arXiv subjects

Madhavi Krishnan

Publications and source records attributed to Madhavi Krishnan.

8 recordsLinked to original sources

arXiv2026

Interparticle Interactions in Nonlocal Media: Attraction and Repulsion from Charge-Polarization Coupling

Recent measurements of microsphere interactions in diverse media suggest that the standard dielectric-continuum models of solution-phase interactions are fundamentally incomplete. Experiments indicate that the interactions of charged particles in liquids can be dominated by solvent structuring at interfaces, thereby motivating the concept of electrosolvation. While interfacial spectroscopy and molecular simulations have established that solvent molecules can exhibit net orientation at interfaces, conventional theoretical frameworks treat the fluid as a structureless medium described by a constant dielectric permittivity. This view does not envisage a contribution of interfacial polarization to interactions at longer range. Here, we employ nonlocal dielectric theory accounting for spatial correlations in polarization to describe interactions in solution. This model permits both charge and polarization to govern interactions, leading to dramatic departures from classical expectations. Specifically, the balance between charge and polarization generates a framework of symmetric (repulsive) and antisymmetric (attractive) interactions, wherein: (i) like-charged surfaces can attract at long range, (ii) oppositely charged objects can repel, and (iii) neutral matter can acquire effective electrical mobility and display long-range forces-potentially explaining long-range hydrophobic attraction. Further, like-charged biomolecules can attract in aqueous electrolytes even for modest polarization correlation lengths ($ξ=2$ Å). Our results also suggest that electrosolvation effects may underpin flocculation in suspended matter, which has traditionally been attributed to attractive dispersion forces. These findings indicate how solvent structuring and correlations may play a dominant, complex role in fluid-phase physics.

cond-mat.soft↗

arXiv2026

Direct measurement of the attractive electrosolvation force between a pair of colloidal particles

In solution, electrically like-charged particles can experience a strong and long-ranged attraction that leads to the formation of stable, slowly reorganizing clusters. The attractive force underpinning this spontaneous organization process has been shown to depend on both the sign of charge of the particle and the nature of the solvent medium. The origin of the attraction has been ascribed to the preferential orientation of solvent molecules at the object-electrolyte interface. Here, we use optical imaging to directly measure the spatial profile of the potential of mean force between isolated pairs of charged microspheres. Working with particles carrying a variety of surface chemistries we find that the range of the electrosolvation attraction is substantially longer than previously held. In particular we show that particles carrying strongly anionic surface coatings composed of DNA or phospholipid bilayers display long-range attraction. We further find that the length scale governing the decay of the attractive force can depend on the properties of the interacting particles. This contrasts with the canonical expectation that the screening length governing the interaction of charged particles in solution depends exclusively on the properties of the intervening electrolyte medium. The observations point to significant departures from current thinking, and the likely need for a model of interactions that accounts for the molecular nature of the solvent, its interfacial behaviour, and spatial correlations. Finally, a strong and long-ranged attraction mediated by anionic matter constituting lipid membranes and chromatin could carry far-reaching implications for biological organization and structure formation.

cond-mat.soft↗

arXiv2025

Measurements of molecular size and shape on a chip

Size and shape are critical discriminators between molecular species and states. We describe a micro-chip based high-throughput imaging approach offering rapid and precise determination of molecular properties under native solution conditions. Our method detects differences in molecular weight across at least three orders of magnitude, and down to two carbon atoms in small molecules. We quantify the strength of molecular interactions over six orders of magnitude in affinity constant, and track reactions in real-time. Highly parallel measurements on individual molecules serve to characterize sample-state heterogeneity at the highest resolution, offering predictive input to model three-dimensional structure. We further leverage the method's structural sensitivity for diagnostics, exploiting ligand-induced conformational changes in the insulin receptor to sense insulin concentration in serum at the sub-nanoliter and sub-zeptomole scale.

physics.bio-ph↗

arXiv2025

Chemical control of self-assembly by the electrosolvation force

Self-assembly of matter in solution generally relies on attractive interactions that overcome entropy and drive the formation of higher-order molecular and particulate structures. Such interactions play key roles in a variety of contexts, e.g., crystallisation, biomolecular folding and condensation, pathological protein aggregation, pharmaceuticals and fine chemicals. The electrosolvation force entails a new conceptual paradigm in the known palette of interactions that drive the spontaneous accretion and organisation of matter. However, an understanding of the underlying physical chemistry, and therefore the ability to exert control over and tune the interaction, remains incomplete. Here we demonstrate that this force arises from the structure of the interfacial electrolyte. Neutral molecules such as a different solvent, osmolytes or surfactants, can - even at very low concentrations in the medium - disrupt or reinforce pre-existing interfacial solvent structure, thereby furnishing unanticipated chemical tuning of the ability of matter to self-assemble. The observations further present unexpected mechanistic elements that may explain the impact of co-solvents and osmolytes on protein structure, stability and pathological protein condensation. Our findings shed new light on microscopic mechanisms that drive the emergence of order and structure from molecular to macroscopic scales in the solution phase.

