Plasmonic catalysis with designer nanoparticles

Catalysis is central to a more sustainable future and a circular economy. If the energy required to drive catalytic processes could be harvested directly from sunlight, the possibility of replacing contemporary processes based on terrestrial fuels by the conversion of light into chemical energy could become a step closer to reality. Plasmonic catalysis is currently at the forefront of photocatalysis, enabling one to overcome the limitations of "classical" wide bandgap semiconductors for solar-driven chemistry. Plasmonic catalysis enables the acceleration and control of a variety of molecular transformations due to the localized surface plasmon resonance (LSPR) excitation. Studies in this area have often focused on the fundamental understanding of plasmonic catalysis and the demonstration of plasmonic catalytic activities towards different reactions. In this feature article, we discuss recent contributions from our group in this field by employing plasmonic nanoparticles (NPs) with controllable features as model systems to gain insights into structure-performance relationships in plasmonic catalysis. We start by discussing the effect of size, shape, and composition in plasmonic NPs over their activities towards LSPR-mediated molecular transformations. Then, we focus on the effect of metal support interactions over activities, reaction selectivity, and reaction pathways. Next, we shift to the control over the structure in hollow NPs and nanorattles. Inspired by the findings from these model systems, we demonstrate a design-driven strategy for the development of plasmonic catalysts based on plasmonic-catalytic multicomponent NPs for two types of molecular transformations: the selective hydrogenation of phenylacetylene and the oxygen evolution reaction. Finally, future directions, challenges, and perspectives in the field of plasmonic catalysis with designer NPs are discussed. We believe that the examples and concepts presented herein may inspire work and progress in plasmonic catalysis encompassing the design of plasmonic multicomponent materials, new strategies to control reaction selectivity, and the unraveling of stability and reaction mechanisms.Peer reviewe

Calcification in free‑living coralline algae is strongly influenced by morphology: Implications for susceptibility to ocean acidification

Rhodolith beds built by free-living coralline algae are important ecosystems for marine biodiversity and carbonate production. Yet, our mechanistic understanding regarding rhodolith physiology and its drivers is still limited. Using three rhodolith species with different branching morphologies, we investigated the role of morphology in species’ physiology and the implications for their susceptibility to ocean acidification (OA). For this, we determined the effects of thallus topography on diffusive boundary layer (DBL) thickness, the associated microscale oxygen and pH dynamics and their relationship with species’ metabolic and light and dark calcification rates, as well as species’ responses to short-term OA exposure. Our results show that rhodolith branching creates low-flow microenvironments that exhibit increasing DBL thickness with increasing branch length. This, together with species’ metabolic rates, determined the light-dependent pH dynamics at the algal surface, which in turn dictated species’ calcification rates. While these differences did not translate in species-specific responses to short-term OA exposure, the differences in the magnitude of diurnal pH fluctuations (~ 0.1–1.2 pH units) between species suggest potential differences in phenotypic plasticity to OA that may result in different susceptibilities to long-term OA exposure, supporting the general view that species’ ecomechanical characteristics must be considered for predicting OA responses

Full characterization of vibrational coherence in a porphyrin chromophore by two-dimensional electronic spectroscopy

In this work we present experimental and calculated two-dimensional electronic spectra for a 5,15-bisalkynyl porphyrin chromophore. The lowest energy electronic Qy transition couples mainly to a single 380 cm–1 vibrational mode. The two-dimensional electronic spectra reveal diagonal and cross peaks which oscillate as a function of population time. We analyze both the amplitude and phase distribution of this main vibronic transition as a function of excitation and detection frequencies. Even though Feynman diagrams provide a good indication of where the amplitude of the oscillating components are located in the excitation-detection plane, other factors also affect this distribution. Specifically, the oscillation corresponding to each Feynman diagram is expected to have a phase that is a function of excitation and detection frequencies. Therefore, the overall phase of the experimentally observed oscillation will reflect this phase dependence. Another consequence is that the overall oscillation amplitude can show interference patterns resulting from overlapping contributions from neighboring Feynman diagrams. These observations are consistently reproduced through simulations based on third order perturbation theory coupled to a spectral density described by a Brownian oscillator model

