Short-range Attractive Forces Research Articles

Mechanism of mitigating organic fouling on an electro-conductive membrane under anaerobic conditions and cathodic operation

Anaerobic electroconductive membrane (ECM) bioreactors are promising wastewater treatment technology, yet their organic antifouling mechanism remains unclear. This research investigated the impact of reactive oxygen species (ROS) oxidation, pH alteration, and electrostatic repulsion on carbon nanotube-based ECM organic fouling. Using a decoupled anode–cathode filtration system ensured unbiased results from the anode while studying distinct conditions near the cathodic ECM surface. The results demonstrated a 50 % reduction in transmembrane pressure (TMP) onset applying potential due to electroosmosis, emphasizing its importance in fouling studies. Fouling experiments using alginate in synthetic wastewater solution showed substantial organic fouling at open circuit potential, −1 and −1.5 V, as the TMP increased by about 2.5 times than the initial value. Fouling decreased significantly at −2.5 V (vs. Ag/AgCl), as indicated by the stable TMP. Analysis of ROS effects and fouling experiments at pH 7–––12 found no influence on organic fouling. Simplified force balance analysis and filtration tests suggested electrostatic repulsion as the antifouling mechanism. At potentials below −2.5 V, electrostatic repulsion maximizes closer to the ECM surface, causing fouling from short-range attractive forces. Electrochemical quartz crystal microbalance analysis at 0.1 V (vs. Ag/AgCl) proposed that a smooth ECM surface can reduce organic fouling at lower potentials.

Ostwald-like ripening in the two-dimensional clustering of passive particles induced by swimming bacteria.

Clustering passive particles by active agents is a promising route for fabrication of colloidal structures. Here, we report the dynamic clustering of micrometric beads in a suspension of motile bacteria. We characterize the coarsening dynamics for various bead sizes, surface fractions, and bacterial concentrations. We show that the time scale τ for the onset of clustering is governed by the time of first encounter of diffusing beads. At large time (t≫τ), we observe a robust cluster growth as t^{1/3}, similar to the Ostwald ripening mechanism. From bead tracking measurements, we extract the short-range bacteria-induced attractive force at the origin of this clustering.

Clusters in colloidal dispersions with a short-range depletion attraction: Thermodynamic identification and morphology

HypothesisParticle aggregation is ubiquitous for many colloidal systems, and drives the phase separation or the formation of materials with a highly heterogeneous large-scale structure, such as gels, porous media and attractive glasses. While the macroscopic properties of such materials strongly depend on the shape and size of these particle aggregates, the morphology and underlining aggregation physical mechanisms are far from being fully understood. Recently, it has been proposed that for reversible colloidal aggregation, the cluster morphology in the case of colloids interacting with short-range attractive forces is determined by a single variable, namely, the reduced second virial coefficient, B2∗. ExperimentsWe examined this proposal by performing confocal microscopy experiments and computer simulations on a large collection of short-ranged attractive colloidal systems with different values of the attraction strength and range. FindingsWe show that in all cases a connection between the colloidal cluster morphology and B2∗ can be established both in experiments and simulations. This physical scenario holds at all investigated thermodynamic conditions, namely, in the fluid state, in the metastable region and in non-equilibrium conditions. Our findings support the connection between reversible colloidal aggregation and the so-called extended law of corresponding states.

Perturbation theories for fluids with short-ranged attractive forces: A case study of the Lennard-Jones spline fluid

