Origin of enhanced water oxidation activity in an iridium single atom anchored on NiFe oxyhydroxide catalyst.

The efficiency of the synthesis of renewable fuels and feedstocks from electrical sources is limited, at present, by the sluggish water oxidation reaction. Single-atom catalysts (SACs) with a controllable coordination environment and exceptional atom utilization efficiency open new paradigms toward designing high-performance water oxidation catalysts. Here, using operando X-ray absorption spectroscopy measurements with calculations of spectra and electrochemical activity, we demonstrate that the origin of water oxidation activity of IrNiFe SACs is the presence of highly oxidized Ir single atom (Ir5.3+) in the NiFe oxyhydroxide under operating conditions. We show that the optimal water oxidation catalyst could be achieved by systematically increasing the oxidation state and modulating the coordination environment of the Ir active sites anchored atop the NiFe oxyhydroxide layers. Based on the proposed mechanism, we have successfully anchored Ir single-atom sites on NiFe oxyhydroxides (Ir0.1/Ni9Fe SAC) via a unique in situ cryogenic-photochemical reduction method that delivers an overpotential of 183 mV at 10 mA ⋅ cm-2 and retains its performance following 100 h of operation in 1 M KOH electrolyte, outperforming the reported catalysts and the commercial IrO2 catalysts. These findings open the avenue toward an atomic-level understanding of the oxygen evolution of catalytic centers under in operando conditions.

Electrochemically scrambled nanocrystals are catalytically active for CO2-to-multicarbons.

Promotion of C-C bonds is one of the key fundamental questions in the field of CO2 electroreduction. Much progress has occurred in developing bulk-derived Cu-based electrodes for CO2-to-multicarbons (CO2-to-C2+), especially in the widely studied class of high-surface-area "oxide-derived" copper. However, fundamental understanding into the structural characteristics responsible for efficient C-C formation is restricted by the intrinsic activity of these catalysts often being comparable to polycrystalline copper foil. By closely probing a Cu nanoparticle (NP) ensemble catalyst active for CO2-to-C2+, we show that bias-induced rapid fusion or "electrochemical scrambling" of Cu NPs creates disordered structures intrinsically active for low overpotential C2+ formation, exhibiting around sevenfold enhancement in C2+ turnover over crystalline Cu. Integrating ex situ, passivated ex situ, and in situ analyses reveals that the scrambled state exhibits several structural signatures: a distinct transition to single-crystal Cu2O cubes upon air exposure, low crystallinity upon passivation, and high mobility under bias. These findings suggest that disordered copper structures facilitate C-C bond formation from CO2 and that electrochemical nanocrystal scrambling is an avenue toward creating such catalysts.

Fate of Dissolved Nitrogen in a Horizontal Levee: Seasonal Fluctuations in Nitrate Removal Processes.

Horizontal levees are a nature-based approach for removing nitrogen from municipal wastewater effluent while simultaneously providing additional benefits, such as flood control. To assess nitrogen removal mechanisms and the efficacy of a horizontal levee, we monitored an experimental system receiving nitrified municipal wastewater effluent for 2 years. Based on mass balances and microbial gene abundance data, we determined that much of the applied nitrogen was most likely removed by heterotrophic denitrifiers that consumed labile organic carbon from decaying plants and added wood chips. Fe(III) and sulfate reduction driven by decay of labile organic carbon also produced Fe(II) sulfide minerals. During winter months, when heterotrophic activity was lower, strong correlations between sulfate release and nitrogen removal suggested that autotrophic denitrifiers oxidized Fe(II) sulfides using nitrate as an electron acceptor. These trends were seasonal, with Fe(II) sulfide minerals formed during summer fueling denitrification during the subsequent winter. Overall, around 30% of gaseous nitrogen losses in the winter were attributable to autotrophic denitrifiers. To predict long-term nitrogen removal, we developed an electron-transfer model that accounted for the production and consumption of electron donors. The model indicated that the labile organic carbon released from wood chips may be capable of supporting nitrogen removal from wastewater effluent for several decades with sulfide minerals, decaying vegetation, and root exudates likely sustaining nitrogen removal over a longer timescale.

