Mechanistic studies on single-electron transfer in frustrated Lewis pairs and its application to main-group chemistry.

Advances in the field of frustrated Lewis pair (FLP) chemistry have led to the discovery of radical pairs, obtained by a single-electron transfer (SET) from the Lewis base to the Lewis acid. Radical pairs are intriguing for their potential to enable cooperative activation of challenging substrates (e.g., CH4, N2) in a homolytic fashion, as well as the exploration of novel radical reactions. In this review, we will cover the two known mechanisms of SET in FLPs-thermal and photoinduced-along with methods (i.e., CV, DFT, UV-vis) to predict the mechanism and to characterise the involved electron donors and acceptors. Furthermore, the available techniques (i.e., EPR, UV-vis, transient absorption spectroscopy) for studying the corresponding radical pairs will be discussed. Initially, two model systems (PMes3/CPh3+ and PMes3/B(C6F5)3) will be reviewed to highlight the difference between a thermal and a photoinduced SET mechanism. Additionally, three cases are analysed to provide further tools and insights into characterizing electron donors and acceptors, and the associated radical pairs. Firstly, a thermal SET process between LiHMDS and [TEMPO][BF4] is discussed. Next, the influence of Lewis acid complexation on the electron acceptor will be highlighted to facilitate a SET between (pBrPh)3N and TCNQ. Finally, an analysis of sulfonium salts as electron acceptors will demonstrate how to manage systems with rapidly decomposing radical species. This framework equips the reader with an expanded array of tools for both predicting and characterizing SET events within FLP chemistry, thereby enabling its extension and application to the broader domain of main-group (photo)redox chemistry.

Whether cycling around the city is in fact healthy in the light of air quality - Results of black carbon.

Studying the air quality and exposure of the inhabitants of urban agglomerations to pollution is the basis for the creation and development of more sustainable cities. Although research on black carbon (BC) has not yet reached the official acceptable levels and guidelines, the World Health Organization clearly indicates the need to measure and control the level of this pollutant. In Poland, monitoring of the level of BC concentration is not included in the air quality monitoring network. To estimate the extent of this pollutant to which pedestrians and cyclists are exposed, mobile measurements were carried out on over 26 km of bicycle paths in Wroclaw. The obtained results indicate the influence of urban greenery next to the bicycle path (especially if the cyclist is separated from the street lane by hedges or other tall plants) and the 'breathability' (i.e., associated with surrounding infrastructure) of the area on the obtained concentrations; the average concentration of BC in such places ranged from 1.3 to 2.2 µg/m3, whereas a cyclist riding directly on bike paths adjacent to the main roads in the city center is exposed to concentrations in the range of 2.3-14 µg/m3. The results of the measurements, also related to stationary measurements made at a selected point of one of the routes, clearly indicate the importance of the infrastructure surrounding the bicycle paths, their location, and the impact of urban traffic on the obtained BC concentrations. The results presented in our study are based only on short-term-field campaigns preliminary studies. To determine the quantitative impact of the characteristics of the bicycle route on the concentration of pollutants, and thus the exposure of users, the systematized research should cover a greater part of the city and be representative in terms of various hours of the day.

Homolytic C-H Bond Activation by Phosphine-Quinone-Based Radical Ion Pairs.

Herein, we present the formation of transient radical ion pairs (RIPs) by single-electron transfer (SET) in phosphine-quinone systems and explore their potential for the activation of C-H bonds. PMes3 (Mes=2,4,6-Me3 C6 H2 ) reacts with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) with formation of the P-O bonded zwitterionic adduct Mes3 P-DDQ (1), while the reaction with the sterically more crowded PTip3 (Tip=2,4,6-iPr3 C6 H2 ) afforded C-H bond activation product Tip2 P(H)(2-[CMe2 (DDQ)]-4,6-iPr2 -C6 H2 ) (2). UV/Vis and EPR spectroscopic studies showed that the latter reaction proceeds via initial SET, forming RIP [PTip3 ]⋅+ [DDQ]⋅- , and subsequent homolytic C-H bond activation, which was supported by DFT calculations. The isolation of analogous products, Tip2 P(H)(2-[CMe2 {TCQ-B(C6 F5 )3 }]-4,6-iPr2 -C6 H2 ) (4, TCQ=tetrachloro-1,4-benzoquinone) and Tip2 P(H)(2-[CMe2 {oQtBu -B(C6 F5 )3 }]-4,6-iPr2 -C6 H2 ) (8, oQtBu =3,5-di-tert-butyl-1,2-benzoquinone), from reactions of PTip3 with Lewis-acid activated quinones, TCQ-B(C6 F5 )3 and oQtBu -B(C6 F5 )3 , respectively, further supports the proposed radical mechanism. As such, this study presents key mechanistic insights into the homolytic C-H bond activation by the synergistic action of radical ion pairs.

