Correction: A tutorial on asymmetric electrocatalysis.

Correction for 'A tutorial on asymmetric electrocatalysis' by Jonas Rein et al., Chem. Soc. Rev., 2023, https://doi.org/10.1039/D3CS00511A.

A tutorial on asymmetric electrocatalysis.

Electrochemistry has emerged as a powerful means to enable redox transformations in modern chemical synthesis. This tutorial review delves into the unique advantages of electrochemistry in the context of asymmetric catalysis. While electrochemistry has historically been used as a green and mild alternative for established enantioselective transformations, in recent years asymmetric electrocatalysis has been increasingly employed in the discovery of novel asymmetric methodologies based on reaction mechanisms unique to electrochemistry. This tutorial review first provides a brief tutorial introduction to electrosynthesis, then explores case studies on homogenous small molecule asymmetric electrocatalysis. Each case study serves to highlight a key advance in the field, starting with the historic electrification of known asymmetric transformations and culminating with modern methods relying on unique electrochemical mechanistic sequences. Finally, we highlight case studies in the emerging reasearch areas at the interface of asymmetric electrocatalysis with biocatalysis and heterogeneous catalysis.

Generality-oriented optimization of enantioselective aminoxyl radical catalysis.

Catalytic enantioselective methods that are generally applicable to a broad range of substrates are rare. We report a strategy for the oxidative desymmetrization of meso-diols predicated on a nontraditional catalyst optimization protocol by using a panel of screening substrates rather than a singular model substrate. Critical to this approach was rational modulation of a peptide sequence in the catalyst incorporating a distinct aminoxyl-based active residue. A general catalyst emerged, providing high selectivity in the delivery of enantioenriched lactones across a broad range of diols, while also achieving up to ~100,000 turnovers.

Regulation and physiological function of proteins for heat tolerance in cowpea (Vigna unguiculata) genotypes under controlled and field conditions.

The expression of heat shock proteins is considered a central adaptive mechanism to heat stress. This study investigated the expression of heat shock proteins (HSPs) and other stress-protective proteins against heat stress in cowpea genotypes under field (IT-96D-610 and IT-16) and controlled (IT-96D-610) conditions. Heat stress response analysis of proteins at 72 h in the controlled environment showed 270 differentially regulated proteins identified using label-free quantitative proteomics in IT-96D-610 plants. These plants expressed HSPs and chaperones [BAG family molecular chaperone 6 (BAG6), Multiprotein bridging factor1c (MBF1C) and cold shock domain protein 1 (CSDP1) in the controlled environment]. However, IT-96D-610 plants expressed a wider variety of small HSPs and more HSPs in the field. IT-96D-610 plants also responded to heat stress by exclusively expressing chaperones [DnaJ chaperones, universal stress protein and heat shock binding protein (HSBP)] and non-HSP proteins (Deg1, EGY3, ROS protective proteins, temperature-induced lipocalin and succinic dehydrogenase). Photosynthesis recovery and induction of proteins related to photosynthesis were better in IT-96D-610 because of the concurrent induction of heat stress response proteins for chaperone functions, protein degradation for repair and ROS scavenging proteins and PSII operating efficiency (Fq'/Fm') than IT-16. This study contributes to identification of thermotolerance mechanisms in cowpea that can be useful in knowledge-based crop improvement.

Proteome changes and associated physiological roles in chickpea (Cicer arietinum) tolerance to heat stress under field conditions.

Interrogative proteome analyses are used to identify and quantify the expression of proteins involved in heat tolerance and to identify associated physiological processes in heat-stressed plants. The objectives of the study were to identify and quantify the expression of proteins involved in heat tolerance and to identify associated physiological processes in chickpea (Cicer arietinum L.) heat-tolerant (Acc#7) and sensitive genotype (Acc#8) from a field study. Proteomic and gene ontological analyses showed an upregulation in proteins related to protein synthesis, intracellular traffic, defence and transport in the heat-tolerant genotype compared to the susceptible one at the warmer site. Results from KEGG analyses indicate the involvement of probable sucrose-phosphate synthase (EC 2.4.1.14) and sucrose-phosphate phosphatase (EC 3.1.3.24) proteins, that were upregulated in the heat-tolerant genotype at the warmer site, in the starch and sucrose pathway. The presence of these differentially regulated proteins including HSP70, ribulose bisphosphate carboxylase/oxygenase activase, plastocyanin and protoporphyrinogen oxidase suggests their potential role in heat tolerance, at flowering growth stage, in field-grown chickpea. This observation supports unaltered physiological and biochemical performance of the heat-tolerant genotypes (Acc#7) relative to the susceptible genotype (Acc#8) in related studies (Makonya et al. 2019). Characterisation of the candidate proteins identified in the current study as well as their specific roles in the tolerance to heat stress in chickpea are integral to further crop improvement initiatives.

