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In this paper, we report a new synthetic procedure to immobilize a transfer hydrogenation catalyst on the surface of colloidal polystyrene particles. Using supports of colloidal dimensions allows for combining a relatively high surface area for catalyst binding, mobility of the catalyst, and facile recovery by centrifugation or sedimentation. The immobilization procedure relies on the covalent attachment of terpyridine moieties on the particle surface. These immobilized terpyridines are subsequently employed as colloidal ligands, which participate in the formation of an active ruthenium-based transfer hydrogenation catalyst. The resulting functional colloidal particles successfully catalyze the transfer hydrogenation of acetophenone with 2-propanol as the hydrogen donor. Thorough analysis of the chemical composition of the colloidal surface led to the determination of the catalyst loading per particle. This enabled us to conduct reference hydrogenations with equal concentrations of the homogeneous transfer hydrogenation catalyst to probe the effect of the immobilization procedure on the catalytic activity. Despite a decrease in transfer hydrogenation activity, full acetophenone conversion is still achievable within 24 h. Preliminary experiments show that the catalytic colloids are recyclable without significant loss of transfer hydrogenation activity.

International audience; Individual regulatory proteins are typically charged with the simultaneous regulation of a battery of different genes. As a result, when one of these proteins is limiting, competitive effects have a significant impact on the transcriptional response of the regulated genes. Here we present a general framework for the analysis of any generic regulatory architecture that accounts for the competitive effects of the regulatory environment by isolating these effects into an effective concentration parameter. These predictions are formulated using the grand-canonical ensemble of statistical mechanics and the fold-change in gene expression is predicted as a function of the number of transcription factors, the strength of interactions between the transcription factors and their DNA binding sites, and the effective concentration of the transcription factor. The effective concentration is set by the transcription factor interactions with competing binding sites within the cell and is determined self-consistently. Using this approach, we analyze regulatory architectures in the grand-canonical ensemble ranging from simple repression and simple activation to scenarios that include repression mediated by DNA looping of distal regulatory sites. It is demonstrated that all the canonical expressions previously derived in the case of an isolated, non-competing gene, can be generalised by a simple substitution to their grand canonical counterpart, which allows for simple intuitive incorporation of the influence of multiple competing transcription factor binding sites. As an example of the strength of this approach, we build on these results to present an analytical description of transcriptional regulation of the lac operon

Chemically anisotropic dumbbell-shaped colloids are prepared starting from cross-linked polymer seed particles coated with a chlorinated outer layer. These chlorinated seeds are swollen with monomer. Subsequently, a liquid protrusion is formed on the surface of the seed particle by phase separation between the monomer and the swollen polymer network. Solidification of these liquid lobes by polymerization leads to the desired dumbbell-shaped colloids. The chlorine groups remain confined on the seed lobe of the particles, ensuring chemical anisotropy of the resulting particles. Exploiting the asymmetric distribution of the chemically reactive surface chlorine groups allows for site-specific surface modifications. Here we show that the geometry of the resulting chemically anisotropic dumbbells can be systematically tuned by a number of experimental parameters including the volume of styrene by which the seeds are swollen, the cross-link density of the chlorinated seeds and chemical composition/thickness of the chlorinated coating deposited on the seed particles. Being able to control the particle geometry, and therefore the Janus balance of these chemically anisotropic particles, provides a promising starting point for the synthesis of sophisticated building blocks for future (self-assembly) studies.

Virus coat proteins spontaneously self-assemble into empty shells in aqueous solution under the appropriate physicochemical conditions, driven by an interaction free energy per bond on the order of 2-5 times the thermal energy kBT. For this seemingly modest interaction strength, each protein building block nonetheless gains a very large binding free energy, between 10 and 20 kBT. Because of this, there is debate about whether the assembly process is reversible or irreversible. Here we discuss capsid polymorphism observed in in vitro experiments from the perspective of nucleation theory and of the thermodynamics of mass action. We specifically consider the potential contribution of a curvature free energy term to the effective interaction potential between the proteins. From these models, we propose experiments that may conclusively reveal whether virus capsid assembly into a mixture of polymorphs is a reversible or an irreversible process.

In colloids with competing short-range attractions and long-range repulsions, microcrystalline gels are experimentally formed under conditions where computer simulations point to a lamellar phase as the ground state. Here, upon applying a low-frequency alternating electric field, we bring the system from an initial gel state to a columnar-like state. While molecular dynamics simulations on monodisperse colloids reveal that a columnar structure spontaneously evolves towards a lamellar phase, the columnar-like state in experiments relaxes back to the initial disordered gel state once the electric field is switched off. Similarly, a columnar phase in molecular dynamics simulations decomposes into finite-size crystalline clusters as the relative polydispersity of the colloids is around 1.0%. We conclude that the experimentally observed melting of the columnar structure is driven by polydispersity. Moreover, further simulations reveal that the critical polydispersity required to destabilize a long-range ordered structure increases with the attraction range, pointing to the possibility of observing periodic structures in experiments if the attraction range is sufficiently long compared to the polydispersity of the colloids.

Anisotropic and binary colloids self-assemble into a variety of novel supracolloidal structures within the thermo-switchable confinement of molecular microtubes, achieving structuring at multiple length scales and dimensionalities. The multistage self-assembly strategy involving hard colloidal particles and a soft supramolecular template is generic for colloids with different geometries and materials as well as their binary mixtures. The colloidal architectures can be controlled by colloid shape, size, and concentration. Colloidal cubes align in chains with face-to-face arrangement, whereas rod-like colloids predominantly self-organize in end-to-end configurations with their long axis parallel with the long axis of the microtubes. The 1D microconfinement imposed on binary mixtures of anisotropic and isotropic colloids further increases the diversity of colloid-in-tube structures. In cube-sphere mixtures, cubes may act as additional confiners, locking in colloidal sphere chains, while a "colloidal Morse code" is generated where rods and spheres alternate in the case of rod-sphere mixtures. The versatile confined colloidal superstructures including their thermoresponsive assembly and disassembly are relevant for the development of stimulus-responsive materials where controlled release and encapsulation are desired. The hierarchical self-assembly of shape-anisotropic colloids and their binary mixtures with isotropic colloids in 1D microconfinement yields a rich variety of novel supracolloidal architectures. The thermo-switchable co-assembly of molecular microtubes and colloidal superstructures is generic for colloids with different geometries, materials, and sizes and may open new routes for controlled release, encapsulation, and data storage applications.