Themed collection Celebrating our 2018 prize and award winners

A personal summary of 40 years research in fungal polyketide biosynthesis is presented and developments in the field in the authors and other laboratories over that period are highlighted.

Polyketides comprise a diverse class of natural products, with many important biological and pharmacological activities. Substrates functioning as starter units and extender units during their assembly significantly contribute to the chemical complexity exhibited by this class of natural products. This highlight provides an overview of the recent advances in understanding the diversity of these polyketide synthase (PKS) building blocks.

The selective proteasome inhibitor carfilzomib (Kyprolis™), derived from the potent antitumor natural product epoxomicin, has been recently approved by the FDA for multiple myeloma. Here we present an account of the journey that began with the discovery of epoxomicin and ended with the successful development of a life-changing drug.

The parameters governing the rate, yield, and mechanism of DNA-mediated charge transport are explored in a variety of experimental systems.

The biological application of metal complexes requires an understanding of cellular uptake; here we describe a variety of techniques used to gain insight into the mechanism of uptake, localization, and efflux.

We demonstrate continuous flow acid–base titration reactions as an educational microfluidic platform for undergraduate and graduate analytical chemistry courses.

The replacement of mercuric chloride in the production of vinyl chloride monomer, a precursor to PVC, would greatly reduce the environmental impact of this large scale industrial process.

Supramolecular engineering comprises the design, synthesis and self-assembly of well-defined molecular modules into dynamic architectures. Scanning tunneling microscopy studies were used to trigger, with a sub-nanometre resolution, the formation of responsive architectures with controlled geometries and properties.

Nanofibrillar morphology is found to be intrinsic to polyaniline chemically synthesized in water. In conventional synthesis (left), the product that readily precipitates out of the solution is a mixture of irregularly-shaped, micron-sized particulates and nanofibers. In interfacial polymerization (middle) and rapidly-mixed reactions (right), the products are pure nanofibers that disperse very well in water.

Scanning probe microscopies offer access to physico-chemical properties of complex molecular adsorbates on the nanoscale. Beyond imaging, e.g. nanomanipulations, the nanomechanics and electronics of molecular objects can be studied.

A series of exciting phenomena that can occur in supramolecular systems away from equilibrium are reviewed.

From tunable reflectors to 3D metamaterials, the self-assembly of block copolymers is advancing nanostructures for photonic applications.

This review covers the discovery of the marine actinomycete genus Salinispora and its development as a model for natural products research.

This review analyses the general physical and chemical properties of the seven main classes of boron reagent that have been employed for SM coupling.

A review of the uses of saliva biomarkers, detection methods and requirements for new biomarkers.

Food allergy is an increasing problem. If we fail to realise the promise of current risk assessment and risk management of food allergens through lack of ability to measure them reproducibly and with traceability to an international unit of measurement, the analytical community will have failed a significant societal challenge.

We aim to establish the effect of bacterial diversity in assessing nanotoxicity.

Design and construction of artificial photoresponsive protocells based on the encapsulation and activation of metallized peptide/porphyrin self-assembled nanofilaments within silica-nanoparticle-stabilized colloidosomes.

We report the synthesis, photophysics and application of a novel semiconducting polymer as a colour converter for high speed visible light communication.

We propose a novel idea to improve the surface properties of carbon-based Pt-free electrocatalysts in Polymer Electrolyte Membrane Fuel Cells (PEMFCs) and Alkaline Fuel Cells (AFCs).

We describe the reactivity of the 2-phosphaethynolate anion (PCO⁻) towards enantiomerically pure α-amino acids (AAs) resulting in the formation of novel salts of phosphinecarboxamides bearing chiral functionalities.

We report a {Cu₁₆} embedded within a {W₄₄} cluster containing four cubane-like [Cu₄O₄] units within an isopolyoxotungstate (isoPOT) in a {Na₄Cu₄[(H₂W₁₁O₃₈) (CH₃COO)(OH)₃]}₄·88H₂O (1) and a polyanion Cu-linked {W₁₁} chain Na₆Cu₂[(H₂W₁₁O₃₈)(CH₃COO)(OH)]·26H₂O (2).

