatial distribution of solute molecules for binary solutions. Partition functions are established based on the displacement of water molecules by solute molecules. The number of displaced water molecules and energy of solute molecules at the surface and in the bulk are key model parameters relating surface tension and solute activity. Number densities of surface molecules from molecular dynamic (MD) simulations available in the literature are applied to determine model parameters. Finally, the model is extended to predict surface tension for mixture solutions, considering both independent and dependent adsorptions of different solute species to the liquid-vapor interface. The proposed model works well for both electrolyte and nonelectrolyte solutions and their mixtures from pure solvent to pure solute.

Accurate Prediction of Organic Aerosol Evaporation Using Kinetic Multilayer Modeling and the Stokes-Einstein Equation.

Organic aerosol can adopt a wide range of viscosities, from liquid to glass, depending on the local humidity. In highly viscous droplets, the evaporation rates of organic components are suppressed to varying degrees, yet water evaporation remains fast. Here, we examine the coevaporation of semivolatile organic compounds (SVOCs), along with their solvating water, from aerosol particles levitated in a humidity-controlled environment. To better replicate the composition of secondary aerosol, nonvolatile organics were also present, creating a three-component diffusion problem. Kinetic modeling reproduced the evaporation accurately when the SVOCs were assumed to obey the Stokes-Einstein relation, and water was not. Crucially, our methodology uses previously collected data to constrain the time-dependent viscosity, as well as water diffusion coefficients, allowing it to be predictive rather than postdictive. Throughout the study, evaporation rates were found to decrease as SVOCs deplete from the particle, suggesting path function type behavior.

Phase-Dependent Surfactant Transport on the Microscale: Interfacial Tension and Droplet Coalescence.

Liquid-liquid emulsion systems are usually stabilized by additives, known as surfactants, which can be observed in various environments and applications such as oily bilgewater, water-entrained diesel fuel, oil production, food processing, cosmetics, and pharmaceuticals. One important factor that stabilizes emulsions is the lowered interfacial tension (IFT) between the fluid phases due to surfactants, inhibiting the coalescence. Many studies have investigated the surfactant transport behavior that leads to corresponding time-dependent lowering of the IFT. For example, the rate of IFT decay depends on the phase in which the surfactant is added (dispersed vs continuous) due in part to differences in the near-surface depletion depth. Other key factors, such as the viscosity ratio between the dispersed and continuous phases and Marangoni stress, will also have an impact on surfactant transport and therefore the coalescence and emulsion stability. In this feature article, the measurement techniques for dynamic IFT are first reviewed due to their importance in characterizing surfactant transport, with a specific focus on macroscale versus microscale techniques. Next, equilibrium isotherm models as well as dynamic diffusion and kinetic equations are discussed to characterize the surfactant and the time scale of the surfactant transport. Furthermore, recent studies are highlighted showing the different IFT decay rates and its long-time equilibrium value depending on the phase into which the surfactant is added, particularly on the microscale. Finally, recent experiments using a hydrodynamic Stokes trap to investigate the impact of interfacial surfactant transport, or "mobility", and the phase containing the surfactant on film drainage and droplet coalescence will be presented.

Insights into the Microscale Coalescence Behavior of Surfactant-Stabilized Droplets Using a Microfluidic Hydrodynamic Trap.

Coalescence of micrometer-scale droplets is impacted by several parameters, including droplet size, viscosities of the two phases, droplet velocity, angle of approach, as well as interfacial tension and surfactant coverage. The thinning dynamics of films between coalescing droplets can be particularly complex in the presence of surfactants, due to the generation of Marangoni stresses and reduced film mobility. Here, a microfluidic hydrodynamic "Stokes" trap is used to gently steer and trap surfactant-laden micrometer-sized droplets at the center of a cross-slot. Water droplets are formed upstream of the cross-slot using a microfluidic T-junction, in heavy and light mineral oils and stabilized using SPAN 80, an oil-soluble surfactant. Incoming droplets are made to coalesce with the trapped droplet, yielding measurements of the film drainage time. Film drainage times are measured as a function of continuous phase viscosity, incoming droplet speed, trapped droplet size, and surfactant concentrations above and below the critical micelle concentration (CMC). As expected, systems with higher surfactant concentrations and slower incoming droplet speed exhibit longer film drainage times. At low surfactant concentrations, the drainage time is longer for the more viscous heavy mineral oil in the continuous phase, whereas at high surfactant concentrations, the dependence on continuous phase viscosity vanishes. Perhaps more surprisingly, larger droplets and high confinement also result in longer film drainage times, potentially due to deformation of the droplet interfaces. The results are used here to determine critical conditions for coalescence, including both an upper and a lower critical capillary number. Moreover, it is shown that induced surfactant concentration gradient effects enable coalescence events after the droplets had originally flocculated, at surfactant concentrations above the CMC. The microfluidic hydrodynamic trap provides new insights into the role of surfactants in film drainage and opens avenues for controlled coalescence studies at micrometer length scales and millisecond time scales.

