Origin and modern microbial ecology of secondary mineral deposits in Lehman Caves, Great Basin National Park, NV, USA.

Lehman Caves is an extensively decorated high desert cave that represents one of the main tourist attractions in Great Basin National Park, Nevada. Although traditionally considered a water table cave, recent studies identified abundant speleogenetic features consistent with a hypogenic and, potentially, sulfuric acid origin. Here, we characterized white mineral deposits in the Gypsum Annex (GA) passage to determine whether these secondary deposits represent biogenic minerals formed during sulfuric acid corrosion and explored microbial communities associated with these and other mineral deposits throughout the cave. Powder X-ray diffraction (pXRD), scanning electron microscopy with electron dispersive spectroscopy (SEM-EDS), and electron microprobe analyses (EPMA) showed that, while most white mineral deposits from the GA contain gypsum, they also contain abundant calcite, silica, and other phases. Gypsum and carbonate-associated sulfate isotopic values of these deposits are variable, with δ34SV-CDT between +9.7‰ and +26.1‰, and do not reflect depleted values typically associated with replacement gypsum formed during sulfuric acid speleogenesis. Petrographic observations show that the sulfates likely co-precipitated with carbonate and SiO2 phases. Taken together, these data suggest that the deposits resulted from later-stage meteoric events and not during an initial episode of sulfuric acid speleogenesis. Most sedimentary and mineral deposits in Lehman Caves have very low microbial biomass, with the exception of select areas along the main tour route that have been impacted by tourist traffic. High-throughput 16S rRNA gene amplicon sequencing showed that microbial communities in GA sediments are distinct from those in other parts of the cave. The microbial communities that inhabit these oligotrophic secondary mineral deposits include OTUs related to known ammonia-oxidizing Nitrosococcales and Thaumarchaeota, as well as common soil taxa such as Acidobacteriota and Proteobacteria. This study reveals microbial and mineralogical diversity in a previously understudied cave and expands our understanding of the geomicrobiology of desert hypogene cave systems.

Compositae-ParaLoss-1272: A complementary sunflower-specific probe set reduces paralogs in phylogenomic analyses of complex systems.

Premise: A family-specific probe set for sunflowers, Compositae-1061, enables family-wide phylogenomic studies and investigations at lower taxonomic levels, but may lack resolution at genus to species levels, especially in groups complicated by polyploidy and hybridization. Methods: We developed a Hyb-Seq probe set, Compositae-ParaLoss-1272, that targets orthologous loci in Asteraceae. We tested its efficiency across the family by simulating target enrichment sequencing in silico. Additionally, we tested its effectiveness at lower taxonomic levels in the historically complex genus Packera. We performed Hyb-Seq with Compositae-ParaLoss-1272 for 19 Packera taxa that were previously studied using Compositae-1061. The resulting sequences from each probe set, plus a combination of both, were used to generate phylogenies, compare topologies, and assess node support. Results: We report that Compositae-ParaLoss-1272 captured loci across all tested Asteraceae members, had less gene tree discordance, and retained longer loci than Compositae-1061. Most notably, Compositae-ParaLoss-1272 recovered substantially fewer paralogous sequences than Compositae-1061, with only ~5% of the recovered loci reporting as paralogous, compared to ~59% with Compositae-1061. Discussion: Given the complexity of plant evolutionary histories, assigning orthology for phylogenomic analyses will continue to be challenging. However, we anticipate Compositae-ParaLoss-1272 will provide improved resolution and utility for studies of complex groups and lower taxonomic levels in the sunflower family.

Correlating structure and photophysical properties in thiazolo[5,4-d]thiazole crystal derivatives for use in solid-state photonic and fluorescence-based optical devices.

