Competition between Self-Assembly and Phase Separation Governs High-Temperature Condensation of a DNA Liquid.

In many biopolymer solutions, attractive interactions that stabilize finite-sized clusters at low concentrations also promote phase separation at high concentrations. Here we study a model biopolymer system that exhibits the opposite behavior, whereby self-assembly of DNA oligonucleotides into finite-sized, stoichiometric clusters tends to inhibit phase separation. We first use microfluidics-based experiments to map a novel phase transition in which the oligonucleotides condense as the temperature increases at high concentrations of divalent cations. We then show that a theoretical model of competition between self-assembly and phase separation quantitatively predicts changes in experimental phase diagrams arising from DNA sequence perturbations. Our results point to a general mechanism by which self-assembly shapes phase boundaries in complex biopolymer solutions.

Physics of self-assembly and morpho-topological changes of Klebsiella pneumoniae in desiccating sessile droplets.

HYPOTHESIS: The bacteria suspended in pure water self-assemble into unique patterns depending on bacteria-bacteria, bacteria-substrate and bacteria-liquid interactions. The physical forces acting on bacteria vary based on their respective spatial location inside the droplet cause an assorted magnitude of physical stress. The shear and dehydration induced stress on pathogens(bacteria) in drying bio-fluid droplets alters the viability and infectivity. EXPERIMENTS: We have investigated the flow and desiccation-driven self-assembly of Klebsiella pneumoniae in the naturally evaporating sessile droplets. Klebsiella pneumoniae exhibits extensive changes in its morphology and forms unique patterns as the droplet dries, revealing hitherto unexplored rich physics governing its survival and infection strategies. Self-assembly of bacteria at the droplet contact line is characterized by order-to-disorder packing transitions with high packing densities and excessive deformations (analysed using scanning electron microscopy and atomic force microscopy). In contrast, thin-film instability-led hole formation at the center of the droplet engenders spatial packing of bacteria analogous to honeycomb weathering. FINDINGS: Self-assembly favors the bacteria at the rim of the droplet, leading to enhanced viability and pathogenesis on the famously known "coffee ring" of the droplet compared to the bacteria present at the center of the droplet residue. Mechanistic insights gained via our study can have far-reaching implications for bacterial infection through droplets, e.g., through open wounds.

Malleable Patterns from the Evaporation of a Colloidal Liquid Bridge: Coffee Ring to the Scallop Shell.

The present article highlights an approach to generating contrasting patterns from drying colloidal droplets in a liquid bridge configuration, different from well-known coffee rings. Reduction of the confinement distance (the gap between the solid surfaces) leads to systematized nanoparticle agglomeration yielding spoke-like patterns similar to those found on scallop shells instead of circumferential edge deposition. Alteration of the confinement distance modulates the curvature that entails variations in the evaporation flux across the liquid-vapor interface. Consequently, flow inside different liquid bridges (LBs) varies significantly for different confinement distance. Small confinement distance results in the stick-slip motion of squeezed liquid bridges. On the contrary, the stretched LBs exhibit pinned contact lines. The confinement distance determines the characteristic length scales of the thin film formed near the contact line, and its theoretical estimations are validated against the experimental observations using reflection interferometry, further exhibiting good agreement (in order of magnitude). We decipher a proposition that a drying liquid thin film (height ∼ O(10-7)m) present during dewetting near the three-phase contact line is responsible for the aligned deposition of particles. The coupled interplay of contact line dynamics, evaporation induced advection, and dewetting of the thin film at a three-phase interface contributes to the differences in deposition patterns.

Multiscale vapor-mediateddendritic pattern formation and bacterial aggregation in complex respiratory biofluid droplets.

HYPOTHESIS: Deposits of biofluid droplets on surfaces (such as respiratory droplets formed during an expiratory) are composed of water-based salt-protein solution that may also contain an infection (bacterial/viral). The final patterns of the deposit formed and bacterial aggregation on the deposits are dictated by the fluid composition and flow dynamics within the droplet. EXPERIMENTS: This work reports the spatio-temporal, topological regulation of deposits of respiratory fluid droplets and control of bacterial aggregation by tweaking flow inside droplets using non-contact vapor-mediated interactions. Desiccated respiratory droplets form deposits with haphazard multiscale dendritic, cruciform-shaped precipitates when evaporated on a glass substrate. However, we showcase that short and long-range vapor-mediated interaction between the droplets can be used as a tool to control these deposits at nano-micro-millimeter scales. We morphologically control hierarchial dendrite size, orientation and subsequently suppress cruciform-shaped crystals by placing a droplet of ethanol in the vicinity of the biofluid droplet. Active living matter in respiratory fluids like bacteria is preferentially segregated and agglomerated without its viability and pathogenesis attenuation. FINDINGS: The nucleation sites can be controlled via preferential transfer of solutes in the droplets; thus, achieving control over crystal occurrence, growth dynamics, and the final topology of the deposit. For the first time, we have experimentally presented a proof-of-concept to control the aggregation of live active matter like bacteria without any direct contact. The methodology can have ramifications in biomedical applications like disease detection and bacterial segregation.

