Lorenzo Di Michele

Multistep kinetic self-assembly of DNA-coated colloids

Equilibrium self-assembly relies on the relaxation of disordered mixtures of building blocks towards an ordered ground state. The main drawback of this traditional approach lies in the kinetic traps that often interrupt the progression of the system towards equilibrium and lead to the formation of arrested phases. The latest techniques to control colloidal interactions open up the possibility of exploiting the tendency to dynamically arrest in order to construct amorphous materials with a specific morphology and local separation between multiple components. Here we propose strategies to direct the gelation of two-component colloidal mixtures by sequentially activating selective interactions. We investigate morphological changes in the structure of the arrested phases both by means of molecular dynamics simulations and experimentally by using DNA-coated colloids. Our approach can be exploited to assemble multicomponent mesoporous materials with possible applications in hybrid photovoltaics, photonics and drug delivery.

Arrested demixing opens route to bigels

Understanding and, ultimately, controlling the properties of amorphous materials is one of the key goals of material science. Among the different amorphous structures, a very important role is played by colloidal gels. It has been only recently understood that colloidal gels are the result of the interplay between phase separation and arrest. When short-ranged attractive colloids are quenched into the phase-separating region, density fluctuations are arrested and this results in ramified amorphous space-spanning structures that are capable of sustaining mechanical stress. We present a mechanism of aggregation through arrested demixing in binary colloidal mixtures, which leads to the formation of a yet unexplored class of materials––bigels. This material is obtained by tuning interspecies interactions. Using a computer model, we investigate the phase behavior and the structural properties of these bigels. We show the topological similarities and the geometrical differences between these binary, interpenetrating, arrested structures and their well-known monodisperse counterparts, colloidal gels. Our findings are supported by confocal microscopy experiments performed on mixtures of DNA-coated colloids. The mechanism of bigel formation is a generalization of arrested phase separation and is therefore universal.

Volume and porosity thermal regulation in lipid mesophases by coupling mobile ligands to soft membranes

Short DNA linkers are increasingly being exploited for driving-specific self-assembly of Brownian objects. DNA-functionalized colloids can assemble into ordered or amorphous materials with tailored morphology. Recently, the same approach has been applied to compliant units, including emulsion droplets and lipid vesicles. The liquid structure of these substrates introduces new degrees of freedom: the tethers can diffuse and rearrange, radically changing the physics of the interactions. Unlike droplets, vesicles are extremely deformable and DNA-mediated adhesion causes significant shape adjustments. We investigate experimentally the thermal response of pairs and networks of DNA-tethered liposomes and observe two intriguing and possibly useful collective properties: negative thermal expansion and tuneable porosity of the liposome networks. A model providing a thorough understanding of this unexpected phenomenon is developed, explaining the emergent properties out of the interplay between the temperature-dependent deformability of the vesicles and the DNA-mediated adhesive forces.

Effect of Inert Tails on the Thermodynamics of DNA Hybridization

The selective hybridization of DNA is of key importance for many practical applications such as gene detection and DNA-mediated self-assembly. These applications require a quantitative prediction of the hybridization free energy. Existing methods ignore the effects of non-complementary ssDNA tails beyond the first unpaired base. We use experiments and simulations to show that the binding strength of complementary ssDNA oligomers is altered by these sequences of non-complementary nucleotides. Even a small number of non-binding bases are enough to raise the hybridization free energy by approximately 1 kcal/mol at physiological salt concentrations. We propose a simple analytical expression that accounts quantitatively for this variation as a function of tail length and salt concentration.

Controlling Self-Assembly Kinetics of DNA-Functionalized Liposomes Using Toehold Exchange Mechanism

The selectivity of Watson-Crick base pairing has allowed the design of DNA-based functional materials bearing an unprecedented level of accuracy. Examples include DNA origami, made of tiles assembling into arbitrarily complex shapes, and DNA coated particles featuring rich phase behaviors. Frequently, the realization of conceptual DNA-nanotechnology designs has been hampered by the lack of strategies for effectively controlling relaxations. In this article, we address the problem of kinetic control on DNA-mediated interactions between Brownian objects. We design a kinetic pathway based on toehold-exchange mechanisms that enables rearrangement of DNA bonds without the need for thermal denaturation, and test it on suspensions of DNA-functionalized liposomes, demonstrating tunability of aggregation rates over more than 1 order of magnitude. While the possibility to design complex phase behaviors using DNA as a glue is already well recognized, our results demonstrate control also over the kinetics of such systems.