Copper-catalyzed carbo-difluoromethylation of alkenes via radical relay.

Organic molecules that contain alkyl-difluoromethyl moieties have received increased attention in medicinal chemistry, but their synthesis in a modular and late-stage fashion remains challenging. We report herein an efficient copper-catalyzed radical relay approach for the carbo-difluoromethylation of alkenes. This approach simultaneously introduces CF2H groups along with complex alkyl or aryl groups into alkenes with regioselectivity opposite to traditional CF2H radical addition. We demonstrate a broad substrate scope and a wide functional group compatibility. This scalable protocol is applied to the late-stage functionalization of complex molecules and the synthesis of CF2H analogues of bioactive molecules. Mechanistic studies and density functional theory calculations suggest a unique ligand effect on the reactivity of the Cu-CF2H species.

Human dietary exposure to chemicals in sub-Saharan Africa: safety assessment through a total diet study.

BACKGROUND: Human dietary exposure to chemicals can result in a wide range of adverse health effects. Some substances might cause non-communicable diseases, including cancer and coronary heart diseases, and could be nephrotoxic. Food is the main human exposure route for many chemicals. We aimed to assess human dietary exposure to a wide range of food chemicals. METHODS: We did a total diet study in Benin, Cameroon, Mali, and Nigeria. We assessed 4020 representative samples of foods, prepared as consumed, which covered more than 90% of the diet of 7291 households from eight study centres. By combining representative dietary surveys of countries with findings for concentrations of 872 chemicals in foods, we characterised human dietary exposure. FINDINGS: Exposure to lead could result in increases in adult blood pressure up to 2·0 mm Hg, whereas children might lose 8·8-13·3 IQ points (95th percentile in Kano, Nigeria). Morbidity factors caused by coexposure to aflatoxin B1 and hepatitis B virus, and sterigmatocystin and fumonisins, suggest several thousands of additional liver cancer cases per year, and a substantial contribution to the burden of chronic malnutrition in childhood. Exposure to 13 polycyclic aromatic hydrocarbons from consumption of smoked fish and edible oils exceeded levels associated with possible carcinogenicity and genotoxicity health concerns in all study centres. Exposure to aluminium, ochratoxin A, and citrinin indicated a public health concern about nephropathies. From 470 pesticides tested across the four countries, only high concentrations of chlorpyrifos in smoked fish (unauthorised practice identified in Mali) could pose a human health risk. INTERPRETATION: Risks characterised by this total diet study underscore specific priorities in terms of food safety management in sub-Saharan Africa. Similar investigations specifically targeting children are crucially needed. FUNDING: Standards and Trade Development Facility.

Copper-Catalyzed Deaminative Difluoromethylation.

The difluoromethyl group (CF2 H) is considered to be a lipophilic and metabolically stable bioisostere of an amino (NH2 ) group. Therefore, methods that can rapidly convert an NH2 group into a CF2 H group would be of great value to medicinal chemistry. We report herein an efficient Cu-catalyzed approach for the conversion of alkyl pyridinium salts, which can be readily synthesized from the corresponding alkyl amines, to their alkyl difluoromethane analogues. This method tolerates a broad range of functional groups and can be applied to the late-stage modification of complex amino-containing pharmaceuticals.

Copper-Catalyzed, Chloroamide-Directed Benzylic C-H Difluoromethylation.

We report herein the first catalytic strategy to harness amidyl radicals derived from N-chloroamides for C-C bond formation, allowing for the discovery of the first catalytic benzylic C-H difluoromethylation. Under copper-catalyzed conditions, a wide variety of N-chlorocarboxamides and N-chlorocarbamates direct selective benzylic C-H difluoromethylation with a nucleophilic difluoromethyl source at room temperature. This scalable protocol exhibits a broad substrate scope and functional group tolerance, enabling late-stage difluoromethylation of bioactive molecules. This copper-catalyzed, chloroamide-directed strategy has also been extended to benzylic C-H pentafluoroethylation and trifluoromethylation. Mechanistic studies on the difluoromethylation reactions support that the reactions involve the formation of benzylic radicals via intramolecular C-H activation, followed by the copper-mediated transfer of difluoromethyl groups to the benzylic radicals.

