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By taking advantage of the orthogonal nature of thiol−ene coupling and anhydride based esterification reactions, a facile and chemoselective strategy to dendritic macromolecules has been developed. The ability to interchange growth steps based on thiol−ene and anhydride chemistry allows the synthesis of fifth-generation dendrimers in only five steps and under benign reaction conditions. In addition, the presented coupling chemistries eliminate the traditional need for protection/deprotection steps and afford dendrimers in high yield and purity. The modularity of this strategy coupled with the latent reactivity of the alkene/hydroxyl chain ends was demonstrated by using different cores (alkene and hydroxyl functional), various AB2 and CD2 monomers and a range of chain end groups. As a result, three dendritic libraries were prepared which exhibited tunability of both the chemical functionality and physical properties including the fabrication of PEG hydrogels.

Superhydrophobic and self-cleaning cellulose surfaces have been obtained via surface-confined grafting of glycidyl methacrylate using atom transfer radical polymerization combined with postmodification reactions. Both linear and branched graft-on-graft architectures were used for the postmodification reactions to obtain highly hydrophobic bio-fiber surfaces by functionalization of the grafts with either poly(dimethylsiloxane), perfluorinated chains, or alkyl chains, respectively. Postfunctionalization using alkyl chains yielded results similar to those of surfaces modified by perfluorination, in terms of superhydrophobicity, self-cleaning properties, and the stability of these properties over time. In addition, highly oleophobic surfaces have been obtained when modification with perfluorinated chains was performed.

Novel thermo-responsive cellulose (filter paper) surfaces of N-isopropylacrylamide (NIPAAm) and pH-responsive cellulose surfaces of 4-vinylpyridine (4VP) have been achieved via surface-initiated ATRP. Dual-responsive (pH and temperature) cellulose surfaces were also obtained through the synthesis of block-copolymer brushes of PNIPAAm and P4VP. With changes in pH and temperature, these "intelligent" surfaces showed a reversible response to both individual triggers, as indicated by the changes in wettability from highly hydrophilic to highly hydrophobic observed by water contact angle measurements. Adjusting the composition of the grafted block-copolymer brushes allowed for further tuning of the wettability of these "intelligent" cellulose surfaces.

The preparation and characterization of a series of first to fourth generation dendronized poly-(norbornene)s are presented. The monomers were synthesized in a divergent fashion from 5-norbornene-2 ...

Nanoparticles have been used to reinforce polymer matrices since the late 1980s, with promising results. Hyperbranched polymers are densely branched molecules with a globular structure, leading to ...

Organic-inorganic hybrid materials consisting of nanosized silica particles with surface grafted PS or PS-b-PMMA were synthesized using ATRP. These hybrid materials were used in the fabrication of ...

A novel initiator for atom transfer radical polymerization, also allowing for selective cleavage of polymer grafts, was designed and immobilized on a solid substrate. After cleavage, the initiator content was determined by utilizing Ellman's reagent and the cleaved polymer grafts were isolated and characterized by size exclusion chromatography.

International audience; Incorporation of orthogonal functional groups into biodegradable polymers permits the fabrication of multi-layered thin films with improved adhesion and tunable degradation profiles. The bi-layer structure also allows for accurate control over small molecule release.

Self-assembling peptide amphiphiles (PAs) have been extensively used in the development of novel biomaterials. Because of their propensity to form cylindrical micelles, their use is limited in applications where small spherical micelles are desired. Here we present a platform method for controlling the self-assembly of biofunctional PAs into spherical 50 nm particles using dendrimers as shape-directing scaffolds. This templating approach results in biocompatible, stable protein-like assemblies displaying peptides with native secondary structure and biofunctionality.

Dendrimer synthesis should not be tedious and time-consuming. By utilizing an AB2−CD2 approach and having orthogonal, “clickable” groups on each monomer, the time for dendrimer assembly can be drastically reduced. This was shown by preparation of a sixth generation dendrimer from starting monomer units in a single day.

