Prediction and realisation of high mobility and degenerate p-type conductivity in CaCuP thin films.

Phosphides are interesting candidates for hole transport materials and p-type transparent conducting applications, capable of achieving greater valence band dispersion than their oxide counterparts due to the higher lying energy and increased size of the P 3p orbital. After computational identification of the indirect-gap semiconductor CaCuP as a promising candidate, we now report reactive sputter deposition of phase-pure p-type CaCuP thin films. Their intrinsic hole concentration and hole mobility exceed 1 × 10 cm and 35 cm V s at room temperature, respectively.

A study of the interaction of cationic dyes with gold nanostructures.

The interaction of methylene blue and crystal violet dyes with a range of gold nanoparticles (AuNPs), gold nanoclusters and gold/silver nanoclusters is reported. It is found that 20 nm citrate-capped AuNPs have strong interactions with these two dyes that result in red-shifted absorption peaks in their electronic absorption spectra. Transmission electron microscopy and dynamic light scattering measurements show that this can be attributed to these AuNPs combining into large agglomerates.

Intramolecular thiomaleimide [2 + 2] photocycloadditions: stereoselective control for disulfide stapling and observation of excited state intermediates by transient absorption spectroscopy.

Thiomaleimides undergo efficient intermolecular [2 + 2] photocycloaddition reactions and offer applications from photochemical peptide stapling to polymer crosslinking; however, the reactions are limited to the formation of the head-to-head isomers. Herein, we present an intramolecular variation which completely reverses the stereochemical outcome of this photoreaction, quantitatively generating adducts which minimise the structural disturbance of the disulfide staple and afford a 10-fold increase in quantum yield. We demonstrate the application of this reaction on a protein scaffold, using light to confer thiol stability to an antibody fragment conjugate.

Enabling the next steps in cancer immunotherapy: from antibody-based bispecifics to multispecifics, with an evolving role for bioconjugation chemistry.

In the past two decades, immunotherapy has established itself as one of the leading strategies for cancer treatment, as illustrated by the exponentially growing number of related clinical trials. This trend was, in part, prompted by the clinical success of both immune checkpoint modulation and immune cell engagement, to restore and/or stimulate the patient's immune system's ability to fight the disease. These strategies were sustained by progress in bispecific antibody production.

Enhanced visible light absorption in layered CsBiBr through mixed-valence Sn(ii)/Sn(iv) doping.

Lead-free halides with perovskite-related structures, such as the vacancy-ordered perovskite CsBiBr, are of interest for photovoltaic and optoelectronic applications. We find that addition of SnBr to the solution-phase synthesis of CsBiBr leads to substitution of up to 7% of the Bi(iii) ions by equal quantities of Sn(ii) and Sn(iv). The nature of the substitutional defects was studied by X-ray diffraction, Cs and Sn solid state NMR, X-ray photoelectron spectroscopy and density functional theory calculations.

CuInS Quantum Dot and Polydimethylsiloxane Nanocomposites for All-Optical Ultrasound and Photoacoustic Imaging.

Dual-modality imaging employing complementary modalities, such as all-optical ultrasound and photoacoustic imaging, is emerging as a well-suited technique for guiding minimally invasive surgical procedures. Quantum dots are a promising material for use in these dual-modality imaging devices as they can provide wavelength-selective optical absorption. The first quantum dot nanocomposite engineered for co-registered laser-generated ultrasound and photoacoustic imaging is presented.

CaSbO and CaBiO: two promising mixed-anion thermoelectrics.

The environmental burden of fossil fuels and the rising impact of global warming have created an urgent need for sustainable clean energy sources. This has led to widespread interest in thermoelectric (TE) materials to recover part of the ∼60% of global energy currently wasted as heat as usable electricity. Oxides are particularly attractive as they are thermally stable, chemically inert, and formed of earth-abundant elements, but despite intensive efforts there have been no reports of oxide TEs matching the performance of flagship chalcogenide materials such as PbTe, BiTe and SnSe.

Multienzyme One-Pot Cascades Incorporating Methyltransferases for the Strategic Diversification of Tetrahydroisoquinoline Alkaloids.

The tetrahydroisoquinoline (THIQ) ring system is present in a large variety of structurally diverse natural products exhibiting a wide range of biological activities. Routes to mimic the biosynthetic pathways to such alkaloids, by building cascade reactions in vitro, represents a successful strategy and can offer better stereoselectivities than traditional synthetic methods. -Adenosylmethionine (SAM)-dependent methyltransferases are crucial in the biosynthesis and diversification of THIQs; however, their application is often limited in vitro by the high cost of SAM and low substrate scope.

Visualization of Directional Beaming of Weakly Localized Raman from a Random Network of Silicon Nanowires.