Cyclist exposure to black carbon, ultrafine particles and heavy metals: An experimental study along two commuting routes near Antwerp, Belgium.

Urban environments typically exhibit large atmospheric pollution variation, in both space and time. In contrast to traditional monitoring networks suffering from a limited spatial coverage, mobile platforms enable personalized high-resolution monitoring, providing valuable insights into personal atmospheric pollution exposure, and the identification of potential pollution hotspots. This study evaluated personal cyclist exposure to UFPs, BC and heavy metals whilst commuting near Antwerp, Belgium, by performing mobile measurements with wearable black carbon (BC) and ultrafine particle (UFP) instruments. Loaded micro-aethalometer filterstrips were chemically analysed and the inhaled pollutant dose determined from the exhibited heart rate. Considerable spatial pollutant variation was observed along the travelled routes, with distinct contributions from spatial factors (e.g. traffic intersections, urban park and market) and temporary events. On average 300% higher BC, 20% higher UFP and changing elemental concentrations are observed along the road traffic route (RT), when compared to the bicycle highway route (BH). Although the overall background pollution determines a large portion of the experienced personal exposure (in this case 53% for BC and 40% for UFP), cyclists can influence their personal atmospheric pollution exposure, by selecting less exposed commuting routes. Our results, hereby, strengthen the body of evidence in favour of further policy investments in isolated bicycle infrastructure.

Biomagnetic Monitoring of Atmospheric Pollution: A Review of Magnetic Signatures from Biological Sensors.

Biomagnetic monitoring of atmospheric pollution is a growing application in the field of environmental magnetism. Particulate matter (PM) in atmospheric pollution contains readily measurable concentrations of magnetic minerals. Biological surfaces, exposed to atmospheric pollution, accumulate magnetic particles over time, providing a record of location-specific, time-integrated air quality information. This review summarizes current knowledge of biological material ("sensors") used for biomagnetic monitoring purposes. Our work addresses the following: the range of magnetic properties reported for lichens, mosses, leaves, bark, trunk wood, insects, crustaceans, mammal and human tissues; their associations with atmospheric pollutant species (PM, NOx, trace elements, PAHs); the pros and cons of biomagnetic monitoring of atmospheric pollution; current challenges for large-scale implementation of biomagnetic monitoring; and future perspectives. A summary table is presented, with the aim of aiding researchers and policy makers in selecting the most suitable biological sensor for their intended biomagnetic monitoring purpose.

Home-produced eggs: An important human exposure pathway of perfluoroalkylated substances (PFAS).

Humans are generally exposed to per- and polyfluoroalkyl substances (PFAS) through their diet. Whilst plenty of data are available on commercial food products, little information exists on the contribution of self-cultivated food, such as home-produced eggs (HPE), to the dietary PFAS intake in humans. The prevalence of 17 legacy and emerging PFAS in HPE (N = 70) from free-ranging laying hens was examined at 35 private gardens, situated within a 10 km radius from a fluorochemical plant in Antwerp (Belgium). Potential influences from housing conditions (feed type and number of individuals) and age of the chickens on the egg concentrations was examined, and possible human health risks were evaluated. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were detected in all samples. PFOS was the dominant compound and concentrations (range: 0.13-241 ng/g wet weight) steeply decreased with distance from the fluorochemical plant, while there was no clear distance trend for other PFAS. Laying hens receiving an obligate diet of kitchen leftovers, exhibited higher PFOS and PFOA concentrations in their eggs than hens feeding only on commercial food, suggesting that garden produce may be a relevant exposure pathway to both chickens and humans. The age of laying hens affected egg PFAS concentrations, with younger hens exhibiting significantly higher egg PFOA concentrations. Based on a modest human consumption scenario of two eggs per week, the European health guideline was exceeded in ≥67% of the locations for all age classes, both nearby and further away (till 10 km) from the plant site. These results indicate that PFAS exposure via HPE causes potential human health risks. Extensive analysis in other self-cultivated food items on a larger spatial scale is highly recommended, taking into account potential factors that may affect PFAS bioavailability to garden produce.

