336 research outputs found

    Hysteretic thermal spin-crossover in heteroleptic Fe(II) complexes using alkyl chain substituted 2,2’-dipyridylamine ligands

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    The alkyl chain carrying ligands N,N-di(pyridin-2-yl)butanamide (LC4) and N,N-di(pyridin-2-yl)decanamide (LC10) were combined with NCS− co-ligands to form the neutral heteroleptic Fe(II) complexes trans-[FeII(LC4)2(NCS)2] (1C4) and trans-[FeII(LC10)2(NCS)2] (1C10). Variable temperature crystallographic studies revealed that 1C4 is in the orthorhombic space group Pna21 between 85–200 K whereas 1C10 is in the monoclinic space group P21/c between 85–140 K. The average Fe–N bond lengths suggest that at 85 K 1C4 contains LS Fe(II) centres; however, the ca. 0.18 Å increase in the average Fe–N bond lengths between 85 and 120 K suggests a spin-transition to the HS state occurs within this temperature interval. 1C10 contains LS Fe(II) centres between 85 and 105 K. Upon warming from 105 to 140 K the average Fe–N bond lengths increase by ca. 0.19 Å, which suggests a spin-transition to the HS state. Solid-state magnetic susceptibility measurements showed that 1C4 undergoes semi-abrupt spin-crossover with T1/2 = 127.5 K and a thermal hysteresis of ca. 13 K whereas, 1C10 undergoes an abrupt spin-crossover with T1/2 = 119.0 K, and is also accompanied by thermal hysteresis of ca. 4 K. The crystallographic and magnetic data show that the length of the complex's alkyl chain substituents can have a large impact on the structure of the crystal lattice as well as a subtle effect on the T1/2 value for thermal spin-crossover

    Agricultural soils and microplastics: Are biosolids the problem?

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    Biosolids are the solid by-product of the wastewater treatment system. They are regularly applied to agricultural land in the UK to fertilize and increase crop yields, but they have been shown to contain high concentrations of microplastics. Here we sampled a selection of agricultural soils in the Southeast of England which had received or never received biosolid treatment. Sites were sampled on two occasions in the summer and winter. Microplastic (MP) numbers were high in both the biosolid treated fields (874 MP/kg) and the untreated fields (664 MP/kg) and a wide variety of polymers were found across sites. However, there was a lack of significant difference between treated and untreated soils. This suggests the influence of other microplastic sources e.g. agricultural plastic and general littering, and external conditions e.g. farm management and rainfall. Microplastic concentrations were higher in the summer suggesting that erosion, runoff, and wind transport may be removing microplastics from these systems. The dynamic nature of the agricultural soils may result in them becoming a vector for microplastics into the wider environment. The high variability in results seen here highlights the complexity of microplastic concentrations in heterogeneous agricultural soils. This study suggests that biosolids, whilst are likely a contributor, are not the sole source of microplastics in agricultural soils. Further research is required to determine source and sink dynamics in these systems. Understanding the sources of microplastic contamination in soils is imperative for future mitigation strategies to be effective

    Ferrocenylmethylphosphanes and the Alpha Process for Methoxycarbonylation: The Original Story

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    The Lucite Alpha process is the predominant technology for the preparation of acrylics. This two-stage process involves the palladium-catalysed formation of methyl propanoate from ethene, CO, and methanol, followed by the oxidative formylation of methyl propanoate into methyl methacrylate. A range of bis-1,2-disubstituted aminomethylferrocenes has been prepared and characterised. These complexes serve as precursors to a variety of bulky ferrocenylmethyldiphosphanes that, in turn, function as ligands in the palladium-catalysed process. We describe the crystal structures of five ligand precursors and provide a rationale for their design. In situ catalyst testing on palladium complexes derived from ferrocenylphosphanes demonstrates that these are highly selective (>99.5%) catalysts for the formation of methyl propanoate from ethene, CO, and methanol and have turnover numbers exceeding 50,000. This article credits those researchers who worked on this project in the early days, who received little or no credit for their achievements and endeavours

    The human male liver is predisposed to inflammation via enhanced myeloid responses to inflammatory triggers

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    BACKGROUND & AIM: Men have a higher prevalence of liver disease. Liver myeloid cells can regulate tissue inflammation, which drives progression of liver disease. We hypothesized that sex alters the responsiveness of liver myeloid cells, predisposing men to severe liver inflammation. METHODS: Luminex was done on plasma from Hepatitis B Virus infected patients undergoing nucleoside analogue cessation in 45 male and female patients. We collected immune cells from the sinusoids of uninfected livers of 53 male and female donors. Multiparametric flow cytometry was used to phenotype and characterize immune composition. Isolated monocytes were stimulated with TLR ligands to measure the inflammatory potential and the expression of regulators of TLR signaling. RESULTS: We confirmed that men experienced more frequent and severe liver damage upon Hepatitis B Virus reactivation, which was associated with inflammatory markers of myeloid activation. No differences were observed in the frequency or phenotype of sinusoidal myeloid cells between male and female livers. However, monocytes from male livers produced more inflammatory cytokines and chemokines in response to TLR stimulation than female monocytes. We investigated negative regulators of TLR signaling and found that TOLLIP was elevated in female liver-derived monocytes. CONCLUSIONS: Our data show that enhanced responsiveness of myeloid cells from the male liver predisposes men to inflammation, which was associated with altered expression of negative regulators of TLR signaling