Copper-Catalyzed Decarboxylative Difluoromethylation.

We report herein a highly efficient Cu-catalyzed protocol for the conversion of aliphatic carboxylic acids to the corresponding difluoromethylated analogues. This robust, operationally simple and scalable protocol tolerates a variety of functional groups and can convert a diverse array of acid-containing complex molecules to the alkyl-CF2H products. Mechanistic studies support the involvement of alkyl radicals.

Chlorophyll fluorescence and carbohydrate concentration as field selection traits for heat tolerant chickpea genotypes.

Chickpea (Cicer arietinum L.), a cool season crop is severely affected by heat stress, predicted to increase due to warming climates. Research for identifying heat tolerance markers for potential chickpea genotype selection is imperative. The study assessed the response of four chickpea genotypes to a natural temperature gradient in the field using chlorophyll fluorescence, non-structural carbohydrate, chlorophyll concentrations, gas exchange and grain yield. Field experiments were carried out in two winter seasons at three locations with known differences in temperature in NE South Africa. Results showed two genotypes were tolerant to heat stress with an Fv/Fm of 0.83-0.85 at the warmer site, while the two sensitive genotypes showed lower Fv/Fm of 0.78-0.80. Both dark-adapted Fv/Fm and Fq'/Fm' (where Fq' = Fm' -F) measured at comparable high light levels correlated positively with grain yield. The two tolerant genotypes also showed higher photosynthetic rates, starch, sucrose and grain yield than the sensitive genotypes at the warmer site. However, these parameters were consistently higher at the cooler sites than at the warmer. These results were further validated by a climate chamber experiment, where higher Fv/Fm decline in the sensitive compared to tolerant genotypes was observed when they were exposed to short-term heat treatments of 30/25 °C and 35/30 °C. Tolerant genotypes had higher Fv/Fm (0.78-0.81) and grain yield plant-1(1.12-2.37g) compared to sensitive genotypes (0.74-0.75) and (0.32-0.89g plant-1) respectively in the 35/30 °C. It is concluded that chlorophyll fluorescence and leaf carbohydrates are suitable tools for selection of heat tolerant chickpea genotypes under field conditions, while the coolest site showed favourable conditions for chickpea production.

Hydrochemical characteristics and quality assessment of groundwater from fractured Albian carbonaceous shale aquifers around Enyigba-Ameri, southeastern Nigeria.

Enyigba-Ameri area is known for its Pb-Zn mining activities and the mine water is usually discharged directly into nearby streams and surface runoff. In order to determine the impacts of mining activities on the quality of water in the area and the general hydrochemical characteristics, field measurements and laboratory tests were carried out on water samples collected from the area. Field measurements and laboratory analyses of physicochemical parameters were determined using standard methods. In addition to the multivariate analyses (principal component analysis and cluster analysis) and ANOVA analysis, ionic cross-plots were used to determine the groundwater physicochemical characteristics and geochemical evolution. From the results, it was observed that Pb4+, Zn2+, Fe2 + & 3+, Ca2+, Mg2+, and K+ had a concentration higher than the stipulated guideline values. Three principal components which explained 87.42% of the total dataset were extracted through the data reduction process. Cluster analysis of the hydrochemical data grouped the water samples into three distinct classes. It was observed that the water chemistry is mainly affected by silicate minerals weathering, carbonate weathering, and base ion exchange processes in descending order. ANOVA analysis showed that Zn2+, Fe2 + & 3+, and Mg2+ had mean values that significantly differed from each other based on the sources of the samples. The Wilcox diagram revealed 4 classes of irrigation water types and the irrigation water quality indices showed that the groundwater in the area is not generally suitable for irrigation purposes.

Modeling the spatial variability in the spread and correlation of childhood malnutrition in Nigeria.