Bone fractures are today stabilized with screws and metal plates. More complicated fractures require alternative treatments that exclude harsh surgical conditions. By adapting the benign and UV initiated thiol-ene reaction, we efficiently fabricated triazine-based, fiber-reinforced adhesive patches within 2 s. To enhance their bone adhesion properties, we found that a pre-treatment step of bone surfaces with phenolic dopamine and poly(parahydroxystyrene) compounds was successful. The latter display the greatest E-module of 3.4 MPa in shear strength. All patches exhibited low cytotoxicity and can therefore find potential use in future treatments of bone fractures.

A fourth wheel: Two sets of bifunctional AB(2)C dendrimers having internal acetylene/azides and external hydroxy groups were constructed utilizing benign synthetic protocols. An in situ postfunctionalization strategy was successfully carried out to illustrate the chemoselective nature of these dendrimers. The dendrimers were also transformed into dendritic nanoparticles or utilized as dendritic crosslinkers for the fabrication hydrogels.

A chemoselective and layered growth approach has been developed for the synthesis of dendrimers, combining Click chemistry with traditional esterification/etherification reactions, without the need for activation steps and with excellent overall yields.

Ordered hexagonal arrays of isoporous films prepared from poly(9,9'-dihexylfluorene) and polystyrene grafted silica nanoparticles (Si-graft-PS) are presented. These close packed arrays were formed in areas of many square millimeters. The pore size varied from 2.9 - 8.5 mu m, depending on the concentration of Si-graft-PS and the processing conditions. Solid state photoluminescence resulted in a significant red shift of up to 30 nm in these films compared to conventional processing techniques. These differences are attributed to induced aggregation of the polymers caused by polymer- solvent interactions. Interfacial properties were investigated, and it was found that hydrophobic surfaces (contact angles of up to 129 degrees) were prepared because of high surface roughness. These ordered porous polymer films may find use in microelectronic and bio- and/or chemical sensor applications.

The interfacial properties of solution-processed conjugated polymer films are investigated. Their surface roughness was controlled by varying the humidity during the film deposition and mechanical exfoliation. A superhydrophobic film was obtained from a rough film of a partially fluorinated conjugated polymer. These films would be beneficial towards robust organic electronic devices.

Die Chemoselektivitat der Klick-Chemie wurde fur die Synthese einer neuen Gruppe difunktioneller AB2C-Dendrimere mit Acetylen/Azidgruppen im Innern und Hydroxygruppen an der Peripherie genutzt. M. Malkoch et al. stellen in der Zuschrift auf S. 2160 ff. einen einfachen Zugang zu zwei Gerusttypen vor. Die Nutzlichkeit der AB2C-Dendrimere wurde durch ihren Einsatz zur nachtraglichen Eintopffunktionalisierung, bei der Entwicklung dendritischer Nanopartikel und zur Bildung von Hydrogelen illustriert.

Dendrimers up to the fourth generation (G1–G4) were successfully synthesized via the efficient copper catalyzed 1,3-dipolar cycloaddition between primary alkynes and azides (CuAAC), also referred to as a click reaction. The synthetic protocol involved the preparation of presynthesized dendron wedges that subsequently were attached to a tetra-valent alkyne functional cyclen core. These constructed structures integrated stable triazole groups “intra-locked” between the cyclen and dendron wedges. The incorporation of a lanthanide metal ion, europium, into the interior of all cyclen dendrimers was monitored by FT-IR. Interestingly, the photophysical results showed that the proximate triazole not only acts as a stable linker but also as a sensitizers, transferring its singlet–singlet excitation in the ultraviolet region (270–290 nm) to the partially filled luminescent lanthanide 4f shell. An increase of luminescence decay time from the lanthanide 5D0 → 7F2 emission was observed with increasing dendrimer size, indicating that the shielding effect of the dendron wedges is important for the relaxation of the photo-excitation and energy transfer. To the best of our knowledge, this is the first time a set of dendron wedges have successfully been attached to a cyclen metal ion cage via the versatile click reaction. Furthermore, the produced triazoles intra-locked in close proximity to the macrocycle core elucidated an interesting photophysical function.