Disordered optical media are an emerging class of materials that can strongly scatter light. These materials are useful to investigate light transport phenomena and for applications in imaging, sensing and energy storage. While coherent light can be generated using such materials, its directional emission is typically hampered by their strong scattering nature.

Synthesis, solution dynamics and chemical vapour deposition of heteroleptic zinc complexes ethyl and amide zinc thioureides.

Ethyl and amide zinc thioureides [LZnEt] (), [L*ZnEt] () and [LZn(N(SiMe))] () have been synthesised from the equimolar reaction of thiourea ligands (HL = PrN(H)CSNMe and HL* = PhN(H)CSNMe) with diethyl zinc and zinc bis[bis(trimethylsilyl)amide] respectively. New routes towards heteroleptic complexes have been investigated through reactions of , and with β-ketoiminates (HL = [(Me)CN(H){Pr}-CHC(Me)[double bond, length as m-dash]O]), bulky aryl substituted β-diiminates (HL = [(Me)CN(H){Dipp}-CHC(Me)[double bond, length as m-dash]N{Dipp}] (Dipp = diisopropylphenyl) and HL* = [(Me)CN(H){Dep}-CHC(Me)[double bond, length as m-dash]N{Dep}] (Dep = diethylphenyl)) and donor-functionalised alcohols (HL = EtN(CH)OH and HL* = MeN(CH)OH) and have led to the formation of the heteroleptic complexes [L*ZnL*] (), [LZnL] (), [LZnL*] (), [L*ZnL] () and [L*ZnL*] (). All complexes have been characterised by H and C NMR, elemental analysis, and the X-ray structures of HL*, , , and have been determined single crystal X-ray diffraction.

A bicyclic -adenosylmethionine regeneration system applicable with different nucleosides or nucleotides as cofactor building blocks.

The ubiquitous cofactor -adenosyl-l-methionine (SAM) is part of numerous biochemical reactions in metabolism, epigenetics, and cancer development. As methylation usually improves physiochemical properties of compounds relevant for pharmaceutical use, the sustainable use of SAM as a methyl donor in biotechnological applications is an important goal. SAM-dependent methyltransferases are consequently an emerging biocatalytic tool for environmentally friendly and selective alkylations.

Mechanochemical reactivity inhibited, prohibited and reversed by liquid additives: examples from crystal-form screens.

We demonstrate that liquid additives can exert inhibitive or prohibitive effects on the mechanochemical formation of multi-component molecular crystals, and report that certain additives unexpectedly prompt the dismantling of such solids into physical mixtures of their constituents. Computational methods were employed in an attempt to identify possible reasons for these previously unrecognised effects of liquid additives on mechanochemical transformations.

Identifying key mononuclear Fe species for low-temperature methane oxidation.

The direct functionalization of methane into platform chemicals is arguably one of the holy grails in chemistry. The actual active sites for methane activation are intensively debated. By correlating a wide variety of characterization results with catalytic performance data we have been able to identify mononuclear Fe species as the active site in the Fe/ZSM-5 zeolites for the mild oxidation of methane with HO at 50 °C.

Direct observation of the evolving metal-support interaction of individual cobalt nanoparticles at the titania and silica interface.

Understanding the metal-support interaction (MSI) is crucial to comprehend how the catalyst support affects performance and whether this interaction can be exploited in order to design new catalysts with enhanced properties. Spatially resolved soft X-ray absorption spectroscopy (XAS) in combination with Atomic Force Microscopy (AFM) and Scanning Helium Ion-Milling Microscopy (SHIM) has been applied to visualise and characterise the behaviour of individual cobalt nanoparticles (CoNPs) supported on two-dimensional substrates (SiO Si(100) ( < 2) and rutile TiO(110)) after undergoing reduction-oxidation-reduction (ROR). The behaviour of the Co species is observed to be strongly dependent on the type of support.

Covalent grafting of molecular catalysts on CN H as robust, efficient and well-defined photocatalysts for solar fuel synthesis.

The covalent attachment of molecules to 2D materials is an emerging area as strong covalent chemistry offers new hybrid properties and greater mechanical stability compared with nanoparticles. A nickel bis-aminothiophenol catalyst was grafted onto a range of 2D carbon nitrides (CN H ) to form noble metal-free photocatalysts for H production. The hybrids produce H beyond 8 days with turnover numbers reaching 1360 based on nickel, a more than 3 fold higher durability than reported molecular catalyst-carbon nitride mixtures, and under longer wavelengths (>475 nm).

Recent advances in low oxidation state aluminium chemistry.

The synthesis and isolation of novel low oxidation state aluminium (Al) compounds has seen relatively slow progress over the 30 years since such species were first isolated. This is largely due to the significant challenges in isolating these thermodynamically unstable compounds. Despite challenges with isolation, their reactivity has been widely explored and they have been utilized in a wide range of processes including the activation of strong chemicals bonds, as ligands to transition metals and in the formation of heterobimetallic M-M compounds.