The average nutritional status of children in Nigeria is, just as in most developing countries, still in an alarmingly bad condition. Prior studies have shown that this status relies on a series of different influences and can be measured by three anthropometric variables for stunting, wasting, and underweight. Different regression modeling techniques have been adopted over the years to explain the determinants and spatial clustering. Those indicators, however, show patterns that are not necessarily full filling requirements for ordinary regression models for the mean and are correlated among each other, a fact that has until now been ignored by most studies. Methods to model outcomes in the light of both, the whole distribution of and the correlation between two or more outcomes based on a set of covariates, have lately been developed. The aim of this paper is to make use of those methods to explain the underlying spatial structure in malnutrition in Nigeria. The study brings to limelight the pattern of spread as well as the interwoven relationships among childhood malnutrition indicators that would have otherwise remained unknown in Nigeria.

Tuning Gold Nanoparticles with Chelating Ligands for Highly Efficient Electrocatalytic CO2 Reduction.

Capped chelating organic molecules are presented as a design principle for tuning heterogeneous nanoparticles for electrochemical catalysis. Gold nanoparticles (AuNPs) functionalized with a chelating tetradentate porphyrin ligand show a 110-fold enhancement compared to the oleylamine-coated AuNP in current density for electrochemical reduction of CO2 to CO in water at an overpotential of 340 mV with Faradaic efficiencies (FEs) of 93 %. These catalysts also show excellent stability without deactivation (<5 % productivity loss) within 72 hours of electrolysis. DFT calculation results further confirm the chelation effect in stabilizing molecule/NP interface and tailoring catalytic activity. This general approach is thus anticipated to be complementary to current NP catalyst design approaches.

Pentocin MQ1: A Novel, Broad-Spectrum, Pore-Forming Bacteriocin From Lactobacillus pentosus CS2 With Quorum Sensing Regulatory Mechanism and Biopreservative Potential.

Micrococcus luteus, Listeria monocytogenes, and Bacillus cereus are major food-borne pathogenic and spoilage bacteria. Emergence of antibiotic resistance and consumer demand for foods containing less of chemical preservatives led to a search for natural antimicrobials. A study aimed at characterizing, investigating the mechanism of action and regulation of biosynthesis and evaluating the biopreservative potential of pentocin from Lactobacillus pentosus CS2 was conducted. Pentocin MQ1 is a novel bacteriocin isolated from L. pentosus CS2 of coconut shake origin. The purification strategy involved adsorption-desorption of bacteriocin followed by RP-HPLC. It has a molecular weight of 2110.672 Da as determined by MALDI-TOF mass spectrometry and a molar extinction value of 298.82 M-1 cm-1. Pentocin MQ1 is not plasmid-borne and its biosynthesis is regulated by a quorum sensing mechanism. It has a broad spectrum of antibacterial activity, exhibited high chemical, thermal and pH stability but proved sensitive to proteolytic enzymes. It is potent against M. luteus, B. cereus, and L. monocytogenes at micromolar concentrations. It is quick-acting and exhibited a bactericidal mode of action against its targets. Target killing was mediated by pore formation. We report for the first time membrane permeabilization as a mechanism of action of the pentocin from the study against Gram-positive bacteria. Pentocin MQ1 is a cell wall-associated bacteriocin. Application of pentocin MQ1 improved the microbiological quality and extended the shelf life of fresh banana. This is the first report on the biopreservation of banana using bacteriocin. These findings place pentocin MQ1 as a potential biopreservative for further evaluation in food and medical applications.

Children and screens: Groupe de Pédiatrie Générale (Société française de pédiatrie) guidelines for pediatricians and families.

The Groupe de Pédiatrie Générale (General Pediatrics Group), a member of the Société française de pédiatrie (French Pediatrics Society), has proposed guidelines for families and doctors regarding children's use of digital screens. A number of guidelines have already been published, in particular by the French Academy of Sciences in 2013 and the American Academy of Pediatrics in 2016. These new guidelines were preceded by an investigation into the location of digital screen use by young children in France, a survey of medical concerns on the misuse of digital devices, and a review of their documented benefits. The Conseil Supérieur de l'Audiovisuel (Higher Council on Audiovisual Technology) and the Union Nationale de Associations Familiales (National Union of Family Associations) have taken part in the preparation of this document. Five simple messages are proposed: understanding without demonizing; screen use in common living areas, but not in bedrooms; preserve time with no digital devices (morning, meals, sleep, etc.); provide parental guidance for screen use; and prevent social isolation.

Linking root traits to superior phosphorus uptake and utilisation efficiency in three Fabales in the Core Cape Subregion, South Africa.

