Road dust resuspension is one of the main sources of particulate matter with impacts on air quality, health and climate. With the aim of characterising the thoracic fraction, a portable resuspension ...chamber was used to collect road dust from five main roads in Oporto and an urban tunnel in Braga, north of Portugal. The PM10 samples were analysed for: i) carbonates by acidification and quantification of the evolved CO2, ii) carbonaceous content (OC and EC) by a thermo-optical technique, iii) elemental composition by ICP-MS and ICP-AES after acid digestion, and iv) organic speciation by GC–MS. Dust loadings of 0.48±0.39mgPM10m−2 were obtained for asphalt paved roads. A much higher mean value was achieved in a cobbled pavement (50mgPM10m−2). In general, carbonates were not detected in PM10. OC and EC accounted for PM10 mass fractions up to 11% and 5%, respectively. Metal oxides accounted for 29±7.5% of the PM10 mass from the asphalt paved roads and 73% in samples from the cobbled street. Crustal and anthropogenic elements, associated with tyre and brake wear, dominated the inorganic fraction. PM10 comprised hundreds of organic constituents, including hopanoids, n-alkanes and other aliphatics, polycyclic aromatic hydrocarbons (PAH), alcohols, sterols, various types of acids, glycerol derivatives, lactones, sugars and derivatives, phenolic compounds and plasticizers. In samples from the cobbled street, these organic classes represented only 439μgg−1PM10, while for other pavements mass fractions up to 65mgg−1PM10 were obtained. Except for the cobbled street, on average, about 40% of the analysed organic fraction was composed of plasticizers. Although the risk via inhalation of PAH was found to be insignificant, the PM10 from some roads can contribute to an estimated excess of 332 to 2183 per million new cancer cases in adults exposed via ingestion and dermal contact.
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•Dust loadings<1mgPM10m−2 were obtained for asphalt paved roads.•These values are lower than those reported for other cities.•Dust loadings about 50 times higher were found for a cobbled pavement.•OC & EC accounted for small PM10 mass fractions, while inorganic components dominate.•OC comprised hundreds of organic constituents; plasticizers were the most abundant.
Protein modification has entered the limelight of chemical and biological sciences, since, by appending small molecules into proteins surfaces, fundamental biological and biophysical processes may be ...studied and even modulated in a physiological context. Herein we present a new strategy to modify the lysine’s ε-amino group and the protein’s N-terminal, based on the formation of stable iminoboronates in aqueous media. This functionality enables the stable and complete modification of these amine groups, which can be reversible upon the addition of fructose, dopamine, or glutathione. A detailed DFT study is also presented to rationalize the observed stability toward hydrolysis of the iminoboronate constructs.
To obtain emission factors and cooking-related chemical signatures, a monitoring campaign was carried out in a modern kitchen where different dishes of the Latin cuisine were prepared. Particulate ...matter (PM10, PM2.5 and PM1) and total volatile organic compounds (TVOCs) were continuously measured. Passive tubes for carbonyls and a high volume PM10 sampler were simultaneously used. PM10 filters were analysed for organic and elemental carbon and for multiple organic compounds, including polyaromatic hydrocarbons (PAHs). The toxic potential of PM10 was evaluated using a bioluminescence inhibition bioassay. Acrolein was never detected, while formaldehyde and acetaldehyde levels were comparable to those in the background air. The protection limit for TVOCs was always exceeded. Fine particles comprised more than 86% of the PM10 mass concentrations. PM10 emission rates ranged from 124 to 369 μg min−1. Relatively low PAH concentrations were obtained. PM10 encompassed alcohols, acids, plasticisers, alkyl esters, sterols, sugars, polyols, glyceridic compounds, phenolics, among others. Total concentrations were 1.9–5.3 times higher during cooking than in the background air but, for some compounds, differences of tens or hundreds of times were registered. PM10 from grilled pork was found to contribute to non-negligible cancer risks and to be very toxic, while samples from other dishes were categorised as toxic.
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•Fried horse mackerel, stuffed chicken and gilled/fried pork were cooked.•Emission rates below values reported for gas ranges and exhaust hood turned off.•PM10 was mainly composed of high-risk respirable sizes.•Grilling pork was found to emit very toxic particles with non-negligible cancer risks.•Heavier PAH, glyceridic compounds, diacids and amino acids correlated with toxicity.