N-Heterocyclic carbene adducts of the parent arsinidene (AsH) were prepared by two different synthetic routes, either by reaction of As(SiMe₃)₃ with 2,2-difluoroimidazolines followed by desilylation or by reaction of [Na(dioxane)_3.31][AsCO] with imidazolium chlorides.

The catalytic enantioselective 6-exo-trig Michael addition-lactonization of enone-acid substrates to form cis-chromenones with high diastereo- and enantiocontrol was developed using the commercially available isothiourea tetramisole.

Isocyanurates can be synthesised through the cyclotrimerisation of primary isocyanates catalysed by low-coordinate manganese(II) and iron(II) m-terphenyl complexes under mild conditions.

Visible-light photoredox catalysis enables the synthesis of biologically relevant isoxazolines and isoxazoles from hydroxyimino acids.

The sustainability of biorefineries can be improved through levoglucosenone production from residual sugars in waste lignin.

Two spontaneous intramolecular cycloadditions lead to the biosynthetic congeners heronamide A and B.

The fabrication, characterisation and controlled cargo release of hollow mesoporous raspberry-like colloids (HMRCs), which are assembled by utilising host–guest complexation of cucurbit[8]uril (CB[8]) are described.

Cell-free gene expression of a fluorescent protein (mCherry) is demonstrated within the molecularly crowded matrix of a polysaccharide/polypeptide coacervate.

Azetidine and oxetane sulfinate salts are easily prepared from commercially available 3-iodoheterocycle precursors in a three-step sequence.

An unprecedented near-linear bis(amide) f-element complex has been prepared by utilizing bulky silylamide ligands. This Sm(II) complex is a blueprint for the next generation of single molecule magnets, where predictions for the Dy(III) analogue suggest they could operate above 77 K.

Engineering the active site of the spore photoproduct lyase, a radical SAM enzyme involved in DNA repair, proves that it is possible to rewire the H-atom transfer pathway in a radical SAM enzyme.

An efficient kinetic resolution of 2-arylpiperidines was developed using a chiral base.

A new class of degradable aliphatic poly(carbonate) resins for use in microstereolithographic process is described.

Scrambling experiments suggest that oligomers cross-linked by four imine bonds are kinetically trapped, limiting the synthesis of covalent ladders with five or more rungs.

Iridium trisboryl complexes containing bisphosphine and bipyridine ligands and pinacolate and catecholate substituents are reported.

Para-hydrogen achieves the hyperpolarisation of amines via SABRE.

A robust precious metal-free photocatalyst system comprised of ligand-free ZnSe quantum dots and a phosphonic acid-functionalised Ni(cyclam) catalyst achieves efficient reduction of aqueous CO₂ to CO.

A hybrid electrolyser utilising anthraquinone disulfonic acid allows H₂ and O₂ production to be decoupled at current densities of up to 3.71 A cm⁻², and provides an inherently safer and more flexible approach to water splitting.

The global iron regulator RirA controls transcription of iron metabolism genes via the binding of a fragile [4Fe–4S] cluster.

Evolved DNA polymerases are used in selections with fully 2′-OMe modified libraries to identify aptamers with high affinity for HNE.

The electrochemical detection and characterisation of individual enzymes via the nano-impact technique is predicted.

The metathesis reaction of a U^V imido complex supported by sterically demanding tris(tert-butoxy)siloxide ligands with CS₂ afforded a terminal U^V thiocarbonate but metathesis with H₂S afforded the first example of a terminal U^V sulfide.

A family of [M^III₂M^II₃]ⁿ⁺ trigonal bipyramidal cages are characterised in the solution and solid state.

A well-defined NHC-Ir(III) catalyst provides access to a wide range of aryl- and heteroarylsilanes by intermolecular dehydrogenative C–H bond silylation.

We present the first ratiometric fluorescent probes for formaldehyde, a major reactive species in biology, operating in the visible region.