It is generally not straightforward to apply molecular-thermodynamic theories to fluids with short-ranged attractive forces between their constituent molecules (or particles). This especially applies to perturbation theories, which, for short-ranged attractive fluids, typically must be extended to high order or may not converge at all. Here, we show that a recent first-order perturbation theory, the uv-theory, holds promise for describing such fluids. As a case study, we apply the uv-theory to a fluid with pair interactions defined by the Lennard-Jones spline potential, which is a short-ranged version of the LJ potential that is known to provide a challenge for equation-of-state development. The results of the uv-theory are compared to those of third-order Barker-Henderson and fourth-order Weeks-Chandler-Andersen perturbation theories, which are implemented using Monte Carlo simulation results for the respective perturbation terms. Theoretical predictions are compared to an extensive dataset of molecular simulation results from this (and previous) work, including vapor-liquid equilibria, first- and second-order derivative properties, the critical region, and metastable states. The uv-theory proves superior for all properties examined. An especially accurate description of metastable vapor and liquid states is obtained, which might prove valuable for future applications of the equation-of-state model to inhomogeneous phases or nucleation processes. Although the uv-theory is analytic, it accurately describes molecular simulation results for both the critical point and the binodal up to at least 99% of the critical temperature. This suggests that the difficulties typically encountered in describing the vapor-liquid critical region are only to a small extent caused by non-analyticity.

Location of the gel-like boundary in patchy colloidal dispersions: Rigidity percolation, structure, and particle dynamics

During the past decade, there has been a hot debate about the physical mechanisms that determine when a colloidal dispersion approaches the gel transition. However, there is still no consensus on a possible unique route that leads to the conditions for the formation of a gel-like state. Based on gel states identified in experiments, Valadez-Pérez etal. [Phys. Rev. E 88, 060302(R) (2013)PLEEE81539-375510.1103/PhysRevE.88.060302] proposed rigidity percolation as the precursor of colloidal gelation in adhesive hard-sphere dispersions with coordination number 〈n_{b}〉 equal to 2.4. Although this criterion was originally established to describe mechanical transitions in network-forming molecular materials with highly directional interactions, it worked well to explain gel formation in colloidal suspensions with isotropic short-range attractive forces. Recently, this idea has also been used to account for the dynamical arrest experimentally observed in attractive spherocylinders. Then, by assuming that rigidity percolation also drives gelation in spherical colloids interacting with short-ranged and highly directional potentials, we locate the thermodynamic states where gelation seems to occur in dispersions made up of patchy colloids. To check whether the criterion 〈n_{b}〉=2.4 also holds in patchy colloidal systems, we apply the so-called bond-bending analysis to determine the fraction of floppy modes at some percolating clusters. This analysis confirms that the condition 〈n_{b}〉=2.4 is a good approximation to determine those percolating clusters that are either mechanically stable or rigid. Furthermore, our results point out that not all combinations of patches and coverages lead to a gel-like state. Additionally, we systematically study the structure and the cluster size distribution along those thermodynamic states identified as gels. We show that for high coverage values, the structure is very similar for systems that have the same coverage regardless the number or the position of the patches on the particle surface. Finally, by using dynamic Monte Carlo computer simulations, we calculate both the mean-square displacement and the intermediate scattering function at and in the neighborhood of the gel-like states.

Colloidal magnetic brushes: influence of the magnetic content and presence of short-range attractive forces in the micro-structure and field response.

The behaviour of supramolecular brushes, whose filaments are composed of sequences of magnetic and non-magnetic colloidal particles, has been studied using Langevin dynamics simulations. Two types of brushes have been considered: sticky or Stockmayer brushes (SB) and non-sticky magnetic brushes (NSB). In both cases, the microstructure and the collective behaviour have been analysed for a wide range of magnetic field strengths including the zero-field case, and negative fields. The results show that, for the same magnetic content, SB placed in a magnetic field present an extensibility up to two times larger than NSB. The analysis of the microstructure of SB at zero field shows that magnetic particles belonging to different filaments in the brush self-organize into ring and chain aggregates, while magnetic colloids in NSB mainly remain in a non-aggregated state. Clustering among magnetic particles belonging to different filaments is observed to gradually fade away as the magnetic content of SB filaments increases towards 100%. Under an external field, SB are observed to form chains, threads and sheets depending on the magnetic content and the applied field strength. The chain-like clusters in SB are observed to decrease in size as the magnetic content in the filaments increases. A non-monotonic field dependence is observed for the average size of these clusters. In spite of the very different microstructure, both NSB and SB are observed to have a very similar magnetization, especially in high strength fields.