Morphological and elemental characterization of leaf-deposited particulate matter from different source types: a microscopic investigation.

Particulate matter (PM) deposition on urban green enables the collection of particulate pollution from a diversity of contexts, and insight into the physico-chemical profiles of PM is key for identifying main polluting sources. This study reports on the morphological and elemental characterization of PM2-10 deposited on ivy leaves from five different environments (forest, rural, roadside, train, industry) in the region of Antwerp, Belgium. Ca. 40,000 leaf-deposited particles were thoroughly investigated by particle-based analysis using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM/EDX) and their physico-chemical characteristics were explored for PM source apportionment purposes. The size distribution of all deposited particles was biased towards small-sized PM, with 32% of the particles smaller than 2.5 µm (PM2.5) and median diameters of 2.80-3.09 µm. The source type influenced both the particles' size and morphology (aspect ratio and shape), with roadside particles being overall the smallest in size and the most spherical. While forest and rural elemental profiles were associated with natural PM, the industry particles revealed the highest anthropogenic metal input. PM2-10 profiles for roadside and train sites were rather comparable and only distinguishable when evaluating the fine (2-2.5 µm) and coarse (2.5-10 µm) PM fractions separately, which enabled the identification of a larger contribution of combustion-derived particles (small, circular, Fe-enriched) at the roadside compared to the train. Random forest prediction model classified the source type correctly for 61-85% of the leaf-deposited PM. The still modest classification accuracy denotes the influence of regional background PM and demands for additional fingerprinting techniques to facilitate source apportionment. Nonetheless, the obtained results demonstrate the utility of leaf particle-based analysis to fingerprint and pinpoint source-specific PM, particularly when considering both the composition and size of leaf-deposited particles.

Impact of urban street canyon architecture on local atmospheric pollutant levels and magneto-chemical PM10 composition: An experimental study in Antwerp, Belgium.

As real-life experimental data on natural ventilation of atmospheric pollution levels in urban street canyons is still scarce and has proven to be complex, this study, experimentally evaluated the impact of an urban street canyon opening on local atmospheric pollution levels, during a 2-week field campaign in a typical urban street canyon in Antwerp, Belgium. Besides following up on atmospheric particulate matter (PM), ultrafine particles (UFPs) and black carbon (BC) levels, the magneto-chemical PM10 composition was quantified to identify contributions of specific elements in enclosed versus open street canyon sections. Results indicated no higher overall PM, UFP and BC concentrations at the enclosed site compared to the open site, but significant day-to-day variability between both monitoring locations, depending on the experienced wind conditions. On days with oblique wind regimes (4 out of 14), natural ventilation was observed at the open location while higher element contributions of Ca, Fe, Co, Ni, Cu, Zn and Sr were exhibited at the enclosed location. Magnetic properties correlated with the PM10 filter loading, and elemental content of Fe, Cr, Mn and Ti. Magnetic bivariate ratios identified finel-grained magnetite carriers with grain sizes below 0.1 µm, indicating similar magnetic source contributions at both monitoring locations. Our holistic approach, combining atmospheric monitoring with magneto-chemical PM characterization has shown the complex impact of real-life wind flow regimes, different source contributions and local traffic dynamics on the resulting pollutant concentrations and contribute to a better understanding on the urban ventilation processes of atmospheric pollution.

Human inflammatory response of endotoxin affected by particulate matter-bound transition metals.