Herein we present the first example of aryl radical formation via the visible light-mediated decarboxylation of aryl carboxylic acids using photoredox catalysis.

Manganese-catalyzed sequential C–H and C–C/C–Het bond activation to synthesize allylic alcohols, allylated arenes, functionalized cyclopentenes and skipped dienes is reported.

Ant pharming: antibacterial polyketides from plant-ant associated bacteria.

A mild palladium-catalyzed ligand-controlled regioselective 1,3-arylfluorination of 2[H]-chromenes has been developed.

Structural investigation on neptunium cyclopentadienyl organometallic complexes in the formal oxidation states II, III, and IV: similarities and differences between Np and U.

Inducing opposite screw senses at the two ends of a helix traps a helix reversal, allowing it to be characterised spectroscopically.

The uranyl(VI) complex UO₂Cl(L) of the redox-active diimino-dipyrrin anion, L⁻ is reported and its reactions with inner- and outer-sphere reductants studied.

Iridium complexes of the PC_sp²P ligand in which the donors are linked by 2,3-benzo[b]thiophene groups engage in the cooperative activation of N₂O and the resulting iridaepoxides can be treated with dihydrogen to effect elimination of water and regeneration of the starting iridium complex.

Pd-η³-C₆H₉ cations bearing the Trost ligand (2) undergo two-stage oligomerisation-aggregation to form high nuclearity aggregates (up to 56 Pd centres), with aggregation strongly modulated by concentration, solvent and counter-anion.

The conformational influence of a single stereogenic centre in an otherwise achiral oligomer behaves as a signal that decays with distance.

The enantioselective amination of carbonyl derivatives is achieved via phase-transfer of aryldiazonium salts by BINAM-derived phosphoric acids.

A series of dynamic combinatorial [2] and [3]catenanes have been prepared. Formation of the [3]catenanes occurs with positive or negative cooperativity, depending on the cyclodextrin homologue. Systems level analysis allows cooperativity to be quantified and MD simulations reveal that cooperativity derives from the extents to which hydrophobic surface area is exposed to the aqueous surroundings.

We describe the regioselective diborylation of 2-methyl hydrosilylarenes by the combination of [Ir(COD)OMe]₂ as metal precursor and 4,4′-di-tert-butyl-2,2′-bipyridine to form diborylbenzylic compounds.

Biosynthesis of the PKS-FAS-NRPS hybrid antibiotic thiomarinol A was investigated using feeding studies in wild type and mutant strains of the marine bacterium Pseudoalteromonas.

Facile reduction of CO₂ by a decamethylscandocene hydridoborate contact ion pair, followed by B(C₆F₅)₃ catalysed hydrosilation constitutes a highly active tandem catalyst system for the hydrosilation of CO₂ to CH₄.

Solvated electrons are generated in methanol, ethanol, and acetonitrile liquid microjets. Their binding energies are studied by photoelectron spectroscopy and compared to solvent cluster findings.

A series of bulky bis(silyl)amide ligands have been utilised to stabilise rare examples of formally 2-coordinate linear or near-linear Mg and Ca complexes.

Heterometallic species with Anderson-like structures are characterised by single-crystal X-ray diffraction, solution- and solid-state NMR spectroscopy, ESI mass spectrometry and SQUID magnetometry.

Optical images of the surface patterns formed by hexaboride (MB₆) and dodecaboride (MB₁₂) phases.

Coregistering quantitative high-resolution metal imaging with fluorescence imaging identifies copper accumulation in megamitochondria within intact neuroretinal slices.

Zinc oxide nanoparticles cause marked up-regulation of pyrimidine biosynthesis and sugar metabolism but consistent down-regulation of amino acid synthesis in MRSA, suggesting a previously unrecognized mechanism of action.

Applications of the bifunctional Lewis acid 1,1′-fc{B(C₆F₅)₂}₂ in FLP chemistry are described, including reactions towards H₂O, NH₃, CO₂ and cyclohexylisocyanate.