Investigating the association between obesity and asthma in 6- to 8-year-old Saudi children:a matched case-control study

Background: Previous studies have demonstrated an association between obesity and asthma, but there remains considerable uncertainty about whether this reflects an underlying causal relationship. Aims: To investigate the association between obesity and asthma in pre-pubertal children and to investigate the roles of airway obstruction and atopy as possible causal mechanisms. Methods: We conducted an age- and sex-matched case–control study of 1,264 6- to 8-year-old schoolchildren with and without asthma recruited from 37 randomly selected schools in Madinah, Saudi Arabia. The body mass index (BMI), waist circumference and skin fold thickness of the 632 children with asthma were compared with those of the 632 control children without asthma. Associations between obesity and asthma, adjusted for other potential risk factors, were assessed separately in boys and girls using conditional logistic regression analysis. The possible mediating roles of atopy and airway obstruction were studied by investigating the impact of incorporating data on sensitisation to common aeroallergens and measurements of lung function. Results: BMI was associated with asthma in boys (odds ratio (OR)=1.14, 95% confidence interval (CI), 1.08–1.20; adjusted OR=1.11, 95% CI, 1.03–1.19) and girls (OR=1.37, 95% CI, 1.26–1.50; adjusted OR=1.38, 95% CI, 1.23–1.56). Adjusting for forced expiratory volume in 1 s had a negligible impact on these associations, but these were attenuated following adjustment for allergic sensitisation, particularly in girls (girls: OR=1.25; 95% CI, 0.96–1.60; boys: OR=1.09, 95% CI, 0.99–1.19). Conclusions: BMI is associated with asthma in pre-pubertal Saudi boys and girls; this effect does not appear to be mediated through respiratory obstruction, but in girls this may at least partially be mediated through increased risk of allergic sensitisation

Cluster analysis of downscaled and explicitly simulated North Atlantic tropical cyclone tracks

A realistic representation of the North Atlantic tropical cyclone tracks is crucial as it allows, for example, explaining potential changes in US landfalling systems. Here we present a tentative study, which examines the ability of recent climate models to represent North Atlantic tropical cyclone tracks. Tracks from two types of climate models are evaluated: explicit tracks are obtained from tropical cyclones simulated in regional or global climate models with moderate to high horizontal resolution (1° to 0.25°), and downscaled tracks are obtained using a downscaling technique with large-scale environmental fields from a subset of these models. For both configurations, tracks are objectively separated into four groups using a cluster technique, leading to a zonal and a meridional separation of the tracks. The meridional separation largely captures the separation between deep tropical and sub-tropical, hybrid or baroclinic cyclones, while the zonal separation segregates Gulf of Mexico and Cape Verde storms. The properties of the tracks’ seasonality, intensity and power dissipation index in each cluster are documented for both configurations. Our results show that except for the seasonality, the downscaled tracks better capture the observed characteristics of the clusters. We also use three different idealized scenarios to examine the possible future changes of tropical cyclone tracks under 1) warming sea surface temperature, 2) increasing carbon dioxide, and 3) a combination of the two. The response to each scenario is highly variable depending on the simulation considered. Finally, we examine the role of each cluster in these future changes and find no preponderant contribution of any single cluster over the others

The business of care: Private placement agencies and female migrant workers in London

This article presents the results of a qualitative research project on private domestic and care placement agencies in London. Although there is a paucity of empirical studies on these private actors, they have become increasingly important in the domestic and care sector in the UK. In a context of growing commodification and marketization, the article shows how domestic and care services constitute an extremely profitable ‘industry’ in which large companies are increasingly investing. Drawing on content analysis of agencies' websites and in‐depth interviews with agencies' managers/owners, migrant workers and key informants, the article sheds light on these intermediary figures' marketing and business strategies as well as on the ways they contribute to establish the language and practice of domestic and care work as a business. Furthermore, it highlights the employment conditions and selection criteria established by these private agencies for female migrant workers, particularly in a context in which commodification/marketization is expected to foster more professionalization. The article thus fills a significant gap in the literature on domestic and care work, gender and migration by analysing the ways in which for‐profit recruitment agencies have become important players in the care industry

Percepção ambiental dos produtores e qualidade do solo em propriedades orgânicas e convencionais.

