Themed collection Celebrating the 2016 RSC Prize and Award Winners
Synthetic chemistry fuels interdisciplinary approaches to the production of artemisinin
In the developing world, multi-drug resistant malaria is an epidemic that claims the lives of 1–3 million people per year. Artemisinin, a naturally occurring small molecule, is a valuable weapon in the fight against this disease. This review highlights interdisciplinary efforts to access artemisinin, with an emphasis on the key role of synthetic chemistry.
Asymmetric 18F-fluorination for applications in positron emission tomography
To date, both transition metal complexes and organomediators have been employed for enantiocontrolled 18F-incorporation as an alternative to conventional resolution of SN2-based radiochemistry.
Lipopeptides: from self-assembly to bioactivity
This Feature Article discusses several classes of lipopeptide with important biomedical applications as antimicrobial and antifungal agents, in immune therapies and in personal care applications among others.
Ring-opening copolymerization (ROCOP): synthesis and properties of polyesters and polycarbonates
This feature article highlights the opportunities presented by ring-opening copolymerization (ROCOP) as a controlled route to prepare polyesters and polycarbonates.
Pyridynes and indolynes as building blocks for functionalized heterocycles and natural products
This feature article showcases the use of pyridynes and indolynes to construct functionalized heterocycles and complex natural products.
Filling the gap between the quantum and classical worlds of nanoscale magnetism: giant molecular aggregates based on paramagnetic 3d metal ions
The syntheses, structures and magnetic properties of giant molecular 3d and 3d/4f paramagnetic metal clusters are surveyed. Such complexes combine fascinating crystal structures, interesting magnetic properties and sizes comparable to those of classical magnetic nanoparticles providing a powerful bottom-up approach to nanoscale magnetic materials.
Alkaline earths as main group reagents in molecular catalysis
The past decade has witnessed some remarkable advances in our appreciation of the structural and reaction chemistry of the heavier alkaline earth (Ae = Mg, Ca, Sr, Ba) elements.
Routes to tin chalcogenide materials as thin films or nanoparticles: a potentially important class of semiconductor for sustainable solar energy conversion
A review of synthetic routes to tin chalcogenides and CTZS, promising materials for sustainable photovoltaics.
Molecule-based magnetic coolers
Improving the cooling power of the magnetic materials through sophisticated molecular design is viable, with a huge expansion in this area in recent years. This review provides an overview of recent developments and suggests some possible future directions.
Natural product modulators of transient receptor potential (TRP) channels as potential anti-cancer agents
Natural products provide privileged scaffolds for transient receptor potential (TRP) channel engagement and a source for chemical probe and/or lead development.
De novo designed
peptides for biological applications
A wide variety of de novo designed building blocks (or tectons) can be used to produce both fibrous, effectively infinite, and discrete materials with potential biological applications.
The frequently overlooked importance of
solvent in free radical syntheses
Many radical reactions exhibit large kinetic solvent effects that have to be carefully considered if good product yields are to be achieved.
Sensitive SERS nanotags for use with 1550 nm (retina-safe) laser excitation
1550 nm SERS nanotags have been developed to provide effective SERS with picomolar detection limits when excited with a retina-safe laser.
Facile kinetic induction of a dihydropyridide to pyrrolide ring contraction
A sterically demanding N-aryl carbodiimide reacts with magnesium 1,4-dihydropyridides to initiate heterocyclic ring contraction and pyrrolide formation under unprecedentedly mild conditions.
Theoretical rationalisation for the mechanism of N-heterocyclic carbene-halide reductive elimination at CuIII, AgIII and AuIII
A dichotomy in carbon versus bromide reductive elimination in CuIII–NHC complexes is rationalized by computational methods (DFT).
Synthesis and characterization of a novel N–F reagent derived from the ethano-Tröger's base: 1JFN coupling constants as a signature for the N–F bond
Methylation followed by fluorination of the ethano-Tröger's base affords a novel N–F reagent more reactive than Selectfluor bis(tetrafluoroborate). This study provides 1JFN coupling constants to characterize the N–F group.
Mixed-monolayer glyconanoparticles for the detection of cholera toxin by surface enhanced Raman spectroscopy
Cholera toxin B subunit (CTB) is detected sensitively in samples of synthetic freshwater by measuring changes in the SERS intensity of the glyconanoparticles upon their binding of CTB and subsequently aggregating. The particles are coated in both galactose and sialic acid.