There is a growing demand for new fluorescent small molecule dyes for solid state applications in the photonics and optoelectronics industry. Thiazolo[5,4-d]thiazole (TTz) is an organic heterocycle moiety which has previously shown remarkable properties as a conjugated polymer and in solution-based studies. For TTz-based small molecules to be incorporated in solid-state fluorescence-based optical devices, a thorough elucidation of their structure-photophysical properties needs to be established. Herein, we have studied four TTz-based materials functionalized with alkyl appendages of varying carbon chain lengths. We report the single crystal structures of the TTz derivatives, three of which were previously unknown. The packing modes of the crystals reveal that molecular arrangements are largely governed by a chorus of synergistic intermolecular non-covalent interactions. Three crystals packed in herringbone mode and one crystal packed in slipped stacks proving that alkyl appendages modulate structural organization in TTz-based materials. Steady state and time-resolved photophysical properties of these crystals were studied via diffuse-reflectance, micro-Raman, and photoluminescence spectroscopy. The crystals fluoresce from orange-red to blue spanning through the whole gamut of the visible spectrum. We have established that photophysical properties are a function of crystal packing in symmetrically substituted TTz-based materials. This correlation was then utilized to fabricate crystalline blends. We demonstrate, for the first time, that symmetrically substituted donor-acceptor-donor TTz-based materials can be used for phosphor-converted color-tuning and white-light emission. Given the cost effectiveness, ease of synthesis and now a structure-photophysics correlation, we present a compelling case for the adoption of TTz-based materials in solid-state photonic and fluorescence-based optical devices.

Complex peptide hormone signaling in plant stem cells.

Peptide hormones influence diverse aspects of plant development through highly coordinated cell-cell signaling pathways. Many peptide hormone families play key roles in stem cell maintenance across land plants. In this review, we focus on recent work in two conserved peptide hormone families, CLAVATA3/EMBRYO-SURROUNDING REGION (CLEs) and ROOT MERISTEM GROWTH FACTOR (RGFs), and their roles in regulating plant stem cells. We discuss recent work establishing downstream crosstalk between peptide hormones and other conserved signaling mechanisms in meristem maintenance as well as highlight advances in peptide hormone gene identification that provide important context for CLE/RGF family evolution across diverse plant lineages. CLE and RGF gene families have greatly expanded in angiosperms, contributing to the complex genetic regulation of stem cell homeostasis observed in model systems over the last 30 years. Peptide hormone duplications have resulted in genetic compensation mechanisms that ensure robust development through the function of paralogous genes. Broad conservation of genetic compensation across angiosperms highlights the importance of these mechanisms in developmental signaling and understanding their regulation could inform broader understanding of morphological diversity and evolutionary innovation.

Microbial communities from weathered outcrops of a sulfide-rich ultramafic intrusion, and implications for mine waste management.

The Duluth Complex (DC) contains sulfide-rich magmatic intrusions that represent one of the largest known economic deposits of copper, nickel, and platinum group elements. Previous work showed that microbial communities associated with experimentally-weathered DC waste rock and tailings were dominated by uncultivated taxa and organisms not typically associated with mine waste. However, those experiments were designed for kinetic testing and do not necessarily represent the conditions expected for long-term environmental weathering. We used 16S rRNA gene methods to characterize the microbial communities present on the surfaces of naturally-weathered and historically disturbed outcrops of DC material. Rock surfaces were dominated by diverse uncultured Ktedonobacteria, Acetobacteria, and Actinobacteria, with abundant algae and other phototrophs. These communities were distinct from microbial assemblages from experimentally-weathered DC rocks, suggesting different energy and nutrient resources in environmental samples. Sulfide mineral incubations performed with and without algae showed that photosynthetic microorganisms could have an inhibitory effect on autotrophic populations, resulting in slightly lower sulfate release and differences in dominant microorganisms. The microbial assemblages from these weathered outcrops show how communities develop during weathering of sulfide-rich DC rocks and represent baseline data that could evaluate the effectiveness of future reclamation of waste produced by large-scale mining operations.

A network of CLAVATA receptors buffers auxin-dependent meristem maintenance.