Detection and susceptibility measurements of a single Dynal bead

In this work we present detection and susceptibility measurement experiments on a single superparamagnetic Dynal bead with a diameter of 1 μm and a magnetic moment of ≈4×108μB. Accurate bead positioning was achieved via non-invasive AFM nanomanipulation. The detection and magnetic characterization of the bead were performed using ultra-sensitive InSb Hall devices. Single bead detection was demonstrated using a step-wise change of the dc magnetic field; measurements were performed using only the in-phase component of the total ac Hall voltage. Very clear evidence of the bead presence is demonstrated simultaneously with explicit separation of parasitic inductive signals. Additional experiments performed using a sweeping change of the dc field allowed susceptibility measurements of a single Dynal bead. The numerical outcomes of both sweeping and stepping experiments are in a very good agreement. The method presented here opens up new possibilities for the reliable and accurate detection of small magnetic mom...

Single particle detection: Phase control in submicron Hall sensors

We present a phase-sensitive ac-dc Hall magnetometry method which allows a clear and reliable separation of real and parasitic magnetic signals of a very small magnitude. High-sensitivity semiconductor-based Hall crosses are generally accepted as a preferential solution for non-invasive detection of superparamagnetic nanobeads used in molecular biology, nanomedicine, and nanochemistry. However, detection of such small beads is often hindered by inductive pick-up and other spurious signals. The present work demonstrates an unambiguous experimental route for detection of small magnetic moments and provides a simple theoretical background for it. The reliability of the method has been tested for a variety of InSb Hall sensors in the range 600 nm–5 μm. Complete characterization of empty devices, involving Hall coefficients and noise measurements, has been performed and detection of a single FePt bead with diameter of 140 nm and magnetic moment of μ≈108 μB has been achieved with a 600 nm-wide sensor.

Analytical theory of polymer-network-mediated interaction between colloidal particles

Nanostructured materials based on colloidal particles embedded in a polymer network are used in a variety of applications ranging from nanocomposite rubbers to organic-inorganic hybrid solar cells. Further, polymer-network-mediated colloidal interactions are highly relevant to biological studies whereby polymer hydrogels are commonly employed to probe the mechanical response of living cells, which can determine their biological function in physiological environments. The performance of nanomaterials crucially relies upon the spatial organization of the colloidal particles within the polymer network that depends, in turn, on the effective interactions between the particles in the medium. Existing models based on nonlocal equilibrium thermodynamics fail to clarify the nature of these interactions, precluding the way toward the rational design of polymer-composite materials. In this article, we present a predictive analytical theory of these interactions based on a coarse-grained model for polymer networks. We apply the theory to the case of colloids partially embedded in cross-linked polymer substrates and clarify the origin of attractive interactions recently observed experimentally. Monte Carlo simulation results that quantitatively confirm the theoretical predictions are also presented.

Interactions between Colloids Induced by a Soft Cross-Linked Polymer Substrate

Using videomicroscopy imaging, we demonstrate the existence of a short-ranged equilibrium attraction between heavy silica colloids diffusing on soft surfaces of cross-linked polymer gels. The intercolloid potential can be tuned by changing the gel stiffness or by coating the colloids with a polymer layer. On sufficiently soft substrates, the interaction induced by the polymer matrix leads to large-scale colloidal aggregation. We correlate the in-plane interaction with a colloid-surface attraction.

Communication: Free energy of ligand-receptor systems forming multimeric complexes

Ligand-receptor interactions are ubiquitous in biology and have become popular in materials in view of their applications to programmable self-assembly. Although complex functionalities often emerge from the simultaneous interaction of more than just two linker molecules, state of the art theoretical frameworks enable the calculation of the free energy only in systems featuring one-to-one ligand/receptor binding. In this Communication, we derive a general formula to calculate the free energy of systems featuring simultaneous direct interaction between an arbitrary number of linkers. To exemplify the potential and generality of our approach, we apply it to the systems recently introduced by Parolini et al. [ACS Nano 10, 2392 (2016)] and Halverson and Tkachenko [J. Chem. Phys. 144, 094903 (2016)], both featuring functionalized Brownian particles interacting via three-linker complexes.