Challenges and Applications of Supramolecular Metalate Chemistry.

While the supramolecular chemistry of simple anions is ubiquitous, the targeting and exploitation of their metal-containing relatives, the metalates, is less well understood. This mini review highlights the latest advances in this emergent area by discussing the supramolecular chemistry of metalates thematically, with a focus on the exploitation of metalates in a diversity of applications, including medical imaging and therapy, environmental remediation, molecular magnetism, catalysis, perovskite materials, and metal separations. The unifying features of these systems are identified with a view to allow the supramolecular chemist to target the unique material properties of the metalates, even in areas that are currently relatively immature.

Shape-Selective Supramolecular Capsules for Actinide Precipitation and Separation.

Improving actinide separations is key to reducing barriers to medical and industrial actinide isotope production and to addressing the challenges associated with the reprocessing of spent nuclear fuel. Here, we report the first example of a supramolecular anion recognition process that can achieve this goal. We have designed a preorganized triamidoarene receptor that induces quantitative precipitation of the early actinides Th(IV), Np(IV), and Pu(IV) from industrially relevant conditions through the formation of self-assembled hydrogen-bonded capsules.

The prevalence of urogenital and intestinal schistosomiasis among school age children (6-13 years) in the Okavango Delta in Botswana.

This study sought to investigate prevalence of urogenital and intestinal schistosomiasis among school age children 6-13 years in selected communities in the Okavango Delta. The termination of the Botswana national schistosomiasis control program in 1993 contributed to its neglect. An outbreak of schistosomiasis in 2017 at one of the primary schools in the northeastern part of the country resulted in 42 positive cases, indicating that the disease exists.

Community Knowledge, Perceptions and Experiences on Healthcare Services for Malaria Prevention and Treatment in the Okavango Delta, Botswana.

This paper analyses community knowledge, perceptions, and experiences of effectiveness of healthcare service provision on malaria prevention/treatment in two disease-endemic villages of the Okavango Delta panhandle in northern Botswana. A stratified random sampling of 355 households was conducted in October-November 2015. Follow-up retrospective cohort interviews were undertaken in August 2016 from 79 households that reported malaria incidences during the household survey.

Selective separation of light rare-earth elements by supramolecular encapsulation and precipitation.

Supramolecular chemical strategies for Rare Earth (RE) element separations are emerging which amplify the small changes in properties across the series to bias selectivity in extraction or precipitation. These advances are important as the REs are crucial to modern technologies yet their extraction, separation, and recycling using conventional techniques remain challenging. We report here a pre-organised triamidoarene platform which, under acidic, biphasic conditions, uniquely and selectively precipitates light RE nitratometalates as supramolecular capsules.

Tuneable separation of gold by selective precipitation using a simple and recyclable diamide.

The efficient separation of metals from ores and secondary sources such as electronic waste is necessary to realising circularity in metal supply. Precipitation processes are increasingly popular and are reliant on designing and understanding chemical recognition to achieve selectivity. Here we show that a simple tertiary diamide precipitates gold selectively from aqueous acidic solutions, including from aqua regia solutions of electronic waste.

Evaluation of cadmium and arsenic effects on wild and cultivated cardoon genotypes selected for metal phytoremediation and bioenergy purposes.

Cynara cardunculus L. is a multipurpose crop, characterized by high production of biomass suitable for energy purposes and green chemistry. Taking advantage of its already demonstrated ability to grow in polluted environments that characterize many world marginal lands, the aim of this work was to investigate the response of different cardoon genotypes to exposure to cadmium (Cd) and arsenic (As) pollution, in order to use this crop for rehabilitation of contaminated sites and its biomass for energy production.

Algal blooms modulate organic matter remineralization in freshwater sediments: A new insight on priming effect.

This study provides a novel insight into the degradation of sediment organic matter (SOM) regulated by algae-derived organic matter (AOM) based on priming effect. We tracked the dynamics of SOM mineralization products and pathways, together with priming effects (PE) using the compound-specific stable isotope (δC) technique following addition of low- and high-density algal debris in sediments. We found that algal debris increased the total carbon oxidation rate, and resulted in denitrification and methanogenesis-dominated SOM mineralization.

Role of plant growth promoting bacteria in driving speciation gradients across soil-rhizosphere-plant interfaces in zinc-contaminated soils.

Inoculation of soil or seeds with plant growth promoting bacteria ameliorates metal toxicity to plants by changing metal speciation in plant tissues but the exact location of these changes remains unknown. Knowing where the changes occur is a critical first step to establish whether metal speciation changes are driven by microbial metabolism or by plant responses. Since bacteria concentrate in the rhizosphere, we hypothesised steep changes in metal speciation across the rhizosphere.