Plant body plans are elaborated in response to both environmental and endogenous cues. How these inputs intersect to promote growth and development remains poorly understood. During reproductive development, central zone stem cell proliferation in inflorescence meristems is negatively regulated by the CLAVATA3 (CLV3) peptide signalling pathway. In contrast, floral primordia formation on meristem flanks requires the hormone auxin. Here we show that CLV3 signalling is also necessary for auxin-dependent floral primordia generation and that this function is partially masked by both inflorescence fasciation and heat-induced auxin biosynthesis. Stem cell regulation by CLAVATA signalling is separable from primordia formation but is also sensitized to temperature and auxin levels. In addition, we uncover a novel role for the CLV3 receptor CLAVATA1 in auxin-dependent meristem maintenance in cooler environments. As such, CLV3 signalling buffers multiple auxin-dependent shoot processes across divergent thermal environments, with opposing effects on cell proliferation in different meristem regions.

Convergent Community Assembly among Globally Separated Acidic Cave Biofilms.

Acidophilic bacteria and archaea inhabit extreme geochemical "islands" that can tell us when and how geographic barriers affect the biogeography of microorganisms. Here, we describe microbial communities from extremely acidic (pH 0 to 1) biofilms, known as snottites, from hydrogen sulfide-rich caves. Given the extreme acidity and subsurface location of these biofilms, and in light of earlier work showing strong geographic patterns among snottite Acidithiobacillus populations, we investigated their structure and diversity in order to understand how geography might impact community assembly. We used 16S rRNA gene cloning and fluorescence in situ hybridization (FISH) to investigate 26 snottite samples from four sulfidic caves in Italy and Mexico. All samples had very low biodiversity and were dominated by sulfur-oxidizing bacteria in the genus Acidithiobacillus. Ferroplasma and other archaea in the Thermoplasmatales ranged from 0 to 50% of total cells, and relatives of the bacterial genera Acidimicrobium and Ferrimicrobium were up to 15% of total cells. Rare phylotypes included Sulfobacillus spp. and members of the phyla "Candidatus Dependentiae" and "Candidatus Saccharibacteria" (formerly TM6 and TM7). Although the same genera of acidophiles occurred in snottites on separate continents, most members of those genera represent substantially divergent populations, with 16S rRNA genes that are only 95 to 98% similar. Our findings are consistent with a model of community assembly where sulfidic caves are stochastically colonized by microorganisms from local sources, which are strongly filtered through environmental selection for extreme acid tolerance, and these different colonization histories are maintained by dispersal restrictions within and among caves. IMPORTANCE Microorganisms that are adapted to extremely acidic conditions, known as extreme acidophiles, are catalysts for rock weathering, metal cycling, and mineral formation in naturally acidic environments. They are also important drivers of large-scale industrial processes such as biomining and contaminant remediation. Understanding the factors that govern their ecology and distribution can help us better predict and utilize their activities in natural and engineered systems. However, extremely acidic habitats are unusual in that they are almost always isolated within circumneutral landscapes. So where did their acid-adapted inhabitants come from, and how do new colonists arrive and become established? In this study, we took advantage of a unique natural experiment in Earth's subsurface to show how isolation may have played a role in the colonization history, community assembly, and diversity of highly acidic microbial biofilms.

A consensus protocol for the recovery of mercury methylation genes from metagenomes.

Mercury (Hg) methylation genes (hgcAB) mediate the formation of the toxic methylmercury and have been identified from diverse environments, including freshwater and marine ecosystems, Arctic permafrost, forest and paddy soils, coal-ash amended sediments, chlor-alkali plants discharges and geothermal springs. Here we present the first attempt at a standardized protocol for the detection, identification and quantification of hgc genes from metagenomes. Our Hg-cycling microorganisms in aquatic and terrestrial ecosystems (Hg-MATE) database, a catalogue of hgc genes, provides the most accurate information to date on the taxonomic identity and functional/metabolic attributes of microorganisms responsible for Hg methylation in the environment. Furthermore, we introduce "marky-coco", a ready-to-use bioinformatic pipeline based on de novo single-metagenome assembly, for easy and accurate characterization of hgc genes from environmental samples. We compared the recovery of hgc genes from environmental metagenomes using the marky-coco pipeline with an approach based on coassembly of multiple metagenomes. Our data show similar efficiency in both approaches for most environments except those with high diversity (i.e., paddy soils) for which a coassembly approach was preferred. Finally, we discuss the definition of true hgc genes and methods to normalize hgc gene counts from metagenomes.

