Adam D. Martin

Multifunctional p-phosphonated calixarenes

p-Phosphonic acid calix[n]arenes and their O-alkylated lower rim analogues are remarkably versatile macrocycles, with applications in selective diameter uptake of single walled carbon nano-tubes, as surfactants in stabilising and protecting nano-particles and graphene sheets, as crystal growth modifiers for inorganic systems, in encapsulating molecules of anti-cancer carboplatin, self assembly into nano-arrays, including nano-fibres and molecular capsules, and for binding metal ions including biologically relevant Ca(2+). They are readily accessible via five or six high yielding steps from the parent p-Bu(t) substituted compounds.

Multifunctional water-soluble molecular capsules based on p-phosphonic acid calix[5]arene

p-Phosphonic acid calix[5]arene forms molecular capsules in water based on two of the molecules, which can be loaded with carboplatin using intense shearing, and attached to single wall carbon nano-tubes. Spin coating of the capsules onto a substrate affords 2 nm fibres of stacked calixarenes, with the self-assembly understood using molecular modelling.

Hirshfeld Surface Investigation of Structure-Directing Interactions within Dipicolinic Acid Derivatives.

Six compounds based on dipicolinic acid esters have been synthesized and Hirshfeld surfaces used to investigate the structure-directing effects of functional groups in controlling their solid-state behavior. Compounds 1–4 are 4-bromo dipicolinic acid esters substituted with methyl, ethyl, propyl, and benzyl groups, respectively. The main structure-directing motif within 1–3 is a pairwise O···H interaction involving two carbonyl oxygen atoms and two aromatic H atoms. The introduction of bulky benzyl groups in 4 forces a significant change in the position of this interaction. Compounds 2 and 4 were used in Suzuki coupling reactions to prepare extended analogues 5 and 6, respectively, and their solid-state behavior was also studied using Hirshfeld surfaces. Extension of these dipicolinic acid esters results in the complete loss of the pairwise O···H interaction in 5, where the dominant structure-directing motifs are π-based interactions. However, the pairwise O···H interaction reappears for the more flexible 6, demonstrating control of the solid-state structure of these dipicolinic acid derivatives through the choice of functional groups.

Biocompatible small peptide super-hydrogelators bearing carbazole functionalities

For the first time we have introduced carbazole capping groups onto two short peptide sequences, namely a diphenylalanine dipeptide and a glycine-diphenylalanine tripeptide, giving compounds 1 and 2, respectively. Both molecules form hydrogels at low concentrations, as low as 0.03% (w/v) for 1- well within the range of supergelators. Both gelators are composed of small ca. 2 nm thick molecular fibres, as elucidated by AFM and are non-cytotoxic towards HeLa cells at concentrations which are at or above their minimum gelation concentration.

A Capped Dipeptide Which Simultaneously Exhibits Gelation and Crystallization Behavior

Short peptides capped at their N-terminus are often highly efficient gelators, yet notoriously difficult to crystallize. This is due to strong unidirectional interactions within fibers, resulting in structure propagation only along one direction. Here, we synthesize the N-capped dipeptide, benzimidazole-diphenylalanine, which forms both hydrogels and single crystals. Even more remarkably, we show using atomic force microscopy the coexistence of these two distinct phases. We then use powder X-ray diffraction to investigate whether the single crystal structure can be extrapolated to the molecular arrangement within the hydrogel. The results suggest parallel β-sheet arrangement as the dominant structural motif, challenging existing models for gelation of short peptides, and providing new directions for the future rational design of short peptide gelators.

Pd-induced ordering of 2D Pt nanoarrays on phosphonated calix[4]arenes stabilised graphenes

p-Phosphonic acid calix[4]arenes render high stability to exfoliated graphenes in water. These calix[4]arenes modified graphenes can be used as highly effective substrates to nucleate ultra-small Pd nanoparticles, which in turn serve as galvanic reaction templates for the generation of high density 2D arrays of Pt nanoparticles.

Effect of heterocyclic capping groups on the self-assembly of a dipeptide hydrogel

The mechanism and design rules associated with the self-assembly of short peptides into hydrogels is currently not well understood. In this work, four diphenylalanine-based peptides have been synthesised, bearing heterocyclic capping groups which have different degrees of hydrogen bonding potential and nitrogen substitution. For these four peptides, zeta potential and electrical impedance spectroscopy measurements were undertaken to monitor gelation, with the impedance data showing different gelation times for each peptide hydrogel. Through a combination of atomic force microscopy and rheological measurmeents, including dynamic strain and frequency sweeps, and thixotropic tests, the relationship between the mechanism of self-assembly in these hydrogels and their macroscopic behaviour can be established. It is observed that the degree of nitrogen substitution affects the self-assembly mechanisms of the hydrogels and as such, that there is an interplay between branching and bundling self-assembly pathways that are responsible for the final properties of each hydrogel.

Spinning up the polymorphs of calcium carbonate

Controlling the growth of the polymorphs of calcium carbonate is important in understanding the changing environmental conditions in the oceans. Aragonite is the main polymorph in the inner shells of marine organisms, and can be readily converted to calcite, which is the most stable polymorph of calcium carbonate. Both of these polymorphs are significantly more stable than vaterite, which is the other naturally occurring polymorph of calcium carbonate, and this is reflected in its limited distribution in nature. We have investigated the effect of high shear forces on the phase behaviour of calcium carbonate using a vortex fluidic device (VFD), with experimental parameters varied to explore calcium carbonate mineralisation. Variation of tilt angle, rotation speed and temperature allow for control over the size, shape and phase of the resulting calcium carbonate.

Phosphonated calix[4]arene-based amphiphiles as scaffolds for fluorescent nano-fibres

p-Phosphonic acid calix[4]arene bearing lower rim O-C(18)H(37) alkyl chains assemble into 6 nm diameter fibres, which deposit from toluene onto mica and graphite, as characterised using Atomic Force Microscopy (AFM). Molecular simulations support a micelle-like arrangement of calixarenes with the alkyl chains directed inwards, and they form a composite material with a fluorescent molecule.

Controlling self-assembly of diphenylalanine peptides at high pH using heterocyclic capping groups

Using small angle neutron scattering (SANS), it is shown that the existence of pre-assembled structures at high pH for a capped diphenylalanine hydrogel is controlled by the selection of N-terminal heterocyclic capping group, namely indole or carbazole. At high pH, changing from a somewhat hydrophilic indole capping group to a more hydrophobic carbazole capping group results in a shift from a high proportion of monomers to self-assembled fibers or wormlike micelles. The presence of these different self-assembled structures at high pH is confirmed through NMR and circular dichroism spectroscopy, scanning probe microscopy and cryogenic transmission electron microscopy.