Ligand-Free Processable Perovskite Semiconductor Ink.

Traditional covalent semiconductors require complex processing methods for device fabrication due to their high cohesive energies. Here, we develop a stable, ligand-free perovskite semiconductor ink that can be used to make patterned semiconductor-based optoelectronics in one step. The perovskite ink is formed via the dissolution of crystals of vacancy-ordered double perovskite Cs2TeX6 (X = Cl-, Br-, I-) in polar aprotic solvents, leading to the stabilization of isolated [TeX6]2- octahedral anions and free Cs+ cations without the presence of ligands. The stabilization of the fundamental perovskite ionic octahedral building blocks in solution creates multifunctional inks with the ability to reversibly transform between the liquid ink and the solid-state perovskite crystalline system in air within minutes. These easily processable inks can be patterned onto various materials via dropcasting, spraying or painting, and stamping, highlighting the crucial role of solvated octahedral complexes toward the rapid formation of phase-pure perovskite structures in ambient conditions.

Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation.

Atomically dispersed catalysts refer to substrate-supported heterogeneous catalysts featuring one or a few active metal atoms that are separated from one another. They represent an important class of materials ranging from single-atom catalysts (SACs) and nanoparticles (NPs). While SACs and NPs have been extensively reported, catalysts featuring a few atoms with well-defined structures are poorly studied. The difficulty in synthesizing such structures has been a critical challenge. Here we report a facile photochemical method that produces catalytic centers consisting of two Ir metal cations, bridged by O and stably bound to a support. Direct evidence unambiguously supporting the dinuclear nature of the catalysts anchored on α-Fe2O3 is obtained by aberration-corrected scanning transmission electron microscopy (AC-STEM). Experimental and computational results further reveal that the threefold hollow binding sites on the OH-terminated surface of α-Fe2O3 anchor the catalysts to provide outstanding stability against detachment or aggregation. The resulting catalysts exhibit high activities toward H2O photooxidation.

Selenium Metabolism in Hemp (Cannabis sativa L.)-Potential for Phytoremediation and Biofortification.

Selenium (Se) deficiency and toxicity affect over a billion people worldwide. Plants can mitigate both problems, via Se biofortification and phytoremediation. Here we explore the potential of hemp (Cannabis sativa L.) for these phytotechnologies. Field surveys in naturally seleniferous agricultural areas in Colorado, United States, found 15-25 µg of Se/g in seed and 5-10 µg of Se/g dry weight (DW) in flowers and leaves. Thus, 4 g of this hemp seed provides the U.S. recommended daily allowance of 55-75 µg of Se. In controlled greenhouse experiments, hemp seedlings grown in Turface supplied with 40-320 µM selenate showed complete tolerance up to 160 µM and accumulated up to 1300 mg of Se/kg shoot dry weight. Mature hemp grown in Turface supplied with 5-80 µM selenate was completely tolerant up to 40 µM selenate and accumulated up to 200 mg of Se/kg DW in leaves, flowers, and seeds. Synchrotron X-ray fluorescence and X-ray absorption spectroscopies of selenate-supplied hemp showed Se to accumulate mainly in the leaf vasculature and in the seed embryos, with predominant Se speciation in C-Se-C forms (57-75% in leaf and more than 86% in seeds). Aqueous seed extracts were found by liquid chromatography mass spectrometry to contain selenomethionine and methyl-selenocysteine (1:1-3 ratio), both excellent dietary Se sources. Floral concentrations of medicinal cannabidiol (CBD) and terpenoids were not affected by Se. We conclude that hemp has good potential for Se phytoremediation while producing Se-biofortified dietary products.

Supported Au Nanoparticles with N-Heterocyclic Carbene Ligands as Active and Stable Heterogeneous Catalysts for Lactonization.