Polarized NORTIA accumulation in response to pollen tube arrival at synergids promotes fertilization.

Signal-mediated regulation of protein trafficking is an elegant mechanism for controlling the delivery of molecules to a precise location for critical signaling events that occur over short time frames. During plant reproduction, the FERONIA receptor complex is critical for intercellular communication that leads to gamete delivery; however, the impact of the FERONIA signal transduction cascade on protein trafficking in synergid cells remains unknown. Live imaging of pollen tube reception has revealed that a key outcome of FERONIA signaling is polar accumulation of the MLO protein NORTIA at the filiform apparatus in response to signals from an arriving pollen tube. Artificial delivery of NORTIA to the filiform apparatus is sufficient to bypass the FERONIA signaling pathway and to promote interspecific pollen tube reception. We propose that polar accumulation of NORTIA leads to the production of a secondary booster signal to ensure that pollen tubes burst to deliver the sperm cells for double fertilization.

II-VI Organic-Inorganic Hybrid Nanostructures with Greatly Enhanced Optoelectronic Properties, Perfectly Ordered Structures, and Shelf Stability of Over 15 Years.

Organic-inorganic hybrids may offer material properties not available from their inorganic components. However, they are typically less stable and disordered. Long-term stability study of the hybrid materials, over the anticipated lifespan of a real-world electronic device, is practically nonexistent. Disordering, prevalent in most nanostructure assemblies, is a prominent adversary to quantum coherence. A family of perfectly ordered II-VI-based hybrid nanostructures has been shown to possess many unusual properties and potential applications. Here, using a prototype structure ß-ZnTe(en)0.5-a hybrid superlattice-and applying an array of optical, structural, surface, thermal, and electrical characterization techniques, in conjunction with density-functional theory calculations, we have performed a comprehensive and correlative study of the crystalline quality, structural degradation, electronic, optical, and transport properties on samples from over 15 years old to the recently synthesized. The findings show that not only do they exhibit an exceptionally high level of crystallinity in both macroscopic and microscopic scale, comparable to high-quality binary semiconductors; and greatly enhanced material properties, compared to those of the inorganic constituents; but also, some of them over 15 years old remain as good in structure and property as freshly made ones. This study reveals (1) what level of structural perfectness is achievable in a complex organic-inorganic hybrid structure or a man-made superlattice, suggesting a nontraditional strategy to make periodically stacked heterostructures with abrupt interfaces; and (2) how the stability of a hybrid material is affected differently by its intrinsic attributes, primarily formation energy, and extrinsic factors, such as surface and defects. By correlating the rarely found long-term stability with the calculated relatively large formation energy of ß-ZnTe(en)0.5 and contrasting with the case of hybrid perovskite, this work illustrates that formation energy can serve as an effective screening parameter for the long-term stability potential of hybrid materials. The results of the prototype II-VI hybrid structures will, on one hand, inspire directions for future exploration of the hybrid materials, and, on the other hand, provide metrics for assessing the structural perfectness and long-term stability of the hybrid materials.

Lighting Effects on the Development and Diversity of Photosynthetic Biofilm Communities in Carlsbad Cavern, New Mexico.

