Food Deserts

A food desert is a geographical area in which there is not easy access to fresh, healthy, and affordable food.https://digitalcommons.cedarville.edu/public_health_posters/1013/thumbnail.jp

Facile access to functionalized chiral secondary benzylic boronic esters via catalytic asymmetric hydroboration

Allylic and homoallylic phosphonates bearing an aryl or heteroaryl substituent at the γ- or δ-position undergo rhodium-catalyzed asymmetric hydroboration by pinacolborane to give functionalized chiral secondary benzylic boronic esters in yields up to 86% and enantiomer ratios up to 99 : 1. Compared to minimally-functionalized terminal and 1,1-disubstituted vinyl arenes, there are relatively few reports of efficient catalytic asymmetric hydroboration (CAHB) of more highly functionalized internal alkenes. Phosphonate substrates bearing a variety of common heterocyclic ring systems, including furan, indole, pyrrole and thiophene derivatives, as well as those bearing basic nitrogen substituents (e.g., morpholine and pyrazine) are tolerated, although donor substituents positioned in close proximity of the alkene can influence the course of the reaction. Stereoisomeric (E)- and (Z)-substrates afford the same major enantiomer of the borated product. Deuterium-labelling studies reveal that rapid (Z)- to (E)-alkene isomerization accounts for the observed (E/Z)-stereoconvergence during CAHB. The synthetic utility of the chiral boronic ester products is illustrated by stereospecific C–B bond transformations including stereoretentive electrophile promoted 1,2-B-to-C migrations, stereoinvertive SE2 reactions of boron-ate complexes with electrophiles, and stereoretentive palladium- and rhodium-catalyzed cross-coupling protocols

Diffuse HI Disks in Isolated Galaxies

In order to investigate the contribution of diffuse components to their total HI emission, we have obtained high precision HI line flux densities with the 100m Green Bank Telescope for a sample of 100 isolated spiral and irregular galaxies which we have previously observed with the 43m telescope. A comparison of the observed HI line fluxes obtained with the two different telescopes, characterized by half-power beam widths of 9 arcmin and 21 arcmin respectively, exploits a ``beam matching'' technique to yield a statistical determination of the occurrence of diffuse HI components in their disks. A simple model of the HI distribution within a galaxy well describes ~75 % of the sample and accounts for all of the HI line flux density. The remaining galaxies are approximately evenly divided into two categories: ones which appear to possess a significantly more extensive HI distribution than the model predicts, and ones for which the HI distribution is more centrally concentrated than predicted. Examples of both extremes can be found in the literature but little attention has been paid to the centrally concentrated HI systems. Our sample has demonstrated that galaxies do not commonly possess extended regions of low surface brightness HI gas which is not accounted for by our current understanding of the structure of HI disks. Eight HI-rich companions to the target objects are identified, and a set of extragalactic HI line flux density calibrators is presented.Comment: 26 page

Advancing ionomer design to boost interfacial and thin-film proton conductivity via styrene-calix[4]arene-based ionomers

Sub-micrometer-thick ion-conducting polymer (ionomer) layers often suffer from poor ionic conductivity at the substrate/catalyst interface. The weak proton conductivity makes the electrochemical reaction at the cathode of proton-exchange-membrane fuel cells sluggish. To address this, here we report on a class of polystyrene-based ionomers having sub-nanometer-sized, sulfonated macrocyclic calix[4]arene-based pendants (PS-calix). In films with thickness comparable to that of ionomer-based binder layers, the conductivity of PS-calix film (∼41 mS/cm) is ∼13 times higher than that of the current state-of-the-art ionomer, Nafion. We observe a similar improvement in proton conductivity when PS-calix interfaces with Pt nanoparticles, demonstrating the potential of PS-calix in catalyst ink. Leveraging a favorable interfacial chemical composition, PS-calix enhances proton conduction at the film-substrate interface, a shortcoming of Nafion. Moreover, the water in PS-calix films diffuses faster than bulk water and the water confined in Nafion films, suggesting an important role played by sub-nanometer-sized calix[4]arene cavities in creating unique water/ion transport pathways

The accuracy of a mobile phone application (Wulira app) compared to standard audiometry in assessing hearing loss among patients on treatment for multidrug-resistant tuberculosis in Uganda

Objectives: Our aim was to validate the “Wulira App” a mHealth application against gold standard audiometry as a pragmatic audiometry solution for under-served and vulnerable groups of patients at risk of hearing loss. The specific objectives were as follows:1) To compare hearing thresholds determined using the Wulira app to standard pure tone audiometry among patients on MDR-TB treatment.2) To determine the correlation between the measured hearing loss with the Wulira app and standard audiometry with patient reported hearing loss.3) To determine the proportion of patients on MDR-TB treatment that experience hearing loss?Materials and Methods: We consecutively recruited patients ≥18 years old and receiving kanamycin in their treatment regimen between February and June 2019 for this study. Clinical and demographic data were obtained from each participant and documented in a secure database. Participants had hearing assessment performed once at enrolment with paired standard audiometry and the Wulira mobile phone app in a soundproof room.Results: A total of 120 MDR-TB patients with a mean age of 34.0 (±9.6) years were recruited for this study and 69 (57.5%) were male. When compared to pure tone audiometry, the Wulira app was able to correctly detect 91.4% hearing loss in right ear and 88.4% in the left ear. The specificity of the Wulira app was equally high, reaching 93.2% in the right ear and 91.5% in the left ear.Conclusion: The Wulira app may be a useful alternative home-based tool for hearing assessment in MDR-TB patients, essentially for early detection of hearing loss following commencement of second-line injectable drugs

Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal−Organic Framework for Photocatalytic Oxidation of Hydrocarbons

Heterogeneous catalysis plays an indispensable role in chemical production and energy conversion. Incorporation of transition metals into metal oxides and zeolites is a common strategy to fine-tune the activity and selectivity of the resulting solid catalysts, as either the active center or promotor. Studying the underlying mechanism is however challenging. Decorating the metal-oxo clusters with transition metals in metal−organic frameworks (MOFs) via postsynthetic modification offers a rational approach to construct well-defined structural models for better understanding of the reaction mechanism. Therefore, it is important to expand the materials scope beyond the currently widely studied zirconium MOFs consisting of Zr6 nodes. In this work, we report the design and synthesis of a new (4,12)- connected Zr-MOF with ith topology that consists of rare Zr9 nodes. FeIII was further incorporated onto the Zr9 nodes of the framework, and the resulting MOF material exhibits significantly enhanced activity and selectivity toward the photocatalytic oxidation of toluene. This work demonstrates a delicate ligand design strategy to control the nuclearity of Zr-oxo clusters, which further dictates the number and binding sites of transition metals and the overall photocatalytic activity toward C−H activation. Our work paves the way for future exploration of the structure−activity study of catalysts using MOFs as the model system

Cautionary Tale of Using Tris(alkyl)phosphine Reducing Agents with NAD+-Dependent Enzymes

Protein biochemistry protocols typically include disulfide bond reducing agents to guard against unwanted thiol oxidation and protein aggregation. Commonly used disulfide bond reducing agents include dithiothreitol, β-mercaptoethanol, glutathione, and the tris(alkyl)phosphine compounds tris(2-carboxyethyl)phosphine (TCEP) and tris(3-hydroxypropyl)phosphine (THPP). While studying the catalytic activity of the NAD(P)H-dependent enzyme Δ1-pyrroline-5-carboxylate reductase, we unexpectedly observed a rapid non-enzymatic chemical reaction between NAD+ and the reducing agents TCEP and THPP. The product of the reaction exhibits a maximum ultraviolet absorbance peak at 334 nm and forms with an apparent association rate constant of 231–491 M−1 s−1. The reaction is reversible, and nuclear magnetic resonance characterization (1H, 13C, and 31P) of the product revealed a covalent adduct between the phosphorus of the tris(alkyl)phosphine reducing agent and the C4 atom of the nicotinamide ring of NAD+. We also report a 1.45 Å resolution crystal structure of short-chain dehydrogenase/reductase with the NADP+–TCEP reaction product bound in the cofactor binding site, which shows that the adduct can potentially inhibit enzymes. These findings serve to caution researchers when using TCEP or THPP in experimental protocols with NAD(P)+. Because NAD(P)+-dependent oxidoreductases are widespread in nature, our results may be broadly relevant

Central Asia and the globalisation of the contemporary legal consciousness

What is the logic which governs the processes of legal globalization? How does the transnational proliferation of legal forms operate in the contemporary geo-juridical space? What are the main defining characteristics of the currently dominant mode of transnational legal consciousness and how can the concept of legal consciousness help us understand better the historical ebb and flow of the Western-led projects of good governance promotion in regions like Central Asia after the fall of the Soviet Union? Using Duncan Kennedy’s seminal essay Three Globalizations of Law and Legal Thought as its starting platform, this essay seeks to explore these and a series of other related questions, while also drawing on the work of the Greek Marxist lawyer-philosopher Nicos Poulantzas to help elucidate some latent analytical stress-points in Kennedy’s broader theoretical framework. Reacting against the neo-Orientalist tone adopted across much of the contemporary field of Central Asian studies, it develops an alternative account of the internal history of the legal-globalizational encounter between the Western-based reform entrepreneurs and the national legal-political elites in Central Asia in the post-1991 period, complementing it with a detailed description of the general institutional and discursive structures within which this encounter took place

When enough should be enough: Improving the use of current agricultural lands could meet production demands and spare natural habitats in Brazil

Providing food and other products to a growing human population while safeguarding natural ecosystems and the provision of their services is a significant scientific, social and political challenge. With food demand likely to double over the next four decades, anthropization is already driving climate change and is the principal force behind species extinction, among other environmental impacts. The sustainable intensification of production on current agricultural lands has been suggested as a key solution to the competition for land between agriculture and natural ecosystems. However, few investigations have shown the extent to which these lands can meet projected demands while considering biophysical constraints. Here we investigate the improved use of existing agricultural lands and present insights into avoiding future competition for land. We focus on Brazil, a country projected to experience the largest increase in agricultural production over the next four decades and the richest nation in terrestrial carbon and biodiversity. Using various models and climatic datasets, we produced the first estimate of the carrying capacity of Brazil's 115 million hectares of cultivated pasturelands. We then investigated if the improved use of cultivated pasturelands would free enough land for the expansion of meat, crops, wood and biofuel, respecting biophysical constraints (i.e., terrain, climate) and including climate change impacts. We found that the current productivity of Brazilian cultivated pasturelands is 32–34% of its potential and that increasing productivity to 49–52% of the potential would suffice to meet demands for meat, crops, wood products and biofuels until at least 2040, without further conversion of natural ecosystems. As a result up to 14.3 Gt CO2 Eq could be mitigated. The fact that the country poised to undergo the largest expansion of agricultural production over the coming decades can do so without further conversion of natural habitats provokes the question whether the same can be true in other regional contexts and, ultimately, at the global scale