Electrochemical radical reactions of alkyl iodides: a highly efficient, clean, green alternative to tin reagents.

An electrochemical 'redox-relay' system has been developed which allows the generation of C-centered radicals. Intermolecular 'tin-like' radical reactions can subsequently be conducted under the most benign of conditions. The yields and efficiency of the processes are competitive and even superior in most cases to comparable conditions with tributyltin hydride.

One-pot thiol-amine bioconjugation to maleimides: simultaneous stabilisation and dual functionalisation.

Maleimide chemistry is widely used in the site-selective modification of proteins. However, hydrolysis of the resultant thiosuccinimides is required to provide robust stability to the bioconjugates. Herein, we present an alternative approach that affords simultaneous stabilisation and dual functionalisation in a one pot fashion.

Environmentally relevant concentrations of titanium dioxide nanoparticles pose negligible risk to marine microbes.

Nano-sized titanium dioxide (nTiO) represents the highest produced nanomaterial by mass worldwide and, due to its prevalent industrial and commercial use, it inevitably reaches the natural environment. Previous work has revealed a negative impact of nTiO upon marine phytoplankton growth, however, studies are typically carried out at concentrations far exceeding those measured and predicted to occur in the environment currently. Here, a series of experiments were carried out to assess the effects of both research-grade nTiO and nTiO extracted from consumer products upon the marine dominant cyanobacterium, , and natural marine communities at environmentally relevant and supra-environmental concentrations (, 1 μg L to 100 mg L).

Enhancing bifunctional catalytic activity of cobalt-nickel sulfide spinel nanocatalysts through transition metal doping and its application in secondary zinc-air batteries.

Developing large-scale and high-performance OER (oxygen evolution reaction) and ORR (oxygen reduction reaction) catalysts have been a challenge for commercializing secondary zinc-air batteries. In this work, transition metal-doped cobalt-nickel sulfide spinels are directly produced a continuous hydrothermal flow synthesis (CHFS) approach. The nanosized cobalt-nickel sulfides are doped with Ag, Fe, Mn, Cr, V, and Ti and evaluated as bifunctional OER and ORR catalyst for Zn-air battery application.

n-Type conducting P doped ZnO thin films chemical vapor deposition.

Extrinsically doped ZnO thin films are of interest due to their high electrical conductivity and transparency to visible light. In this study, P doped ZnO thin films were grown on glass substrates aerosol assisted chemical vapour deposition. The results show that P is a successful dopant for ZnO in the V+ oxidation state and is able to reduce resistivity to 6.

Reactions of triosmium and triruthenium clusters with 2-ethynylpyridine: new modes for alkyne C-C bond coupling and C-H bond activation.

The reaction of the trimetallic clusters [HOs(CO)] and [Ru(CO)L] (L = CO, MeCN) with 2-ethynylpyridine has been investigated. Treatment of [HOs(CO)] with excess 2-ethynylpyridine affords [HOs(CO)(μ-CHNCH=CH)] (1), [HOs(CO)(μ-CHNC[double bond, length as m-dash]CH)] (2), [HOs(CO)(μ-CHNC[double bond, length as m-dash]CCO)] (3), and [HOs(CO)(μ-CH[double bond, length as m-dash]CHCHN)] (4) formed through either the direct addition of the Os-H bond across the C[triple bond, length as m-dash]C bond or acetylenic C-H bond activation of the 2-ethynylpyridine substrate. In contrast, the dominant pathway for the reaction between [Ru(CO)] and 2-ethynylpyridine is C-C bond coupling of the alkyne moiety to furnish the triruthenium clusters [Ru(CO)(μ-CO){μ-CHNC[double bond, length as m-dash]CHC(CHN)[double bond, length as m-dash]CH}] (5) and [Ru(CO)(μ-CO){μ-CHNCCHC(CHN)CHCHC(CHN)}] (6).

Polymorph exploration of bismuth stannate using first-principles phonon mode mapping.

Accurately modelling polymorphism in crystalline solids remains a key challenge in computational chemistry. In this work, we apply a theoretically-rigorous phonon mode-mapping approach to understand the polymorphism in the ternary metal oxide BiSnO. Starting from the high-temperature cubic pyrochlore aristotype, we systematically explore the structural potential-energy surface and recover the two known low-temperature phases alongside three new metastable phases, together with the transition pathways connecting them.

The Role of Phosphate Group in Doped Cobalt Molybdate: Improved Electrocatalytic Hydrogen Evolution Performance.

The hydrogen evolution reaction (HER) is a critical process in the electrolysis of water. Recently, much effort has been dedicated to developing low-cost, highly efficient, and stable electrocatalysts. Transition metal phosphides are investigated intensively due to their high electronic conductivity and optimized absorption energy of intermediates in acid electrolytes.