cond-mat.soft↗

arXiv2025

Surface polarization strongly influences electrostatics in a nonlocal medium

Electrostatics in the solution phase is governed by free electrical charges such as ions, as well as by bound charges that arise when a polarizable medium responds to an applied field. In a local medium, described by a constant dielectric permittivity, the sign of the far-field electrostatic potential distribution around an object is governed by its electrical charge. We demonstrate significant departures from this expectation in a nonlocal medium characterized by a wave vector-dependent dielectric function. Here, surface polarization due to the solvent, or indeed non-solvent dipoles, may wield significant influence at large distances. The polarization correlation length may not only significantly augment the effective screening length, but we also show that the electrical contribution from polarization can compete with and even invert the sign of the electrical potential and the field arising from charge alone. These results hold ramifications for a range of apparently anomalous electrically governed observations such as underscreening, electrophoretic mobilities of charge-neutral objects, and long-ranged attraction between like-charged entities in water and other solvents.

cond-mat.soft↗

arXiv2022

A charge dependent long-ranged force drives tailored assembly of matter in solution

The interaction between charged objects in solution is generally expected to recapitulate two central principles of electromagnetics: (i) like-charged objects repel, and (ii) they do so regardless of the sign of their electrical charge. Here we demonstrate experimentally that the solvent plays a hitherto unforeseen but crucial role in interparticle interactions, and importantly, that interactions in the fluid phase can break charge-reversal symmetry. We show that in aqueous solution, negatively charged particles can attract at long range while positively charged particles repel. In solvents that exhibit an inversion of the net molecular dipole at an interface, such as alcohols, we find that the converse can be true: positively charged particles may attract whereas negatives repel. The observations hold across a wide variety of surface chemistries: from inorganic silica and polymeric particles to polyelectrolyte- and polypeptide-coated surfaces in aqueous solution. A theory of interparticle interactions that invokes solvation at an interface explains the observations. Our study establishes a specific and unanticipated mechanism by which the molecular solvent may give rise to a strong and long-ranged force in solution, with immediate ramifications for a variety of particulate and molecular processes including tailored self-assembly, gelation and crystallization, as well as biomolecular condensation, coacervation and phase segregation. These findings also shed light on the solvent-induced interfacial electrical potential - an elusive quantity in electrochemistry and interface science implicated in many natural and technological processes, such as atmospheric chemical reactions, electrochemical energy storage and conversion, and the conduction of ions across cell membranes.

cond-mat.soft↗

arXiv2019

Interfacial solvation explains attraction between like-charged objects in aqueous solution

Over the past few decades the experimental literature has consistently reported observations of attraction between like-charged colloidal particles and macromolecules in solution. Examples include nucleic acids and colloidal particles in bulk solution and under confinement, and biological liquid-liquid phase separation. This observation is at odds with the intuitive expectation of an interparticle repulsion that decays monotonically with distance. Although attraction between like-charged particles can be theoretically rationalised in the strong-coupling regime, for example, in the presence of multivalent counterions, recurring accounts of long-range attraction in aqueous solution containing monovalent ions at low ionic strength have posed an open conundrum. Here we show that the behaviour of molecular water at an interface - traditionally disregarded in the continuum electrostatics picture, provides a mechanism to explain attraction between like-charged objects in a broad spectrum of experiments. This basic principle will have important ramifications in the ongoing quest to better understand intermolecular interactions in solution.

cond-mat.soft↗

arXiv2008

Comment on `Nanoconfinement-enhanced conformational response of single DNA molecules to changes in ionic environment'

In the present Comment we show that, contrary to the recent findings of Reisner et al. [Phys. Rev. Lett. 99, 058302 (2007)], the excluded volume effect does not play an important role in determining DNA behavior in nanochannels at low ionic strength. We argue that the DNA extension data are described very well without the notion of an effective polymer width using the entropic depletion theory due to Odijk.

cond-mat.soft↗