Highly efficient planar perovskite solar cells through band alignment engineering
Planar perovskite solar cells exhibit a conduction band misalignment of the perovskite with TiO2, but not with SnO2. The system using the latter yielded power conversion efficiencies over 18%.
An extended framework of cages formed of pre-synthesised and functionalised heterometallic cages
A metal–organic framework is reported which is formed from reacting a heterometallic ring, which is functionalised to act as a 4,4′-bipyridyl linear linker, and an oxo-centred metal-triangle.
One-pot synthesis of super-bright fluorescent nanogel contrast agents containing a dithiomaleimide fluorophore
Fluorescent nanogels with radii ranging from 12–17 nm, high quantum yield, concentration-independent emission, and fluorescent lifetimes of ca. 25 ns have been synthesised in a one-pot process.
Production of few-layer phosphorene by liquid exfoliation of black phosphorus
We report the liquid exfoliation of black phosphorus to form few-layer phosphorene nanosheets.
Iron-catalysed, general and operationally simple formal hydrogenation using Fe(OTf)3 and NaBH4
An operationally simple and environmentally benign formal hydrogenation protocol has been developed using a highly abundant iron(III) salt and an inexpensive, bench stable, stoichiometric reductant, NaBH4, in ethanol, under ambient conditions.
Na0.67Mn1−xMgxO2 (0 ≤ x ≤ 0.2): a high capacity cathode for sodium-ion batteries
Earth-abundant Na0.67[Mn1−xMgx]O2 (0 ≤ x ≤ 0.2) cathode materials with the P2 structure have been synthesized as positive electrodes for sodium-ion batteries.
coumarin derivatives that inhibit transthyretin amyloidogenesis and serve as fluorescent transthyretin folding sensors
Two coumarin derivatives obtained by structure-based design are potent transthyretin kinetic stabilizers (amyloid inhibitors) and sensitive fluorescent transthyretin folding sensors.
Quantized friction across
ionic liquid thin films
Integer numbers of ion layers give rise to discrete friction regimes.
Highly sensitive, operationally simple, cost/time effective
detection of the mycolactones from the human pathogen Mycobacterium ulcerans
A boronate-assisted fluorogenic chemosensor in a solid phase is developed, selectively to detect the mycolactones produced by the human pathogen Mycobacterium ulcerans.
Skeletal diversity construction via a branching synthetic strategy
A branching synthetic strategy was used to efficiently generate structurally diverse scaffolds, which span a broad area of chemical descriptor space, and their biological activity against MRSA was demonstrated.
Direct observation by time-resolved infrared spectroscopy of the bright and the dark excited states of the [Ru(phen)2(dppz)]2+ light-switch compound in solution and when bound to DNA
Strikingly different TRIR spectra are recorded for the complex in D2O or CD3CN or when DNA-bound.
Imposing control on self-assembly: rational design and synthesis of a mixed-metal, mixed-ligand coordination cage containing four types of component
A stepwise assembly method, using a combination of kinetically inert and kinetically labile components, allows formation of a coordination cage based on four types of component with each component directed to a specific site.
Isolation of cationic and neutral (allenylidene)(carbene) and bis(allenylidene)gold complexes
The one-electron reduction of a cationic (allenylidene)[cyclic(alkyl)(amino)carbene]gold(I) complex leads to the corresponding neutral, paramagnetic, formally gold(0) complex.
An optoelectronic nose for identification of explosives
A portable optoelectronic nose for the identification of explosives uses a highly cross-reactive colorimetric sensor array and a handheld scanner.
Importance of dipole moments and ambient polarity for the conformation of Xaa–Pro moieties – a combined experimental and theoretical study
The trans : cis isomer ratio of Xaa–Pro bonds is significantly affected by the polarity of the environment. Computational and NMR spectroscopic studies revealed an intricate balance between polarity effects and interactions of carbonyl groups.
Stereocontrolled protein surface recognition using chiral oligoamide proteomimetic foldamers
An oligoamide helix mimicking foldamer with well-defined conformation is shown to recognize its target protein hDM2 in a manner that depends upon the composition, spatial projection and stereochemistry of functional groups appended to the scaffold.
Thymine functionalised porphyrins, synthesis and heteromolecular surface-based self-assembly
The synthesis and surface-based self-assembly of thymine-functionalised porphyrins is described.
A catalytic role for methionine revealed by a combination of computation and experiments on phosphite dehydrogenase
Novel role for methionine in enzyme catalysis.