In the low-P soil of the fynbos biome, plants have evolved several morphological and physiological P acquisition and use mechanisms, leading to variable uptake and use efficiencies. We expected that plants grown in low-P soils would exhibit greater P acquisition traits and hypothesised that Aspalathus linearis (Burm. f.) R. Dahlgren, a cluster-root-forming species adapted to drier and infertile soils, would be the most efficient at P acquisition compared with other species. Three fynbos Fabales species were studied: A. linearis and Podalyria calyptrata (Retz.) Willd, both legumes, and Polygala myrtifolia L., a nonlegume. A potted experiment was conducted where the species were grown in two soil types with high P (41.18mgkg-1) and low P (9.79mgkg-1). At harvest, biomass accumulation, foliar nutrients and P acquisition mechanisms were assessed. Polygala myrtifolia developed a root system with greater specific root length, root hair width and an average root diameter that exuded a greater amount of citrate and, contrary to the hypothesis, exhibited greater whole-plant P uptake efficiency. However, P. calyptrata had higher P use efficiency, influenced by N availability through N2 fixation. Specific root length, root length and root:shoot ratio were promising morphological traits for efficient foraging of P, whereas acid phosphatase exudation was the best physiological trait for solubilisation of P.

Differential Preference of Burkholderia and Mesorhizobium to pH and Soil Types in the Core Cape Subregion, South Africa.

Over 760 legume species occur in the ecologically-heterogeneous Core Cape Subregion (CCR) of South Africa. This study tested whether the main symbionts of CCR legumes (Burkholderia and Mesorhizobium) are phylogenetically structured by altitude, pH and soil types. Rhizobial strains were isolated from field nodules of diverse CCR legumes and sequenced for 16S ribosomic RNA (rRNA), recombinase A (recA) and N-acyltransferase (nodA). Phylogenetic analyses were performed using Bayesian and maximum likelihood techniques. Phylogenetic signals were determined using the D statistic for soil types and Pagel's λ for altitude and pH. Phylogenetic relationships between symbionts of the narrowly-distributed Indigofera superba and those of some widespread CCR legumes were also determined. Results showed that Burkholderia is restricted to acidic soils, while Mesorhizobium occurs in both acidic and alkaline soils. Both genera showed significant phylogenetic clustering for pH and most soil types, but not for altitude. Therefore, pH and soil types influence the distribution of Burkholderia and Mesorhizobium in the CCR. All strains of Indigofera superba were identified as Burkholderia, and they were nested within various clades containing strains from outside its distribution range. It is, therefore, hypothesized that I. superba does not exhibit rhizobial specificity at the intragenic level. Implications for CCR legume distributions are discussed.

Prioritisation of native legume species for further evaluation as potential forage crops in water-limited agricultural systems in South Africa.

In the face of climate change, identification of forage species suitable for dryland farming under low rainfall conditions in South Africa is needed. Currently, there are only a limited number of forage species suitable for dryland farming under such conditions. The objective of this study was to identify and prioritise native legume species that could potentially be used in dryland farming systems in water-limited agro-ecosystems in South Africa. Using a combination of ecological niche modelling techniques, plant functional traits, and indigenous knowledge, 18 perennial herbaceous or stem-woody legume species were prioritised for further evaluation as potential fodder species within water-limited agricultural areas. These species will be evaluated further for their forage quality and their ability to survive and produce enough biomass under water limitation and poor edaphic conditions.

Methodology design of the regional Sub-Saharan Africa Total Diet Study in Benin, Cameroon, Mali and Nigeria.

The core food model was described more than three decades ago, and has been used ever since to identify main food contributors to dietary intakes for both nutrients and other food chemicals. The Sub-Saharan Africa Total Diet Study (SSA-TDS) uses this model to describe the food consumption habits of some selected populations of Benin, Cameroon, Mali, and Nigeria, prior to use in the completion of quantitative risk assessments with regard to food chemicals. Food consumption data were derived from food expenditure data contained in national household budget surveys that were provided by the national institutes of statistics in each country. A classification of African foods was established for the purpose of the study and core foods were selected, so as to reflect 96 ± 1% of the average national total diet expressed in weight. Populations from eight study centers were selected by national stakeholders. This approach involves the purchase of 4020 individual foods, prepared as consumed and pooled into 335 food composite samples, for analysis of mycotoxins, PAHs, PCBs and dioxins, pesticides, metals and trace elements, PFAs, and BFRs. This sampling plan aims to provide a representative, cost effective, and replicable approach for deterministic dietary exposure assessments in developing countries.