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Abstract The interaction between charged objects in solution is generally expected to recapitulate two central principles of electromagnetics: (1) like-charged objects repel, and (2) 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 solvent structuring at an interface captures the observations. Our study establishes a nanoscopic interfacial mechanism by which solvent molecules may give rise to a strong and long-ranged force in solution, with immediate ramifications for a range of particulate and molecular processes across length scales such as self-assembly, gelation and crystallization, biomolecular condensation, coacervation, and phase segregation.
Wang et al. (Fri,) studied this question.