Ara Anja Palmans

Benzene-1,3,5-tricarboxamide : a versatile ordering moiety for supramolecular chemistry

After their first synthesis in 1915 by Curtius, benzene-1,3,5-tricarboxamides (BTAs) have become increasingly important in a wide range of scientific disciplines. Their simple structure and wide accessibility in combination with a detailed understanding of their supramolecular self-assembly behaviour allow full utilization of this versatile, supramolecular building block in applications ranging from nanotechnology to polymer processing and biomedical applications. While the opportunities in the former cases are connected to the self-assembly of BTAs into one-dimensional, nanometer-sized rod like structures stabilised by threefold H-bonding, their multivalent nature drives applications in the biomedical field. This review summarises the different types of BTAs that appeared in the recent literature and the applications they have been evaluated in. Currently, the first commercial applications of BTAs are emerging. The adaptable nature of this multipurpose building block promises a bright future.

Understanding Cooperativity in Hydrogen-Bond-Induced Supramolecular Polymerization: A Density Functional Theory Study

Understanding the molecular mechanism of cooperative self-assembly is a key component in the design of self-assembled supramolecular architectures across multiple length scales with defined function and composition. In this work, we use density functional theory to rationalize the experimentally observed cooperative growth of C(3)-symmetrical trialkylbenzene-1,3,5-tricarboxamide- (BTA-) based supramolecular polymers that self-assemble into ordered one-dimensional supramolecular structures through hydrogen bonding. Our analysis shows that the cooperative growth of these structures is caused by electrostatic interactions and nonadditive effects brought about by redistribution of the electron density with aggregate length.

Hydrolases in Polymer Chemistry: Chemoenzymatic Approaches to Polymeric Materials

Lipases show high activity in the polymerization of a range of monomers using ring-opening polymerization and polycondensation. The range of polymer structures from this enzymatic polymerization can be further increased by combination with chemical methods. This paper reviews the developments of the last 5–8 years in chemoenzymatic strategies towards polymeric materials. Special emphasis is on the synthesis of polymer architectures like block and graft copolymers and polymer networks. Moreover, the combination of chemical and enzymatic catalysis for the synthesis of unique chiral polymers is highlighted.

Synthesis of biodegradable chiral polyesters by asymmetric enzymatic polymerization and their formulation into microspheres

Materials with selective bio-responsiveness could have potential in medical applications. Here we report the synthesis of chiral microspheres obtained from non-crystalline aliphatic polyesters, with the aim to use chirality to program polymer microsphere degradation. By enzymatic enantioselective kinetic resolution polymerization from racemic monomers, hydroxyl-terminated (R)-, (S)- and racemic poly-(4-methylcaprolatone) (PMCL) were successfully synthesized. Preliminary degradation experiments with Candida Antarctica Lipase B show that the degradation rate can be tuned by the polymer chirality. Chiral microspheres around 40 microns were obtained after acrylation of the polymers and subsequent in situ cross-linking in an oil-in-water (O-W) emulsion evaporation approach.

Stimuli-responsive colloidal assembly driven by surface-grafted supramolecular moieties

A robust method is described for precisely functionalizing silica colloids with short-chain alkanes and self-associating o-nitrobenzyl protected benzene-1,3,5-tricarboxamides (BTAs). Controlled deprotection affords activation of the latent supramolecular moieties by facilitating short-range hydrogen-bonding interactions between surface-functionalized silica particles. Control of mesoscale assembly of the responsive colloidal suspensions is demonstrated with two different external triggers. First, the amount of active (i.e., deprotected) BTAs is efficiently tuned by varying the exposure time to UV radiation. Controlled activation of the BTAs translates to regulating the valence of the system. After activation, the binding strength of individual BTAs can be modulated with temperature, providing an additional handle with which the assembly behavior is manipulated. This dual-regulation approach is a powerful and sensitive avenue for controlling colloidal assembly processes.

Consequences of subtle chiral effects : from'Majority-Rules' to'Minority-Rules'

Mixing experiments were conducted on dilute solutions of asymmetrically substituted benzene-1,3,5-tricarboxamides (BTAs) with stereogenic methyl groups ranging from the α- to the δ-position with respect to the amide in one of the three side groups. While normally the majority compound determines the helical sense preference of the formed supramolecular polymers, we find here that several combinations show a helical preference governed by the minority compound. BTAs with the methyl substituent at the α- and γ-position overrule the helical preference of BTAs with the methyl substituent at the β- and δ-position. This new effect is referred to as a ‘minority-rules’ system.