An Immobilized (Carbene)Nickel Catalyst for Water Oxidation.

The oxygen evolution reaction (OER) of water splitting is essential to electrochemical energy storage applications. While nickel electrodes are widely available heterogeneous OER catalysts, homogeneous nickel catalysts for OER are underexplored. Here we report two carbene-ligated nickel(II) complexes that are exceptionally robust and efficient homogeneous water oxidation catalysts. Remarkably, these novel nickel complexes can assemble a stable thin film onto a metal electrode through poly-imidazole bridges, making them supported heterogeneous electrochemical catalysts that are resilient to leaching and stripping. Unlike molecular catalysts and nanoparticle catalysts, such electrode-supported metal-complex catalysts for OER are rare and have the potential to inspire new designs. The electrochemical OER with our nickel-carbene catalysts exhibits excellent current densities with high efficiency, low Tafel slope, and useful longevity for a base metal catalyst. Our data show that imidazole carbene ligands stay bonded to the nickel(II) centers throughout the catalysis, which allows the facile oxygen evolution.

Topology stabilized fluctuations in a magnetic nodal semimetal.

The interplay between magnetism and electronic band topology enriches topological phases and has promising applications. However, the role of topology in magnetic fluctuations has been elusive. Here, we report evidence for topology stabilized magnetism above the magnetic transition temperature in magnetic Weyl semimetal candidate CeAlGe. Electrical transport, thermal transport, resonant elastic X-ray scattering, and dilatometry consistently indicate the presence of locally correlated magnetism within a narrow temperature window well above the thermodynamic magnetic transition temperature. The wavevector of this short-range order is consistent with the nesting condition of topological Weyl nodes, suggesting that it arises from the interaction between magnetic fluctuations and the emergent Weyl fermions. Effective field theory shows that this topology stabilized order is wavevector dependent and can be stabilized when the interband Weyl fermion scattering is dominant. Our work highlights the role of electronic band topology in stabilizing magnetic order even in the classically disordered regime.

An ambient pressure, direct hydrogenation of ketones.

We report two bifunctional (pyridyl)carbene-iridium(I) complexes that catalyze ketone and aldehyde hydrogenation at ambient pressure. Aryl, heteroaryl, and alkyl groups are demonstrated, and mechanistic studies reveal an unusual polarization effect in which the rate is dependant of proton, rather than hydride, transfer. This method introduces a convenient, waste-free alternative to traditional borohydride and aluminum hydride reagents.

SEEMS: A Single Event Effects and Muon Spectroscopy facility at the Spallation Neutron Source.

This study outlines a concept that would leverage the existing proton accelerator at the Spallation Neutron Source (SNS) of Oak Ridge National Laboratory to enable transformative science via one world-class facility serving two missions: Single Event Effects (SEE) and Muon Spectroscopy (µSR). The µSR portion would deliver the world's highest flux and highest resolution pulsed muon beams for material characterization purposes, with precision and capabilities well beyond comparable facilities. The SEE capabilities deliver neutron, proton, and muon beams for aerospace industries that are facing an impending challenge to certify equipment for safe and reliable behavior under bombardment from atmospheric radiation originating from cosmic and solar rays. With negligible impact on the primary neutron scattering mission of the SNS, the proposed facility will have enormous benefits for both science and industry. We have designated this facility "SEEMS."

Synthesis of 1,4-Diazacycles by Hydrogen Borrowing.

We report the syntheses of 1,4-diazacycles by diol-diamine coupling, uniquely made possible with a (pyridyl)phosphine-ligated ruthenium(II) catalyst (1). The reactions can exploit either two sequential N-alkylations or an intermediate tautomerization pathway to yield piperazines and diazepanes; diazepanes are generally inaccessible by catalytic routes. Our conditions tolerate different amines and alcohols that are relevant to key medicinal platforms. We show the syntheses of the drugs cyclizine and homochlorcyclizine in 91% and 67% yields, respectively.

Polystyrene Upcycling into Fungal Natural Products and a Biocontrol Agent.

