Numerical analysis of Pickering emulsion stability: insights from ABMD simulations

The issue of the stability of Pickering emulsions is tackled at a mesoscopic level using dissipative particle dynamics simulations within the Adiabatic Biased Molecular Dynamics framework. We consider the early stage of the coalescence process between two spherical water droplets in a decane solvent. The droplets are stabilized by Janus nanoparticles of different shapes (spherical and ellipsoidal) with different three-phase contact angles. Given a sufficiently dense layer of particles on the droplets, we show that the stabilization mechanism strongly depends on the collision speed. This is consistent with a coalescence mechanism governed by the rheology of the interfacial region. When the system is forced to coalesce sufficiently slowly, we investigate at a mesoscopic level how the ability of the nanoparticles to stabilize Pickering emulsions is discriminated by nanoparticle mobility and the associated caging effect. These properties are both related to the interparticle interaction and the hydrodynamic resistance in the liquid film between the approaching interfaces

Buckling in armored droplets

The buckling mechanism in droplets stabilized by solid particles (armored droplets) is tackled at a mesoscopic level using dissipative particle dynamics simulations. We consider one spherical water droplet in a decane solvent coated with nanoparticle monolayers of two different types: Janus (particles whose surface shows two regions with different wetting properties) and homogeneous. The chosen particles yield comparable initial three-phase contact angles, selected to maximize the adsorption energy at the interface. We study the interplay between the evolution of droplet shape, layering of the particles, and their distribution at the interface when the volume of the droplets is reduced. We show that Janus particles affect strongly the shape of the droplet with the formation of a crater-like depression. This evolution is actively controlled by a close-packed particle monolayer at the curved interface. In contrast, homogeneous particles follow passively the volume reduction of the droplet, whose shape does not deviate too much from spherical, even when a nanoparticle monolayer/bilayer transition is detected at the interface. We discuss how these buckled armored droplets might be of relevance in various applications including potential drug delivery systems and biomimetic design of functional surfaces

Role of structural rigidity and collective behaviour in the molecular design of gas hydrate anti-agglomerants

Anti-agglomerants (AAs) are surface active molecules widely used in the petroleum industry, among others. It is believed that AAs strongly adsorb onto the surface of hydrate particles to prevent the growth of clathrate hydrate within oil pipelines. Small changes in their molecular structures can strongly affect the thermodynamic and kinetic stability of the system as a whole. Here we employ molecular dynamics simulations to study the interplay between the modification of the molecular structure, rigidity and collective effects of AAs designed to prevent hydrate agglomeration under the conditions encountered in rocking cell experiments. The AAs are surface-active compounds with a complex hydrophilic head and three hydrophobic tails whose structural rigidity is enhanced with the attachment of an aromatic group. Extrapolating from our simulation results, we predict that the aromatic group can positively or negatively affect the performance of the AAs, depending on its location along the hydrophobic tail. Our approach is based on first quantifying the molecular mechanisms responsible for the macroscopic performance and then altering the AA molecular structure to amplify said molecular mechanisms. Although the mechanisms at play depend on the application, the methodology implemented could be applicable to other high-tech industries, where the agglomeration of small particles must be controlled

Separation of the optical and mass features of particle components in different aerosol mixtures by using POLIPHON retrievals in synergy with continuous polarized Micro-Pulse Lidar (P-MPL) measurements