Photosynthetic cave communities ("lampenflora") proliferate in Carlsbad Cavern and other show caves worldwide due to artificial lighting. These biofilms mar the esthetics and can degrade underlying cave surfaces. The National Park Service recently modernized the lighting in Carlsbad Cavern to a light-emitting diode (LED) system that allows adjustment of the color temperature and intensity. We hypothesized that lowering the color temperature would reduce photopigment development. We therefore assessed lampenflora responses to changes in lighting by monitoring photosynthetic communities over the course of a year. We measured photopigments using reflected-light spectrophotometric observations and analyzed microbial community composition with 16S and 18S rRNA gene amplicon sequencing. Reflected-light spectrophotometry revealed that photosynthetic biofilm development is affected by lighting intensity, color temperature, substrate type, and cleaning of the substrate. Gene sequencing showed that the most abundant phototrophs were Cyanobacteria and members of the algal phyla Chlorophyta and Ochrophyta At the end of the study, visible growth of lampenflora was seen at all sites. At sites that had no established biofilm at the start of the study period, Cyanobacteria became abundant and outpaced an increase in eukaryotic algae. Microbial diversity also increased over time at these sites, suggesting a possible pattern of early colonization and succession. Bacterial community structure showed significant effects of all variables: color temperature, light intensity, substrate type, site, and previous cleaning of the substrate. These findings provide fundamental information that can inform management practices; they suggest that altering lighting conditions alone may be insufficient to prevent lampenflora growth.IMPORTANCE Artificial lighting in caves visited by tourists ("show caves") can stimulate photosynthetic algae and cyanobacteria, called "lampenflora," which are unsightly and damage speleothems and other cave surfaces. The most common mitigation strategy employs bleach, but altering intensities and wavelengths of light might be effective and less harsh. Carlsbad Cavern in New Mexico, a U.S. National Park and UNESCO World Heritage Site, has visible lampenflora despite adjustment of LED lamps to decrease the energetic blue light. This study characterized the lampenflora communities and tested the effects of color temperature, light intensity, rock or sediment texture, and time on lampenflora development. DNA amplicon sequence data show a variety of algae and cyanobacteria and also heterotrophic bacteria. This study reveals microbial dynamics during colonization of artificially lit surfaces and indicates that while lowering the color temperature may have an effect, management of lampenflora will likely require additional chemical or UV treatment.

Insights into the Geomicrobiology of Biovermiculations from Rock Billet Incubation Experiments.

Biovermiculations are uniquely patterned organic rich sediment formations found on the walls of caves and other subterranean environments. These distinctive worm-like features are the combined result of physical and biological processes. The diverse microbial communities that inhabit biovermiculations may corrode the host rock, form secondary minerals, and produce biofilms that stabilize the sediment matrix, thus altering cave surfaces and contributing to the formation of these wall deposits. In this study, we incubated basalt, limestone, and monzonite rock billets in biovermiculation mixed natural community enrichments for 468-604 days, and used scanning electron microscopy (SEM) to assess surface textures and biofilms that developed over the course of the experiment. We observed alteration of rock billet surfaces associated with biofilms and microbial filaments, particularly etch pits and other corrosion features in olivine and other silicates, calcite dissolution textures, and the formation of secondary minerals including phosphates, clays, and iron oxides. We identified twelve distinct biofilm morphotypes that varied based on rock type and the drying method used in sample preparation. These corrosion features and microbial structures inform potential biological mechanisms for the alteration of cave walls, and provide insight into possible small-scale macroscopically visible biosignatures that could augment the utility of biovermiculations and similarly patterned deposits for astrobiology and life detection applications.

CLAVATA Signaling Ensures Reproductive Development in Plants across Thermal Environments.