Size dependent droplet interfacial tension and surfactant transport in liquid-liquid systems, with applications in shipboard oily bilgewater emulsions.

Many liquid-liquid emulsions, including shipboard oily bilgewater (oil-in-water) and water entrained in diesel fuels (water-in-oil), are chemically stabilized by surfactants and additives and require treatment to destabilize and separate. The interfacial tension (IFT) of surfactant-laden interfaces between the continuous and dispersed phase, as well as the size of the dispersed droplets, are significant factors in determining emulsion stability. In particular, the timescale associated with a dynamic change in IFT due to surfactant transport is indicative of how fast the emulsion will stabilize. In the present work, the dynamic IFT of droplets at micro-scale (∼80 µm) and milli-scale (∼2 mm) is measured with simulated bilgewater with soluble surfactant systems. It is found that the IFT of micro-scale droplets decays faster than that of the milli-scale droplets due to smaller diffusion boundary layer thickness. The change in IFT was also studied for water-soluble surfactants added into the dispersed phase and continuous phase for both milli- and micro-scaled droplets. The results show that the IFT of micro-scale droplets decreases to the equilibrium value faster when the surfactant is in outer phase than in the inner phase, while the IFT does not change significantly for the milli-scale droplets. The observations are explained by the change in diffusion limited to kinetic limited surfactant transport. Finally, the surfactant diffusivities, adsorption and desorption rate constants are calculated using Langmuir's equation. The results presented here provide insight into the fundamental mechanism of the surfactant transport and helps improve mitigation strategies of oil-water emulsions.

Microfluidic rheology of methylcellulose solutions in hyperbolic contractions and the effect of salt in shear and extensional flows.

Methylcellulose solutions are known to form microfibrils at elevated temperatures or in the presence of salt. The fibrils have a significant impact on the solution's rheological properties. Here, the shear and extensional properties of methylcellulose solutions with added salt are measured using hyperbolic microfluidic channels, allowing for new characterization at lower molecular weights and higher shear and strain rates that are difficult to access by macroscale rheology studies. 1 and 2 wt% methylcellulose solutions with molecular weight of 150 kg mol-1 with NaCl content between 0 to 5 wt% have been characterized. All solutions were found to be shear thinning, with power law thinning behavior at shear rates above 100 s-1. The addition of NaCl up to 5 wt% had only small effects on shear viscosity at the shear rates probed (100 s-1 and 10 000 s-1). Extensional viscosities as low as 0.02 Pa s were also measured. Unlike the results for shear viscosity, the addition of 5 wt% NaCl caused significant changes in extensional viscosity, increasing by up to 10 times, depending on extension rate. Additionally, all solutions tested showed apparent extensional thinning in the high strain rate regime (>100 s-1), which has not been reported in other studies of methylcellulose solutions. These findings may provide insight for those using methylcellulose solutions in process designs involving extensional flows over a wide range of strain rates.

Increasing Isoprene Epoxydiol-to-Inorganic Sulfate Aerosol Ratio Results in Extensive Conversion of Inorganic Sulfate to Organosulfur Forms: Implications for Aerosol Physicochemical Properties.

Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX), key isoprene oxidation products, with inorganic sulfate aerosol yields substantial amounts of secondary organic aerosol (SOA) through the formation of organosulfur compounds. The extent and implications of inorganic-to-organic sulfate conversion, however, are unknown. In this article, we demonstrate that extensive consumption of inorganic sulfate occurs, which increases with the IEPOX-to-inorganic sulfate concentration ratio (IEPOX/Sulfinorg), as determined by laboratory measurements. Characterization of the total sulfur aerosol observed at Look Rock, Tennessee, from 2007 to 2016 shows that organosulfur mass fractions will likely continue to increase with ongoing declines in anthropogenic Sulfinorg, consistent with our laboratory findings. We further demonstrate that organosulfur compounds greatly modify critical aerosol properties, such as acidity, morphology, viscosity, and phase state. These new mechanistic insights demonstrate that changes in SO2 emissions, especially in isoprene-dominated environments, will significantly alter biogenic SOA physicochemical properties. Consequently, IEPOX/Sulfinorg will play an important role in understanding the historical climate and determining future impacts of biogenic SOA on the global climate and air quality.

Surface Tensions of Picoliter Droplets with Sub-Millisecond Surface Age.