Attachment of N-heterocyclic carbenes (NHCs) on the surface of metal nanoparticle (NP) catalysts permits fine-tuning of catalytic activity and product selectivity. Yet, NHC-coated Au NPs have been seldom used in catalysis beyond hydrogenation chemistry. One challenge in this field has been to develop a platform that permits arbitrary ligand modification without having to compromise NP stability toward aggregation or leaching. Herein, we exploit the strategy of supported dendrimer-encapsulated metal clusters (DEMCs) to achieve aggregation-stable yet active heterogeneous Au NP catalysts with NHC ligands. Dendrimers function as aggregation-inhibitors during the NP synthesis, and NHCs, well-known for their strong attachment to the gold surface, provide a handle to modify the stereochemistry, stereoelectronics, and chemical functionality of the NP surface. Indeed, compared to "ligandless" Au NPs which are virtually inactive below 80 °C, the NHC-ligated Au NP catalysts enable a model lactonization reaction to proceed at 20 °C on the same time scale (hours). Based on Eyring analysis, proto-deauration is the turnover-limiting step accelerated by the NHC ligands. Furthermore, the use of chiral NHCs led to asymmetric induction (up to 16% enantiomeric excess) in the lactonization transformations, which demonstrates the potential of supported DEMCs with ancillary ligands in enantioselective catalysis.

Bioinspired Metal-Organic Framework Catalysts for Selective Methane Oxidation to Methanol.

Particulate methane monooxygenase (pMMO) is an enzyme that oxidizes methane to methanol with high activity and selectivity. Limited success has been achieved in incorporating biologically relevant ligands for the formation of such active site in a synthetic system. Here, we report the design and synthesis of metal-organic framework (MOF) catalysts inspired by pMMO for selective methane oxidation to methanol. By judicious selection of a framework with appropriate topology and chemical functionality, MOF-808 was used to postsynthetically install ligands bearing imidazole units for subsequent metalation with Cu(I) in the presence of dioxygen. The catalysts show high selectivity for methane oxidation to methanol under isothermal conditions at 150 °C. Combined spectroscopies and density functional theory calculations suggest bis(µ-oxo) dicopper species as probable active site of the catalysts.

Correlative Cryogenic Spectromicroscopy to Investigate Selenium Bioreduction Products.

Accurate mapping of the composition and structure of minerals and associated biological materials is critical in geomicrobiology and environmental research. Here, we have developed an apparatus that allows the correlation of cryogenic transmission electron microscopy (cryo-TEM) and synchrotron hard X-ray microprobe (SHXM) data sets to precisely determine the distribution, valence state, and structure of selenium in biofilms sampled from a contaminated aquifer near Rifle, CO. Results were replicated in the laboratory via anaerobic selenate-reducing enrichment cultures. 16S rRNA analyses of field-derived biofilm indicated the dominance of Betaproteobacteria from the Comamonadaceae family and uncultivated members of the Simplicispira genus. The major product in field and culture-derived biofilms is ∼25-300 nm red amorphous Se0 aggregates of colloidal nanoparticles. Correlative analyses of the cultures provided direct evidence for the microbial dissimilatory reduction of Se(VI) to Se(IV) to Se0. Extended X-ray absorption fine-structure spectroscopy showed red amorphous Se0 with a first shell Se-Se interatomic distance of 2.339 ± 0.003 Å. Complementary scanning transmission X-ray microscopy revealed that these aggregates are strongly associated with a protein-rich biofilm matrix. These findings have important implications for predicting the stability and mobility of Se bioremediation products and understanding of Se biogeochemical cycling. The approach, involving the correlation of cryo-SHXM and cryo-TEM data sets from the same specimen area, is broadly applicable to biological and environmental samples.

Evolution of selenium hyperaccumulation in Stanleya (Brassicaceae) as inferred from phylogeny, physiology and X-ray microprobe analysis.