An Ionic Limit to Life in the Deep Subsurface.

The physical and chemical factors that can limit or prevent microbial growth in the deep subsurface are not well defined. Brines from an evaporite sequence were sampled in the Boulby Mine, United Kingdom between 800 and 1300 m depth. Ionic, hydrogen and oxygen isotopic composition were used to identify two brine sources, an aquifer situated in strata overlying the mine, and another ambiguous source distinct from the regional groundwater.

Metal internalization by bacterial cells depends on metal biotoxicity and metal to biomass ratio.

Unlabelled: The traditional view of metal adsorption to bacterial surfaces is that it can act as a protective mechanism by externalizing the metal outside the cell. However, numerous studies focussing on the biodynamics of metal uptake using biotic ligand models consider metal adsorption to cell surfaces as an important first step in metal uptake and internalization. In order to resolve these conflicting views, we adsorbed two metals (copper and cadmium) with contrasting metal biotoxicity on E.

Soil Bacteria Override Speciation Effects on Zinc Phytotoxicity in Zinc-Contaminated Soils.

The effects of zinc (Zn) speciation on plant growth in Zn-contaminated soil in the presence of bacteria are unknown but are critical to our understanding of metal biodynamics in the rhizosphere where bacteria are abundant. A 6-week pot experiment investigated the effects of two plant growth promoting bacteria (PGPB), Rhizobium leguminosarum and Pseudomonas brassicacearum, on Zn accumulation and speciation in Brassica juncea grown in soil amended with 600 mg kg elemental Zn as three Zn species: soluble ZnSO and nanoparticles of ZnO and ZnS. Measures of plant growth were higher across all Zn treatments inoculated with PGPB compared to uninoculated controls, but Zn species effects were not significant.

16S rRNA gene metabarcoding and TEM reveals different ecological strategies within the genus Neogloboquadrina (planktonic foraminifer).

Uncovering the complexities of trophic and metabolic interactions among microorganisms is essential for the understanding of marine biogeochemical cycling and modelling climate-driven ecosystem shifts. High-throughput DNA sequencing methods provide valuable tools for examining these complex interactions, although this remains challenging, as many microorganisms are difficult to isolate, identify and culture. We use two species of planktonic foraminifera from the climatically susceptible, palaeoceanographically important genus Neogloboquadrina, as ideal test microorganisms for the application of 16S rRNA gene metabarcoding.

Orphans' perspectives on grief and loss in Botswana.

This paper seeks to examine orphaned children's experiences on grief and loss in Botswana, and its impact on their well-being and make policy recommendations. A cross sectional design which utilized survey questionnaires was employed. Data were collected from 11 districts (3 urban and 8 rural) among orphan children aged 10-18 years.

The Croton megalobotrys Müll Arg. traditional medicine in HIV/AIDS management: Documentation of patient use, in vitro activation of latent HIV-1 provirus, and isolation of active phorbol esters.

Ethnopharmacological Relevance: Current HIV therapies do not act on latent cellular HIV reservoirs; hence they are not curative. While experimental latency reversal agents (LRAs) can promote HIV expression in these cells, thereby exposing them to immune recognition, existing LRAs exhibit limited clinical efficacy and high toxicity. We previously described a traditional 3-step medicinal plant regimen used for HIV/AIDS management in Northern Botswana that inhibits HIV replication in vitro.

Memories of environmental change and local adaptations among molapo farming communities in the Okavango Delta, Botswana-A gender perspective.

This paper focuses on ways in which three riparian communities (Xobe, Shorobe and Tubu) practising flood recession (molapo) farming along the fringes of the Okavango Delta in Ngamiland District in north-western Botswana, present memories of experiential impacts of and adaptation to key environmental and anthropogenic change events. Participatory methodological tools were used to capture local knowledge of people who had resided in the Okavango wetlands for many years. Findings indicate that key environmental change events were characterized by intergenerational experiences of severe and frequent droughts, floods, and recurrent outbreaks of human and animal disease.

Croton megalobotrys Müll Arg. and Vitex doniana (Sweet): Traditional medicinal plants in a three-step treatment regimen that inhibit in vitro replication of HIV-1.

Ethnopharmacological Relevance: Human Immunodeficiency Virus (HIV) strains resistant to licensed anti-retroviral drugs (ARVs) continue to emerge. On the African continent, uneven access to ARVs combined with occurrence of side-effects after prolonged ARV therapy have led to searches for traditional medicines as alternative or complementary remedies to conventional HIV/AIDS management.

Aim Of The Study: Here we characterize a specific three-step traditional HIV/AIDS treatment regimen consisting of Cassia sieberiana root, Vitex doniana root, and Croton megalobotrys bark by combining qualitative interviews of traditional medical knowledge users in Botswana with in vitro HIV replication studies.

