U.S. anxiety over the ‘rise of China’ is nothing new

It has been more than three years since the then Secretary of State, Hillary Clinton announced the Obama Administration’s ‘Pivot to Asia’, with subsequent comments from President Obama affirming U.S. interests in the region. Ben Coulson argues that this pivot to Asia should be seen against the background of more than six decades of U.S. anxiety and tension over the role of China in the region. He writes that for the U.S., China still represents a challenge to the ‘conventional’ narrative that the U.S. has a pre-eminent role to play in world politics, and in East Asia

Carbon Nitride as a Ligand: Synthesis, Characterisation and Application

Carbon nitride’s properties can be tuned through the coordination of metal atoms, which can lead to enhanced catalytic activity. However, to date, there are few reported examples of inner-sphere coordination of metal complex fragments to carbon nitride. Therefore, the effects of coordination of metal complex fragments to carbon nitride haves been investigated. Reaction of the rhenium carbonyl complex, [ReCl(CO)5] with the surface of urea-derived carbon nitride (UCN) results in [ReCl(CO)3(UCN)], with a rhenium concentration of 0.39 mmol g-1. The synthesis of the manganese analogue resulted in manganese oxidation leading to [Mn(UCN)] ([Mn] = 0.24 mmol g-1). Infrared spectroscopy, along with crystal structures of molecular analogues, [MCl(CO)3(DMNA-κ2N, N’)] (M = Re, Mn) was used to gain insight into the coordination of metals complex fragments to carbon nitride. Two morphologies of carbon nitride, unstructured urea-derived carbon nitride (UCN) and porous cyanamide derived carbon nitride (CCN), were then decorated with [Ru(bpy)2]2+ fragments. The carbon nitride structure affected metal loading, as [Ru(bpy)2(UCN)](PF6)2 ([Ru] = 0.016 mmol g-1) showed lower metal loading compared to [Ru(bpy)2(CCN)](PF6)2 ([Ru] = 0.076 mmol g-1). [Ru(bpy)2(DMNA-κ2N, N’)](PF6)2 was synthesised as a molecular analogue to gain insight into the coordination mode. The photocatalytic activities of [Ru(bpy)2(UCN)](PF6)2 and [Ru(bpy)2(UCN)](PF6)2 were completely inhibited compared to the undecorated materials. EPR and photoluminescence suggested the presence of rapid, efficient quenching of excited states in ruthenium decorated carbon nitride. [IrCl2Cp*(UCN)] ([Ir] = 0.069 mmol g-1) was synthesised to design a novel, recyclable hydrogenation catalyst. Direct hydrogenation reactions were carried out using hexane as a solvent, and despite low activity, [IrCl2Cp*(UCN)] showed good selectivity toward terminal alkenes and over 80% of catalytic activity was retained after 5 catalytic runs. Direct coordination of metal complex fragments to carbon nitride is shown to be a viable route to tuning the properties of carbon nitride and developing recyclable novel catalysts

Effects of the sustainable forestry Initiative on landscape function as measured by patterns of vertebrate habitats

The Sustainable Forestry Initiative (SFI) adopted in 1995 by the American Forest and Paper Association is currently applied over 90% of industrial forests in the US. This program has potential effects on forest landscape structure and function, including biodiversity. Here we analyze the effects of SFI application on the abundance and spatial pattern of vertebrate habitats in a 6,000-ha forested watershed in East Texas. Simulations of landscape structure changes in the study area were conducted based on forest inventory data and SFI rules such as regeneration harvest areas limits of 49 ha for pine and 12 ha for hardwoods, streamside management zones 30 m or more wide, and a three-year green-up interval. The 266 species (83 herps, 132 birds, 51 mammals) of vertebrates potentially occurring in the study area were grouped into 12 clusters based upon their habitat requirements. One species per cluster was selected as the indicator species for the cluster. Habitat Suitability Index models were used to develop habitat suitability maps for the indicator species based on the landscape simulations. Habitat abundance and spatial characteristics for individual vertebrate species were evaluated at different points of time to assess the effects of the SFI on vertebrate habitats as compared to reference scenarios

