Reaction Monitoring and Structural Characterisation of Coordination Driven Self-Assembled Systems by Ion Mobility-Mass Spectrometry

Nature creates exquisite molecular assemblies, required for the molecular-level functions of life, via self-assembly. Understanding and harnessing these complex processes presents an immense opportunity for the design and fabrication of advanced functional materials. However, the significant industrial potential of self-assembly to fabricate highly functional materials is hampered by a lack of knowledge of critical reaction intermediates, mechanisms, and kinetics. As we move beyond the covalent synthetic regime, into the domain of non-covalent interactions occupied by self-assembly, harnessing and embracing complexity is a must, and non-targeted analyses of dynamic systems are becoming increasingly important. Coordination driven self-assembly is an important subtype of self-assembly that presents several wicked analytical challenges. These challenges are “wicked” due the very complexity desired confounding the analysis of products, intermediates, and pathways, therefore limiting reaction optimisation, tuning, and ultimately, utility. Ion Mobility-Mass Spectrometry solves many of the most challenging analytical problems in separating and analysing the structure of both simple and complex species formed via coordination driven self-assembly. Thus, due to the emerging importance of ion mobility mass spectrometry as an analytical technique tackling complex systems, this review highlights exciting recent applications. These include equilibrium monitoring, structural and dynamic analysis of previously analytically inaccessible complex interlinked structures and the process of self-sorting. The vast and largely untapped potential of ion mobility mass spectrometry to coordination driven self-assembly is yet to be fully realised. Therefore, we also propose where current analytical approaches can be built upon to allow for greater insight into the complexity and structural dynamics involved in self-assembly

Metal-Size Influence in Iso-Selective Lactide Polymerization

Iso-selective initiators for the ring-opening polymerization (ROP) of rac-lactide are rare outside of Group 13. We describe the first examples of highly iso-selective lutetium initiators. The phosphasalen lutetium ethoxide complex shows excellent iso-selectivity, with a Pi value of 0.81–0.84 at 298 K, excellent rates, and high degrees of polymerization control. Conversely, the corresponding La derivative exhibits moderate heteroselectivity (Ps=0.74, 298 K). Thus, the choice of metal center is shown to be crucial in determining the level and mode of stereocontrol. The relative order of rates for the series of complexes is inversely related to metallic covalent radius: that is, La>Y>Lu

A Cross-Sectional Survey of the Knowledge, Attitudes, and Practices of Antimicrobial Users and Providers in an Area of High-Density Livestock-Human Population in Western Kenya

Background: Antimicrobial resistance (AMR) is one of the most important global health crises in recent times and is driven primarily by antimicrobial consumption. In East Africa, there is a paucity of data regarding the knowledge, attitudes, and practices (KAP) related to antimicrobial use (AMU). We investigate the ways in which antimicrobial users in the veterinary sector accessed veterinary antimicrobials, and common behaviors of veterinary antimicrobial users and prescribers associated with AMU and AMR. // Methods: In total, 70 farmers, staff at 49 agricultural-veterinary antimicrobial shops (agrovet staff) and 28 veterinary animal healthcare workers or veterinary surgeons (veterinary professionals) were interviewed in Busia county, western Kenya in 2016 using a standard questionnaire as a framework for structured interviews. Data recorded included participant demographics, level of education, access to and sources of veterinary antimicrobials, prescribing patterns, and knowledge of AMR and antimicrobial withdrawal periods. // Results: The majority of antimicrobials were accessed through informal means, purchased from agroveterinary shops; more than half of staff did not hold nationally mandated qualifications to advise on or sell veterinary antimicrobials. Approximately 40% of veterinary antimicrobials were sold without a prescription and it was noted that both price and customer preference were important factors when selling antimicrobials in almost all agrovet shops. Knowledge of the dangers associated with AMR and AMU were mostly superficial. Treatment failure occurred often, and there was a lack of differentiation between AMR and simply treatment failure. // Conclusion: In this study area in East Africa with high-density human and livestock populations, AMU was primarily for maintenance of livestock health. These findings have highlighted several aspects surrounding inappropriate access to antimicrobials, and as such require attention from policy makers concerned with AMR in both livestock and human medicine sectors. Improving prescribing practices and ensuring a minimum level of general education and awareness of prescribers, as well as expanding the role of agrovet staff in antimicrobial stewardship programmes, may help begin to mitigate the maintenance and transmission of AMR, particularly amongst livestock