Clinical Malaria Transmission Trends and Its Association with Climatic Variables in Tubu Village, Botswana: A Retrospective Analysis.

Good knowledge on the interactions between climatic variables and malaria can be very useful for predicting outbreaks and preparedness interventions. We investigated clinical malaria transmission patterns and its temporal relationship with climatic variables in Tubu village, Botswana. A 5-year retrospective time series data analysis was conducted to determine the transmission patterns of clinical malaria cases at Tubu Health Post and its relationship with rainfall, flood discharge, flood extent, mean minimum, maximum and average temperatures.

Mixed planting with a leguminous plant outperforms bacteria in promoting growth of a metal remediating plant through histidine synthesis.

The effectiveness of plant growth promoting bacteria (PGPB) in improving metal phytoremediation is still limited by stunted plant growth under high soil metal concentrations. Meanwhile, mixed planting with leguminous plants is known to improve yield in nutrient deficient soils but the use of a metal tolerant legume to enhance metal tolerance of a phytoremediator has not been explored. We compared the use of Pseudomonas brassicacearum, Rhizobium leguminosarum, and the metal tolerant leguminous plant Vicia sativa to promote the growth of Brassica juncea in soil contaminated with 400 mg Zn kg(-1), and used synchrotron based microfocus X-ray absorption spectroscopy to probe Zn speciation in plant roots.

Bacteria-zinc co-localization implicates enhanced synthesis of cysteine-rich peptides in zinc detoxification when Brassica juncea is inoculated with Rhizobium leguminosarum.

Some plant growth promoting bacteria (PGPB) are enigmatic in enhancing plant growth in the face of increased metal accumulation in plants. Since most PGPB colonize the plant root epidermis, we hypothesized that PGPB confer tolerance to metals through changes in speciation at the root epidermis. We employed a novel combination of fluorophore-based confocal laser scanning microscopic imaging and synchrotron based microscopic X-ray fluorescence mapping with X-ray absorption spectroscopy to characterize bacterial localization, zinc (Zn) distribution and speciation in the roots of Brassica juncea grown in Zn contaminated media (400 mg kg(-1) Zn) with the endophytic Pseudomonas brassicacearum and rhizospheric Rhizobium leguminosarum.

The influence of biofilms on the mobility of bare and capped zinc oxide nanoparticles in saturated sand and glass beads.

Biofilms are a common constituent of the subsurface and are known to influence contaminant transport; however only a few studies to date have addressed microbial controls on nanoparticle mobility in porous media. The impact of a 3-day Pantoea agglomerans biofilm on the mobility of zinc oxide (ZnO) nanoparticles was studied in column experiments containing sand and glass beads at near-neutral pH and constant ionic strength. Bare ZnO nanoparticles (bZnO-NPs) and ZnO nanoparticles capped with tri-aminopropyltriethoxysilane (cZnO-NPs) were used in the experiments.

Transport and viability of Escherichia coli cells in clean and iron oxide coated sand following coating with silver nanoparticles.

A mechanistic understanding of processes controlling the transport and viability of bacteria in porous media is critical for designing in situ bioremediation and microbiological water decontamination programs. We investigated the combined influence of coating sand with iron oxide and silver nanoparticles on the transport and viability of Escherichia coli cells under saturated conditions. Results showed that iron oxide coatings increase cell deposition which was generally reversed by silver nanoparticle coatings in the early stages of injection.

Use of bioreporters and deletion mutants reveals ionic silver and ROS to be equally important in silver nanotoxicity.

The mechanism of antibacterial action of silver nanoparticles (AgNp) was investigated by employing a combination of microbiology and geochemical approaches to contribute to the realistic assessment of nanotoxicity. Our studies showed that suspending AgNp in media with different levels of chloride relevant to environmental conditions produced low levels of ionic silver thereby suggesting that dissolution of silver ions from nanoparticulate surface could not be the sole mechanism of toxicity. An Escherichia coli based bioreporter strain responsive to silver ions together with mutant strains of E.

Mechanisms behind bacteria induced plant growth promotion and Zn accumulation in Brassica juncea.

The growth and metal-extraction efficiency of plants exposed to toxic metals has been reported to be enhanced by inoculating plants with certain bacteria but the mechanisms behind this process remain unclear. We report results from glasshouse experiments on Brassica juncea plants exposed to 400mgZnkg(-1) that investigated the abilities of Pseudomonas brassicacearum and Rhizobium leguminosarum to promote growth, coupled with synchrotron based μXANES analysis to probe Zn speciation in the plant roots. P.