The ability to thrive in diverse environments requires that species maintain development and reproduction despite dynamic conditions. Many developmental processes are stabilized through robust signaling pathways that cooperatively ensure proper development.1 During reproduction, plants like Arabidopsis thaliana continuously generate flowers on growing indeterminate inflorescences.2 Flower primordia initiation and outgrowth depends on the hormone auxin and is robust across diverse environments.3-6 Here, we show that reproductive development under different thermal conditions requires the integration of multiple pathways regulating auxin-dependent flower production. In colder/ambient temperatures, the receptor complex CLAVATA2/CORYNE (CLV2/CRN) is necessary for continuous flower outgrowth during inflorescence development. CLV2/CRN signaling is independent of CLAVATA1 (CLV1)-related receptor signaling but involves the CLAVATA3 INSENSITIVE RECEPTOR KINASE (CIK) family co-receptors, with higher order cik mutant combinations phenocopying clv2/crn flower outgrowth defects. Developing crn inflorescences display reduced auxin signaling, and restoration of auxin biosynthesis is sufficient to restore flower outgrowth in colder and ambient temperatures. In contrast, at higher temperatures, both clv2/crn signaling and heat-induced auxin biosynthesis via YUCCA family genes are synergistically required to maintain flower development. Our work reveals a novel mechanism integrating peptide hormone and auxin signaling in the regulation of flower development across diverse thermal environments.

Diverse Communities of hgcAB+ Microorganisms Methylate Mercury in Freshwater Sediments Subjected to Experimental Sulfate Loading.

Methylmercury (MeHg) is a bioaccumulative neurotoxin produced by certain sulfate-reducing bacteria and other anaerobic microorganisms. Because microorganisms differ in their capacity to methylate mercury, the abundance and distribution of methylating populations may determine MeHg production in the environment. We compared rates of MeHg production and the distribution of hgcAB genes in epilimnetic sediments from a freshwater lake that were experimentally amended with sulfate levels from 7 to 300 mg L-1. The most abundant hgcAB sequences were associated with clades of Methanomicrobia, sulfate-reducing Deltaproteobacteria, Spirochaetes, and unknown environmental sequences. The hgcAB+ communities from higher sulfate amendments were less diverse and had relatively more Deltaproteobacteria, whereas the communities from lower amendments were more diverse with a larger proportion of hgcAB sequences affiliated with other clades. Potential methylation rate constants varied 52-fold across the experiment. Both potential methylation rate constants and % MeHg were the highest in sediments from the lowest sulfate amendments, which had the most diverse hgcAB+ communities and relatively fewer hgcAB genes from clades associated with sulfate reduction. Although pore water sulfide concentration covaried with hgcAB diversity across our experimental sulfate gradient, major changes in the community of hgcAB+ organisms occurred prior to a significant buildup of sulfide in pore waters. Our results indicate that methylating communities dominated by diverse anaerobic microorganisms that do not reduce sulfate can produce MeHg as effectively as communities dominated by sulfate-reducing populations.

An Improved hgcAB Primer Set and Direct High-Throughput Sequencing Expand Hg-Methylator Diversity in Nature.

The gene pair hgcAB is essential for microbial mercury methylation. Our understanding of its abundance and diversity in nature is rapidly evolving. In this study we developed a new broad-range primer set for hgcAB, plus an expanded hgcAB reference library, and used these to characterize Hg-methylating communities from diverse environments. We applied this new Hg-methylator database to assign taxonomy to hgcA sequences from clone, amplicon, and metagenomic datasets. We evaluated potential biases introduced in primer design, sequence length, and classification, and suggest best practices for studying Hg-methylator diversity. Our study confirms the emerging picture of an expanded diversity of HgcAB-encoding microbes in many types of ecosystems, with abundant putative mercury methylators Nitrospirae and Chloroflexi in several new environments including salt marsh and peat soils. Other common microbes encoding HgcAB included Phycisphaerae, Aminicenantes, Spirochaetes, and Elusimicrobia. Combined with high-throughput amplicon specific sequencing, the new primer set also indentified novel hgcAB sequences similar to Lentisphaerae, Bacteroidetes, Atribacteria, and candidate phyla WOR-3 and KSB1 bacteria. Gene abundance data also corroborate the important role of two "classic" groups of methylators (Deltaproteobacteria and Methanomicrobia) in many environments, but generally show a scarcity of hgcAB+ Firmicutes. The new primer set was developed to specifically target hgcAB sequences found in nature, reducing degeneracy and providing increased sensitivity while maintaining broad diversity capture. We evaluated mock communities to confirm primer improvements, including culture spikes to environmental samples with variable DNA extraction and PCR amplification efficiencies. For select sites, this new workflow was combined with direct high-throughput hgcAB sequencing. The hgcAB diversity generated by direct amplicon sequencing confirmed the potential for novel Hg-methylators previously identified using metagenomic screens. A new phylogenetic analysis using sequences from freshwater, saline, and terrestrial environments showed Deltaproteobacteria HgcA sequences generally clustered among themselves, while metagenome-resolved HgcA sequences in other phyla tended to cluster by environment, suggesting horizontal gene transfer into many clades. HgcA from marine metagenomes often formed distinct subtrees from those sequenced from freshwater ecosystems. Overall the majority of HgcA sequences branch from a cluster of HgcAB fused proteins related to Thermococci, Atribacteria (candidate division OP9), Aminicenantes (OP8), and Chloroflexi. The improved primer set and library, combined with direct amplicon sequencing, provide a significantly improved assessment of the abundance and diversity of hgcAB+ microbes in nature.