The Effect of Corona Discharges on Droplets Settlement

To increase the ion density by corona discharge is an efficient way to generate charged nucleus from atmospheric aerosols and induce precipitation or eliminate fog. Here, we compare the brightness of discharge and optical emission spectrum (OES) of positive and negative corona discharges, and find the discharge intensity of the negative corona discharge is stronger than positive corona discharge at the same applied voltage. The combination of aerosols and more ions generated by negative corona discharges can produce numerous charged nucleus, which eventually generates large droplets and enhance precipitation through the short-range attractive force between charged nucleus and aerosols. The excessive condensation of water molecules on the negative electrode should be avoided for the application of large corona discharge systems in the mist-shrouded high mountains or airport.

Carbon as an electron donor atom

There are a number of C-containing entities which can donate electrons. The C atom of the CN− anion contains a lone pair which can be transferred to a Lewis acid. Even if the acid molecule is anionic, short-range attractive forces can overcome the long-range ion-ion repulsion to approach close enough to engage in a strong bonding interaction. The CN− anion can be surrounded by a number of ligands that interact through a host of different types of bonds. The C lone pair of the MeCH2− carbanion is also available for donation. Neutral C-containing molecules can function as electron source as well. Despite the absence of any C lone pair, a CH3M unit can donate electron density from its σ-bonding orbitals to a neutral molecule within the framework of a ditetrel bond. The C lone pairs of carbenes may also be donated to form strong bonds within the covalent range. The π-systems of alkenic or aromatic molecules represent an alternate source, although generally weaker than the interactions arising from C lone pairs.

Analytical photo-centrifuge-based prediction of shelf-life and droplet packing behaviour of nanoemulsions upon removal of excess micelles

An analytical photo-centrifuge was used to develop novel experimental methods to predict the shelf-life, rheology, and inter-droplet interactions in 40 wt% canola oil-in-water nanoemulsions stabilized by 3 and 5 wt% citric acid esters of monoglyceride (Citrem). The combined influence of micellar concentration and oil droplet size on the rheology, creaming stability, and compression behaviour was studied under a series of accelerated gravitations. Nanoemulsions without excess Citrem micelles were obtained by removing them from the continuous phase using multiple cycles of ultracentrifugation. Reduction in droplet size with an increase in Citrem concentration and the removal of excess micelles resulted in a significant increase in plateau storage moduli leading to a change in phase behaviour of the nanoemulsions from liquid to viscoelastic gels. Moreover, it also showed a simultaneous drastic decrease in nanodroplets creaming velocity under accelerated gravitation. The flow behaviour of the gels was well correlated with a critical relative centrifugal force required to initiate flow under accelerated gravitation. Additionally, the colloidal forces responsible for instability was satisfactorily explained by the packing behaviour of the nanodroplets studied under a series of compression and dilatational cycles of centrifugation. We showed that the strong electrostatic repulsive force between the nanodroplets without excess micelles led to a lower packing density during compaction that did not change significantly during successive dilatational cycles. The higher packing density or compaction in the presence of excess micelles was explained by the short-range attractive depletion forces leading to weak flocculation of nanodroplets. Overall, the presence and absence of excess micelles showed a significant influence on the rheology and accelerated stability of nanoemulsions, which can be further described by the colloidal forces between the nanodroplets using the real-time advanced photo-centrifuge.

The Effect of Dissolved Gases on the Short-Range Attractive Force between Hydrophobic Surfaces in the Absence of Nanobubble Bridging.

The short-range attractive forces between hydrophobic surfaces are key factors in a wide range of areas such as protein folding, lipid self-assembly, and particle-bubble interaction such as in industrial flotation. Little is certain about the effect of dissolved (well-controlled) gases on the interaction forces, in particular in those systems where the formation of surface nanobubble bridges is suppressed. Here, we probe the short-range attractive force between hydrophobized silica surfaces in aqueous solutions with varying but well-controlled isotherms of gas solubility. The first contact approach force measurement method using AFM shows that decreasing gas solubility results in a decrease of the force magnitude as well as shortening of its range. The behavior was found to be consistent across all four aqueous systems and gas solubilities tested. Using numerical computations, we corroborate that attractive force can be adequately explained by a multilayer dispersion force model, which accounts for an interfacial gas enrichment (IGE), that results in the formation of a dense gas layer (DGL) adjacent to the hydrophobic surface. We found that the DGL on the hydrophobic surface is affected only by the concentration of dissolved gases and is independent of the salt type, used to control the gas solubility, which excludes the effect of electrical double-layer interactions on the hydrophobic force.

