Clusters of polymersomes and Janus nanoparticles hierarchically self-organized and controlled by DNA hybridization

The combination of "hard", structurally well-defined particles with "soft", functional compartments bears great potential to produce structurally intricate hybrid nanomaterials that promote a multitude of applications that require multimodal agents and that permit the production of molecular factories. However, the co-assembly of "hard" and "soft" components in a programmable and directional manner is challenging due to the strongly differing mechanical properties of such disparate entities. Here, a versatile strategy to generate clusters by the directional and controlled self-organization of "hard" Janus nanoparticles (JNPs) with "soft" polymersomes is described. The hybridization of complementary ssDNA strands bound to the components drives cluster formation, while the asymmetry of the JNPs governs the directionality of the self-organization. Various factors have been explored to simultaneously preserve the integrity of the polymersomes and program the cluster formation. Differently loaded polymersomes on each lobe of the JNPs preserved their architecture in the clusters which, were shown to be non-toxic when interacting with cell lines. The architecture of the clusters, as a molecular factory where each component can be separately controlled bears great promise for use in advanced medical applications, including theranostics and correlative imaging

Peptide-Based Nanoassemblies in Gene Therapy and Diagnosis: Paving the Way for Clinical Application

Nanotechnology approaches play an important role in developing novel and efficient carriers for biomedical applications. Peptides are particularly appealing to generate such nanocarriers because they can be rationally designed to serve as building blocks for self-assembling nanoscale structures with great potential as therapeutic or diagnostic delivery vehicles. In this review, we describe peptide-based nanoassemblies and highlight features that make them particularly attractive for the delivery of nucleic acids to host cells or improve the specificity and sensitivity of probes in diagnostic imaging. We outline the current state in the design of peptides and peptide-conjugates and the paradigms of their self-assembly into well-defined nanostructures, as well as the co-assembly of nucleic acids to form less structured nanoparticles. Various recent examples of engineered peptides and peptide-conjugates promoting self-assembly and providing the structures with wanted functionalities are presented. The advantages of peptides are not only their biocompatibility and biodegradability, but the possibility of sheer limitless combinations and modifications of amino acid residues to induce the assembly of modular, multiplexed delivery systems. Moreover, functions that nature encoded in peptides, such as their ability to target molecular recognition sites, can be emulated repeatedly in nanoassemblies. Finally, we present recent examples where self-assembled peptide-based assemblies with "smart" activity are used in vivo. Gene delivery and diagnostic imaging in mouse tumor models exemplify the great potential of peptide nanoassemblies for future clinical applications

Evolution of self-organized microcapsules with variable conductivities from self-assembled nanoparticles at interfaces

Self-organization dramatically affects the surface properties of materials on a macroscopic scale, such as wettability and adhesion. Fundamentally, it is equally interesting when self-organization at the nanoscale affects the bulk properties and thus provides a means to engineer the optoelectronic properties of the materials on larger scales. In this work, we report the evolution of conductive self-organized polymer microcapsules from a monomer emulsion droplet stabilized by a monolayer of conductive Janus nanoparticles (JNPs) via a mechanism resembling morphogenesis. The wall of the resulting conductive microcapsule has a honeycomb-like structure with highly oriented JNPs occupying each hollow cell. The JNPs consist of an electrically conductive lobe and an insulating lobe; because of their orientation and presence in the honeycomb, the conductivity of the microcapsule is greatly enhanced as compared to that of each of the constituting materials. This method can be universally applied to induce self-organization in conductive polymers forming by oxidative addition

Self‐assembly of strongly amphiphilic Janus nanoparticles into freestanding membranes

Amphiphilic nanoparticles can adsorb at interfaces between immiscible phases and form membranes. The ability to handle nanoparticle monolayers/bilayers as freestanding membranes independently from the interfaces on which they form can be of significant practical interest. Janus nanoparticles (JNPs) could generate membranes that have tunable pore size and are amphiphilic. Here it is shown how freestanding membranes from JNPs can be generated. First, strongly amphiphilic Janus nanoparticles that generate foams in surfactant-free conditions are synthesized. Upon drying the foam lamellae remain as freestanding membranes consisting of perfectly oriented bilayers or monolayers of JNPs, thus providing direct evidence of structural organization of amphiphiles in foam lamellae. The wet foam lamellae can be picked up on grids and upon drying generate freestanding membranes. Sturdy freestanding membranes by transferring monolayers of JNPs from the air–water interfaces onto grids with fine openings are also prepared

Semiconductive materials with tunable electrical resistance and surface polarity obtained by asymmetric functionalization of Janus nanoparticles

Janus nanoparticles (JNPs) can offer significant potential for synthesis of multifunctional materials, due to their inherent property contrast between the lobes. Asymmetric surface chemical modifications on JNPs can be performed such that each lobe can carry different surface and/or bulk‐like properties, which could be combined in surprising ways. In this work, it is shown that snowman‐type polymeric JNPs can be used to make conductive materials with tunable resistance and surface polarity. By changing the relative size between a conductive and an electrically insulating lobe, the bulk powder conductivity within a series of JNPs by a factor of 10 without changing the intrinsic conductivity of the polymer can be tuned. In the same time, the surface polarity of the powder material decreased by a factor of 5. The possibility to synthesize multifunctional materials from JNPs building blocks that enable the coupling of a bulk‐like property with a surface functionality is therefore demonstrated

pH-responsive pickering foams generated by surfactant-free soft hydrogel particles

Pickering foams are foams stabilized by particles and are generally known to have good stability. A special subclass of particle-stabilized foams includes stimuli-responsive Pickering foams that can be formed or deconstructed by applying an external stimuli or changing the environmental conditions; such intelligent particles could find use in many practical applications. Here, we synthesized surfactant-free biocompatible poly[2(diethylamino)ethyl methacrylate] (PDEAEMA) hydrogel particles (HGPs) by emulsion polymerization. The morphology, structure, and surface charge of the HGPs were characterized by TEM, DLS, and the zeta potential, respectively. We have observed that the pH values of the aqueous solution have a strong influence on the formation of the Pickering foams in the presence of PDEAEMA HGPs. Namely, at pH values ≤4.0 no Pickering foams were produced, while at pH values >4.0 stable Pickering foams were formed. Moreover, the height, size and bubble size distribution of Pickering foams are strongly influenced by the pH values of aqueous solution and PDEAEMA HGPs concentration. The formed Pickering foams in basic aqueous solution can all be conveniently deconstructed by changing the pH values to below 4.0. Interestingly, the dried lamellas of the Pickering foams were constituted by either monolayers or multilayers of PDEAEMA HGPs as demonstrated by SEM

Memory of Chirality Approach to the Enantiodivergent Synthesis of Chiral Benzo[<i>d</i>]sultams

The “memory of chirality” stereodivergent synthesis of polyfluorobenzo[<i>d</i>]sultams has been developed. The interest of this protocol resides in the possibility of using the chirality of a starting sulfonamide single enantiomer to synthesize the target sultams in both absolute configurations, by using different base systems, under homogeneous conditions

Memory of Chirality Approach to the Enantiodivergent Synthesis of Chiral Benzo[<i>d</i>]sultams

The “memory of chirality” stereodivergent synthesis of polyfluorobenzo[<i>d</i>]sultams has been developed. The interest of this protocol resides in the possibility of using the chirality of a starting sulfonamide single enantiomer to synthesize the target sultams in both absolute configurations, by using different base systems, under homogeneous conditions