Aerosols are key components of the atmosphere and play important roles in many industrial processes. Because aerosol particles have high surface-to-volume ratios, their surface properties are especially important. However, direct measurement of the surface properties of aerosol particles is challenging. In this work, we describe an approach to measure the surface tension of picoliter volume droplets with surface age <1 ms by resolving their dynamic oscillations in shape immediately after ejection from a microdroplet dispenser. Droplet shape oscillations are monitored by highly time-resolved (500 ns) stroboscopic imaging, and droplet surface tension is accurately retrieved across a wide range of droplet sizes (10-25 µm radius) and surface ages (down to ∼100 µs). The approach is validated for droplets containing sodium chloride, glutaric acid, and water, which all show no variation in surface tension with surface age. Experimental results from the microdroplet dispenser approach are compared to complementary surface tension measurements of 5-10 µm radius droplets with aged surfaces using a holographic optical tweezers approach and predictions of surface tension using a statistical thermodynamic model. These approaches combined will allow investigation of droplet surface tension across a wide range of droplet sizes, compositions, and surface ages.

Direct Determination of Aerosol pH: Size-Resolved Measurements of Submicrometer and Supermicrometer Aqueous Particles.

Measuring the acidity of atmospheric aerosols is critical, as many key multiphase chemical reactions involving aerosols are highly pH-dependent. These reactions impact processes, such as secondary organic aerosol (SOA) formation, that impact climate and health. However, determining the pH of atmospheric particles, which have minute volumes (10-23-10-18 L), is an analytical challenge due to the nonconservative nature of the hydronium ion, particularly as most chemical aerosol measurements are made offline or under vacuum, where water can be lost and acid-base equilibria shifted. Because of these challenges, there have been no direct methods to probe atmospheric aerosol acidity, and pH has typically been determined by proxy/indirect methods, such as ion balance, or thermodynamic models. Herein, we present a novel and facile method for direct measurement of size-resolved aerosol acidity from pH 0 to 4.5 using quantitative colorimetric image processing of cellular phone images of (NH4)2SO4-H2SO4 aqueous aerosol particles impacted onto pH-indicator paper. A trend of increasing aerosol acidity with decreasing particle size was observed that is consistent with spectroscopic measurements of individual particle pH. These results indicate the potential for direct measurements of size-resolved atmospheric aerosol acidity, which is needed to improve fundamental understanding of pH-dependent atmospheric processes, such as SOA formation.

In situ polymer flocculation and growth in Taylor-Couette flows.

Flocculation of small particulates suspended in solution is a key process in many industries, including drinking water treatment. The particles are aggregated during mixing to form larger aggregates, known as flocs, through use of a polyelectrolyte flocculant. The flocculation of these particulates in water treatment, however, are subject to a wide spatial variation of hydrodynamic flow states, which has consequences for floc size, growth rate, and microstructure. Floc assembly dynamics are explored here using a commercially available cationic polyacrylamide, commonly used in water treatment, and anisotropic Na-bentonite clay particles under a variety of hydrodynamic mixing conditions. A Taylor-Couette cell with the unique ability to radially inject fluid into the rotating annulus was used to study how specific hydrodynamic flow fields affect assembly and structure of these materials during the flocculation process. Faster floc growth rates and decreased floc fractal dimensions were observed for higher order flow states, indicating improved mass transfer of the polymer flocculant and breakage at the edges of the flocs (shear rounding), respectively. This work sheds more light on the complexities of polymer-induced flocculation, towards improving dosing and efficiency of large-scale operations.

Influence of particle viscosity on mass transfer and heterogeneous ozonolysis kinetics in aqueous-sucrose-maleic acid aerosol.

Mass transfer between the gas and condensed phases in aerosols can be limited by slow bulk diffusion within viscous particles. During the heterogeneous and multiphase reactions of viscous organic aerosol particles, it is necessary to consider the interplay of numerous mass transfer processes and how they are impacted by viscosity, including the partitioning kinetics of semi-volatile organic reactants, water and oxidants. To constrain kinetic models of the heterogeneous chemistry, measurements must provide information on as many observables as possible. Here, the ozonolysis of maleic acid (MA) in ternary aerosol particles containing water and sucrose is used as a model system. By varying the mass ratio of sucrose to MA and by performing reactions over a wide range of relative humidity, direct measurements show that the viscosity of the particle can be varied over 7 orders of magnitude. Measurements of the volatilisation kinetics of MA show that this range in viscosity leads to a suppression in the effective vapour pressure of MA of 3-4 orders of magnitude. The inferred values of the diffusion coefficient of MA in the particle phase closely mirror the expected change in diffusion coefficient from the Stokes-Einstein equation and the change in viscosity. The kinetics of ozonolysis show a similar dependence on particle viscosity that can be further investigated using the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB). Two scenarios, one constraining the diffusion coefficients for MA to those expected based on the Stokes-Einstein equation and the other including the diffusion coefficients as a fit parameter, yield similarly adequate representations of the ozonolysis kinetics, as inferred from the experimental decay in the signature of the vinylic C-H stretching vibration of MA. However, these two scenarios provide very different parameterisations of the compositional dependence of the diffusion coefficients of ozone within the condensed phase, yielding qualitatively different time-dependent internal concentration profiles. We suggest that this highlights the importance of providing additional experimental observables (e.g. particle size, heterogeneity in composition) if measurements and models are to be universally reconciled.