A novel walkability index for London predicts walking time in adults

Objective: To develop a novel walkability index for London and test it through measurement of associations between neighbourhood walkability and walking among adults using data from the Whitehall II Study. Background: Physical activity is essential for health; walking is the easiest way to incorporate it into everyday life. Many studies have reported positive associations between neighbourhood walkability and walking but the majority have focused on cities in North America and Australasia. Urban form with respect to street connectivity, residential density and land use mix – common components of walkability indices – is likely to differ in European cities. Methods: A walkability index for the 633 spatially contiguous census area statistics wards of London was constructed, comprising three core dimensions associated with walking behaviours: residential dwelling density, street connectivity and land use mix. Walkability was expressed as quartile scores, with wards scoring 1 being in the bottom 25% in terms of walkability, and those scoring 4 in the top 25%. A neighbourhood walkability score was assigned to each London-dwelling Whitehall II Study participant (2003-04, N=3020, mean +/-SD age=61.0y +/-6.0) as the walkability score of the ward in which their residential postcode fell. Associations between neighbourhood walkability and weekly walking time were measured using multiple logistic regression. Results: After adjustment for individual level factors and area deprivation, people in the most walkable neighbourhoods were significantly more likely to spend ≥6hr/wk (Odds Ratio 1.4; 95%Confidence Interval 1.1-1.9), than those in the least walkable. Conclusions: The walkability index constructed can predict walking time in adults: living in a more walkable neighbourhood is associated with longer weekly walking time. The index may help urban planners identify and design neighbourhoods in London with characteristics that are potentially more supportive of walking and, thereby, promote public health

Development of a novel walkability index for London, United Kingdom: cross-sectional application to the Whitehall II study

BACKGROUND: Physical activity is essential for health; walking is the easiest way to incorporate activity into everyday life. Previous studies report positive associations between neighbourhood walkability and walking but most focused on cities in North America and Australasia. Urban form with respect to street connectivity, residential density and land use mix-common components of walkability indices-differs in European cities. The objective of this study was to develop a walkability index for London and test the index using walking data from the Whitehall II Study.  METHODS: A neighbourhood walkability index for London was constructed, comprising factors associated with walking behaviours: residential dwelling density, street connectivity and land use mix. Three models were produced that differed in the land uses included. Neighbourhoods were operationalised at three levels of administrative geography: (i) 21,140 output areas, (ii) 633 wards and (iii) 33 local authorities. A neighbourhood walkability score was assigned to each London-dwelling Whitehall II Study participant (2003-04, N = 3020, mean ± SD age = 61.0 years ± 6.0) based on residential postcode. The effect of changing the model specification and the units of enumeration on spatial variation in walkability was examined. RESULTS: There was a radial decay in walkability from the centre to the periphery of London. There was high inter-model correlation in walkability scores for any given neighbourhood operationalisation (0.92-0.98), and moderate-high correlation between neighbourhood operationalisations for any given model (0.39-0.70). After adjustment for individual level factors and area deprivation, individuals in the most walkable neighbourhoods operationalised as wards were more likely to walk >6 h/week (OR = 1.4; 95 % CI: 1.1-1.9) than those in the least walkable. CONCLUSIONS: Walkability was associated with walking time in adults. This walkability index could help urban planners identify and design neighbourhoods in London with characteristics more supportive of walking, thereby promoting public health

Genomic variations define divergence of water/wildlife-associated Campylobacter jejuni niche specialists from common clonal complexes

Although the major food-borne pathogen Campylobacter jejuni has been isolated from diverse animal, human and environmental sources, our knowledge of genomic diversity in C. jejuni is based exclusively on human or human food-chain-associated isolates. Studies employing multilocus sequence typing have indicated that some clonal complexes are more commonly associated with particular sources. Using comparative genomic hybridization on a collection of 80 isolates representing diverse sources and clonal complexes, we identified a separate clade comprising a group of water/wildlife isolates of C. jejuni with multilocus sequence types uncharacteristic of human food-chain-associated isolates. By genome sequencing one representative of this diverse group (C. jejuni 1336), and a representative of the bank-vole niche specialist ST-3704 (C. jejuni 414), we identified deletions of genomic regions normally carried by human food-chain-associated C. jejuni. Several of the deleted regions included genes implicated in chicken colonization or in virulence. Novel genomic insertions contributing to the accessory genomes of strains 1336 and 414 were identified. Comparative analysis using PCR assays indicated that novel regions were common but not ubiquitous among the water/wildlife group of isolates, indicating further genomic diversity among this group, whereas all ST-3704 isolates carried the same novel accessory regions. While strain 1336 was able to colonize chicks, strain 414 was not, suggesting that regions specifically absent from the genome of strain 414 may play an important role in this common route of Campylobacter infection of humans. We suggest that the genomic divergence observed constitutes evidence of adaptation leading to niche specialization