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DNA hybridization onto DNA-functionalized nanoparticle surfaces (e.g., in the form of a spherical nucleic acid (SNA)) is known to be enhanced relative to hybridization free in solution. Surprisingly, via isothermal titration calorimetry, we reveal that this enhancement is enthalpically, as opposed to entropically, dominated by ~20 kcal/mol. Coarse-grained molecular dynamics simulations suggest that the observed enthalpic enhancement results from structurally confining the DNA on the nanoparticle surface and preventing it from adopting enthalpically unfavorable conformations like those observed in the solution case. The idea that structural confinement leads to the formation of energetically more stable duplexes is evaluated by decreasing the degree of confinement a duplex experiences on the nanoparticle surface. Both experiment and simulation confirm that when the surface-bound duplex is less confined, i.e., at lower DNA surface density or at greater distance from the nanoparticle surface, its enthalpy of formation approaches the less favorable enthalpy of duplex formation for the linear strand in solution. This work provides insight into one of the most important and enabling properties of SNAs and will inform the design of materials that rely on the thermodynamics of hybridization onto DNA-functionalized surfaces, including diagnostic probes and therapeutic agents.

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Spontaneous pattern formation plays an important role in a wide variety of natural phenomena and materials systems. A key ingredient for the occurrence of modulated phases is the presence of competing interactions, generally of different physical origins. We demonstrate that in dipolar films, a prototypical system for pattern formation, patterns can be induced by dielectric effects alone. A rich phase diagram arises, where striped and circular morphologies emerge with geometric properties that can be controlled through variation of particle shape and substrate permittivity or permeability. These effects are particularly enhanced by metamaterial substrates.

In this study, we have investigated the fluctuations of particle motion, i.e. the non-affine motion, during the avalanche process, discovering a rich dynamic from the microscopic to the macroscopic scales. We find that there is a strong correlation between the magnitude of the velocity fluctuation and the velocity magnitude in the spatial and temporal domains. The possible connection between this finding and the theory of the shear transformation zones is discussed based on the direct measurement of the T1 events. In addition, the velocity magnitude of the system and the stress fluctuations of the system are strongly temporally correlated. Our finding will pose challenges to the development of more rigorous theories to describe avalanche dynamics based on the microscopic approach. Moreover, our finding presents a plausible mechanism of particle entrainment in a simple system.