Past studies have identified herbivory as a likely selection pressure for the evolution of hyperaccumulation, but few have tested the origin(s) of hyperaccumulation in a phylogenetic context. We focused on the evolutionary history of selenium (Se) hyperaccumulation in Stanleya (Brassicaceae). Multiple accessions were collected for all Stanleya taxa and two outgroup species. We sequenced four nuclear gene regions and performed a phylogenetic analysis. Ancestral reconstruction was used to predict the states for Se-related traits in a parsimony framework. Furthermore, we tested the taxa for Se localization and speciation using X-ray microprobe analyses. True hyperaccumulation was found in three taxa within the S. pinnata/bipinnata clade. Tolerance to hyperaccumulator Se concentrations was found in several taxa across the phylogeny, including the hyperaccumulators. X-ray analysis revealed two distinct patterns of leaf Se localization across the genus: marginal and vascular. All taxa accumulated predominantly (65-96%) organic Se with the C-Se-C configuration. These results give insight into the evolution of Se hyperaccumulation in Stanleya and suggest that Se tolerance and the capacity to produce organic Se are likely prerequisites for Se hyperaccumulation in Stanleya.

Do selenium hyperaccumulators affect selenium speciation in neighboring plants and soil? An X-Ray Microprobe Analysis.

Neighbors of Se hyperaccumulators Stanleya pinnata and Astragalus bisulcatus were found earlier to have elevated Se levels. Here we investigate whether Se hyperaccumulators affect Se localization and speciation in surrounding soil and neighboring plants. X-ray fluorescence mapping and X-ray absorption near-edge structure spectroscopy were used to analyze Se localization and speciation in leaves of Artemisia ludoviciana, Symphyotrichum ericoides and Chenopodium album growing next to Se hyperaccumulators or non-accumulators at a seleniferous site. Regardless of neighbors, A. ludoviciana, S. ericoides and C. album accumulated predominantly (73-92%) reduced selenocompounds with XANES spectra similar to the C-Se-C compounds selenomethionine and methyl-selenocysteine. Preliminary data indicate that the largest Se fraction (65-75%), both in soil next to hyperaccumulator S. pinnata and next to nonaccumulator species was reduced Se with spectra similar to C-Se-C standards. These same C-Se-C forms are found in hyperaccumulators. Thus, hyperaccumulator litter may be a source of organic soil Se, but soil microorganisms may also contribute. These findings are relevant for phytoremediation and biofortification since organic Se is more readily accumulated by plants, and more effective for dietary Se supplementation.

Distribution and chemical speciation of arsenic in ancient human hair using synchrotron radiation.

Pre-Columbian populations that inhabited the Tarapacá mid river valley in the Atacama Desert in Chile during the Middle Horizon and Late Intermediate Period (AD 500-1450) show patterns of chronic poisoning due to exposure to geogenic arsenic. Exposure of these people to arsenic was assessed using synchrotron-based elemental X-ray fluorescence mapping, X-ray absorption spectroscopy, X-ray diffraction and Fourier transform infrared spectromicroscopy measurements on ancient human hair. These combined techniques of high sensitivity and specificity enabled the discrimination between endogenous and exogenous processes that has been an analytical challenge for archeological studies and criminal investigations in which hair is used as a proxy of premortem metabolism. The high concentration of arsenic mainly in the form of inorganic As(III) and As(V) detected in the hair suggests chronic arsenicism through ingestion of As-polluted water rather than external contamination by the deposition of heavy metals due to metallophilic soil microbes or diffusion of arsenic from the soil. A decrease in arsenic concentration from the proximal to the distal end of the hair shaft analyzed may indicate a change in the diet due to mobility, though chemical or microbiologically induced processes during burial cannot be entirely ruled out.

A role for iron and oxygen chemistry in preserving soft tissues, cells and molecules from deep time.

