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We explore the intricate dynamics of imbibition by a viscoelastic electrolyte within an arbitrarily oriented, nonuniform microcapillary, while under the stimulus of external electromagnetic fields and internal electroviscous forces stemming from streaming potential. The microcapillary walls are envisaged to be tapered relative to each other, with the entire system inclined with respect to the horizontal plane. The rheological behavior of the electrolyte is characterized using the Phan-Thien-Tanner (PTT) model. To manipulate the imbibition dynamics, external transverse magnetic and electric fields are imposed. Incorporating all contributing forces, we obtain semianalytical formulations for the velocity and shear stress distributions. We identify distinct stages during the imbibition process: (i) initial, (ii) filling, (iii) oscillatory, and (iv) stagnation stages. Moreover, we scrutinize the impact of four pivotal parameters, namely, the Weissenberg number (Wi), the Hartmann number (Ha), the transverse electric to viscous force (EVF) number ( S ), and the electric Reynolds number (Re e ), on the imbibition dynamics across different inclinations and taper angles. We also delineate the parameter space for these four parameters, identifying where the onset of oscillations occurs. Finally, through scaling analysis, we establish the existence of four distinct regimes corresponding to the aforementioned stages: (i) the linear regime, (ii) the Washburn regime, (iii) the oscillatory regime, and (iv) the equilibrium regime. Our findings are anticipated to enhance the understanding of capillary imbibition under such complex flow conditions and contribute significantly to the advancement of capillarity-driven microfluidic devices.

We probe the evaporation mechanisms of wettability-moderated, confined capillary bridges and bulges. For the first time, we explore the internal Marangoni hydrodynamics and external Stefan advection dynamics in the surrounding gaseous domain due to evaporative effects. A transient simulation approach based on the level set (LS) method and the Arbitrary Lagrangian-Eulerian (ALE) framework was adopted to computationally model the capillary bridge profiles and evaporation phenomenon with generic contact line dynamics (both CCR and CCA modes). The governing equations corresponding to the transport processes in both the liquid and gaseous domains are simulated in a fully coupled manner with appropriate boundary conditions to precisely trace the liquid-vapor interface and the three-phase contact point during evaporation. The effect of the bridge confinement phenomenon, i.e., the extent of confined ambient surrounding the liquid-vapor interface between the solid surfaces, is explored. Also, the role of wetting state and contact line dynamics during CCR and CCA modes of evaporation were probed, and good agreement with experimental observations was noted. Results show that the evaporation rate is primarily dictated by the confinement phenomenon, and wettability effects play a marginal role. A higher confinement curtails the evaporation rate due to an increased local vapor concentration around the liquid bridges. However, the wetting state substantially affects the internal Marangoni effect dynamics and the Stefan advection dynamics due to its explicit influence on the nonuniform evaporative flux along the liquid-vapor interface. Between superhydrophobic confinements, the contact lines are confined in the wedge-shaped region, thereby locally augmenting the vapor concentration. As a result, the large evaporative flux near the bulge region develops a higher temperature gradient, thereby inducing upscaled thermal Marangoni flow compared to hydrophilic confinements. These findings may have significant implications for the efficient designing and development of thermofluidic systems involving thermal transport, mixing, and deposition of dissolved particles in liquid bridges.