Stepwise Assembly of an Electroactive Framework from a Co6 S8 Superatomic Metalloligand and Cuprous Iodide Building Units.

Invited for the cover of this issue is Christopher Bejger and co-workers at UNC Charlotte, Columbia University, and Donghua University. The image depicts a pair of star clusters in the constellation Perseus as the structure of two metal clusters in the reported framework. Read the full text of the article at 10.1002/chem.20201215.

Accessing new microporous polyspirobifluorenes via a C/Si switch.

Microporous spirosilabifluorene networks were synthesized via Yamamoto coupling of tetrabromospirosilabifluorene precursors. They exhibit bright fluorescence that is quenched in the presence of nitroaromatics. The C/Si switch has subtle effects on the optical properties of the spirobifluorene network and provides a convenient route to 3,3',6,6'-coupled and other polybifluorenes.

Stepwise Assembly of an Electroactive Framework from a Co6 S8 Superatomic Metalloligand and Cuprous Iodide Building Units.

The design of metal-organic frameworks (MOFs) that incorporate more than one metal cluster constituent is a challenging task. Conventional one-pot reaction protocols require judicious selection of ligand and metal ion precursors, yet remain unpredictable. Stable, preformed nanoclusters, with ligand shells that can undergo additional coordination-driven reactions, provide a platform for assembling multi-cluster solids with precision. Herein, a discrete Co6 S8 (PTA)6 (PTA=1,3,5-triaza-7-phosphaadamantane) superatomic-metalloligand is assembled into a three-dimensional (3D) coordination polymer comprising Cu4 I4 secondary building units (SBUs). The resulting heterobimetallic framework (1) contains two distinct cluster constituents and bifunctional PTA linkers. Solid-state diffuse reflectance studies reveal that 1 is an optical semiconductor with a band-gap of 1.59 eV. Framework-modified electrodes exhibit reversible redox behavior in the solid state arising from the Co6 S8 superatoms, which remain intact during framework synthesis.

Desymmetrized hexasubstituted [3]radialene anions as aqueous organic catholytes for redox flow batteries.

Negatively substituted trimethylenecyclopropane dianions, a subclass of hexasubstituted [3]radialenes, are candidates for use as active species in redox flow batteries (RFBs) due to their stability in water, reversible electrochemistry, and tailorable synthesis. Hexacyano[3]radialene disodium is investigated as a pH 7 aqueous organic catholyte. The dianion and radical anion are stable in air and aqueous solutions at neutral pH. Systematic introduction of asymmetry via step-wise synthesis leads to enhanced solubility and higher capacity retention during galvanostatic cycling. An aqueous flow cell comprising a diester-tetracyano[3]radialene catholyte, sulfonated-methyl viologen as the anolyte, and a cation exchange membrane provides an operating Vcell = 0.9 V, 99.609% coulombic efficiency, and minimum capacity fade over 50 cycles.