The persistence of original soft tissues in Mesozoic fossil bone is not explained by current chemical degradation models. We identified iron particles (goethite-αFeO(OH)) associated with soft tissues recovered from two Mesozoic dinosaurs, using transmission electron microscopy, electron energy loss spectroscopy, micro-X-ray diffraction and Fe micro-X-ray absorption near-edge structure. Iron chelators increased fossil tissue immunoreactivity to multiple antibodies dramatically, suggesting a role for iron in both preserving and masking proteins in fossil tissues. Haemoglobin (HB) increased tissue stability more than 200-fold, from approximately 3 days to more than two years at room temperature (25°C) in an ostrich blood vessel model developed to test post-mortem 'tissue fixation' by cross-linking or peroxidation. HB-induced solution hypoxia coupled with iron chelation enhances preservation as follows: HB + O2 > HB - O2 > -O2 >> +O2. The well-known O2/haeme interactions in the chemistry of life, such as respiration and bioenergetics, are complemented by O2/haeme interactions in the preservation of fossil soft tissues.

Roles of rhizobial symbionts in selenium hyperaccumulation in Astragalus (Fabaceae).

PREMISE OF THE STUDY: Are there dimensions of symbiotic root interactions that are overlooked because plant mineral nutrition is the foundation and, perhaps too often, the sole explanation through which we view these relationships? In this paper we investigate how the root nodule symbiosis in selenium (Se) hyperaccumulator and nonaccumulator Astragalus species influences plant selenium (Se) accumulation. METHODS: In greenhouse studies, Se was added to nodulated and nonnodulated hyperaccumulator and nonaccumulator Astragalus plants, followed by investigation of nitrogen (N)-Se relationships. Selenium speciation was also investigated, using x-ray microprobe analysis and liquid chromatography-mass spectrometry (LC-MS). KEY RESULTS: Nodulation enhanced biomass production and Se to S ratio in both hyperaccumulator and nonaccumulator plants. The hyperaccumulator contained more Se when nodulated, while the nonaccumulator contained less S when nodulated. Shoot [Se] was positively correlated with shoot N in Se-hyperaccumulator species, but not in nonhyperaccumulator species. The x-ray microprobe analysis showed that hyperaccumulators contain significantly higher amounts of organic Se than nonhyperaccumulators. LC-MS of A. bisulcatus leaves revealed that nodulated plants contained more γ-glutamyl-methylselenocysteine (γ-Glu-MeSeCys) than nonnodulated plants, while MeSeCys levels were similar. CONCLUSIONS: Root nodule mutualism positively affects Se hyperaccumulation in Astragalus. The microbial N supply particularly appears to contribute glutamate for the formation of γ-Glu-MeSeCys. Our results provide insight into the significance of symbiotic interactions in plant adaptation to edaphic conditions. Specifically, our findings illustrate that the importance of these relationships are not limited to alleviating macronutrient deficiencies.

Inoculation of selenium hyperaccumulator Stanleya pinnata and related non-accumulator Stanleya elata with hyperaccumulator rhizosphere fungi--investigation of effects on Se accumulation and speciation.

Little is known about how fungi affect elemental accumulation in hyperaccumulators (HAs). Here, two rhizosphere fungi from selenium (Se) HA Stanleya pinnata, Alternaria seleniiphila (A1) and Aspergillus leporis (AS117), were used to inoculate S. pinnata and related non-HA Stanleya elata. Growth and Se and sulfur (S) accumulation were analyzed. Furthermore, X-ray microprobe analysis was used to investigate elemental distribution and speciation. Growth of S. pinnata was not affected by inoculation or by Se. Stanleya elata growth was negatively affected by AS117 and by Se, but combination of both did not reduce growth. Selenium translocation was reduced in inoculated S. pinnata, and inoculation reduced S translocation in both species. Root Se distribution and speciation were not affected by inoculation in either species; both species accumulated mainly (90%) organic Se. Sulfur, in contrast, was present equally in organic and inorganic forms in S. pinnata roots. Thus, these rhizosphere fungi can affect growth and Se and/or S accumulation, depending on host species. They generally enhanced root accumulation and reduced translocation. These effects cannot be attributed to altered plant Se speciation but may involve altered rhizosphere speciation, as these fungi are known to produce elemental Se. Reduced Se translocation may be useful in applications where toxicity to herbivores and movement of Se into the food chain is a concern. The finding that fungal inoculation can enhance root Se accumulation may be useful in Se biofortification or phytoremediation using root crop species.