Microscopic theory of onset of decaging and bond-breaking activated dynamics in ultradense fluids with strong short-range attractions.

We theoretically study thermally activated "in cage" elementary dynamical processes that precede full structural relaxation in ultradense particle liquids interacting via strong short-range attractive forces. The analysis is based on a microscopic theory formulated at the particle trajectory level built on the dynamic free energy concept and an explicit treatment of how attractive forces control the formation and lifetime of physical bonds. Mean time scales for bond breaking, the early stage of cage escape, and non-Fickian displacement by a fixed amount are analyzed in the repulsive glass, bonded repulsive (attractive) glass, fluid, and dense gel regimes. The theory predicts a strong length-scale-dependent growth of these time scales with attractive force strength at fixed packing fraction, a much weaker slowing down with density at fixed attraction strength, and a strong decoupling of the shorter bond-breaking time with the other two time scales that are controlled mainly by perturbed steric caging. All results are in good accord with simulations, and additional testable predictions are made. The classic statistical mechanical projection approximation of replacing all bare attractive and repulsive forces with a single effective force determined by pair structure incurs major errors for describing processes associated with thermally activated escape from transiently localized states.

Concentrated Pickering emulsions stabilised by hemp globulin-caseinate nanoparticles: tuning the rheological properties by adjusting the hemp globulin : caseinate ratio.

Industrial hemp (Cannabis sativa L.) is an underutilised novel protein source. However, the utilisation of hemp seed protein is limited by its low solubility in water. Soluble nanoparticles were made by complexing hemp globulin (HG) with sodium caseinate (SC) via a pH-cycling method. Oil-in-water Pickering emulsions were made with these co-assembled protein nanoparticles. The emulsions were composed of 70% oil phase and 30% water phase (v/v), and contained 2% protein (w/v, pure SC or HG-SC nanoparticles with an HG : SC ratio of 1 : 2 or 1 : 1). All emulsions were stable during 21 days of storage, as there was no phase separation, coalescence or flocculation. At day 0, all emulsions were solid-like (G' > G'') regardless of the protein composition. The rheological properties of the emulsions during storage could be tuned by controlling the HG : SC ratio in the HG-SC nanoparticles, i.e. the emulsions became more solid-like over time when there was more HG in the nanoparticles. In contrast, emulsions stabilised by pure SC became more liquid-like during storage. The internal structure and interactions within the emulsions were evaluated by fitting frequency sweep test data according to a co-operative theory of flow. The result suggested that the solid-like emulsion resulted from stronger short-range interactions between flocs of oil droplets, which developed during storage when there was more HG in the HG-SC nanoparticles, and not from the formation of a three-dimensional network. These HG-SC nanoparticles can be used to control the rheological properties of an emulsion during its shelf life.

Microscopic theory of the influence of strong attractive forces on the activated dynamics of dense glass and gel forming fluids.

We theoretically study the nonmonotonic (re-entrant) activated dynamics associated with a finite time scale kinetically defined repulsive glass to fluid to attractive glass transition in high volume fraction particle suspensions interacting via strong short range attractive forces. The classic theoretical "projection" approximation that replaces all microscopic forces by a single effective force determined solely by equilibrium pair correlations is revisited based on the "projectionless dynamic theory" (PDT). A hybrid-PDT approximation is formulated that explicitly quantifies how attractive forces induce dynamical constraints, while singular hard core interactions are treated based on the projection approach. Both the effects of interference between repulsive and attractive forces, and structural changes due to attraction-induced bond formation that competes with caging, are included. Combined with the microscopic Elastically Collective Nonlinear Langevin Equation (ECNLE) theory of activated relaxation, the resultant approach appears to properly capture both the re-entrant dynamic crossover behavior and the strong nonmonotonic variation of the activated structural relaxation time with attraction strength and range at very high volume fractions as observed experimentally and in simulations. Testable predictions are made. Major differences compared to both ideal mode coupling theory and ECNLE theory based on the full force projection approximation are identified. Calculations are also performed for smaller time and length scale intracage dynamics relevant to the non-Gaussian parameter based on analyzing the dynamic free energy that controls particle trajectories. Implications of the new theory for thermal glass forming liquids with relatively long range attractive forces are briefly analyzed.