Polystyrene (PS) is one of the most used yet infrequently recycled plastics. Although manufactured on the scale of 300 million tons per year globally, current approaches toward PS degradation are energy- and carbon-inefficient, slow, and/or limited in the value that they reclaim. We recently reported a scalable process to degrade post-consumer polyethylene-containing waste streams into carboxylic diacids. Engineered fungal strains then upgrade these diacids biosynthetically to synthesize pharmacologically active secondary metabolites. Herein, we apply a similar reaction to rapidly convert PS to benzoic acid in high yield. Engineered strains of the filamentous fungus Aspergillus nidulans then biosynthetically upgrade PS-derived crude benzoic acid to the structurally diverse secondary metabolites ergothioneine, pleuromutilin, and mutilin. Further, we expand the catalog of plastic-derived products to include spores of the industrially relevant biocontrol agent Aspergillus flavus Af36 from crude PS-derived benzoic acid.

Conversion of Polyethylenes into Fungal Secondary Metabolites.

Waste plastics represent major environmental and economic burdens due to their ubiquity, slow breakdown rates, and inadequacy of current recycling routes. Polyethylenes are particularly problematic, because they lack robust recycling approaches despite being the most abundant plastics in use today. We report a novel chemical and biological approach for the rapid conversion of polyethylenes into structurally complex and pharmacologically active compounds. We present conditions for aerobic, catalytic digestion of polyethylenes collected from post-consumer and oceanic waste streams, creating carboxylic diacids that can then be used as a carbon source by the fungus Aspergillus nidulans. As a proof of principle, we have engineered strains of A. nidulans to synthesize the fungal secondary metabolites asperbenzaldehyde, citreoviridin, and mutilin when grown on these digestion products. This hybrid approach considerably expands the range of products to which polyethylenes can be upcycled.

Out of Thin Air? Catalytic Oxidation of Trace Aqueous Aldehydes with Ambient Dissolved Oxygen.

Water reuse is expanding due to increased water scarcity. Water reuse facilities treat wastewater effluent to a very high purity level, typically resulting in a product water that is essentially deionized water, often containing less than 100 µg/L organic carbon. However, recent research has found that low-molecular-weight aldehydes, which are toxic electrophiles, comprise a significant fraction of the final organic carbon pool in recycled wastewater in certain treatment configurations. In this manuscript, we demonstrate oxidation of trace aqueous aldehydes to their corresponding acids using a heterogeneous catalyst (5% Pt on C), with ambient dissolved oxygen serving as the terminal electron acceptor. Mass balances are essentially quantitative across a range of aldehydes, and pseudo-first-order reaction kinetics are observed in batch reactors, with kobs varying from 0.6 h-1 for acetaldehyde to 4.6 h-1 for hexanal, while they are low for unsaturated aldehydes. Through kinetic and isotopic labeling experiments, we demonstrate that while oxygen is essential for the reaction to proceed, it is not involved in the rate-limiting step, and the reaction appears to proceed primarily through a base-promoted ß-hydride elimination mechanism from the hydrated gem-diol form of the corresponding aldehyde. This is the first report we are aware of that demonstrates useful abiotic oxidation of a trace organic contaminant using dissolved oxygen.

Kinetics and mechanistic details of bulk ZnO dissolution using a thiol-imidazole system.

Oxide dissolution is important for metal extraction from ores and has become an attractive route for the preparation of inks for thin film solution deposition; however, oxide dissolution is often kinetically challenging. While binary "alkahest" systems comprised of thiols and N-donor species, such as amines, are known to dissolve a wide range of oxides, the mechanism of dissolution and identity of the resulting solute(s) remain unstudied. Here, we demonstrate facile dissolution of both bulk synthetic and natural mineral ZnO samples using an "alkahest" that operates via reaction with thiophenol and 1-methylimidazole (MeIm) to give a single, pseudotetrahedral Zn(SPh)2(MeIm)2 molecular solute identified by X-ray crystallography. The kinetics of ZnO dissolution were measured using solution 1H NMR, and the reaction was found to be zero-order in the presence of excess ligands, with more electron withdrawing para-substituted thiophenols resulting in faster dissolution. A negative entropy of activation was measured by Eyring analysis, indicating associative ligand binding in, or prior to, the rate determining step. Combined experimental and computational surface binding studies on ZnO reveal stronger, irreversible thiophenol binding compared to MeIm, leading to a proposed dissolution mechanism initiated by thiol binding to the ZnO surface with the liberation of water, followed by alternating MeIm and thiolate ligand additions, and ultimately cleavage of the ligated zinc complex from the ZnO surface. Design rules garnered from the mechanistic insight provided by this study should inform the dissolution of other bulk oxides into inks for solution processed thin films.