Analysis of selenium accumulation, speciation and tolerance of potential selenium hyperaccumulator Symphyotrichum ericoides.

Symphyotrichum ericoides was shown earlier to contain hyperaccumulator levels of selenium (Se) in the field (>1000 mg kg(-1) dry weight (DW)), but only when growing next to other Se hyperaccumulators. It was also twofold larger next to hyperaccumulators and suffered less herbivory. This raised two questions: whether S. ericoides is capable of hyperaccumulation without neighbor assistance, and whether its Se-derived benefit is merely ecological or also physiological. Here, in a comparative greenhouse study, Se accumulation and tolerance of S. ericoides were analyzed in parallel with hyperaccumulator Astragalus bisulcatus, Se accumulator Brassica juncea and related Asteraceae Machaeranthera tanacetifolia. Symphyotrichum ericoides and M. tanacetifolia accumulated Se up to 3000 and 1500 mg Se kg(-1) DW, respectively. They were completely tolerant to these Se levels and even grew 1.5- to 2.5-fold larger with Se. Symphyotrichum ericoides showed very high leaf Se/sulfur (S) and shoot/root Se concentration ratios, similar to A. bisulcatus and higher than M. tanacetifolia and B. juncea. Se X-ray absorption near-edge structure spectroscopy showed that S. ericoides accumulated Se predominantly (86%) as C-Se-C compounds indistinguishable from methyl-selenocysteine, which may explain its Se tolerance. Machaeranthera tanacetifolia accumulated 55% of its Se as C-Se-C compounds; the remainder was inorganic Se. Thus, in this greenhouse study S. ericoides displayed all of the characteristics of a hyperaccumulator. The larger size of S. ericoides when growing next to hyperaccumulators may be explained by a physiological benefit, in addition to the ecological benefit demonstrated earlier.

Synthesis and characterization of a nanocrystalline diamond aerogel.

Aerogel materials have myriad scientific and technological applications due to their large intrinsic surface areas and ultralow densities. However, creating a nanodiamond aerogel matrix has remained an outstanding and intriguing challenge. Here we report the high-pressure, high-temperature synthesis of a diamond aerogel from an amorphous carbon aerogel precursor using a laser-heated diamond anvil cell. Neon is used as a chemically inert, near-hydrostatic pressure medium that prevents collapse of the aerogel under pressure by conformally filling the aerogel's void volume. Electron and X-ray spectromicroscopy confirm the aerogel morphology and composition of the nanodiamond matrix. Time-resolved photoluminescence measurements of recovered material reveal the formation of both nitrogen- and silicon- vacancy point-defects, suggesting a broad range of applications for this nanocrystalline diamond aerogel.

Autotrophic biofilms sustained by deeply sourced groundwater host diverse bacteria implicated in sulfur and hydrogen metabolism.