Spatio-temporal modulation of self-assembled central aggregates of buoyant colloids in sessile droplets using vapor mediated interactions.

A functional sessile droplet containing buoyant colloids (ubiquitous in applications like chemical sensors, drug delivery systems, and nanoreactors) forms self-assembled aggregates. The particles initially dispersed over the entire drop-flocculates at the center. We attribute the formation of such aggregates to the finite radius of curvature of the drop and the buoyant nature of particles. Initially, larger particles rise to the top of the droplet (due to higher buoyancy force), and later the smaller particles join the league, leading to the graded size distribution of the central aggregate. This can be used to segregate polydisperse hollow spheres based on size. The proposed scaling analysis unveils insights into the distinctive particle transport during evaporation. However, the formation of prominent aggregates can be detrimental in applications like spray painting, sprinkling of pesticides, washing, coating, lubrication, etc. One way to avoid the central aggregate is to spread the droplets completely (contact angle ~ 00), thus theoretically creating an infinite radius of curvature leading to uniform deposition of buoyant particles. Practically, this requires a highly hydrophilic surface, and even a small inhomogeneity on the surface would pin the droplet giving it a finite radius of curvature. Here, we demonstrate using non-intrusive vapor mediated Marangoni convection (Velocity scale ~ O(103) higher than the evaporation-driven convection) can be vital to an efficient and on-demand manipulation of the suspended micro-objects. The interplay of surface tension and buoyancy force results in the transformation of flow inside the droplet leads to spatiotemporal disbanding of agglomeration at the center of the droplet.

Enhancement of mixing in a viscous, non-volatile droplet using a contact-free vapor-mediated interaction.

Mixing at small fluidic length scales is especially challenging in viscous and non-volatile droplets frequently encountered in bio-chemical assays. In situ methods of mixing, which depend on diffusion or evaporation-driven capillary flow, are typically slow and inefficient, while thermal or electro-capillary methods that are either complicated to implement or may cause sample denaturing. This article demonstrates an enhanced mixing timescale in a sessile droplet of glycerol by simply introducing a droplet of ethanol in its near vicinity. The fast evaporation of ethanol introduces molecules in the proximity of the glycerol droplet, which are preferentially adsorbed (more on the side closer to ethanol) creating a gradient of surface tension driving the Marangoni convection in the droplet. We conclusively show that for the given volume of the droplet, the mixing time reduces by ∼10 hours due to the vapour-mediated Marangoni convection. Simple scaling arguments are used to predict the enhancement of the mixing timescale. Experimental evidence obtained from fluorescence imaging is used to quantify mixing and validate the analytical results. This is the first proof of concept of enhanced mixing in a viscous, sessile droplet using the vapour mediation technique.

Controlling self-assembly and buckling in nano fluid droplets through vapour mediated interaction of adjacent droplets.

HYPOTHESIS: Sessile droplets of contrasting volatilities can communicate via long range (∼O (1) mm) vapour-mediated interactions which allow the remote control of the flow driven self-assembly of nanoparticles in the drop of lower volatility. This allows morphological control of the buckling instability observed in evaporating nanofluid droplets. EXPERIMENTS: A nanofluid droplet is dispensed adjacent to an ethanol droplet. Asymmetrical adsorption induced Marangoni flow (∼O (1) mm/s) internally segregates the particle population. Particle aggregation occurs preferentially on one side of the droplet leaving the other side to develop a relatively weaker shell which buckles under the effect of evaporation driven capillary pressure. FINDINGS: The inter-droplet distance is varied to demonstrate the effect on the precipitate shape (flatter to dome shaped) and the location of the buckling (top to side). In addition to being a simple template for hierarchical self-assembly, the presented exposition also promises to enhance mixing rates (∼1000 times) in droplet-based bioassays with minimal contamination.