The development of novel protein-based therapeutics, such as monoclonal antibodies (mAbs), is often limited due to challenges associated with maintaining the stability of these formulations during manufacturing, storage, and clinical administration. An undesirable consequence of the instability of protein therapeutics is the formation of protein particles. MAbs can adsorb to interfaces and have the potential to undergo partial unfolding as well as to form viscoelastic gels. Further, the viscoelastic properties may be correlated with their aggregation potential. In this work, a passive microrheology technique was used to correlate the evolution of surface adsorption with the evolution of surface rheology of the National Institute of Standards and Technology (NIST) mAb reference material (NIST mAb) and interface-induced subvisible protein particle formation. The evolution of the surface adsorption and interfacial shear rheological properties of the NIST mAb was recorded in four formulation conditions: two different buffers (histidine vs phosphate-buffered saline) and two different pHs (6.0 and 7.6). Our results together demonstrate the existence of multiple stages for both surface adsorption and surface rheology, characterized by an induction period that appears to be purely viscous, followed by a sharp increase in protein molecules at the interface when the film rheology is viscoelastic and ultimately a slowdown in the surface adsorption that corresponds to the formation of solid-like or glassy films at the interface. When the transitions between the different stages occurred, they were dependent on the buffer/pH of the formulations. The onset of these transitions can also be correlated to the number of protein particles formed at the interface. Finally, the addition of polysorbate 80, an FDA-approved surfactant used to mitigate protein particle formation, led to the interface being surfactant-dominated, and the resulting interface remained purely viscous.

This study explores the thermal Marangoni hydrodynamics in an immiscible, binary-liquid thin-film system, which is open to the gas phase at the top and rests on a heated substrate with wavy topology. The sinusoidal contour of the heated (constant-temperature) substrate results in temperature gradients along the liquid-liquid and liquid-gas interfaces, causing fluctuations in the interfacial tension, ultimately leading to Marangoni hydrodynamics in the liquid-liquid films. This type of flow is notable in liquid film coatings on patterned surfaces, which are widely used in MEMS/NEMS applications (Weinstein, S. J.; Palmer, H. J. Liquid Film Coating: Scientific Principles and Their Technological Implications ; 1997, pp 19-62; Palacio, M.; Bhushan, B. Adv. Mater. 2008 , 20 , 1194-1198) and biological cell sorting operations (Witek, M. A.; Freed, I. M.; Soper, S. A. Anal. Chem. 2019 , 92 , 105-131). We solve the coupled Navier-Stokes and energy equations by the perturbation technique to obtain approximate analytical solutions and an understanding of the thermal and hydrodynamic transport in the system domain. Our study explores the parametric influence of the relative thermal conductivity of the liquid layers ( k ), film thickness ratio ( r ), and the system's Biot number ( Bi ) on these transport phenomena. While the strength of the thermal Marangoni effect that is generated reduces with an increase in the relative thermal conductivity ( k ), the impact of r depends on the k value. We observe that for k > 1 the intensity of Marangoni flow increases with r ; however, the opposite holds for k < 1. Furthermore, larger values of Bi induce higher resistance to the vertical conduction from the wavy substrate compared to the convection resistance offered at the top surface, destructively interfering with the ability of the patterned substrate to generate interfacial temperature fluctuations and hence weakening the Marangoni flow.

Droplets may rebound/levitate when deposited over a hot substrate (beyond a critical temperature) due to the formation of a stable vapor microcushion between the droplet and the substrate. This is known as the Leidenfrost phenomenon. In this article, we experimentally allow droplets to impact the hot surface with a certain velocity, and the temperature at which droplets show the onset of rebound with minimal spraying is known as the dynamic Leidenfrost temperature ( T DL ). Here we propose and validate a novel paradigm of augmenting the T DL by employing droplets with stable nanobubbles dispersed in the fluid. In this first-of-its-kind report, we show that the T DL can be delayed significantly by the aid of nanobubble-dispersed droplets. We explore the influence of the impact Weber number ( We ), the Ohnesorge number ( Oh ), and the role of nanobubble concentration on the T DL . At a fixed impact velocity, the T DL was noted to increase with the increase in nanobubble concentration and decrease with an increase in impact velocity for a particular nanobubble concentration. Finally, we elucidated the overall boiling behaviors of nanobubble-dispersed fluid droplets with the substrate temperature in the range of 150-400 °C against varied impact We through a detailed phase map. These findings may be useful for further exploration of the use of nanobubble-dispersed fluids in high heat flux and high-temperature-related problems and devices.