BACKGROUND: Biofilms in sulfide-rich springs present intricate microbial communities that play pivotal roles in biogeochemical cycling. We studied chemoautotrophically based biofilms that host diverse CPR bacteria and grow in sulfide-rich springs to investigate microbial controls on biogeochemical cycling. RESULTS: Sulfide springs biofilms were investigated using bulk geochemical analysis, genome-resolved metagenomics, and scanning transmission X-ray microscopy (STXM) at room temperature and 87 K. Chemolithotrophic sulfur-oxidizing bacteria, including Thiothrix and Beggiatoa, dominate the biofilms, which also contain CPR Gracilibacteria, Absconditabacteria, Saccharibacteria, Peregrinibacteria, Berkelbacteria, Microgenomates, and Parcubacteria. STXM imaging revealed ultra-small cells near the surfaces of filamentous bacteria that may be CPR bacterial episymbionts. STXM and NEXAFS spectroscopy at carbon K and sulfur L2,3 edges show that filamentous bacteria contain protein-encapsulated spherical elemental sulfur granules, indicating that they are sulfur oxidizers, likely Thiothrix. Berkelbacteria and Moranbacteria in the same biofilm sample are predicted to have a novel electron bifurcating group 3b [NiFe]-hydrogenase, putatively a sulfhydrogenase, potentially linked to sulfur metabolism via redox cofactors. This complex could potentially contribute to symbioses, for example, with sulfur-oxidizing bacteria such as Thiothrix that is based on cryptic sulfur cycling. One Doudnabacteria genome encodes adjacent sulfur dioxygenase and rhodanese genes that may convert thiosulfate to sulfite. We find similar conserved genomic architecture associated with CPR bacteria from other sulfur-rich subsurface ecosystems. CONCLUSIONS: Our combined metagenomic, geochemical, spectromicroscopic, and structural bioinformatics analyses of biofilms growing in sulfide-rich springs revealed consortia that contain CPR bacteria and sulfur-oxidizing Proteobacteria, including Thiothrix, and bacteria from a new family within Beggiatoales. We infer roles for CPR bacteria in sulfur and hydrogen cycling. Video Abstract.

Asymmetric catalysis at the mesoscale: gold nanoclusters embedded in chiral self-assembled monolayer as heterogeneous catalyst for asymmetric reactions.

Research to develop highly versatile, chiral, heterogeneous catalysts for asymmetric organic transformations, without quenching the catalytic reactivity, has met with limited success. While chiral supramolecular structures, connected by weak bonds, are highly active for homogeneous asymmetric catalysis, their application in heterogeneous catalysis is rare. In this work, asymmetric catalyst was prepared by encapsulating metallic nanoclusters in chiral self-assembled monolayer (SAM), immobilized on mesoporous SiO2 support. Using olefin cyclopropanation as an example, it was demonstrated that by controlling the SAM properties, asymmetric reactions can be catalyzed by Au clusters embedded in chiral SAM. Up to 50% enantioselectivity with high diastereoselectivity were obtained while employing Au nanoclusters coated with SAM peptides as heterogeneous catalyst for the formation of cyclopropane-containing products. Spectroscopic measurements correlated the improved enantioselectivity with the formation of a hydrogen-bonding network in the chiral SAM. These results demonstrate the synergetic effect of the catalytically active metallic sites and the surrounding chiral SAM for the formation of a mesoscale enantioselective catalyst.

Inoculation of Astragalus racemosus and Astragalus convallarius with selenium-hyperaccumulator rhizosphere fungi affects growth and selenium accumulation.

Little is known about how fungi affect plant selenium (Se) accumulation. Here we investigate the effects of two fungi on Se accumulation, translocation, and chemical speciation in the hyperaccumulator Astragalus racemosus and the non-accumulator Astragalus convallarius. The fungi, Alternaria astragali (A3) and Fusarium acuminatum (F30), were previously isolated from Astragalus hyperaccumulator rhizosphere. A3-inoculation enhanced growth of A. racemosus yet inhibited growth of A. convallarius. Selenium treatment negated these effects. F30 reduced shoot-to-root Se translocation in A. racemosus. X-ray microprobe analysis showed no differences in Se speciation between inoculation groups. The Astragalus species differed in Se localization and speciation. A. racemosus root-Se was distributed throughout the taproot and lateral root and was 90 % organic in the lateral root. The related element sulfur (S) was present as a mixture of organic and inorganic forms in the hyperaccumulator. Astragalus convallarius root-Se was concentrated in the extreme periphery of the taproot. In the lateral root, Se was exclusively in the vascular core and was only 49 % organic. These findings indicate differences in Se assimilation between the two species and differences between Se and S speciation in the hyperaccumulator. The finding that fungi can affect translocation may have applications in phytoremediation and biofortification.