Outer Sphere Electron Transfer Enabling High-Voltage Aqueous Electrolytes.

Aqueous electrolytes with a low voltage window (1.23 V) and prone side reactions, such as hydrogen evolution reaction and cathode dissolution, compromise the advantages of high safety and low cost of aqueous metal-ion batteries. Herein, introducing catechol (CAT) into the aqueous electrolyte, an outer sphere electron transfer mechanism is initiated to inhibit the water reactivity, achieving an electrochemical window of 3.

Dynamic Chalcogen Squares for Material and Topological Control over Macromolecules.

Herein we introduce chalcogen squares via selenadiazole motifs as a new class of dynamic supramolecular bonding interactions for the modification and control of soft matter materials. We showcase selenadiazole motifs in supramolecular networks of varying primary chain length prepared through polymerization using tandem step-growth/Passerini multicomponent reactions (MCRs). Compared to controls lacking the selenadiazole motif, these networks display increased glass transition temperatures and moduli due to the chalcogen bonding linkages formed between chains.

pH-Controlled Reversible Folding of Copolymers via Formation of β-sheet Secondary Structures.

Protein functions are enabled by their perfectly arranged 3D structure, which is the result of a hierarchical intramolecular folding process. Sequence-defined polypeptide chains form locally ordered secondary structures (i.e.

Earthquake-enhanced dissolved carbon cycles in ultra-deep ocean sediments.

Hadal trenches are unique geological and ecological systems located along subduction zones. Earthquake-triggered turbidites act as efficient transport pathways of organic carbon (OC), yet remineralization and transformation of OC in these systems are not comprehensively understood. Here we measure concentrations and stable- and radiocarbon isotope signatures of dissolved organic and inorganic carbon (DOC, DIC) in the subsurface sediment interstitial water along the Japan Trench axis collected during the IODP Expedition 386.

Embedding Peptides into Synthetic Polymers: Radical Ring-Opening Copolymerization of Cyclic Peptides.

Biopolymers such as proteins and nucleic acids are the key building blocks of life. Synthetic polymers have nevertheless revolutionized our everyday life through their robust synthetic accessibility. Combining the unmatched functionality of biopolymers with the robustness of tailorable synthetic polymers holds the promise to create materials that can be designed ad hoc for a wide array of applications.

Conversion of Catalytically Inert 2D Bismuth Oxide Nanosheets for Effective Electrochemical Hydrogen Evolution Reaction Catalysis via Oxygen Vacancy Concentration Modulation.

Oxygen vacancies (V) in electrocatalysts are closely correlated with the hydrogen evolution reaction (HER) activity. The role of vacancy defects and the effect of their concentration, however, yet remains unclear. Herein, BiO, an unfavorable electrocatalyst for the HER due to a less than ideal hydrogen adsorption Gibbs free energy (ΔG), is utilized as a perfect model to explore the function of V on HER performance.

A Self-Catalyzed Visible Light Driven Thiol Ligation.

We introduce a highly efficient ligation system based on a visible light-induced rearrangement affording a thiophenol which rapidly undergoes thiol-Michael additions. Unlike conventional light-triggered thiol-ene/yne systems, which rely on the use of photocaged bases/nucleophiles, (organo)-photo catalysts, or radical photoinitiators, our system provides a light-induced reaction in the absence of any additives. The ligation is self-catalyzed the pyridine mediated deprotonation of the photochemically generated thiophenol.

The kinetics and mechanism of interconversion within a system of [FeL] helicates and [FeL] cages.

Nature builds simple molecules into highly complex assemblies, which are involved in all fundamental processes of life. Some of the most intriguing biological assemblies are those that can be precisely reconfigured to achieve different functions using the same building blocks. Understanding the reconfiguration of synthetic self-assembled systems will allow us to better understand the complexity of proteins and design useful artificial chemical systems.

Wavelength-Gated Photochemical Synthesis of Phenalene Diimides.

Herein, we pioneer a wavelength-gated synthesis route to phenalene diimides. Consecutive Diels-Alder reactions of methylisophthalaldehydes and maleimides afford hexahydro-phenalene-1,6-diol diimides via 5-formyl-hexahydro-benzo[f]isoindoles as the intermediate. Both photoreactions are efficient (82-99 % yield) and exhibit excellent diastereoselectivity (62-98 % d.

3D characterisation and quantification of an offshore freshened groundwater system in the Canterbury Bight.

Although offshore freshened groundwater (OFG) systems have been documented in numerous continental margins worldwide, their geometry, controls and emplacement dynamics remain poorly constrained. Here we integrate controlled-source electromagnetic, seismic reflection and borehole data with hydrological modelling to quantitatively characterise a previously unknown OFG system near Canterbury, New Zealand. The OFG system consists of one main, and two smaller, low salinity groundwater bodies.

Earthquakes drive large-scale submarine canyon development and sediment supply to deep-ocean basins.

Although the global flux of sediment and carbon from land to the coastal ocean is well known, the volume of material that reaches the deep ocean-the ultimate sink-and the mechanisms by which it is transferred are poorly documented. Using a globally unique data set of repeat seafloor measurements and samples, we show that the moment magnitude () 7.8 November 2016 Kaikōura earthquake (New Zealand) triggered widespread landslides in a submarine canyon, causing a powerful "canyon flushing" event and turbidity current that traveled >680 km along one of the world's longest deep-sea channels.

