Based on the growing demand for facile and sustainable synthetic methods to structurally perfect polymers, we herein describe a significant improvement of esterification reactions capitalizing on 1,1'-carbonyldiimidazole (CDI). Cesium fluoride was shown to be an essential catalyst for these reactions to reach completion. This approach was successfully applied to the synthesis of structurally flawless and highly functional polyester dendrimers employing traditional and accelerated growth strategies. A sixth generation bis-MPA dendrimer with a molecular weight of 22.080 Da and 192 peripheral hydroxy groups was isolated in less than one day of total reaction time. Large quantities of dendrimers were obtained in high yields (>90%) using simple purification steps under sustainable conditions. The fluoride-promoted esterification (FPE) via imidazolide-activated compounds is wide in scope and constitutes a potentially new approach toward functional polymers and other materials.

Reactive imidazole intermediates based on AB2 and A3 monomers, i.e. bis(methylol) propionic acid (bis-MPA) and trimethylolpropane (TMP) have successfully been synthesized and isolated on a 100 gram scale via a facile synthetic protocol using 1,1′-carbonyldiimidazole (CDI) as a key reagent.

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 2,2bis(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 3-caprolactone. A library of star branched polymers with poly(3-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 selfassembled micelles loaded with doxorubicin anticancer drug and ordered honeycomb membranes with enhanced surface area were successfully fabricated and characterized.

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Fluoride-Promoted Carbonylation (FPC) polymerization is herein presented as a novel catalytic polymerization methodology that complements ROP and unlocks a greater synthetic window to advanced polycarbonates.

A non‐toxic hydrolytically fast‐degradable antibacterial hydrogel is herein presented to preemptively treat surgical site infections during the first crucial 24 h period without relying on conventional antibiotics. The approach capitalizes on a two‐component system that form antibacterial hydrogels within 1 min and consist of i) an amine functional linear‐dendritic hybrid based on linear poly(ethylene glycol) and dendritic 2,2‐bis(hydroxymethyl)propionic acid, and ii) a di‐N‐hydroxysuccinimide functional poly(ethylene glycol) cross‐linker. Broad spectrum antibacterial effect is achieved by multivalent representation of catatonically charged β‐alanine on the dendritic periphery of the linear dendritic component. The hydrogels can be applied readily in an in vivo setting using a two‐component syringe delivery system and the mechanical properties can accurately be tuned in the range equivalent to fat tissue and cartilage (G′ = 0.5–8 kPa). The antibacterial effect is demonstrated both in vitro toward a range of relevant bacterial strains and in an in vivo mouse model of surgical site infection.

Step-growth polymerization and degradation behavior of fully sugar-derived high Tg alternating and random polycarbonates from isosorbide and dihydroxyacetone.

The identification of a unique set of advanced materials that can bear extraordinary loads for use in bone and tooth repair will inevitably unlock unlimited opportunities for clinical use. Herein, the design of high‐performance thermosets is reported based on triazine‐trione (TATO) monomers using light‐initiated thiol‐yne coupling (TYC) chemistry as a polymerization strategy. In comparison to traditional thiol‐ene coupling (TEC) systems, TYC chemistry has yielded highly dense networks with unprecedented mechanical properties. The most promising system notes 4.6 GPa in flexural modulus and 160 MPa in flexural strength, an increase of 84% in modulus and 191% in strength when compared to the corresponding TATO system based on TEC chemistry. Remarkably, the mechanical properties exceed those of polylactide (PLA) and challenge poly(ether ether ketone) PEEK and today's methacrylate‐based dental resin composites. All the materials display excellent biocompatibility, in vitro, and are successfully: i) molded into medical devices for fracture repair, and ii) used as bone adhesive for fracture fixation and as tooth fillers with the outstanding bond strength that outperform methacrylate systems used today in dental restoration application. Collectively, a new era of advanced TYC materials is unfolded that can fulfill the preconditions as bone fixating implants and for tooth restorations.