Carbon nitride as a ligand: edge-site coordination of ReCl(CO)3-fragments to g-C3 N4

IR spectroscopy and model structural studies show binding of ReCl(CO) 3-fragments to carbon nitride (g-C 3N 4) occurs via κ 2 N,N′ bidentate coordination

Light-Induced Activation of a Molybdenum Oxotransferase Model within a Ru(II)-Mo(VI) Dyad

Nature uses molybdenum-containing enzymes to catalyze oxygen atom transfer (OAT) from water to organic substrates. In these enzymes, the two electrons that are released during the reaction are rapidly removed, one at a time, by spatially separated electron transfer units. Inspired by this design, a Ru(II)-Mo(VI) dyad was synthesized and characterized, with the aim of accelerating the rate-determining step in the cis-dioxo molybdenum-catalyzed OAT cycle, the transfer of an oxo ligand to triphenyl phosphine, via a photo-oxidation process. The dyad consists of a photoactive bis(bipyridyl)-phenanthroline ruthenium moiety that is covalently linked to a bioinspired cis-dioxo molybdenum thiosemicarbazone complex. The quantum yield and luminescence lifetimes of the dyad [Ru(bpy)2(L(2))MoO2(solv)](2+) were determined. The major component of the luminescence decay in MeCN solution (τ = 1149 ± 2 ns, 67%) corresponds closely to the lifetime of excited [Ru(bpy)2(phen-NH2)](2+), while the minor component (τ = 320 ± 1 ns, 31%) matches that of [Ru(bpy)2(H2-L(2))](2+). In addition, the (spectro)electrochemical properties of the system were investigated. Catalytic tests showed that the dyad-catalyzed OAT from dimethyl sulfoxide to triphenyl phosphine proceeds significantly faster upon irradiation with visible light than in the dark. Methylviologen acts as a mediator in the photoredox cycle, but it is regenerated and hence only required in stoichiometric amounts with respect to the catalyst rather than sacrificial amounts. It is proposed that oxidative quenching of the photoexcited Ru unit, followed by intramolecular electron transfer, leads to the production of a reactive one-electron oxidized catalyst, which is not accessible by electrochemical methods. A significant, but less pronounced, rate enhancement was observed when an analogous bimolecular system was tested, indicating that intramolecular electron transfer between the photosensitizer and the catalytic center is more efficient than intermolecular electron transfer between the separate components

Exploring the influence of polymorphism and chromophore co-ligands on linkage isomer photoswitching in [Pd(bpy4dca)(NO2)2]

The polymorphic Pd(II)–nitrite complex [Pd(bpy4dca)(NO2)2] (1) (bpy4dca = 2,2′-bipyridine-4,4′-dicarboxylic acid methyl ester) is shown to undergo photoinduced nitro → nitrito linkage isomer switching in two crystal forms, to varying excited state population levels. Detailed photocrystallographic kinetic studies, structural analyses of the ground and photoexcited states and density functional theory calculations all combine to explain the unusually high maximum excited state population of 80% in 1, where other linkage isomer complexes containing strong chromophore co-ligands have traditionally been challenging to excite. Comparison of the photo-response in crystals for forms I and II reveals that, while the local crystal packing environment has a role in controlling the maximum photostationary population that can be achieved, the rate of isomerisation is comparable across different nitrite ligand environments. Our results reinforce the hypothesis that a complex combination of steric, electronic and kinetic factors govern the progress of linkage isomer switching in the solid-state and highlight the need for better understanding of the structural dynamics involved in isomer switching at the molecular level

Uncovering the role of non-covalent interactions in solid-state photoswitches by non-spherical structure refinements with NoSpherA2

