Dispersions of Monodisperse Hybrid Rod-Like Particles by Mineralization of Filamentous Viruses

In this work, we report on the synthesis through a direct chemical approach of hybrid organic/inorganic rod-like particles with a very high aspect ratio (length/diameter) by the use of a biotemplate, the fd virus. A synthetic route is proposed based on an initial step of steric stabilization of the colloidal template by hydrophilic polymer grafting. Thanks to this polymer functionalization, the filamentous viruses are well-dispersed in solution during their mineralization by different inorganic salts, leading to suspensions of individual hybrid rod-like particles such as virus/SiO₂ and virus/TiO₂. This aqueous solution based approach is shown to be highly reproducible, scalable for large production synthesis, and versatile to different inorganic materials

Rod-Like Virus-Based Multiarm Colloidal Molecules

We report on the construction of multiarm colloidal molecules by tip-linking filamentous bacteriophages, functionalized either by biological engineering or chemical conjugation. The affinity for streptavidin of a genetically modified vector phage displaying Strep-tags fused to one end of the viral particle is measured by determining the dissociation constant, <i>K</i>_d. In order to improve both the colloidal stability and the efficiency of the self-assembly process, a biotinylation protocol having a chemical yield higher than 90% is presented to regioselectively functionalize the cystein residues located at one end of the bacteriophages. For both viral systems, a theoretical comparison is performed by developing a quantitative model of the self-assembly and interaction of the modified viruses with streptavidin compounds, which accurately accounts for our experimental results. Multiarm colloidal structures of different valencies are then produced by conjugation of these tip-functionalized viruses with streptavidin activated nanoparticles. We succeed to form stable virus-based colloidal molecules, whose number of arms, called valency, is solely controlled by tuning the molar excess. Thanks to a fluorescent labeling of the viral arms, the dynamics of such systems is also presented in real time by fluorescence microscopy

Self-Assembly of Ionizable “Clicked” P3HT‑<i>b</i>‑PMMA Copolymers: Ionic Bonding Group/Counterion Effects on Morphology

A novel methodology used to overcome the predominance of π–π interactions on the organization of rod–coil copolymer is reported in this paper. We demonstrated changes in the self-assembly morphology of poly­(3-hexylthiophene)-<i>b</i>-poly­(methyl methacrylate) (P3HT-<i>b</i>-PMMA) block copolymer BCP, by introducing an ionic group to the linking unit between the two blocks. A neutral polymer precursor was synthesized from ethynyl-terminated P3HT and azido-terminated PMMA via Huisgen’s 1,3-dipolar cycloaddition. Then two 1,2,3-triazolium-based block copolymers with different counteranions were obtained by a quaternization of 1,2,3-triazole groups with methyl iodide, and subsequent anion exchange was observed with a fluorinated salt, bis­(trifluoromethane) sulfonimide salt. Atomic force microscopy, modulated differential scanning calorimetry, and X-ray scattering were used to prove that the crystallization of the conjugated block is disrupted by the additional ionic interactions imposed to the system. The 1,2,3-triazolium-based BCP with iodide as the counterion exhibited highly organized well-defined fibrils, as the diblock phase segregation χ becomes predominant over the rod–rod interaction μ. When the more stable and larger NTf₂^– was used as counterion, P3HT phase was disrupted and no crystallization was observed. This methodology could be a useful strategy to open the range of nanomorphologies reachable with a semiconducting polymer for electronic or photovoltaic applications