The application of the POLIPHON (POlarization-LIdar PHOtometer Networking) method is presented for the first time in synergy with continuous 24/7 polarized Micro-Pulse Lidar (P-MPL) measurements to derive the vertical separation of two or three particle components in different aerosol mixtures, and the retrieval of their particular optical properties. The procedure of extinction-to-mass conversion, together with an analysis of the mass extinction efficiency (MEE) parameter, is described, and the relative mass contribution of each aerosol component is also derived in a further step. The general POLIPHON algorithm is based on the specific particle linear depolarization ratio given for different types of aerosols and can be run in either 1-step (POL-1) or 2 steps (POL-2) versions with dependence on either the 2- or 3-component separation. In order to illustrate this procedure, aerosol mixing cases observed over Barcelona (NE Spain) are selected: a dust event on 5 July 2016, smoke plumes detected on 23 May 2016 and a pollination episode observed on 23 March 2016. In particular, the 3-component separation is just applied for the dust case: a combined POL-1 with POL-2 procedure (POL-1/2) is used, and additionally the fine-dust contribution to the total fine mode (fine dust plus non-dust aerosols) is estimated. The high dust impact before 12:00UTC yields a mean mass loading of 0.6±0.1gm-2 due to the prevalence of Saharan coarse-dust particles. After that time, the mean mass loading is reduced by two-thirds, showing a rather weak dust incidence. In the smoke case, the arrival of fine biomass-burning particles is detected at altitudes as high as 7km. The smoke particles, probably mixed with less depolarizing non-smoke aerosols, are observed in air masses, having their origin from either North American fires or the Arctic area, as reported by HYSPLIT back-trajectory analysis. The particle linear depolarization ratio for smoke shows values in the 0.10–0.15 range and even higher at given times, and the daily mean smoke mass loading is 0.017±0.008gm-2, around 3% of that found for the dust event. Pollen particles are detected up to 1.5km in height from 10:00UTC during an intense pollination event with a particle linear depolarization ratio ranging between 0.10 and 0.15. The maximal mass loading of Platanus pollen particles is 0.011±0.003gm-2, representing around 2% of the dust loading during the higher dust incidence. Regarding the MEE derived for each aerosol component, their values are in agreement with others referenced in the literature for the specific aerosol types examined in this work: 0.5±0.1 and 1.7±0.2m2g-1 are found for coarse and fine dust particles, 4.5±1.4m2g-1 is derived for smoke and 2.4±0.5m2g-1 for non-smoke aerosols with Arctic origin, and a MEE of 2.4±0.8m2g-1 is obtained for pollen particles, though it can reach higher or lower values depending on predominantly smaller or larger pollen grain sizes. Results reveal the high potential of the P-MPL system, a simple polarization-sensitive elastic backscatter lidar working in a 24/7 operation mode, to retrieve the relative optical and mass contributions of each aerosol component throughout the day, reflecting the daily variability of their properties. In fact, this procedure can be simply implemented in other P-MPLs that also operate within the worldwide Micro-Pulse Lidar Network (MPLNET), thus extending the aerosol discrimination at a global scale. Moreover, the method has the advantage of also being relatively easily applicable to space-borne lidars with an equivalent configuration such as the ongoing Cloud-Aerosol LIdar with Orthogonal Polarization (CALIOP) on board NASA CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation) and the forthcoming Atmospheric Lidar (ATLID) on board the ESA EarthCARE mission.Peer ReviewedPostprint (published version

Biohybrid membrane formation by directed insertion of Aquaporin into a solid-state nanopore

Technical challenges in molecule sensing and chemical detection have created an increasing demand for transformative materials with high sensitivity and specificity. Biohybrid nanopores have attracted growing interest as they can ideally combine the durability of solid-state nanopores with the precise structure of biological nanopores. Particular care must be taken to control how biological nanopores adapt to their surroundings once in contact with the solid-state nanopore. Two major challenges are to precisely control this adaptability under dynamic conditions and provide predesigned functionalities that can be manipulated for engineering applications. Here, we report on the computational design of a distinctive class of biohybrid active membrane layer, built from the directed insertion of an aquaporin-incorporated lipid shell into a silica nanopore. First, we describe in detail the mechanisms at play in the insertion of the biological membrane into the solid-state nanopore. Then we analyze the structural stability of the system and demonstrate that its water permeability is comparable to the one measured in the biological environment. Finally, we discuss how the technology implemented could be applicable to environmental and biomedical applications, such as water desalination and drug discovery, where targeting and controlled permeation of small molecules must be efficiently addressed.Comment: 12 pages, 10 figures (including Supporting Information

Biohybrid Membrane Formation by Directed Insertion of Aquaporin into a Solid-State Nanopore

Biohybrid nanopores combine the durability of solid-state nanopores with the precise structure and function of biological nanopores. Particular care must be taken to control how biological nanopores adapt to their surroundings once they come into contact with the solid-state nanopores. Two major challenges are to precisely control this adaptability under dynamic conditions and provide predesigned functionalities that can be manipulated for engineering applications. In this work, we report on the computational design of a distinctive class of biohybrid active membrane layers, built from the directed-insertion of an aquaporin-incorporated lipid nanodisc into a model alkyl-functionalized silica pore. We show that in an aqueous environment when a pressure difference exists between the two sides of the solid-state nanopore, the preferential interactions between the hydrocarbon tail of the lipid molecules that surround the aquaporin protein and the alkyl group functionalizing the interior surface of the silica nanopore enable the insertion of the aquaporin-incorporated lipid shell into the nanopore by forcing out the water molecules. The same preferential interactions are responsible for the structural stability of the inserted aquaporin-incorporated lipid shell as well as the water sealing properties of the lipid-alkyl interface. We further show that the aquaporin protein stabilized in the alkyl-functionalized silica nanopore preserves its biological structure and function in both pure and saline water, and, remarkably, its water permeability is equal to the one measured in the biological environment. The designed biohybrid membrane could pave the way for the development of durable transformative devices for water filtration