Tactics for probing aryne reactivity: mechanistic studies of silicon–oxygen bond cleavage during the trapping of (HDDA-generated) benzynes by silyl ethers
Mechanistic features of the trapping reaction of an HDDA-generated aryne by pendant silyl ethers were probed using, e.g., an intramolecular clock reaction (cf. k2).
Structure and bonding of group 4-nickel heterobimetallics supported by 2-(diphenylphosphino)pyrrolide ligands
The synthesis of a full series of group 4/nickel complexes supported by a 2-(diphenylphosphino)pyrrolide (NP) ligand is reported.
Quantitative analysis of trace palladium contamination in solution using electrochemical X-ray fluorescence (EC-XRF)
Electrochemical X-ray fluorescence for the quantitative analysis of trace level Pd in solution in the presence of excess electroactive species.
A novel design strategy for nanoparticles on nanopatterns: interferometric lithographic patterning of Mms6 biotemplated magnetic nanoparticles
Top-down surface patterning technique, interferometric lithography, is combined with bottom-up magnetite nanoparticle biomineralisation using Mms6 to form magnetic nanoscale arrays.
Circular extinction of plasmonic silver nanocaps and gas sensing
The logical and psychological structure of physical chemistry and its relevance to graduate students' opinions about the difficulties of the major areas of the subject
Phosphorescence quenching of fac-tris(2-phenylpyridyl)iridium(III) complexes in thin films on dielectric surfaces
Surface quenching of triplet excitons at the film interface is investigated in iridium-cored phosphorescent dendrimer films.
Molecular design for growth of supramolecular membranes with hierarchical structure
Computational and experimental investigation of interfacial self-assembly between peptide amphiphiles and polyelectrolytes into microstructured membranes.
Antibacterial properties of Cu–ZrO2 thin films prepared via aerosol assisted chemical vapour deposition
The antibacterial properties of a Cu–ZrO2 film grown via aerosol assisted chemical vapour deposition are presented.
Exciton–exciton annihilation and relaxation pathways in semiconducting carbon nanotubes
After non-linear annihilation in semiconducting carbon nanotubes a doubly-excited exciton relaxes directly to its E11 state bypassing the intermediate E22 manifold.
Monitoring guanine photo-oxidation by enantiomerically resolved Ru(II) dipyridophenazine complexes using inosine-substituted oligonucleotides
Assessing the stability of a proficiency test material by participant-blind re-use after a period of storage
Stability of a reference material characterised by proficiency test is monitored inexpensively by a participant-blind issue of the same material in two rounds of the test separated by a suitable period.
Exploration of the HIF-1α/p300 interface using peptide and Adhiron phage display technologies
A range of experimental approaches are used to understand the HIF-1α/p300 interface – an important anticancer drug development target – in greater detail.
Unraveling the complexity of protein backbone dynamics with combined 13C and 15N solid-state NMR relaxation measurements
Combined analysis of 13C′ and 15N R1 and R1ρ relaxation rates measured at two magnetic fields leads to improved modeling of backbone dynamics in crystalline protein and provides unique insights into how the same motions contribute differently to relaxation rates in solution and solid state.
On the nature of niobium substitution in niobium doped titania thin films by AACVD and its impact on electrical and optical properties
Niobium doped TiO2 thin films were deposited on silica coated glass substrate using aerosol assisted chemical vapour deposition (AACVD) from hexane solution, at 500 °C.
Understanding corrosion inhibition with van der Waals DFT methods: the case of benzotriazole
Life cycle inventory improvement in the pharmaceutical sector: assessment of the sustainability combining PMI and LCA tools
Pharmaceutical chemicals are complex, high value added products that typically impose significantly greater impacts on the environment per kilogram compared to basic chemicals.
A dual radiolabelling approach for tracking metal complexes: investigating the speciation of copper bis(thiosemicarbazonates) in vitro and in vivo
A pair of [123I]/[64Cu]-copper bis(thiosemicarbazonates), radiolabelled at either the metal or at the ligand, was used to examine the roles of the copper metal and the ligand in the in vitro and in vivo behaviour of this class of hypoxia PET imaging agent.
Continuous catalytic upgrading of ethanol to n-butanol and >C4 products over Cu/CeO2 catalysts in supercritical CO2
Direct production of BuOH from EtOH is compared over four Cu catalysts, supported on different solid acids. The activity of these catalysts to perform the Guerbet reaction was assessed using a continuous flow reactor and the effect of using scCO2 was also monitored. Cu on high surface area CeO2 showed the best activity for BuOH formation, with yields above 30%.