Evidence of the Zanclean megaflood in the eastern Mediterranean Basin.

The Messinian salinity crisis (MSC) - the most abrupt, global-scale environmental change since the end of the Cretaceous - is widely associated with partial desiccation of the Mediterranean Sea. A major open question is the way normal marine conditions were abruptly restored at the end of the MSC. Here we use geological and geophysical data to identify an extensive, buried and chaotic sedimentary body deposited in the western Ionian Basin after the massive Messinian salts and before the Plio-Quaternary open-marine sedimentary sequence.

Interactions of iodoperfluorobenzene compounds with gold nanoparticles.

Understanding the interactions of small molecules with gold nanoparticles is important for controlling their surface chemistry and, hence, how they can be used in specific applications. The interaction of iodoperfluorobenzene compounds with gold nanoparticles was investigated by UV-Vis difference spectroscopy, surface enhanced Raman spectroscopy (SERS) and Synchrotron X-ray photoelectron spectroscopy (XPS). Results from UV-Vis difference spectroscopy demonstrated that iodoperfluorobenzene compounds undergo charge transfer complexation with gold nanoparticles.

The evaluation of new and isotopically labeled isoindoline nitroxides and an azaphenalene nitroxide for EPR oximetry.

Isoindoline nitroxides are potentially useful probes for viable biological systems, exhibiting low cytotoxicity, moderate rates of biological reduction and favorable Electron Paramagnetic Resonance (EPR) characteristics. We have evaluated the anionic (5-carboxy-1,1,3,3-tetramethylisoindolin-2-yloxyl; CTMIO), cationic (5-(N,N,N-trimethylammonio)-1,1,3,3-tetramethylisoindolin-2-yloxyl iodide, QATMIO) and neutral (1,1,3,3-tetramethylisoindolin-2-yloxyl; TMIO) nitroxides and their isotopically labeled analogs ((2)H(12)- and/or (2)H(12)-(15)N-labeled) as potential EPR oximetry probes. An active ester analogue of CTMIO, designed to localize intracellularly, and the azaphenalene nitroxide 1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl (TMAO) were also studied.

Halogen bonding between an isoindoline nitroxide and 1,4-diiodotetrafluorobenzene: new tools and tectons for self-assembling organic spin systems.

Radical assembly: Halogen bonding has been observed for the first time between an isoindoline nitroxide and an iodoperfluorocarbon (see figure), which cocrystallize to form a discrete 2:1 supramolecular compound in which N--O(.)I halogen bonding is the dominant intermolecular interaction. This illustrates the potential use of halogen bonding and isoindoline nitroxide tectons for the assembly of organic spin systems.

Electron spin-lattice relaxation of nitroxyl radicals in temperature ranges that span glassy solutions to low-viscosity liquids.

Electron spin-lattice relaxation rates, 1/T1, at X-band of nitroxyl radicals (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, 3-carbamoyl-2,2,5,5-tetramethylpyrrolidin-1-oxyl and 3-carbamoyl-2,2,5,5-tetramethylpyrrolin-1-oxyl) in glass-forming solvents (decalin, glycerol, 3-methylpentane, o-terphenyl, 1-propanol, sorbitol, sucrose octaacetate, and 1:1 water:glycerol) at temperatures between 100 and 300K were measured by long-pulse saturation recovery to investigate the relaxation processes in slow-to-fast tumbling regimes. A subset of samples was also studied at lower temperatures or at Q-band. Tumbling correlation times were calculated from continuous wave lineshapes.

Application of the new EPR spin trap 1,1,3-trimethylisoindole N-oxide (TMINO) in trapping HO. and related biologically important radicals.

The new EPR spin trap, 1,1,3-trimethylisoindole N-oxide (TMINO), very efficiently scavenges several Fenton-derived carbon- and oxygen-centred radicals including hydroxyl, formyl and alkyl radicals. The adducts display good stability and narrow EPR line-widths, allowing the detection of the expected radicals as well as two-dimensional (time-resolved) EPR experiments. Trapping experiments were also undertaken with superoxide radicals (giving no EPR signals) and nitric oxide (which gave strong EPR signals attributed to the action of higher oxides of nitrogen).

Synthesis and EPR spin trapping properties of a new isoindole-based nitrone: 1,1,3-trimethylisoindole N-oxide (TMINO).

Here we describe the synthesis and characterisation of a new isoindole-based nitrone spin trap, 1,1,3-trimethylisoindole N-oxide (TMINO). This nitrone and its radical adducts (isoindoline nitroxides) exhibit enhanced stability with respect to other commonly used spin traps and their adducts. We also report EPR trapping studies of this new nitrone with some carbon- and oxygen-centred radicals including alkyl, aryl, hydroxyl and benzoyloxyl systems.

Synthesis and reactions of aminoporphyrazines with annulated five- and seven-membered rings.

The novel five- and seven-membered ring appended aminoporphyrazines 3 and 12 have been prepared via mixed Linstead macrocyclization. The structures of both have been unequivocally established by X-ray crystallographic studies. Reductive deselenation of selenadiazole 3 in the presence of 9,10-phenanthrenequinone or 2,3-butanedione results in the formation of pyrazines 6a,b, whereas oxidation of porphyrazine 12 gave the corresponding seco derivative 14.