1-d gravity in infinite point distributions

The dynamics of infinite, asymptotically uniform, distributions of self-gravitating particles in one spatial dimension provides a simple toy model for the analogous three dimensional problem. We focus here on a limitation of such models as treated so far in the literature: the force, as it has been specified, is well defined in infinite point distributions only if there is a centre of symmetry (i.e. the definition requires explicitly the breaking of statistical translational invariance). The problem arises because naive background subtraction (due to expansion, or by "Jeans' swindle" for the static case), applied as in three dimensions, leaves an unregulated contribution to the force due to surface mass fluctuations. Following a discussion by Kiessling, we show that the problem may be resolved by defining the force in infinite point distributions as the limit of an exponentially screened pair interaction. We show that this prescription gives a well defined (finite) force acting on particles in a class of perturbed infinite lattices, which are the point processes relevant to cosmological N-body simulations. For identical particles the dynamics of the simplest toy model is equivalent to that of an infinite set of points with inverted harmonic oscillator potentials which bounce elastically when they collide. We discuss previous results in the literature, and present new results for the specific case of this simplest (static) model starting from "shuffled lattice" initial conditions. These show qualitative properties (notably its "self-similarity") of the evolution very similar to those in the analogous simulations in three dimensions, which in turn resemble those in the expanding universe.Comment: 20 pages, 8 figures, small changes (section II shortened, added discussion in section IV), matches final version to appear in PR

The malaria parasite cyclic GMP-dependent protein kinase plays a central role in blood-stage schizogony

A role for the Plasmodium falciparum cyclic GMP (cGMP)-dependent protein kinase (PfPKG) in gametogenesis in the malaria parasite was elucidated previously. In the present study we examined the role of PfPKG in the asexual blood-stage of the parasite life cycle, the stage that causes malaria pathology. A specific PKG inhibitor (compound 1, a trisubstituted pyrrole) prevented the progression of P. falciparum schizonts through to ring stages in erythrocyte invasion assays. Addition of compound 1 to ring-stage parasites allowed normal development up to 30 h postinvasion, and segmented schizonts were able to form. However, synchronized schizonts treated with compound 1 for ≥6 h became large and dysmorphic and were unable to rupture or liberate merozoites. To conclusively demonstrate that the effect of compound 1 on schizogony was due to its selective action on PfPKG, we utilized genetically manipulated P. falciparum parasites expressing a compound 1-insensitive PfPKG. The mutant parasites were able to complete schizogony in the presence of compound 1 but not in the presence of the broad-spectrum protein kinase inhibitor staurosporine. This shows that PfPKG is the primary target of compound 1 during schizogony and provides direct evidence of a role for PfPKG in this process. Discovery of essential roles for the P. falciparum PKG in both asexual and sexual development demonstrates that cGMP signaling is a key regulator of both of these crucial life cycle phases and defines this molecule as an exciting potential drug target for both therapeutic and transmission blocking action against malaria

Acute gastrointestinal haemorrhage on board a cruise ship in the Antarctic Peninsula

Antarctic tourism on board cruise ships has expanded since the 1990s, essentially in the Antarctic Peninsula. Due to remoteness, medical cases may evolve into life threatening conditions as emergency medical evacuations are challenging. We discuss the case of a young crew member who suddenly fainted with an epigastric pain and abundant rectal bleeding while on board a cruise ship heading to the Deception Island (62°57.6 South, 60°29.5 West), 44 h away from Ushuaia by sea. A medical evacuation was necessary to save the patient whose haemoglobin level rapidly decreased from 11 g/dL to 8.7 g/dL over an 8 h period due to uncontrolled gastrointestinal bleeding. Following discussions between the French, Chilean and Argentinean Medical Top Side Support and Maritime Rescue Authorities and despite poor weather conditions, an emergency medical evacuation by air to Chile was made possible. The evacuation, which was 2 days shorter compared to an evacuation by sea, allowed the patient to reach a hospital facility in time to save his life whereas he decompensated in haemorrhagic shock. As passengers on cruise ships are typically elderly and often following anticoagulant therapies, the risk of bleeding is most important. Facing a gastric haemorrhage, a transfusion is often required. In remote areas, transfusion of fresh whole blood to stabilize a critical patient until he reaches a hospital must be considered.