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Synthetic biflavonoids are associated with interesting biological activities, yet they remain poorly explored within drug discovery. Recent years have witnessed a growing interest in synthetic approaches that can provide access to structurally novel biflavonoids so that the biological usefulness of this compound class can be more fully investigated. Herein, we report upon the exploration of strategies based around Suzuki-Miyaura cross-coupling and alcohol methylenation for the synthesis of two classes of biflavonoids: (i) rare ‘hybrid’ derivatives containing flavonoid monomers belonging to different subclasses, and (ii) homodimeric compounds in which the two flavonoid monomers are linked by a methylenedioxy group. Application of these strategies enabled the preparation of a structurally diverse collection of novel biflavonoids from readily-available starting materials, thereby facilitating the probing of uncharted regions of biologically interesting chemical space.

Dihydrochalcones and 5-deoxyflavones are types of compounds possessing various biologically interesting properties. Herein, we report the concise and divergent total syntheses of several naturally occurring dihydrochalcones and 5-deoxyflavones from readily available starting materials. The divergent strategy is based around manipulation of a common chalcone scaffold and features application of Algar–Flynn–Oyamada oxidation and benzoquinone C–H activation methodologies. These are the first reported total syntheses of these biologically interesting compounds and the concise and flexible route should be readily amenable to future analogue generation. Furthermore, this work provides an illustration of the utility of divergent synthesis for the expedient and step-economical preparation of natural product libraries.

The concise and step-economical total syntheses of three hydroxyaurones and one polymethoxyflavone from readily available starting materials is described. A divergent synthetic strategy is employed, which centres on a common chalcone scaffold from which both the aurone and flavone frameworks can be accessed through the use of different oxidative cyclisation methods. These are the first reported total syntheses of these biologically interesting compounds.

Self-assembled supramolecular structures such as optical wires, films and 2D slabs offer a new generation of electronic and optical devices. In particular, self-assembled porphyrin devices, including those integrated onto silica and silicon platforms, open new opportunities in photonic applications spanning molecular biosensing, photovoltaics and telecommunications. All reports to date, however, largely highlight the potential but have not established a clear pathway to the actual implementation of more complex device prototypes. In this paper, we propose and demonstrate the use of a focused ion beam (FIB) to process and fabricate devices in porphyrin-based supramolecular structures. These self-assembled structures have an initial root mean squared (rms) values for surface roughness of0.5 nm as measured by atomic force microscopy. Under appropriate FIB processing and cutting conditions, the rms value for surface roughness falls to0.4 nm, comparable with some of the best optical flatnesses obtained within, for example, structured optical fibres and integrated optical waveguides. The milling rate of the porphyrin structures was estimated to be approximately 70% of that of silica. The versatility of a FIB as a tool for rapid processing and fabricating 1D and 2D photonic waveguide structures within supramolecular self-assembled platforms is demonstrated by fabricating a 2D coupler, setting the groundwork for true optical device engineering and integration using these new organic systems.

Self-assembled microrods {based on 5-nitro-10,15,20-trialkylporphyrins [(CnH2n+1)3-NO2P]} and microplates {based on 5,10,15,20-tetraheptylporphyrin [(C7H15)4-P]} are fabricated and characterised using optical microscopy, atomic force microscopy (AFM), and scanning electron microscopy (SEM). The length of the alkyl chains and the deposition surface are found to influence the optical properties and microrod self-assembly. When the deposition surface is silica (α-quartz), 5-nitro-trialkylporphyrins, (C5H11)3-NO2P, (C7H15)3-NO2P and (C11H23)3-NO2P all form microrods of 0.7–0.8 micron diameter; the average length of the microrods varies from 170 microns for (C5H11)3-NO2P to about 11 microns for (C7H15)3-NO2P and (C11H23)3-NO2P, whereas (C19H39)3-NO2P with much longer alkyl chains only gives powders. Controlling the precipitation is crucial in preventing the disordered aggregation of assembled layers observed in the bulk. Very interestingly, the microrods formed from (C7H15)3-NO2P show marked iridescent character. When (C7H15)3-NO2P is deposited on silicon, however, longer curved microrods which do not show iridescence are produced. Single crystal X-ray crystallography of (C7H15)3-NO2P reveals the packing of the bulk material which explains the packing topology of the layers observed by AFM but not the iridescence. The observed structural colour of the (C7H15)3-NO2P microrods is explained by staggering of the layers to produce a corrugated surface with a period of 125 nm, as measured by AFM.

Biflavonoids are associated with a variety of biologically useful properties. However, synthetic biflavonoids are poorly explored within drug discovery. There is considerable structural diversity possible within this compound class and large regions of potentially biologically relevant biflavonoid chemical space remain untapped or underexplored. Herein, we report the development of a modular and divergent strategy towards biflavonoid derivatives which enabled the step-economical preparation of a structurally diverse collection of novel unnatural biflavonoids. Preliminary studies established that the strategy could also be successfully extended to the preparation of very rare triflavonoids, which are also expected to be useful tools for biological intervention. Prompted by previous inhibitory studies with flavonoid libraries, amyloid anti-aggregation screening was performed, which led to the identification of several structurally novel inhibitors of the aggregation of the amyloid β peptide (Aβ42). Aggregated Aβ42 is a pathological hallmark of Alzheimer's disease and the use of small molecules to inhibit the aggregation process has been identified as a potentially valuable therapeutic strategy for disease treatment. Methylated biaurones were associated with highest levels of potency (the most active compound had an IC50 value of 16 μM), establishing this scaffold as a starting point for inhibitor development.