In this article, we propose, with the aid of detailed experiments and scaling analysis, the existence of magneto-elastic effects in the impact hydrodynamics of non-Newtonian ferrofluid droplets on superhydrophobic surfaces in the presence of a magnetic field. The effects of magnetic Bond number ( Bo m ), Weber number ( We ), polymer concentration, and magnetic nanoparticle (Fe 3 O 4 ) concentration in the ferrofluids were investigated. In comparison to Newtonian ferrofluid droplets, addition of polymers caused rebound suppression of the droplets relatively at lower Bo m for a fixed magnetic nanoparticle concentration and We . We further observed that for a fixed polymer concentration and We , increasing magnetic nanoparticle concentration also triggers earlier rebound suppression with increasing Bo m . In the absence of the magnetic nanoparticles, the non-Newtonian droplets do not show rebound suppression for the range of Bo m investigated. Likewise, the Newtonian ferrofluids show rebound suppression at large Bo m . This intriguing interplay of elastic effects of polymer chains and the magnetic nanoparticles, dubbed as the magneto-elastic effect, is noted to lead to the rebound suppression. We establish a scaling relationship to show that the rebound suppression is observed as a manifestation of the onset of magneto-elastic instability only when the proposed magnetic Weissenberg number ( Wi m ) exceeds unity. We also put forward a phase map to identify the various regimes of impact ferrohydrodynamics of such droplets and the occurrence of the magneto-elastic effect.

This article reports the hitherto unreported phenomenon of arrested evaporation dynamics in pendant droplets because of electric field stimulus. The evaporation kinetics of pendant droplets of electrically conducting saline solutions in the presence of a transverse, alternating electric field is investigated experimentally. While the increase of field strength reduces the evaporation rate, increment in field frequency has the opposite effect. The same has been explained on the solvation kinetics of ions in polar water. Theoretical analysis reveals that change in surface tension and the diffusion-driven evaporation model cannot predict the decelerated evaporation. With the aid of particle image velocimetry, suppression of internal circulation velocity within the droplet is observed under electric field stimulus, which directly affects the evaporation rate. A mathematical scaling model is proposed to quantify the effects of electrohydrodynamic circulation and electrothermal and electrosolutal advection on the evaporation kinetics. The analysis encompasses major governing parameters, namely, the thermal and solutal Marangoni numbers, the electrohydrodynamic number, the electro-Prandtl and electro-Schmidt numbers, and their respective contributions. It has been shown that the electrothermal Marangoni effect is suppressed by the electric field, leading to deteriorated evaporation rates. Additionally, the electrosolutal Marangoni effect further suppresses the internal advection, further reducing the evaporation rate by a larger proportion. Stability analysis reveals that the electric body force retards the stable internal advection. The stability mapping also illustrates that if the field strength is high enough for the electrosolutal advection to overshadow the solutal Marangoni effect completely, it can lead to improvement in evaporation rates.

Sessile droplets seated on superhydrophobic surfaces are known to exhibit internal circulation patterns. The present article experimentally demonstrates and theoretically confirms, for the very first time, that the nature and velocity of the internal circulation in sessile droplets seated on superhydrophobic surfaces are strongly governed by the curvature of the surface and its directionality. Sessile droplets were rested on concave and convex superhydrophobic surfaces, and both with one curvature (cylindrical) and two curvatures (spherical) and varying droplet diameter to curve diameters were studied. Particle image velocimetry (PIV) was employed for flow visualization and quantification. It was observed that increasing convexity of the surface leads to deterioration in the velocity of advection within the droplet, whereas increasing concavity of the surface augments the velocity of circulation. A scaling model based on the effective curvature-modulated change in wettability has been put forward to predict the phenomenon, but it was found to be weak in deducing the circulation velocities. Consequently, potential flow theory is employed and the curvatures are approximated as equivalent wedges, with the rested droplet engulfing the wedge partly. Based on the curvature of the surface, the equivalent included wedge angle is deduced. Flow theory over wedged structures is employed to deduce the changes in the internal velocity in the presence of curved surfaces. The spatiotemporally averaged experimental velocities are found to conform to predictions from the proposed model, and good agreement between the theoretical predictions and experimental observations is achieved. The present findings may have strong implications in thermofluidic transport phenomena or multiphase transport processes at the interfacial and/or microscale.