We present a charge density study of two linkage isomer photoswitches, [Pd(Bu4dien)(NO2)]BPh4·THF (1) and [Ni(Et4dien)(NO2)2] (2) using Hirshfeld Atom Refinement (HAR) methods implemented via the NoSpherA2 interface in Olex2. HAR is used to explore the electron density distribution in the photoswitchable molecules of 1 and 2, to gain an in-depth understanding of key bonding features and their influence on the single-crystal-to-single-crystal reaction. HAR analysis is also combined with ab initio calculations to explore the non-covalent interactions that influence physical properties of the photoswitches, such as the stability of the excited state nitrito-(η1-ONO) isomer. This insight can be fed back into the crystal engineering process to develop new and improved photoswitches that can be optimised towards specific applications

Enhancing the repeatability and sensitivity of low-cost PCB, pH-sensitive field-effect transistors

Discrete, extended gate pH-sensitive field-effect transistors (dEGFETs) fabricated on printed circuit boards (PCBs) are a low-cost, simple to manufacture analytical technology that can be applied to a wide range of applications. Electrodeposited iridium oxide (IrOx) films have emerged as promising pH-sensitive layers owing to their theoretically high pH sensitivity and facile deposition, but typically exhibit low pH sensitivity or lack repro- ducibility. Moreover, to date, a combined IrOx and dEGFET PCB system has not yet been realised. In this study, we demonstrate a dEGFET pH sensor based on an extended gate manufactured on PCB that is rendered pH sensitive through an electrodeposited IrOx film, which can reliably and repeatably display beyond-Nernstian pH response. Using a combination of complementary surface analysis techniques, we show that the high pH sensitivity and repeatability of the dEGFETs are dependent on both the chemical composition and critically the uniformity of the IrOx film. The IrOx film uniformity can be enhanced through electrochemical polishing of the extended gate electrode prior to electrodeposition, leading to dEGFETs that exhibit a median pH sensitivity of 70.7 ± 5 mV/pH (n = 56) compared to only 31.3 ± 14 mV/pH (n = 31) for IrOx electrodeposited on non- polished PCB electrodes. Finally, we demonstrate the applicability of these devices by demonstrating the detection and quantification of ampicillin due to β-Lactamase enzyme activity, thus laying the foundation for cheap and ubiquitous sensors which can be applied to a range of global challenges across healthcare and environmental monitoring

Single atom Cu(I) promoted mesoporous titanias for photocatalytic Methyl Orange depollution and H 2 production

Tailoring the physicochemical properties and hence reactivity of semiconductor photocatalysts in a predictable fashion, remains a challenge to their industrial application. Here we demonstrate the striking promotional effect of incorporating single Cu(I) atoms, on aqueous phase photocatalytic dye degradation and H2 production over surfactant-templated mesoporous TiO2. X-ray absorption spectroscopy reveals that ultra-low concentrations of copper (0.02-0.1 wt%) introduced into the mesoporous TiO2 surface create isolated Cu (I) species which suppress charge recombination, and confer a six-fold photocatalytic promotion of Methyl Orange degradation and four-fold enhancement of H2 evolution. The impact of mesopore structure and photophysical properties on photocatalytic activity is also quantified for the first time: calcination increases mesopore size and nanocrystalline order, and induces an anatase to rutile phase transition that is accompanied by a decrease in the optical band gap, increased charge carrier lifetime, and a concomitant significant activity enhancement

Efficient photoelectrochemical Kolbe C-C coupling at BiVO4 electrodes under visible light irradiation

Electrochemical Kolbe C-C coupling of carboxylic acids at Pt electrodes has been studied for over 150 years and remains relevant today because renewable electricity is envisaged to make an increasing contribution to clean chemical processes and carboxylic acids are readily available precursors for chemical synthesis. Traditional electrochemical Kolbe occurs typically at very high potential (>10 V) which is required to achieve high selectivity for C-C coupling. Here we describe porous BiVO4 photoelectrodes that mediate C-C Kolbe coupling with near quantitative faradaic efficiency under visible light irradiation at <2 V. High substrate concentrations are also found to stabilise the double layer avoiding the need for additional supporting electrolyte. Comparison with related literature describing photocatalytic Kolbe C-C coupling shows that the apparent quantum yield can be raised from <1% to 12% demonstrating the distinct advantage of using photoelectrochemistry in this system