Heterofunctional polyester dendrimers up to the third generation, containing 21 internally queued bromine atoms, have been successfully synthesized for the first time using a divergent growth approach. Direct azidation reactions enabled the conversion of the bromide groups to clickable azide pendant functionalities. Therapeutic and chemical moeities could then be coupled to the internal azide or bromide functionalities and external hydroxyl groups of the heterofunctional dendrimers through CuAAC, thiol-bromo click and esterification reactions, expanding their potential for biomedical applications.

Redox-sensitive hyperbranched dendritic-linear polymers (HBDLPs) were prepared and stabilized individually as unimolecular micelles with diameters in the range 25–40 nm. The high molecular weight (500–950 kDa), core–shell amphiphilic structures were synthesized through a combination of self-condensing vinyl copolymerization (SCVCP) and atom transfer radical polymerization (ATRP). Cleavable disulfide bonds were introduced, either in the backbone, or in pendant groups, of the hyperbranched core of the HBDLPs. By triggered reductive degradation, the HBDLPs showed up to a 7-fold decrease in molecular weight, and the extent of degradation was tuned by the amount of incorporated disulfides. The HBDLP with pendant disulfide-linked functionalities in the hyperbranched core was readily postfunctionalized with a hydrophobic dye, as a mimic for a drug. An instant release of the dye was observed as a response to a reductive environment similar to the one present intracellularly. The proposed strategy shows a facile route to highly stable unimolecular micelles, which attractively exhibit redox-responsive degradation and cargo release properties.

Well-defined dendronized cellulose substrates displaying multiple representations of dual-functionality were constructed by taking advantage of the efficiency of the click reaction combined with traditional anhydride chemistry. First, activated cellulose surfaces were decorated with several generations of dendrons, and their peripheral reactive groups were subsequently reacted with a trifunctional orthogonal monomer. The generated substrate tool box was successfully explored by accurately tuning the surface function using a versatile orthogonal dual postfunctionalization approach. In general, the reactions were monitored by using a click-dye reagent or a quartz crystal microbalance (QCM) technique, and the resulting surfaces were well-characterized using XPS, and contact angle measurements. Utilizing this approach two different surfaces have been obtained; that is, triethylenglycol oligomers and amoxicillin molecules were efficiently introduced to the dendritic surface. As a second example, mannose-decorated hydroxyl functional surfaces illustrated their potential as biosensors by multivalent detection of lectin protein at concentration as low as 5 nM.

Linear dendritic hybrid materials enable a range of architectural variations which offers novel possibilities in the tailoring of polymeric materials. In this study dendrons based on the 2,2-bis(methylol)propionic acid (bis-MPA) building block, bearing click chemistry moieties in the core and peripheral hydroxyl functionalities, have been used as macroinitiators for ring opening polymerization of ε-caprolactone. A library of star branched polymers with poly(ε-caprolactone) chains was initially constructed using dendrons up to 4^th generation. In a second step, the popular CuAAC or thiol–ene click reaction was efficiently used to attach poly(ethylene glycol) chains of different lengths to the core. Potential applications of the resulted amphiphilic linear dendritic hybrids were investigated. Both self-assembled micelles loaded with doxorubicin anticancer drug and ordered honeycomb membranes with enhanced surface area were successfully fabricated and characterized.

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 AB(2) 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.

A simple synthetic strategy has been developed for accessing internally functionalized dendrimers. The key feature of this approach is the use of two orthogonal and efficient reactions` epoxy-amine' and 'thiol-ene' coupling-for rapid growth of the dendritic scaffold. This sequence of reactions allows for the introduction of reactive hydroxyl groups at each dendritic layer.