O sistema orgânico de produção deve resultar na utilização mais racional dos recursos naturais, sobretudo do solo. Os produtores orgânicos devem adotar práticas conservacionistas, além de atender a outros princípios deste sistema de produção. Neste trabalho foram avaliadas as práticas de manejo e conservação do solo adotadas por produtores orgânicos e convencionais nas regiões dos municípios de Socorro (Serra da Mantiqueira e Mogiana) e Ibiúna, situados no Estado de São Paulo. O objetivo dessa pesquisa foi verificar o grau de adoção de práticas conservacionistas pelos produtores e avaliar a qualidade do solo na agricultura orgânica e convencional. Foi elaborado e aplicado um questionário, com visitas locais para verificação das práticas conservacionistas e ocorrência de erosão, em 30 propriedades. Os resultados foram expressos em índices indicadores de diversidade de uso do solo, atitude conservacionista, percepção de erosão e do impacto sobre os recursos hídricos. Foram também realizadas análises de atributos químicos, físicos e biológicos indicadores da qualidade do solo. Concluiu-se que os produtores orgânicos têm maior percepção quanto à atitude conservacionista e nas propriedades orgânicas há maior diversidade de cultivos, embora não haja maior diversidade geral de uso do solo. A produção orgânica de alface, em Ibiúna proporcionou maior atividade biológica no solo e maior colonização por fungos micorrízicos arbusculares. O sistema orgânico possui maiores teores de matéria orgânica e menores de potássio e não houve diferença entre os atributos físicos do solo dos sistemas orgânico e convencional

Lying in Wait: The Resurgence of Dengue Virus After the Zika Epidemic in Brazil

After the Zika virus (ZIKV) epidemic in the Americas in 2016, both Zika and dengue incidence declined to record lows in many countries in 2017-2018, but in 2019 dengue resurged in Brazil, causing ~2.1 million cases. In this study we use epidemiological, climatological and genomic data to investigate dengue dynamics in recent years in Brazil. First, we estimate dengue virus force of infection (FOI) and model mosquito-borne transmission suitability since the early 2000s. Our estimates reveal that DENV transmission was low in 2017-2018, despite conditions being suitable for viral spread. Our study also shows a marked decline in dengue susceptibility between 2002 and 2019, which could explain the synchronous decline of dengue in the country, partially as a result of protective immunity from prior ZIKV and/or DENV infections. Furthermore, we performed phylogeographic analyses using 69 newly sequenced genomes of dengue virus serotype 1 and 2 from Brazil, and found that the outbreaks in 2018-2019 were caused by local DENV lineages that persisted for 5-10 years, circulating cryptically before and after the Zika epidemic. We hypothesize that DENV lineages may circulate at low transmission levels for many years, until local conditions are suitable for higher transmission, when they cause major outbreaks

IL1B-CGTC haplotype is associated with colorectal cancer in admixed individuals with increased African ancestry

Single-nucleotide polymorphisms (SNPs) in cytokine genes can affect gene expression and thereby modulate inflammation and carcinogenesis. However, the data on the association between SNPs in the interleukin 1 beta gene (IL1B) and colorectal cancer (CRC) are conflicting. We found an association between a 4-SNP haplotype block of the IL1B (-3737C/-1464G/-511T/-31C) and CRC risk, and this association was exclusively observed in individuals with a higher proportion of African ancestry, such as individuals from the Coastal Colombian region (odds ratio, OR 2.06; 95% CI 1.31–3.25; p < 0.01). Moreover, a significant interaction between this CRC risk haplotype and local African ancestry dosage was identified in locus 2q14 (p = 0.03). We conclude that Colombian individuals with high African ancestry proportions at locus 2q14 harbour more IL1B-CGTC copies and are consequently at an increased risk of CRC. This haplotype has been previously found to increase the IL1B promoter activity and is the most frequent haplotype in African Americans. Despite of limitations in the number of samples and the lack of functional analysis to examine the effect of these haplotypes on CRC cell lines, our results suggest that inflammation and ethnicity play a major role in the modulation of CRC risk