Lipid membranes, a major component of cells, are subjected to significant changes in pH depending on their location in the cell: the outer leaflet of the cell membrane is exposed to a pH of 7.4 whereas lipid membranes that make up late endosomes and lysosomes are exposed to a pH of as low as 4.4. The purpose of this study is to evaluate how changes in the environmental pH within cells alter the fluidity of phospholipid membranes. Specifically, we studied pH-induced alterations in the surface arrangement of monounsaturated lipids with zwitterionic headgroups (phosphoethanolamine (PE) and phosphocholine (PC)) that are abundant in plasma membranes as well as anionic lipids (phosphatidylserine (PS) and phosphatidylglycerol (PG)) that are abundant in inner membranes using a combination of techniques including surface tension vs area measurements, interfacial microrheology, and fluorescence/atomic force microscopy. Using an active interfacial microrheology technique, we find that phospholipids with zwitterionic headgroups show a significant increase in their surface viscosity at acidic pH. This increase in surface viscosity is also found to depend on the size of the lipid headgroup, with a smaller headgroup showing a greater increase in viscosity. The observed pH-induced increase in viscosity is also accompanied by an increase in the cohesion pressure between zwitterionic molecules at acidic pH and a decrease in the average molecular area of the lipids, as measured by fitting the surface pressure isotherms to well-established equations of state. Because fluorescent images show no change in the phase of the lipids, we attribute this change in surface viscosity to the pH-induced reorientation of the P - -N + dipoles that form part of the polar lipid headgroup, resulting in increased lipid-lipid interactions. Anionic PG headgroups do not demonstrate this pH-induced change in viscosity, suggesting that the presence of a net negative charge on the headgroup causes electrostatic repulsion between the headgroups. Our results also show that active interfacial microrheology is a sensitive technique for detecting minute changes in the lipid headgroup orientation induced by changes in the local membrane environment, even in unsaturated phospholipids where the surface viscosity is close to the experimental detection limit.

While a body of literature on the spreading dynamics of surfactants and a few studies on the spreading dynamics of nanocolloids exist, to the best of the authors' knowledge, there are no reports on the effect of presence of surfactants on the spreading dynamics of nanocolloidal suspensions. For the first time the present study reports an extensive experimental and theoretical study on the effect of surfactant impregnated nanocolloidal complex fluids in modulating the spreading dynamics. A segregation analysis of the effect of surfactants alone, nanoparticle alone, and the combined effect of nanoparticle and surfactants in altering the spreading dynamics have been studied in detail. The spreading dynamics of nanocolloidal solutions alone and of the surfactant impregnated nanocolloidal solutions are found to be grossly different, and particle morphology is found to play a predominant role. For the first time the present study experimentally proves that the classical Tanner's law is disobeyed by the complex fluids in the case of particle alone and combined particle and surfactant case. We also discuss the role of imbibitions across the particle wedge in the precursor film in tuning spreading dynamics. We propose an analytical model to predict the nature of dependency of contact radius on time for the complex colloids. A detailed theoretical examination of the governing factors, the interacting forces at the three phase contact line, and the effects of interplay of surfactants and the nanoparticles at the precursor film in modulating the spreading dynamics has been presented for such complex colloids.

