Reactive nitrogen oxides (NOy; NOy= NO + NO2+ HONO) decrease air quality and impact radiative forcing, yet the factors responsible for their emission from nonpoint sources (i.e., soils) remain poorly understood. We investigated the factors that control the production of aerobic NOyin forest soils using molecular techniques, process-based assays, and inhibitor experiments. We subsequently used these data to identify hotspots for gas emissions across forests of the eastern United States. Here, we show that nitrogen oxide soil emissions are mediated by microbial community structure (e.g., ammonium oxidizer abundances), soil chemical characteristics (pH and C:N), and nitrogen (N) transformation rates (net nitrification). We find that, while nitrification rates are controlled primarily by chemoautotrophic ammonia-oxidizing archaea (AOA), the production of NOyis mediated in large part by chemoautotrophic ammonia-oxidizing bacteria (AOB). Variation in nitrification rates and nitrogen oxide emissions tracked variation in forest communities, as stands dominated by arbuscular mycorrhizal (AM) trees had greater N transformation rates and NOyfluxes than stands dominated by ectomycorrhizal (ECM) trees. Given mapped distributions of AM and ECM trees from 78,000 forest inventory plots, we estimate that broadleaf forests of the Midwest and the eastern United States as well as the Mississippi River corridor may be considered hotspots of biogenic NOyemissions. Together, our results greatly improve our understanding of NOyfluxes from forests, which should lead to improved predictions about the atmospheric consequences of tree species shifts owing to land management and climate change.

Fungal mycelium is increasingly recognized as a central component of soil biogeochemical cycling, yet our current understanding of the ecological controls on fungal necromass decomposition is limited to single sites and vegetation types. By deploying common fungal necromass substrates in a temperate oak savanna and hardwood forest in the midwestern USA, we assessed the generality of the rate at which high‐ and low‐quality fungal necromass decomposes; further, we investigated how the decomposer ‘necrobiome’ varies both across and within sites under vegetation types dominated by either arbuscular or ectomycorrhizal plants. The effects of necromass quality on decay rate were robust to site and vegetation type differences, with high‐quality fungal necromass decomposing, on average, 2.5 times faster during the initial stages of decay. Across vegetation types, bacterial and fungal communities present on decaying necromass differed from bulk soil microbial communities and were influenced by necromass quality. Moulds, yeasts and copiotrophic bacteria consistently dominated the necrobiome of high‐quality fungal substrates. Synthesis. We show that regardless of differences in decay environments, high‐quality fungal substrates decompose faster and support different types of decomposer micro‐organisms when compared with low‐quality fungal tissues. These findings help to refine our theoretical understanding of the dominant factors affecting fast cycling components of soil organic matter and the microbial communities associated with rapid decay.

A diamidocarbene was coordinated to an antimony(III) dichloride Lewis acid. Subsequent reduction with magnesium gave a monomeric, formally antimony(I) fragment that is supported by the diamidocarbene. Spectroscopic, crystallographic, and computational analyses demonstrated that the carbene ligand engages the antimony(I) center in π-backbonding resulting in a short (2.068(7) Å) Sb-C interaction that is comparable to those observed in known stibaalkenes.

Volatile nitrogen oxides (N2O, NO, NO2, HONO, …) can negatively impact climate, air quality, and human health. Using soils collected from temperate forests across the eastern United States, we show microbial communities involved in nitrogen (N) cycling are structured, in large part, by the composition of overstory trees, leading to predictable N‐cycling syndromes, with consequences for emissions of volatile nitrogen oxides to air. Trees associating with arbuscular mycorrhizal (AM) fungi promote soil microbial communities with higher N‐cycle potential and activity, relative to microbial communities in soils dominated by trees associating with ectomycorrhizal (ECM) fungi. Metagenomic analysis and gene expression studies reveal a 5 and 3.5 times greater estimated N‐cycle gene and transcript copy numbers, respectively, in AM relative to ECM soil. Furthermore, we observe a 60% linear decrease in volatile reactive nitrogen gas flux (NOy ≡ NO, NO2, HONO) as ECM tree abundance increases. Compared to oxic conditions, gas flux potential of N2O and NO increase significantly under anoxic conditions for AM soil (30‐ and 120‐fold increase), but not ECM soil—likely owing to small concentrations of available substrate (NO3‐) in ECM soil. Linear mixed effects modeling shows that ECM tree abundance, microbial process rates, and geographic location are primarily responsible for variation in peak potential NOy flux. Given that nearly all tree species associate with either AM or ECM fungi, our results indicate that the consequences of tree species shifts associated with global change may have predictable consequences for soil N cycling.

