Assembling quantum dots via critical Casimir forces

AbstractProgrammed assembly of colloidal inorganic nanocrystal superstructures is crucial for the realization of future artificial solids as well as present optoelectronic applications. Here, we present a new way to assemble quantum dots reversibly using binary solvents. By tuning the temperature and composition of the binary solvent mixture, we achieve reversible aggregation of nanocrystals in solution induced by critical Casimir forces. We study the temperature-sensitive quantum-dot assembly with dynamic light scattering. We show that careful screening of the electrostatic repulsion by adding salt provides a further parameter to tune the reversible assembly

Dendrimer-encapsulated nanoparticle-core micelles as a modular strategy for particle-in-a-box-in-a-box nanostructures

The hierarchically controlled synthesis and characterization of self-assembling macromolecules and particles are key to explore and exploit new nanomaterials. Here we present a versatile strategy for constructing particle-in-a-box-in-a-box systems by assembling dendrimer-encapsulated gold nanoparticles (DENs) into dendrimicelles. This is realized by combining positively charged PAMAM dendrimers with a negative-neutral block copolymer. The number of particles per dendrimicelle can be controlled by mixing DENs with empty PAMAM dendrimers. The dendrimicelles are stable in solution for months and provide improved resistance for the nanoparticles against degradation. The dendrimicelle strategy provides a flexible platform with a plethora of options for variation in the type of nanoparticles, dendrimers and block copolymers used, and hence is tunable for applications ranging from nanomedicine to catalysis.</p

Multicompartment dendrimicelles with binary, ternary and quaternary core composition

Hierarchically built-up multicompartment nanoaggregate systems are of interest for, e.g., novel materials and medicine. Here we present a versatile strategy to generate and unambiguously characterize complex coacervate-core micelles by exploiting four different dendrimeric subcomponents as core-units. The resulting mesoscale structures have a hydrodynamic diameter of 50 nm and a core size of 33 nm, and host about thirty 6th generation polyamidoamine (PAMAM) dendrimers. We have used FRET (efficiency of similar to 0.2) between fluorescein and rhodamine moieties immobilized on separate PAMAM dendrimers (G6-F and G6-R, respectively) to prove synchronous encapsulation in the micelle core. Tuning the proximity of the FRET pair molecules either by varying the G6-F : G6-R ratio, or by co-assembling non-functionalized dendrimer (G6-E) in the core, reveals the optimal FRET efficiency to occur at a minimum of 70% loading with G6-F and G6-R. Additional co-encapsulation of 6th generation gold dendrimer-encapsulated nanoparticles (G6-Au) in the micelle core shows a dramatic reduction of the FRET efficiency, which can be restored by chemical etching of the gold nanoparticles from within the micellar core with thiols, leaving the micelle itself intact. This study reveals the controlled co-assembly of up to four different types of subcomponents in one single micellar core and concomitantly shows the wide variety of structures that can be made with a well-defined basic set of subcomponents. It is straightforward to design related strategies, to incorporate inside one micellar core, e.g., even more than 4 different dendrimers, or other classes of (macro)molecules, with different functional groups, other FRET pairs or different encapsulated metal nanoparticles.Imaging- and therapeutic targets in neoplastic and musculoskeletal inflammatory diseas

Obtaining control of cell surface functionalizations via Pre-targeting and Supramolecular host guest interactions

The use of mammalian cells for therapeutic applications is finding its way into modern medicine. However, modification or “training” of cells to make them suitable for a specific application remains complex. By envisioning a chemical toolbox that enables specific, but straight-forward and generic cellular functionalization, we investigated how membrane-receptor (pre)targeting could be combined with supramolecular host-guest interactions based on β-cyclodextrin (CD) and adamantane (Ad). The feasibility of this approach was studied in cells with membranous overexpression of the chemokine receptor 4 (CXCR4). By combining specific targeting of CXCR4, using an adamantane (Ad)-functionalized Ac-TZ14011 peptide (guest; KD = 56 nM), with multivalent host molecules that entailed fluorescent β-CD-Poly(isobutylene-alt-maleic-anhydride)-polymers with different fluorescent colors and number of functionalities, host-guest cell-surface modifications could be studied in detail. A second set of Ad-functionalized entities enabled introduction of additional surface functionalities. In addition, the attraction between CD and Ad could be used to drive cell-cell interactions. Combined we have shown that supramolecular interactions, that are based on specific targeting of an overexpressed membrane- receptor, allow specific and stable, yet reversible, surface functionalization of viable cells and how this approach can be used to influence the interaction between cells and their surroundings.</p

Chemically augmented malaria sporozoites display an altered immunogenic profile

Despite promising results in malaria-naïve individuals, whole sporozoite (SPZ) vaccine efficacy in malaria-endemic settings has been suboptimal. Vaccine hypo-responsiveness due to previous malaria exposure has been posited as responsible, indicating the need for SPZ vaccines of increased immunogenicity. To this end, we here demonstrate a proof-of-concept for altering SPZ immunogenicity, where supramolecular chemistry enables chemical augmentation of the parasite surface with a TLR7 agonist-based adjuvant (SPZ-SAS(CL307)). In vitro, SPZ-SAS(CL307) remained well recognized by immune cells and induced a 35-fold increase in the production of pro-inflammatory IL-6 (p + cells 11.1 ± 1.8 vs. 9.4 ± 1.5%, p + T cells (4.7 ± 4.3 vs. 1.8 ± 0.7%, p + T cells (3.6 ± 1.4 vs. 2.5 ± 0.9%, p Host-parasite interactio

Simple 3D Printed Scaffold-Removal Method for the Fabrication of Intricate Microfluidic Devices

An easy and cheap fabrication method for intricate polydimethylsiloxane microfluidic devices is presented. The acrylonitrile butadiene styrene scaffold-removal method uses cheap, off-the-shelf materials and equipment for the fabrication of intricate microfluidic devices. The versatility of the method is proven by the fabrication of 3D multilayer, ship-in-a-bottle, selective heating, sensing, and NMR microfluidic devices. The methodology is coined ESCARGOT: Embedded SCAffold RemovinG Open Technology

A method of manufacturing a microfluidic device

A method of manufacturing a microfluidic device, said method comprising placing a length of material in a liquid polymer, configuring the length of material to define the path of a microfluidic channel, curing or setting the polymer liquid to form a solid polymer around the configured length of material, and dissolving the configured length of material with a solvent to provide a microfluidic channel in the solid polymer

A method of manufacturing a microfluidic device

A method of manufacturing a microfluidic device, said method comprising placing a length of material in a liquid polymer, configuring the length of material to define the path of a microfluidic channel, curing or setting the polymer liquid to form a solid polymer around the configured length of material, and dissolving the configured length of material with a solvent to provide a microfluidic channel in the solid polymer