Bacterial endotoxins are a component of particulate matter (PM) with anticipated health implications, yet we know little about how host reception of endotoxin through toll-like receptor 4 (TLR4) is affected by its association with other PM components. Subsequently, we investigated the relationship between endotoxin concentration (recombinant Factor C (rFC) assay) and host recognition (HEK Blue-TLR4 NF-kB reporter cell line based assay) in various compositions of urban PM, including road traffic, industrial and urban green land use classes. While the assays did not correlate strongly between each other, the TLR4 reporter cell line was found to be better correlated to the IL-8 response of PM. Furthermore, the ability of the quantified endotoxin (rFC assay) to stimulate the TLR4/MD-2 complex was significantly affected by the urban land use class, where traffic locations were found to be significantly higher in bioactive endotoxin than the industrial and green locations. We subsequently turned our attention to PM composition and characterized the samples based on transition metal content (through ICP-MS). The effect of nickel and cobalt - previously reported to activate the hTLR4/MD-2 complex - was found to be negligible in comparison to that of iron. Here, the addition of iron as a factor significantly improved the regression model between the two endotoxin assays, explaining 77% of the variation of the TLR4 stimulation and excluding the significant effect of land use class. Moreover, the effect of iron proved to be more than a correlation, since dosing LPS with Fe2+ led to an increase up to 64% in TLR4 stimulation, while Fe2+ without LPS was unable to stimulate a response. This study shows that endotoxin quantification assays (such as the rFC assay) may not always correspond to human biological recognition of endotoxin in urban PM, while its toxicity can be synergistically influenced by the associated PM composition.

Biomagnetic monitoring as a validation tool for local air quality models: a case study for an urban street canyon.

Biomagnetic monitoring of tree leaf deposited particles has proven to be a good indicator of the ambient particulate concentration. The objective of this study is to apply this method to validate a local-scale air quality model (ENVI-met), using 96 tree crown sampling locations in a typical urban street canyon. To the best of our knowledge, the application of biomagnetic monitoring for the validation of pollutant dispersion modeling is hereby presented for the first time. Quantitative ENVI-met validation showed significant correlations between modeled and measured results throughout the entire in-leaf period. ENVI-met performed much better at the first half of the street canyon close to the ring road (r=0.58-0.79, RMSE=44-49%), compared to second part (r=0.58-0.64, RMSE=74-102%). The spatial model behavior was evaluated by testing effects of height, azimuthal position, tree position and distance from the main pollution source on the obtained model results and magnetic measurements. Our results demonstrate that biomagnetic monitoring seems to be a valuable method to evaluate the performance of air quality models. Due to the high spatial and temporal resolution of this technique, biomagnetic monitoring can be applied anywhere in the city (where urban green is present) to evaluate model performance at different spatial scales.

On the link between biomagnetic monitoring and leaf-deposited dust load of urban trees: relationships and spatial variability of different particle size fractions.

Biomagnetic monitoring of urban tree leaves has proven to be a good estimator of ambient particulate matter. We evaluated its relevancy by determining leaf area normalised weight (mg m(-2)) and SIRM (A) of leaf-deposited particles within three different size fractions (>10 µm, 3-10 µm and 0.2-3 µm) and the SIRM of the leaf-encapsulated particles. Results showed that throughout the in-leaf season, the trees accumulated on average 747 mg m(-2) of dust on their leaves, of which 74 mg m(-2) was within the 0.2-10 µm (∼PM10) size range and 40 mg m(-2) within the 0.2-3 µm (∼PM3) size range. A significant correlation between the SIRM and weight of the surface-deposited particles confirms the potential of biomagnetic monitoring as a proxy for the amount of leaf-deposited particles. Spatial variation of both SIRM and weight throughout the street canyon suggests traffic and wind as key factors for respectively the source and distribution of urban particulates.

Reprint of On the link between biomagnetic monitoring and leaf-deposited dust load of urban trees: relationships and spatial variability of different particle size fractions.