Road dust resuspension has a significant contribution to the atmospheric particulate matter levels in urban areas, but loadings, emission factors, and chemical source profiles vary geographically, ...hampering the accuracy of emission inventories and source contribution estimates. Given the dearth of studies on the variability of road dust, in the present study, an in-situ resuspension chamber was used to collect PM10 samples from seven representative streets in Viana do Castelo, the northernmost coastal city in Portugal. PM10 samples were analysed for organic and elemental carbon by a thermo-optical technique, elemental composition by ICP-MS and ICP-AES, and organic constituents by GC–MS. Emission factors were estimated to be, on average, 340 and 41.2 mg veh−1 km−1 for cobbled and asphalt pavements, respectively. Organic carbon accounted for 5.56 ± 1.24% of the PM10 mass. Very low concentrations of PAHs and their alkylated congeners were detected, denoting a slight predominance of petrogenic compounds. Si, Al, Fe, Ca and K were the most abundant elements. The calculation of various geochemical indices (enrichment factor, geoaccumulation index, pollution index and potential ecological risk) showed that road dust was extremely enriched and contaminated by elements from tyre and brake wear (e.g. Sb, Sn, Cu, Bi and Zn), while lithophile elements showed no enrichment. For As, the geochemical and pollution indices reached their maximum in the street most influenced by agricultural activities. Sb, Cd, Cu and As can pose a very high ecological risk. Sb can be regarded as the pollutant of highest concern, since it represented 57% of the total ecological risk. Hazard indices higher than 1 for some anthropogenic elements indicate that non-carcinogenic effects may occur. Except for a street with more severe braking, the total carcinogenic risks can be considered insignificant.
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•The thoracic fraction of road dust was sampled with an in-situ resuspension chamber.•Emission factors of 340 (cobbled) and 41 (asphalt) mg PM10 veh−1 km−1 were estimated.•Road dust was extremely contaminated by elements from tyre and brake wear.•Elements from tyre and brake wear can pose a very high ecological risk.•High pollution indices for arsenic in samples impacted by agricultural activities.
Background and purpose
Spain has been one of the countries more heavily stricken by SARS‐CoV‐2, which has had huge implications for stroke care. The aim was to analyse the impact of the COVID‐19 ...epidemic outbreak on reperfusion therapies for acute ischaemic stroke in the northwest of Spain.
Methods
This was a Spanish multicentre retrospective observational study based on data from tertiary hospitals of the NORDICTUS network. All patients receiving reperfusion therapy for ischaemic stroke between 30 December 2019 and 3 May 2020 were recorded, and their baseline, clinical and radiological characteristics, extra‐ and intra‐hospital times of action, Code Stroke activation pathway, COVID‐19 status, reperfusion rate, and short‐term outcome before and after the setting of the emergency state were analysed.
Results
A total of 796 patients received reperfusion therapies for ischaemic stroke. There was a decrease in the number of patients treated per week (46.5 patients per week vs. 39.0 patients per week, P = 0.043) and a delay in out‐of‐hospital (95.0 vs. 110.0 min, P = 0.001) and door‐to‐needle times (51.0 vs. 55.0, P = 0.038). Patients receiving endovascular therapy obtained less successful reperfusion rates (92.9% vs. 86.6%, P = 0.016). COVID‐19 patients had more in‐hospital mortality.
Conclusion
A decrease in the number of patients benefiting from reperfusion therapies was found, with a delay in out‐of‐hospital and door‐to‐needle times and worse reperfusion rates in northwest Spain. COVID‐19 patients had more in‐hospital mortality.
Abstract
The high brightness temperatures, Tb ≳ 1013 K, detected in several active galactic nuclei by RadioAstron space VLBI observations challenge theoretical limits. Refractive scattering by the ...interstellar medium may affect such measurements. We quantify the scattering properties and the sub-mas scale source parameters for the quasar B0529+483. Using RadioAstron correlated flux density measurements at 1.7, 4.8, and 22 GHz on projected baselines up to 240 000 km we find two characteristic angular scales in the quasar core, about 100 and 10 μas. Some indications of scattering substructure are found. Very high brightness temperatures, Tb ≥ 1013 K, are estimated at 4.8 and 22 GHz even taking into account the refractive scattering. Our findings suggest a clear dominance of the particle energy density over the magnetic field energy density in the core of this quasar.
