The authors review recent advances in the physics of strongly interacting charged systems functioning in water at room temperature. In these systems, many phenomena go beyond the framework of mean-field theories, whether linear Debye-Hückel or nonlinear Poisson-Boltzmann, culminating in charge inversion—a counterintuitive phenomenon in which a strongly charged particle, called a macroion, binds so many counterions that its net charge changes sign. The review discusses the universal theory of charge inversion based on the idea of a strongly correlated liquid of adsorbed counterions, similar to a Wigner crystal. This theory has a vast array of applications, particularly in biology and chemistry; for example, in the presence of positive multivalent ions (e.g., polycations), the DNA double helix acquires a net positive charge and drifts as a positive particle in an electric field. This simplifies DNA uptake by the cell as needed for gene therapy, because the cell membrane is negatively charged. Analogies of charge inversion to other fields of physics are also discussed.

A theory of condensation and resolubilization of a dilute DNA solution with growing concentration of multivalent cations, $\mathrm{N,}$ is suggested. It is based on a new theory of screening of a macroion by multivalent cations, which shows that due to strong cation correlations at the surface of DNA the net charge of DNA changes sign at some small concentration of cations $N_0.$ DNA condensation takes place in the vicinity of $N_0,$ where absolute value of the DNA net charge is small and the correlation induced short range attraction dominates the Coulomb repulsion. At ${\mathrm{N>N}}_0$ positive DNA should move in the opposite direction in an electrophoresis experiment. From comparison of our theory with experimental values of condensation and resolubilization thresholds for DNA solution containing ${\mathrm{Spe}}^{\mathrm{4+}},$ we obtain that $N_0\text{=3.2\hspace{0.05em}}\mathrm{mM}$ and that the energy of DNA condensation per nucleotide is ${\text{0.07\hspace{0.5em}k}}_B\mathrm{T.}$

Screening of a macroion such as a charged solid particle, a charged membrane, double helix DNA, or actin by multivalent counterions is considered. Small colloidal particles, charged micelles, short or long polyelectrolytes can play the role of multivalent counterions. Due to strong lateral repulsion at the surface of the macroion such multivalent counterions form a strongly-correlated liquid, with the short-range order resembling that of a Wigner crystal. These correlations create additional binding of multivalent counterions to the macroion surface with binding energy larger than kBT. As a result even for a moderate concentration of multivalent counterions in the solution, their total charge at the surface of the macroion exceeds the bare macroion charge in absolute value. Therefore, the net charge of the macroion inverts its sign. In the presence of a high concentration of monovalent salt the absolute value of inverted charge can be larger than the bare one. This strong inversion of charge can be observed by electrophoresis or by direct counting of multivalent counterions.

Screening of a strongly charged macroion by oppositely charged colloidal particles, micelles, or short polyelectrolytes is considered. Because of strong lateral repulsion such multivalent counterions form a strongly correlated liquid at the surface of the macroion. This liquid provides correlation-induced attraction of multivalent counterions to the macroion surface. As a result even a moderate concentration of multivalent counterions in the solution inverts the sign of the net macroion charge. We show that at high concentration of monovalent salt the absolute value of inverted charge can be larger than the bare one. This giant inversion of charge can be observed in electrophoresis.

Complexation of a long flexible polyelectrolyte (PE) molecule with oppositely charged spherical particles such as colloids, micelles, or globular proteins in a salty water solution is studied. PE binds spheres winding around them, while spheres repel each other and form almost periodic necklace. If the total charge of PE in the solution is larger than total charge of spheres, repulsive correlations of PE turns on a sphere lead to inversion of the net charge of each sphere. In the opposite case when the total charge of spheres is larger, we predict another correlation effect; spheres bind to the PE in such a great number that they invert the charge of the PE. The inverted charge by absolute value can be larger than the bare charge of PE even when screening by monovalent salt is weak. At larger concentrations of monovalent salt, the inverted charge can reach giant proportions. Near the isoelectric point where total charges of spheres and PE are equal, necklaces condense into macroscopic bundles. Our theory is in qualitative agreement with recent experiments on micelles–PE systems.