Two 6-methoxy-4-oxo-1,3-diaryl-3,4-dihydropyrimidinium salts (2a and 2b) have been prepared as precursors to novel amino-acrylamido carbenes. Treatment of 2a (where the aryl groups are mesityl groups) with one equivalent of sodium hexamethyldisilazide in aromatic hydrocarbons affords the persistent amino-acrylamido carbene 3a, which has been characterized spectroscopically. This novel carbene has been trapped with Ir(I) transition metal fragments as well as electrophilic carbon disulfide and nucleophilic isocyanides. Infrared spectroscopic studies carried out on 3a-Ir(CO) 2 Cl (5a) indicated that this carbene exhibits a Tolman electronic parameter (TEP) of 2049 cm −1 , a value that suggests that 3a is a stronger donor than both diamidocarbenes (DACs) and a recently reported amino-ureido carbene (DAC TEPs ≈ 2057 cm −1 ; amino-ureido TEP = 2058 cm −1 ), but similar σ-donating properties to a monoamido-amino carbene (TEP = 2050 cm −1 ). This result has been corroborated by DFT analyses carried out on all four species, which indicated that the HOMO and LUMO energies of 3a are comparable to the amino-ureido and monoamido-amino carbenes, whereas the DAC was shown to be more electrophilic with a much lower energy LUMO than the other three carbenes. Surprisingly, deprotonation of 2b (where the N-substituents are 2,6-diisopropylphenyl groups) does not afford the anticipated carbene. Indeed, 1 H NMR spectroscopic analysis indicates the formation of a novel bent allene or carbodicarbene (3b), which decomposes rapidly in solution at room temperature.

Recently, high dosage doping on Si multi-gate field effect transistors and III–V planar structures using a self-limiting monolayer doping technique was reported to overcome challenges in scaling nano-sized transistors. The stoichiometry or composition of the capping layer was found to affect the diffusion efficiency of this process. In this work, we study the effect of a capping layer in sulfur monolayer doping on III–V junctions. Various capping temperatures and growth methods were compared. Based on the theoretical and experimental results, we suggest an optimized scheme consisting of a bi-layer capping structure. From Hall measurements and secondary ion mass spectrometry, a SiNx/BeO bi-layer capping, compared to single layer cap, exhibited the best results with a surface sheet resistance of 232 Ω/sq, junction depth of 11 nm, dopant profile abruptness of 3.5 nm/dec, electrically active S concentration of 4.9 × 1019/cm3 (=1.34 × 1013/cm2), and 3 times higher activation efficiency without significant transient-enhanced dopant diffusion.

1-Diphenylphosphinonaphthyl-8-triphenylstibonium triflate ([][OTf]) was prepared in excellent yield by treating 1-lithio-8-diphenylphosphinonaphthalene with dibromotriphenylstiborane followed by halide abstraction with AgOTf. This antimony(v) cation was found to be stable toward oxygen and water, and exhibited exceptional Lewis acidity. The Lewis acidity of [][OTf] was exploited in the catalytic reductive coupling of a variety of aldehydes into symmetric ethers of type in good to excellent yields under mild conditions using Et3SiH as the reductant. Additionally, [][OTf] was found to selectively catalyze the Aldol condensation reaction to afford α-β unsaturated aldehydes () when aldehydes with 2 α-hydrogen atoms were used. Finally, [][OTf] catalyzed the cyclotrimerization of aliphatic and aromatic aldehydes to afford the industrially-useful 1,3,5 trioxanes () in good yields, and with great selectivity. This phosphine-stibonium motif represents one of the first catalytic systems of its kind that is able to catalyze these reactions with aldehydes in a controlled, efficient manner. The mechanism of these processes has been explored both experimentally and theoretically. In all cases the Lewis acidic nature of the antimony(v) cation was found to promote these reactions.

No abstract