Racemic mixtures of boronic acid-derived salicylidenehydrazone (BASHY) complexes were enantiomerically resolved. The chiroptical properties of the stereoisomers, containing an asymmetric boron as the ...only stereogenic unit, are translated into mirror-imaged electronic circular dichroism spectra and circularly polarized luminescence (CPL, dissymmetry factors of 3–5 × 10–4) is observed. The spectral position of the CPL emission is determined by the push–pull character of the dye. These features expand the functional scope of the brightly emitting BASHY dye platform.
Antibody-drug conjugates (ADCs) are among the fastest-growing classes of therapeutics in oncology. Although ADCs are in the spotlight, they still present significant engineering challenges. ...Therefore, there is an urgent need to develop more stable and effective ADCs. Most rabbit light chains have an extra disulfide bridge, that links the variable and constant domains, between Cys80 and Cys171, which is not found in the human or mouse. Thus, to develop a new generation of ADCs, we explored the potential of rabbit-derived VL-single-domain antibody scaffolds (sdAbs) to selectively conjugate a payload to Cys80. Hence, a rabbit sdAb library directed towards canine non-Hodgkin lymphoma (cNHL) was subjected to in vitro and in vivo phage display. This allowed the identification of several highly specific VL-sdAbs, including C5, which specifically target cNHL cells in vitro and present promising in vivo tumor uptake. C5 was selected for SN-38 site-selective payload conjugation through its exposed free Cys80 to generate a stable and homogenous C5-DAB-SN-38. C5-DAB-SN-38 exhibited potent cytotoxicity activity against cNHL cells while inhibiting DNA-TopoI activity. Overall, our strategy validates a platform to develop a novel class of ADCs that combines the benefits of rabbit VL-sdAb scaffolds and the canine lymphoma model as a powerful framework for clinically translation of novel therapeutics for cancer.
Separation and purification of biomacromolecules either in biopharmaceuticals and fine chemicals manufacturing, or in diagnostics and biological characterization, can substantially benefit from ...application of microfluidic devices. Small volumes of equipment, very efficient mass and heat transfer together with high process control result in process intensification, high throughputs, low energy consumption and reduced waste production as compared to conventional processing. This review highlights microfluidics-based separation and purification of proteins and nucleic acids with the focus on liquid-liquid extractions, particularly with biocompatible aqueous two-phase systems, which represent a cost-effective and green alternative. A variety of microflow set-ups are shown to enable sustainable and efficient isolation of target biomolecules both for preparative, as well as for analytical purposes.
Separation and purification of biomacromolecules either in biopharmaceuticals and fine chemicals manufacturing, or in diagnostics and biological characterization, can substantially benefit from application of microfluidic devices.
Different microRNAs (miRNAs), including miR-29 family, may play a role in the development of heart failure (HF), but the underlying molecular mechanisms in HF pathogenesis remain unclear. We aimed at ...characterizing mice deficient in miR-29 in order to address the functional relevance of this family of miRNAs in the cardiovascular system and its contribution to heart disease. In this work, we show that mice deficient in miR-29a/b1 develop vascular remodeling and systemic hypertension, as well as HF with preserved ejection fraction (HFpEF) characterized by myocardial fibrosis, diastolic dysfunction, and pulmonary congestion, and die prematurely. We also found evidence that the absence of miR-29 triggers the up-regulation of its target, the master metabolic regulator PGC1α, which in turn generates profound alterations in mitochondrial biogenesis, leading to a pathological accumulation of small mitochondria in mutant animals that contribute to cardiac disease. Notably, we demonstrate that systemic hypertension and HFpEF caused by miR-29 deficiency can be rescued by PGC1α haploinsufficiency, which reduces cardiac mitochondrial accumulation and extends longevity of miR-29-mutant mice. In addition, PGC1α is overexpressed in hearts from patients with HF. Collectively, our findings demonstrate the in vivo role of miR-29 in cardiovascular homeostasis and unveil a novel miR-29/PGC1α regulatory circuitry of functional relevance for cell metabolism under normal and pathological conditions.
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