Pressurized Formic Acid Dehydrogenation: An Entropic Spring Replaces Hydrogen Compression Cost.

Formic acid is unique among liquid organic hydrogen carriers (LOHCs), because its dehydrogenation is highly entropically driven. This enables the evolution of high-pressure hydrogen at mild temperatures that is difficult to achieve with other LOHCs, conceptually by releasing the "spring" of energy stored entropically in the liquid carrier. Applications calling for hydrogen-on-demand, such as vehicle filling, require pressurized H2. Hydrogen compression dominates the cost for such applications, yet there are very few reports of selective, catalytic dehydrogenation of formic acid at elevated pressure. Herein, we show that homogenous catalysts with various ligand frameworks, including Noyori-type tridentate (PNP, SNS, SNP, SNPO), bidentate chelates (pyridyl)NHC, (pyridyl)phosphine, (pyridyl)sulfonamide, and their metallic precursors, are suitable catalysts for the dehydrogenation of neat formic acid under self-pressurizing conditions. Quite surprisingly, we discovered that their structural differences can be related to performance differences in their respective structural families, with some tolerant or intolerant of pressure and others that are significantly advantaged by pressurized conditions. We further find important roles for H2 and CO in catalyst activation and speciation. In fact, for certain systems, CO behaves as a healing reagent when trapped in a pressurizing reactor system, enabling extended life from systems that would be otherwise deactivated.

Decay and renormalization of a longitudinal mode in a quasi-two-dimensional antiferromagnet.

An ongoing challenge in the study of quantum materials, is to reveal and explain collective quantum effects in spin systems where interactions between different modes types are important. Here we approach this problem through a combined experimental and theoretical study of interacting transverse and longitudinal modes in an easy-plane quantum magnet near a continuous quantum phase transition. Our inelastic neutron scattering measurements of Ba2FeSi2O7 reveal the emergence, decay, and renormalization of a longitudinal mode throughout the Brillouin zone. The decay of the longitudinal mode is particularly pronounced at the zone center. To account for the many-body effects of the interacting low-energy modes in anisotropic magnets, we generalize the standard spin-wave theory. The measured mode decay and renormalization is reproduced by including all one-loop corrections. The theoretical framework developed here is broadly applicable to quantum magnets with more than one type of low energy mode.

Cluster Frustration in the Breathing Pyrochlore Magnet LiGaCr_{4}S_{8}.

We present a comprehensive neutron scattering study of the breathing pyrochlore magnet LiGaCr_{4}S_{8}. We observe an unconventional magnetic excitation spectrum with a separation of high- and low-energy spin dynamics in the correlated paramagnetic regime above a spin-freezing transition at 12(2) K. By fitting to magnetic diffuse-scattering data, we parametrize the spin Hamiltonian. We find that interactions are ferromagnetic within the large and small tetrahedra of the breathing pyrochlore lattice, but antiferromagnetic further-neighbor interactions are also essential to explain our data, in qualitative agreement with density-functional-theory predictions [Ghosh et al., npj Quantum Mater. 4, 63 (2019)2397-464810.1038/s41535-019-0202-z]. We explain the origin of geometrical frustration in LiGaCr_{4}S_{8} in terms of net antiferromagnetic coupling between emergent tetrahedral spin clusters that occupy a face-centered-cubic lattice. Our results provide insight into the emergence of frustration in the presence of strong further-neighbor couplings, and a blueprint for the determination of magnetic interactions in classical spin liquids.

Heterobimetallic complexes of IrM (M = FeII, CoII, and NiII) core and bridging 2-(diphenylphosphino)pyridine: electronic structure and electrochemical behavior.