Selective NaOH-catalysed hydration of aromatic nitriles to amides
The selective synthesis of aromatic and heteroaromatic amides through base-catalysed hydration of nitriles was achieved using inexpensive and commercially available NaOH as the only catalyst.
Mapping atomic motions with ultrabright electrons: towards fundamental limits in space-time resolution
Taking a hard line with biotemplating: cobalt-doped magnetite magnetic nanoparticle arrays
A cysteine-mutated biomineralisation protein (Mms6) patterned onto gold biotemplates magnetic nanoparticle arrays of magnetite and higher coercivity cobalt-doped magnetite. This demonstrates an adaptable, green approach for the future of nanofabrication.
In situ Fe K-edge X-ray absorption spectroscopy study during cycling of Li2FeSiO4 and Li2.2Fe0.9SiO4 Li ion battery materials
The valence and local structures of Fe during battery cycling of Li2FeSiO4 and Li2.2Fe0.9SiO4 are studied by in situ (XAS) measurements.
Ethylene polymerisation using solid catalysts based on layered double hydroxides
We report here the use of methylaluminoxane (MAO) modified aqueous miscible organic solvent treated (AMOST) layered double hydroxide, Mg6Al2(OH)16CO3·4H2O (AMO-Mg3Al-CO3) as a catalyst support system for the slurry phase polymerisation of ethylene using immobilised metallocene and non-metallocene metal complexes.
Epitope topography controls bioactivity in supramolecular nanofibers
Bioactivity of RGDS epitopes presented on the surface of the supramolecular nanofibers is highly dependent on their spatial presentation, which dictates the interaction with cell-surface integrin receptors.
Regulating exocytosis of nanoparticles via host–guest chemistry
Regulating exocytosis of AuNPs by using host–guest interactions between AuNPs and CB molecules.
A route to convert CO2: synthesis of 3,4,5-trisubstituted oxazolones
CO2 can react with various propargylic amines to form 3,4,5-trisubstituted oxazolones catalyzed by the active, selective and stable ionic liquids.
Probing a chemical compass: novel variants of low-frequency reaction yield detected magnetic resonance
We present a new spectroscopic technique to characterise a model chemical compass. The data obtained inform the interpretation of animal behaviour studies into the origin of avian magnetoreception.
The first airborne comparison of N2O5 measurements over the UK using a CIMS and BBCEAS during the RONOCO campaign
An assessment of simultaneous airborne measurements of dinitrogen pentoxide by a CIMS and BBCEAS.
Cross-strand histidine–aromatic interactions enhance acyl-transfer rates in beta-hairpin peptide catalysts
A His–aryl interaction in a beta-hairpin catalyst provides rate enhancements of up to 18 000 for acyl transfer catalysis.
High-resolution imaging with SEM/T-SEM, EDX and SAM as a combined methodical approach for morphological and elemental analyses of single engineered nanoparticles
A quick, comprehensive surface/bulk analysis of mesoporous and coated nanoparticles by (T-)SEM, EDX and SAM.
Exploring the mechanism of the hydroboration of alkenes by amine–boranes catalysed by [Rh(xantphos)]+
The [Rh(xantphos)]+ fragment acts as an effective catalyst for the hydroboration of the alkene TBE (tert-butyl ethene) using the amine–borane H3B·NMe3 at low (0.5 mol%) catalyst loadings to give the linear product.
Preparation and characterisation of high-density ionic liquids incorporating halobismuthate anions
1-Butyl-3-methylimidazolium tetrahalobismuthates. Chlorobismuthates are colourless. Upon substitution of chloride for bromide or iodide the liquids become progressively more yellow or red.
A heterogeneous water oxidation catalyst from dicobalt octacarbonyl and 1,2-bis(diphenylphosphino)ethane
A cobalt-based material catalyzes anodic water oxidation in neutral and alkaline solutions, and is most active in borate electrolyte.
High throughput screening of organic residues in archaeological potsherds using direct acidified methanol extraction
The variable properties of archaeological pottery and complex chemical nature of absorbed organic residues deposited during use demands new analytical methods to answer major questions concerning how people lived in the past.
About this collection
In celebration of the 2016 Royal Society of Chemistry Prizes and Awards, we have collected together some of the exciting research recently published by the winners. This collection showcases articles authored by the winners from across the Royal Society of Chemistry’s journals portfolio – these articles are free to access until 5 August 2016. A full list of winners and more information about Royal Society of Chemistry Prizes and Awards can be found at: rsc.li/awards-prizes-2016
Why not also have a look at last year’s collection of articles by our 2015 winners – http://rsc.li/rscwinners2015-collection