11The flavonoid components of New Zealand mānuka (Leptospermum scoparium) honey have been 12 quantified in a series of 31 honeys of varying non-peroxide antibacterial activity to clarify 13 discrepancies between previous studies reported in the literature. Total flavonoid content was 14 1.16 mg/100 g honey. The principal flavonoids present were pinobanksin, pinocembrin, luteolin 15 and chrysin and together these represented 61% of the total flavonoid content. 1, 2-formyl-5-(2-16 methoxyphenyl)-pyrrole , which was weakly correlated with the non-peroxide antibacterial activity, 17 was isolated from the flavonoid fraction and separately synthesised.

This paper investigates small molecules that self-assemble to display multivalent ligand arrays for heparin binding. In water, the self-assembled multivalent (SAMul) heparin binder is highly competitive with the current clinical heparin reversal agent, protamine. On addition of salt, the dimensions of the self-assembled nanostructure increase. This unique feature is due to the dynamic, responsive nature of assembly, predicted using multiscale modelling and proven experimentally, enhancing heparin binding of SAMul systems relative to fixed covalent multivalent nanostructures. Conversely, the presence of serum adversely affects the heparin binding of SAMul systems relative to covalent nanostructures due to partial destabilisation of the assemblies. Nonetheless, clotting assays in human plasma demonstrate that the SAMul system acts as a functional heparin reversal agent. Compound degradation, inducing nanostructure disassembly and loss of SAMul binding, takes place over 24 hours due to ester hydrolysis – but when bound to heparin, stability is enhanced. Heparin reversal in plasma, and the therapeutically useful degradation profile, make this SAMul approach of potential therapeutic value in replacing protamine, which has a number of adverse effects when used in the clinic

Self-assembled multivalent (SAMul) ligands based on palmitic acid functionalised with cationic l/d-lysine bind polyanionic heparin or DNA with no chiral preference. Inserting a glycine spacer unit switches on chiral discrimination - a rare example of controlled chiral recognition at a SAMul nanoscale interface.

Amine-functionalised pyrene derivatives are reported and their ability to detect heparin via a fluorescent response determined - different responses are observed dependent on whether self-assembled multivalent binding between sensor and analyte takes place, and ratiometric heparin sensors which can detect this surgically-relevant polyanion in competitive media are reported.

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