Three complexes based on an Ir-M (M = FeII, CoII, and NiII) heterobimetallic core and 2-(diphenylphosphino)pyridine (Ph2PPy) ligand were synthesized via the reaction of trans-[IrCl(CO)(Ph2PPy)2] and the corresponding metal chloride. Their structures were established by single-crystal X-ray diffraction as [Ir(CO)(µ-Cl)(µ-Ph2PPy)2FeCl2]·2CH2Cl2 (2), [IrCl(CO)(µ-Ph2PPy)2CoCl2]·2CH2Cl2 (3), and [Ir(CO)(µ-Cl)(µ-Ph2PPy)2NiCl2]·2CH2Cl2 (4). Time-dependent DFT computations suggest a donor-acceptor interaction between a filled 5dz2 orbital on iridium and an empty orbital on the first-row metal atom, which is supported by UV-vis studies. Magnetic moment measurements show that the first-row metals are in their high-spin electronic configurations. Cyclic voltammetry data show that all the complexes undergo irreversible decomposition upon either reduction or oxidation. Reduction of 4 proceeds through an ECE mechanism. While these complexes are not stable to electrocatalysis conditions, the data presented here refine our understanding of the bonding synergies of the first-row and third-row metals.

Ruthenium Catalyzed Tandem Pictet-Spengler Reaction.

We report a pyridyl-phosphine ruthenium(II) catalyzed tandem alcohol amination/Pictet-Spengler reaction sequence to synthesize tetrahydro-ß-carbolines from an alcohol and tryptamine. Our conditions use a Lewis acid cocatalyst, In(OTf)3, that is compatible with typically base catalyzed amination and an acid catalyzed Pictet-Spengler cyclization. This method proceeds well with benzylic alcohols, heterocyclic carbinols, and aliphatic alcohols. We also show how combining this reaction with a subsequent cycloamination enables a direct synthesis of tetracyclic alkaloids like harmicine.

A New Mechanism of Metal-Ligand Cooperative Catalysis in Transfer Hydrogenation of Ketones.

We report iridium catalysts IrCl(η5-Cp*)(κ2-(2-pyridyl)CH2NSO2C6H4X) (1-Me, X = CH3 and 1-F, X = F) for transfer hydrogenation of ketones with 2-propanol that operate by a previously unseen metal-ligand cooperative mechanism. Under the reaction conditions, complexes 1 (1-Me and 1-F) derivatize to a series of catalytic intermediates: Ir(η5-Cp*)(κ2-(C5H4N)CHNSO2Ar) (2), IrH(η5Cp*)(κ2-(2-pyridyl)CH2NSO2Ar) (3), and Ir(η5-Cp*)(κ3-(2-pyridyl)CH2NSO2Ar) (4). The structures of 1-Me and 4-Me were established by single-crystal X-ray diffraction. A rate-determining, concerted hydrogen transfer step (2 + R2CHOH ⇄ 3 + R2CO) is suggested by kinetic isotope effects, Eyring parameters (ΔH ≠ = 29.1(8) kcal mol-1 and ΔS ≠ = -17(19) eu), proton-hydride fidelity, and DFT calculations. According to DFT, a nine-membered cyclic transition state is stabilized by an alcohol molecule that serves as a proton shuttle.

Surface coordination chemistry of germanium nanocrystals synthesized by microwave-assisted reduction in oleylamine.

As surface ligands play a critical role in the colloidal stability and optoelectronic properties of semiconductor nanocrystals, we used solution NMR experiments to investigate the surface coordination chemistry of Ge nanocrystals synthesized by a microwave-assisted reduction of GeI2 in oleylamine. The as-synthesized Ge nanocrystals are coordinated to a fraction of strongly bound oleylamide ligands (with covalent X-type Ge-NHR bonds) and a fraction of more weakly bound (or physisorbed) oleylamine, which readily exchanges with free oleylamine in solution. The fraction of strongly bound oleylamide ligands increases with increasing synthesis temperature, which also correlates with better colloidal stability. Thiol and carboxylic acid ligands bind to the Ge nanocrystal surface only upon heating, suggesting a high kinetic barrier to surface binding. These incoming ligands do not displace native oleylamide ligands but instead appear to coordinate to open surface sites, confirming that the as-prepared nanocrystals are not fully passivated. These findings will allow for a better understanding of the surface chemistry of main group nanocrystals and the conditions necessary for ligand exchange to ultimately maximize their functionality.

A Walk in Nature: Sesquiterpene Lactones as Multi-Target Agents Involved in Inflammatory Pathways.