Hierarchical self-assembly and emergent function of densely glycosylated peptide nanofibers

Glycosylation alters protein form and function by establishing intermolecular forces that mediate specific interactions while preventing non-specific aggregation. Self-assembled peptide nanofibers modified with carbohydrates are increasingly used as biomaterials to mimic glycosylated protein function, yet the influence of carbohydrate conjugates on nanofiber structure remains poorly defined. Here we show that a dense carbohydrate surface layer can facilitate hierarchical organization of peptide nanofibers into anisotropic networks. Glycosylated peptide nanofibers remain dispersed in dilute conditions, whereas non-glycosylated nanofibers tend to aggregate. In crowded conditions, some glycosylated nanofibers laterally associate and align. This behavior depends on carbohydrate chemistry, particularly hydroxyls, suggesting involvement of short-range attractive forces. Macroscopic gels fabricated from densely glycosylated peptide nanofibers are resistant to non-specific interactions with proteins, mammalian cells, and bacteria, yet selectively bind lectins, analogous to natural low-fouling mucosal barriers. Collectively, these observations demonstrate that glycosylation can inform structure in addition to endowing function to peptide-based supramolecular biomaterials.

Strong Substrate Mediation of Attractive Lateral Interactions of CO on Cu(110).

The mechanism of chemical reactions between adsorbed species is defined by the combined effects of the adsorbate-substrate potential landscape and lateral interactions. Such lateral interactions are therefore integral to catalytic processes, but their study is often complicated by "substrate mediation", the regulation of a two-body potential between adsorbed particles by the surface itself. Substrate mediation can influence the sign and magnitude of lateral interactions. There are notable exceptions of ordered structures forming at low coverage, indicative of short-range attractive forces where repulsive forces are expected to dominate, suggesting a strong substrate-mediated contribution. To explore further the origins of such interactions, we have investigated the adsorption of CO on Cu(110) using a combination of low-temperature microscopy and first-principles calculations. Our studies reveal that lateral adsorbate interactions, which are constrained by the metal surface, regulate the bonding between the adsorbate and substrate. Anisotropic CO-CO coupling is seen to arise from a perfect balance between the intermolecular accumulation of charge that acts as a glue (chemical coupling) at sufficiently large distances to avoid repulsive effects (dipole-dipole coupling and Pauli's repulsion between electron clouds).

Direct Measurement of the Magnitude of the van der Waals Interaction of Single and Multilayer Graphene

Vertical stacking of monolayers via van der Waals (vdW) assembly is an emerging field that opens promising routes toward engineering physical properties of two-dimensional materials. Industrial exploitation of these engineering heterostructures as robust functional materials still requires bounding their measured properties so as to enhance theoretical tractability and assist in experimental designs. Specifically, the short-range attractive vdW forces are responsible for the adhesion of chemically inert components and are recognized to play a dominant role in the functionality of these structures. Here, we reliably quantify the strength of ambient vdW forces in terms of an effective Hamaker coefficient for chemical vapor deposition-grown graphene and show how it scales by a factor of two or three from single to multiple layers on standard supporting surfaces such as copper or silicon oxide. Furthermore, direct measurements on freestanding graphene provide the means to discern the interplay between the vdW potential of graphene and its supporting substrate. Our results demonstrated that the underlying substrates could be controllably exploited to enhance or reduce the vdW force of graphene surfaces. We interpret the physical phenomena in terms of a Lifshitz theory-based analytical model.