Biomagnetic monitoring of urban tree leaves has proven to be a good estimator of ambient particulate matter. We evaluated its relevancy by determining leaf area normalised weight (mg m(-2)) and SIRM (A) of leaf-deposited particles within three different size fractions (>10 µm, 3-10 µm and 0.2-3 µm) and the SIRM of the leaf-encapsulated particles. Results showed that throughout the in-leaf season, the trees accumulated on average 747 mg m(-2) of dust on their leaves, of which 74 mg m(-2) was within the 0.2-10 µm (∼PM10) size range and 40 mg m(-2) within the 0.2-3 µm (∼PM3) size range. A significant correlation between the SIRM and weight of the surface-deposited particles confirms the potential of biomagnetic monitoring as a proxy for the amount of leaf-deposited particles. Spatial variation of both SIRM and weight throughout the street canyon suggests traffic and wind as key factors for respectively the source and distribution of urban particulates.

On the temporal variation of leaf magnetic parameters: seasonal accumulation of leaf-deposited and leaf-encapsulated particles of a roadside tree crown.

Understanding the accumulation behaviour of atmospheric particles inside tree leaves is of great importance for the interpretation of biomagnetic monitoring results. In this study, we evaluated the temporal variation of the saturation isothermal remanent magnetisation (SIRM) of leaves of a roadside urban Platanus × acerifolia Willd. tree in Antwerp, Belgium. We hereby examined the seasonal development of the total leaf SIRM signal as well as the leaf-encapsulated fraction of the deposited dust, by washing the leaves before biomagnetic analysis. On average 38% of the leaf SIRM signal was exhibited by the leaf-encapsulated particles. Significant correlations were found between the SIRM and the cumulative daily average atmospheric PM10 and PM2.5 measurements. Moreover, a steady increase of the SIRM throughout the in-leaf season was observed endorsing the applicability of biomagnetic monitoring as a proxy for the time-integrated PM exposure of urban tree leaves. Strongest correlations were obtained for the SIRM of the leaf-encapsulated particles which confirms the dynamic nature of the leaf surface-accumulated particles.

Spatial distribution assessment of particulate matter in an urban street canyon using biomagnetic leaf monitoring of tree crown deposited particles.

Recently, biomagnetic monitoring of tree leaves has proven to be a good estimator for ambient particulate concentration. This paper investigates the usefulness of biomagnetic leaf monitoring of crown deposited particles to assess the spatial PM distribution inside individual tree crowns and an urban street canyon in Ghent (Belgium). Results demonstrate that biomagnetic monitoring can be used to assess spatial PM variations, even within single tree crowns. SIRM values decrease exponentially with height and azimuthal effects are obtained for wind exposed sides of the street canyon. Edge and canyon trees seem to be exposed differently. As far as we know, this study is the first to present biomagnetic monitoring results of different trees within a single street canyon. The results not only give valuable insights into the spatial distribution of particulate matter inside tree crowns and a street canyon, but also offer a great potential as validation tool for air quality modelling.

A comparison of non-destructive sampling strategies to assess the exposure of white-tailed eagle nestlings (Haliaeetus albicilla) to persistent organic pollutants.

To circumvent difficulties associated with monitoring adult predatory birds, we investigated the feasibility of different non-destructive strategies for nestling white-tailed eagles (Haliaeetus albicilla). We were able to quantify polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorinated pesticides (OCPs) in body feathers (16.92, 3.37 and 7.81ngg(-1) dw, respectively), blood plasma (8.37, 0.32 and 5.22ngmL(-1) ww, respectively), and preen oil (1157.95, 30.92 and 440.74ngg(-1) ww, respectively) of all nestlings (N=14). Strong significant correlations between blood plasma and preen oil concentrations (0.565≤r≤0.801; P<0.05) indicate that preen oil levels closely reflect the internal state of contamination. We found fewer significant correlations between body feather and blood plasma concentrations, which were almost exclusively between PCB concentrations (0.554≤r≤0.737; P<0.05). These results differ from a previous study on younger nestlings, and may indicate that the nestlings studied here, ready to fledge the nest, were possibly undergoing certain physiological changes that may have confounded the use of body feathers as biomonitor matrix. Finally, we provide an integrated discussion on the use of body feathers and preen oil as non-destructive biomonitor strategies for nestling predatory birds.