Iron-catalysed alkene and heteroarene H/D exchange by reversible protonation of iron-hydride intermediates

C–H functionalisation reactions offer a sustainable method for molecular construction and diversification. These reactions however remain dominated by precious metal catalysis. While significant interest in iron-catalysed C–H activation reactions has emerged, the isolation, characterisation and mechanistic understanding of these processes remain lacking. Herein the iron-catalysed C(sp²)–H bond hydrogen/deuterium exchange reaction using CD₃OD is reported for both heterocycles and, for the first time, alkenes (38 examples). Isolation and characterisation, including by single-crystal X-ray diffraction, of the key iron-aryl and iron-alkenyl C–H metallation intermediates provided evidence for a reversible protonation of the active iron hydride catalyst. Good chemoselectivity was observed for both substrate classes. The developed procedure is orthogonal to previous iron-catalysed H/D exchange methods which used C₆D₆, D₂, or D₂O as the deuterium source, and uses only bench-stable reagents, including the iron(ii) pre-catalyst. Further, a new mechanism of iron-hydride formation is reported in which β-hydride elimination from an alcohol generates the iron hydride. The ability to produce, isolate and characterise the organometallic products arising from C–H activation presents a basis for future discovery and development.

The iron-catalysed C(sp²)–H bond H/D exchange reaction using CD₃OD is reported for both heterocycles and alkenes. Characterisation of the key C–H metallation intermediates provided evidence for reversible protonation of the iron hydride catalyst.     

Potential Benefits of Black Chokeberry (Aronia melanocarpa) Fruits and Their Constituents in Improving Human Health

Aronia berry (black chokeberry) is a shrub native to North America, of which the fresh fruits are used in the food industry to produce different types of dietary products. The fruits of Aronia melanocarpa (Aronia berries) have been found to show multiple bioactivities potentially beneficial to human health, including antidiabetic, anti-infective, antineoplastic, antiobesity, and antioxidant activities, as well as heart-, liver-, and neuroprotective effects. Thus far, phenolic compounds, such as anthocyanins, cyanidins, phenolic acids, proanthocyanidins, triterpenoids, and their analogues have been identified as the major active components of Aronia berries. These natural products possess potent antioxidant activity, which contributes to the majority of the other bioactivities observed for Aronia berries. The chemical components and the potential pharmaceutical or health-promoting effects of Aronia berries have been summarized previously. The present review article focuses on the molecular targets of extracts of Aronia berries and the examples of promising lead compounds isolated from these berries, including cyanidin-3-O-galactoside, chlorogenic acid, quercetin, and ursolic acid. In addition, presented herein are clinical trial investigations for Aronia berries and their major components, including cancer clinical trials for chlorogenic acid and COVID-19 trial studies for quercetin. Additionally, the possible development of Aronia berries and their secondary metabolites as potential therapeutic agents is discussed. It is hoped that this contribution will help stimulate future investigations on Aronia berries for the continual improvement of human health.     

Nickelmodifiedlarge poremesoporoussilicas ascatalysts for methanol decomposition

Summary Ni-modifiedlarge poremesoporous silicasarecharacterized by XRD, N₂physisorption and TPR with H₂. Theeffectof the supportpore structure on their catalytic behaviorin methanol decomposition to H₂, CO and CH₄is studied.     

Measuring charge transport from transient photovoltage rise times. A new tool to investigate electron transport in nanoparticle films

Charge transport rate at open-circuit potential (V(oc)) is proposed as a new characterization method for dye-sensitized (DS) and other nanostructured solar cells. At V(oc), charge density is flat and measurable, which simplifies quantitative comparison of transport and charge density. Transport measured at V(oc) also allows meaningful comparison of charge transport rates between different treatments, temperatures, and types of cells. However, in typical DS cells, charge transport rates at V(oc) often cannot be measured by photocurrent transients or modulation techniques due to RC limitations and/or recombination losses. To circumvent this limitation, we show that charge transport at V(oc) can be determined directly from the transient photovoltage rise time using a simple, zero-free-parameter model. This method is not sensitive to RC limitation or recombination losses. In trap limited devices, such as DS cells, the comparison of transport rates between different devices or conditions is only valid when the Fermi level in the limiting conductor is at the same distance from the band edge. We show how to perform such comparisons, correcting for conduction band shifts using the density of states (DOS) distribution determined from the same photovoltage transients. Last we show that the relationship between measured transport rate and measured charge density is consistent with the trap limited transport model.     

Interface engineering for solid-state dye-sensitised nanocrystalline solar cells: the use of an organic redox cascade

We demonstrate the formation of a charge transfer cascade at a nanostructured TiO2/dye/polymer/molecular hole transport multilayer interface. Charge recombination dynamics at this interface are shown to be retarded when the ionisation potential of the polymer layer exceeds that of the molecular hole transport layer.     

Coating single-walled carbon nanotubes with phospholipids

Single-walled carbon nanotubes (SWNTs), being hydrophobic by nature, aggregate in water to form large bundles. However, isolated SWNTs possess unique physical and chemical properties that are desirable for sensing and biological applications. Conventionally isolated SWNTs can be obtained by wrapping the tubes with biopolymers or surfactants. The binding modes proposed for these solubilization schemes, however, are less than comprehensive. Here we characterize the efficacies of solubilizing SWNTs through various types of phospholipids and other amphiphilic surfactants. Specifically, we demonstrate that lysophospholipids, or single-chained phospholipids offer unprecedented solubility for SWNTs, while double-chained phospholipids are ineffective in rendering SWNTs soluble. Using transmission electron microscopy (TEM) we show that lysophospholipids wrap SWNTs as striations whose size and regularity are affected by the polarity of the lysophospholipids. We further show that wrapping is only observed when SWNTs are in the lipid phase and not the vacuum phase, suggesting that the environment has a pertinent role in the binding process. Our findings shed light on the debate over the binding mechanism of amphiphilic polymers and cylindrical nanostructures and have implications on the design of novel supramolecular complexes and nanodevices.     

Measuring inter-DNA potentials in solution

Interactions between short strands of DNA can be tuned from repulsive to attractive by varying solution conditions and have been quantified using small angle x-ray scattering techniques. The effective DNA interaction charge was extracted by fitting the scattering profiles with the generalized one-component method and inter-DNA Yukawa pair potentials. A significant charge is measured at low to moderate monovalent counterion concentrations, resulting in strong inter-DNA repulsion. The charge and repulsion diminish rapidly upon the addition of divalent counterions. An intriguing short range attraction is observed at surprisingly low divalent cation concentrations, approximately 16 mM Mg2+. Quantitative measurements of inter-DNA potentials are essential for improving models of fundamental interactions in biological systems.     

Total Syntheses of Xiamycins A,C, F,H and Oridamycin A and Preliminary Evaluation of their Anti‐Fungal Properties

Divergent and enantiospecific total syntheses of the indolosesquiterpenoids xiamycins A, C, F, H and oridamycin A have been accomplished. The syntheses, which commence from (R)‐carvone, employ a key photoinduced benzannulation sequence to forge the carbazole moiety characteristic of these natural products. Late‐stage diversification from a common intermediate enabled the first syntheses of xiamycins C and F, and an unexpected one‐pot oxidative decarboxylation, which may prove general, led to xiamycin H. All synthetic intermediates and the natural products were tested for anti‐fungal activity. Xiamycin H emerged as an inhibitor of three agriculturally relevant fungal pathogens.