Inflammatory states are among the most common and most treated medical conditions. Inflammation comes along with swelling, pain and uneasiness in using the affected area. Inflammation is not always a simple symptom; more often is part of a defensive response of the body to an external threat or is a sign that the damaged tissue has not healed yet and needs to rest. The management of the pain associated with an inflammatory state could be a tricky task. In fact, most remedies simply quench the pain, leaving the inflammatory state unaltered. This review focuses on sesquiterpene lactones, a class of natural compounds, that represents a future promise in the treatment of inflammation. Sesquiterpene lactones are efficient inhibitors of multiple targets of the inflammatory process. Their natural sources are often ancient remedies with relevant traditional uses in folk medicines. This work also aims to elucidate how these compounds may represent the starting material for the development of new anti-inflammatory drugs.

Mechanism and Catalysis of Oxidative Degradation of Fiber-Reinforced Epoxy Composites.

Carbon fiber-reinforced polymer (CFRP) materials are widely used in aerospace and recreational equipment, but there is no efficient procedure for their end-of-life recycling. Ongoing work in the chemistry and engineering communities emphasizes recovering carbon fibers from such waste streams by dissolving or destroying the polymer binding. By contrast, our goal is to depolymerize amine-cured epoxy CFRP composites catalytically, thus enabling not only isolation of high-value carbon fibers, but simultaneously opening an approach to recovery of small molecule monomers that can be used to regenerate precursors to new composite resin. To do so will require understanding of the molecular mechanism(s) of such degradation sequences. Prior work has shown the utility of hydrogen peroxide as a reagent to affect epoxy matrix decomposition [1]. Herein we describe the chemical transformations involved in that sequence: the reaction proceeds by oxygen atom transfer to the polymer's linking aniline group, forming an N-oxide intermediate. The polymer is then cleaved by an elimination and hydrolysis sequence. We find that elimination is the slower step. Scandium trichloride is an efficient catalyst for this step, reducing reaction time in homogeneous model systems and neat cured matrix blocks. The conditions can be applied to composed composite materials, from which pristine carbon fibers can be recovered.

Iridium Catalysts for Acceptorless Dehydrogenation of Alcohols to Carboxylic Acids: Scope and Mechanism.

We introduce iridium-based conditions for the conversion of primary alcohols to potassium carboxylates (or carboxylic acids) in the presence of potassium hydroxide and either [Ir(2-PyCH2(C4H5N2))(COD)]OTf (1) or [Ir(2-PyCH2PBu2 t)(COD)]OTf (2). The method provides both aliphatic and benzylic carboxylates in high yield and with outstanding functional group tolerance. We illustrate the application of this method to a diverse variety of primary alcohols, including those involving heterocycles and even free amines. Complex 2 reacts with alcohols to form crystallographically-characterized catalytic intermediates [IrH(η 1,η 3-C8H12)(2-PyCH2PtBu2)] (2a) and [Ir2H3(CO)(2-PyCH2PtBu2){µ-(C5H3N)CH2PtBu2}] (2c). The unexpected similarities in reactivities of 1 and 2 in this reaction, along with synthetic studies on several of our iridium intermediates, enable us to form a general proposal of the mechanisms of catalyst activation that govern the disparate reactivities of 1 and 2, respectively in glycerol and formic acid dehydrogenation. Moreover, careful analysis of the organic intermediates in the oxidation sequence enable new insights into the role of Tishchenko and Cannizzaro reactions in the overall oxidation.

Upgrading Biodiesel from Vegetable Oils by Hydrogen Transfer to its Fatty Esters.

Conversion of vegetable-derived triglycerides to fatty acid methyl esters (FAMEs) is a popular approach to the generation of biodiesel fuels and the basis of a growing industry. Drawbacks of the strategy are that (a) the glycerol backbone of the triglyceride is discarded as waste, and (2) most available natural triglycerides in the U.S. are multi-unsaturated or fully saturated, giving inferior fuel performance and causing engine problems. Here we show that catalysis by iridium complex 1 can address both of these problems through selective reduction of triglycerides high in polyunsaturation. This is realized using hydrogen from methanol or those imbedded in the triglyceride backbone, concurrently generating lactate as a value-added C3 product. Additional methanol or glycerol as a hydrogen source enables reduction of corn and soybean oils to > 80% oleate. The cost of the iridium catalyst is mitigated by its recovery through aqueous extraction. The process can be further driven with a supporting iron-based catalyst for the complete saturation of all olefins. Preparative procedures are established for synthesis and separation of methyl esters of the hydrogenated fatty acids, enabling instant access to upgraded biofuels.