Dynamic forces between emulsified water drops coated with Poly-Glycerol-Poly-Ricinoleate (PGPR) in canola oil

The dynamic collision of emulsified water drops in the presence of non-ionic surfactants plays a crucial role in many practical applications. Interaction force between water drops coated with non-ionic food grade surfactants is expected to exhibit rich dynamic behavior that is not yet explored. The collision forces between immobilized water drops in canola oil in the presence of a well-known food grade surfactant polyglycerol polyricinoleate (PGPR) are measured at concentrations well below typically used to form stable emulsions. An extension or kink, attributed to a short-range attractive interaction due to PGPR bridging between the drops, was observed in the retract portion of the force curves at higher applied forces or slower collision velocities. The Stokes-Reynolds-Young-Laplace (SRYL) model was used to calculate theoretical force curves. For higher collisions velocities, the agreement between the calculated and experiment data was acceptable, but the SRYL model failed to describe the extension or kink feature observed at slower velocities below. Both the AFM data and the comparison to the model calculation indicated the presence of a short-range attractive force, not of a hydrodynamic origin, attributed to the bridging and extension of PGPR molecules on the surface of water drops below saturation of the interface.

Phase behavior and bulk structural properties of a microphase former with anisotropic competing interactions: A density functional theory study.

Using classical density functional theory, we investigate systems exhibiting interactions where a short-range anisotropic attractive force competes with a long-range spherically symmetric repulsive force. The former is modelled within Wertheim's first-order perturbation theory for patchy particles, and the repulsive part is assumed to be a Yukawa potential which is taken into account via a mean-field approximation. From previous studies of systems with spherically symmetric competing interactions, it is well known that such systems can exhibit stable bulk cluster phases (microphase separation) provided that the repulsion is sufficiently weak compared to the attraction. For the present model system, we find rich phase diagrams including both reentrant clustering and liquid-gas binodals. In particular, the model predicts inhomogeneous bulk phases at extremely low packing fractions, which cannot be observed in systems with isotropic competing interactions.

Salt Triggers the Simple Coacervation of an Underwater Adhesive When Cations Meet Aromatic π Electrons in Seawater

Adhesive systems in many marine organisms are postulated to form complex coacervates (liquid-liquid phase separation) through a process involving oppositely charged polyelectrolytes. Despite this ubiquitous speculation, most well-characterized mussel adhesive proteins are cationic and polyphenolic, and the pursuit of the negatively charged proteins required for bulk complex coacervation formation internally remains elusive. In this study, we provide a clue for unraveling this paradox by showing the bulky fluid/fluid separation of a single cationic recombinant mussel foot protein, rmfp-1, with no additional anionic proteins or artificial molecules, that is triggered by a strong cation-π interaction in natural seawater conditions. With the similar condition of salt concentration at seawater level (>0.7 M), the electrostatic repulsion between positively charged residues of mfp-1 is screened significantly, whereas the strong cation-π interaction remains unaffected, which leads to the macroscopic phase separation (i.e., bulky coacervate formation). The single polyelectrolyte coacervate shows interesting mechanical properties including low friction, which facilitates the secretion process of the mussel. Our findings reveal that the cation-π interaction modulated by salt is a key mechanism in the mussel adhesion process, providing new insights into the basic understanding of wet adhesion, self-assembly processes, and biological phenomena that are mediated by strong short-range attractive forces in water.

Particle-level simulations of flocculation in a fiber suspension flowing through a diffuser

We investigate flocculation in dilute suspensions of rigid, straight fibers in a decelerating flow field of a diffuser. We carry out numerical studies using a particle-level simulation technique that takes into account the fiber inertia and the non-creeping fiber-flow interactions. The fluid flow is governed by the Reynolds-averaged Navier-Stokes equations with the standard k-omega eddy-viscosity turbulence model. A one-way coupling between the fibers and the flow is considered with a stochastic model for the fiber dispersion due to turbulence. The fibers interact through short-range attractive forces that cause them to aggregate into flocs when fiber-fiber collisions occur. We show that ballistic deflection of fibers greatly increases the flocculation in the diffuser. The inlet fiber kinematics and the fiber inertia are the main parameters that affect fiber flocculation in the prediffuser region.