Unlabelled: The dynamics of coalescence and consequent spreading of conducting polymer droplets on a solid substrate impacting at an offset are crucial in understanding the stability of inkjet printed patterns, which find application in organic flexible electronic devices. Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (, Pedot: PSS) dispersion in water is a widely used commercial conducting polymer for the fabrication of electron devices. The effects of droplet spacing, impact velocity, substrate hydrophilicity, polymer concentration, and charges on the coalescence of two sessile droplets have been experimentally investigated, and the characteristics of dynamic spreading during the coalescence process are determined through image processing. The equilibrium spreading length of the coalesced droplets decreases with concentration and spacing of the droplets, revealing the necessity of optimum fluid properties (viscosity and surface tension) for the stability of the desired pattern. The droplet's impact energy governs the maximum extent of spreading and receding dynamics, as the velocity gradients developed in polymer droplets during coalescence are a function of the inertia of the fluid elements. Hydrophilicity affects the maximum spreading extent but it has no influence on the equilibrium droplet diameter. The spreading length dynamics of charge-neutralized, Pedot: PSS is found similar to the charged droplets, which show that the charged nature of the polymer does not affect the coalescence behavior. Furthermore, different spreading regimes are identified and the governing forces in each regime are described using a semianalytical formulation derived for the coalescence of two droplets. The model has been found to accurately provide insight into the various mechanisms that play a role during the complex spreading event.

The focus of this work is to elucidate how phospholipid composition can modulate lipid nanoparticle interactions in phospholipid monolayer systems. We report on alterations in lipid domain formation induced by anionically engineered carbon nanodiamonds (ECNs) as a function of lipid headgroup charge and alkyl chain saturation. Using surface pressure vs area isotherms, monolayer compressibility, and fluorescence microscopy, we found that anionic ECNs induced domain shape alterations in zwitterionic phosphatidylcholine lipids, irrespective of the lipid alkyl chain saturation, even when the surface pressure vs area isotherms did not show any significant changes. Bean-shaped structures characteristic of dipalmitoylphosphatidylcholine (DPPC) were converted to multilobed, fractal, or spiral domains as a result of exposure to ECNs, indicating that ECNs lower the line tension between domains in the case of zwitterionic lipids. For membrane systems containing anionic phospholipids, ECN-induced changes in domain packing were related to the electrostatic interactions between the anionic ECNs and the anionic lipid headgroups, even when zwitterionic lipids are present in excess. By comparing the measured size distributions with our recently developed theory derived by minimizing the free energy associated with the domain energy and mixing entropy, we found that the change in line tension induced by anionic ECNs is dominated by the charge in the condensed lipid domains. Atomic force microscopy images of the transferred anionic films confirm that the location of the anionic ECNs in the lipid monolayers is also modulated by the charge on the condensed lipid domains. Because biological membranes such as lung surfactants contain both saturated and unsaturated phospholipids with different lipid headgroup charges, our results suggest that when studying potential adverse effects of nanoparticles on biological systems the role of lipid compositions cannot be neglected.

Noncovalently condensed complexes of genetic material, cell penetrating peptides (CPPs), and calcium chloride present a nonviral route to improve transfection efficiency of nucleic acids (e.g., pDNA and siRNA). However, the exact mechanisms of membrane insertion and delivery of macromolecule complexes to intracellular locations as well as their stability in the intracellular environment are not understood. We show that calcium condensed gene complexes containing different hydrophilic (i.e., dTAT, K9, R9, and RH9) and amphiphilic (i.e., RA9, RL9, and RW9) CPPs formed stable cationic complexes of hydrodynamic radii 100 nm at neutral pH. However, increasing the acidity caused the complexes to become neutral or anionic and increase in size. Using zwitterionic and anionic phospholipid monolayers as models that mimic the membrane composition of the outer leaflet of cell membranes and intracellular vesicles and pHs that mimic the intracellular environment, we study the membrane insertion potential of these seven gene complexes (CPP/pDNA/Ca(2+) complexes) into model membranes. At neutral pH, all gene complexes demonstrated the highest insertion potential into anionic phospholipid membranes, with complexes containing amphiphilic peptides showing the maximum insertion. However, at acidic pH, the gene complexes demonstrated maximum monolayer insertion into zwitterionic lipids, irrespective of the chemical composition of the CPP in the complexes. Our results suggest that in the neutral environment the complexes are unable to penetrate the zwitterionic lipid membranes but can penetrate through the anionic lipid membranes. However, the acidic pH mimicking the local environment in the late endosomes leads to a significant increase in adsorption of the complexes to zwitterionic lipid headgroups and decreases for anionic headgroups. These membrane-gene complex interactions may be responsible for the ability of the complexes to efficiently enter the intracellular environment through endocytosis and escape from the endosomes to effectively deliver their genetic payload.

Collagen microfibrils biomimetically intercalate graphitic structures in aqueous media to form graphene nanoplatelet-collagen complexes (G-Cl). Synthesized G-Cl-based stable, aqueous bionanocolloids exhibit anomalously augmented charge transportation capabilities oversimple collagen or graphene based colloids. The concentration tunable electrical transport properties of synthesized aqueous G-Cl bionanocolloids has been experimentally observed, theoretically analyzed, and mathematically modeled. A comprehensive approach to mathematically predict the electrical transport properties of simple graphene and collagen based colloids has been presented. A theoretical formulation to explain the augmented transport characteristics of the G-Cl bionanocolloids based on the physicochemical interactions among the two entities, as revealed from extensive characterizations of the G-Cl biocomplex, has also been proposed. Physical interactions between the zwitterionic amino acid molecules within the collagen triple helix with the polar water molecules and the delocalized π electrons of graphene and subsequent formation of partially charged entities has been found to be the crux mechanism behind the augmented transport phenomena. The analysis has been observed to accurately predict the degree of enhancement in transport of the concentration tunable composite colloids over the base colloids. The electrically active G-Cl bionanocolloids with concentration tunability promises find dual utility in novel gel bioelectrophoresis-based protein separation techniques and advanced surface charge modulated drug delivery using biocolloids.

Cell penetrating peptides (CPPs) have been established as excellent candidates for mediating drug delivery into cells. When designing synthetic CPPs for drug delivery applications, it is important to understand their ability to penetrate the cell membrane. In this paper, anionic or zwitterionic phospholipid monolayers at the air-water interface are used as model cell membranes to monitor the membrane insertion potential of synthetic CPPs. The insertion potential of CPPs having different cationic and hydrophobic amino acids were recorded using a Langmuir monolayer approach that records peptide adsorption to model membranes. Fluorescence microscopy was used to visualize alterations in phospholipid packing due to peptide insertion. All CPPs had the highest penetration potential in the presence of anionic phospholipids. In addition, two of three amphiphilic CPPs inserted into zwitterionic phospholipids, but none of the hydrophilic CPPs did. All the CPPs studied induced disruptions in phospholipid packing and domain morphology, which were most pronounced for amphiphilic CPPs. Overall, small changes to amino acids and peptide sequences resulted in dramatically different insertion potentials and membrane reorganization. Designers of synthetic CPPs for efficient intracellular drug delivery should consider small nuances in CPP electrostatic and hydrophobic properties.

We present a study of static and dynamic interfacial properties of self-assembled polyelectrolyte complex nanoparticles (size 110-120 nm) containing entrapped surfactant molecules at a fluid/fluid interface. Surface tension vs time measurements of an aqueous solution of these polyelectrolyte complex nanoparticles (PCNs) show a concentration-dependent biphasic adsorption to the air/water interface while interfacial microrheology data show a concentration-dependent initial increase in the surface viscosity (up to 10(-7) N·m/s), followed by a sharp decrease (10(-9) N·m/s). Direct visualization of the air/water interface shows disappearance of particles from the interface over time. On the basis of these observations, we propose that the PCNs at fluid/fluid interfaces exist in two states: initial accumulation of PCNs at the air/water interface as nanoparticles, followed by interface induced disassembly of the accumulated PCNs into their components. The lack of change in particle size, charge, and viscosity of the bulk aqueous solution of PCNs with time indicates that this disintegration of the self-assembled PCNs is an interfacial phenomenon. Changes in energy encountered by the PCNs at the interface lead to instability of the self-assembled system and dissociation into its components. Such systems can be used for applications requiring directed delivery and triggered release of entrapped surfactants or macromolecules at fluid/fluid interfaces.