    Developing a systematic method for extraction of microplastics in soils

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    Microplastics are an environmental issue of global concern. Although they have been found in a range of environments worldwide, their contamination in the terrestrial environment is poorly understood. The lack of standardised methods for their detection and quantification is a major obstacle for determining the risk they pose to soil environments. Here we present a systematic comparison of microplastic extraction methods from soils, taking into account the characteristics of the soil medium to determine the best methods for quantification. The efficiency of organic matter removal using hydrogen peroxide, potassium hydroxide and Fenton's reagent was measured. Soils with a range of particle size distribution and organic matter content were spiked with a variety of microplastic types. Density separation methods using sodium chloride, zinc chloride and canola oil were tested. Recovery efficiencies were calculated and the impact of the reagents on the microplastics was quantified using Attenuated Total Reflectance (ATR) Fourier Transform-Infrared (FTIR) spectroscopy. The optimal organic removal method was found to be hydrogen peroxide. The recovery efficiency of microplastics was variable across polymer types. Overall, canola oil was shown to be the optimal method for density separation, however, efficiency was dependent on the amount of organic matter in the soil. This outcome highlights the importance of including matrix-specific calibration in future studies considering a wide range of microplastic types, to avoid underestimation of microplastic contamination. We show here that methods for extracting microplastics from soils can be simple, cost-effective and widely applicable, which will enable the advancement of microplastic research in terrestrial environments

    Developing a systematic method for extraction of microplastics in soils

    Get PDF
    Microplastics are an environmental issue of global concern. Although they have been found in a range of environments worldwide, their contamination in the terrestrial environment is poorly understood. The lack of standardised methods for their detection and quantification is a major obstacle for determining the risk they pose to soil environments. Here we present a systematic comparison of microplastic extraction methods from soils, taking into account the characteristics of the soil medium to determine the best methods for quantification. The efficiency of organic matter removal using hydrogen peroxide, potassium hydroxide and Fenton's reagent was measured. Soils with a range of particle size distribution and organic matter content were spiked with a variety of microplastic types. Density separation methods using sodium chloride, zinc chloride and canola oil were tested. Recovery efficiencies were calculated and the impact of the reagents on the microplastics was quantified using Attenuated Total Reflectance (ATR) Fourier Transform-Infrared (FTIR) spectroscopy. The optimal organic removal method was found to be hydrogen peroxide. The recovery efficiency of microplastics was variable across polymer types. Overall, canola oil was shown to be the optimal method for density separation, however, efficiency was dependent on the amount of organic matter in the soil. This outcome highlights the importance of including matrix-specific calibration in future studies considering a wide range of microplastic types, to avoid underestimation of microplastic contamination. We show here that methods for extracting microplastics from soils can be simple, cost-effective and widely applicable, which will enable the advancement of microplastic research in terrestrial environments

    Alkyl chain functionalised Ir(iii) complexes: synthesis, properties and behaviour as emissive dopants in microemulsions

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    Six iridium(III) complexes of the general form [Ir(C^N)2(N^N)]X (where C^N = cyclometalating ligand; N^N = disubstituted 2,2′-bipyridine), and incorporating alkyl chains of differing lengths (C8, C10, C12), have been synthesised and characterised. The complexes have been characterised using a variety of methods including spectroscopies (NMR, IR, UV-Vis, luminescence) and analytical techniques (high resolution mass spectrometry, cyclic voltammetry, X-ray diffraction). Two dodecyl-functionalised complexes were studied for their behaviour in aqueous solutions. Although the complexes did not possess sufficient solubility to determine their critical micelle concentrations (CMC) in water, they were amenable for use as emissive dopants in a N-methyl C12 substituted imidazolium salt microemulsion carrier system with a CMC = 36.5 mM. The investigation showed that the metal doped microemulsions had increased CMCs of 40.4 and 51.3 mM and luminescent properties characterised by the dopant

    Middle and Late Pleistocene environmental history of the Marsworth area, south-central England

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    To elucidate the Middle and Late Pleistocene environmental history of south-central England, we report the stratigraphy, sedimentology, palaeoecology and geochronology of some deposits near the foot of the Chiltern Hills scarp at Marsworth, Buckinghamshire. The Marsworth site is important because its sedimentary sequences contain a rich record of warm stages and cold stages, and it lies close to the Anglian glacial limit. Critical to its history are the origin and age of a brown pebbly silty clay (diamicton) previously interpreted as weathered till. The deposits described infill a river channel incised into chalk bedrock. They comprise clayey, silty and gravelly sediments, many containing locally derived chalk and some with molluscan, ostracod and vertebrate remains. Most of the deposits are readily attributed to periglacial and fluvial processes, and some are dated by optically stimulated luminescence to Marine Isotope Stage (MIS) 6. Although our sedimentological data do not discriminate between a glacial or periglacial interpretation of the diamicton, amino-acid dating of three molluscan taxa from beneath it indicates that it is younger than MIS 9 and older than MIS 5e. This makes a glacial interpretation unlikely, and we interpret the diamicton as a periglacial slope deposit. The Pleistocene history reconstructed for Marsworth identifies four key elements: (1) Anglian glaciation during MIS 12 closely approached Marsworth, introducing far-travelled pebbles such as Rhaxella chert and possibly some fine sand minerals into the area. (2) Interglacial environments inferred from fluvial sediments during MIS 7 varied from fully interglacial conditions during sub-stages 7e and 7c, cool temperate conditions during sub-stage 7b or 7a, temperate conditions similar to those today in central England towards the end of the interglacial, and cool temperate conditions during sub-stage 7a. (3) Periglacial activity during MIS 6 involved thermal contraction cracking, permafrost development, fracturing of chalk bedrock, fluvial activity, slopewash, mass movement and deposition of loess and coversand. (4) Fully interglacial conditions during sub-stage 5e led to renewed fluvial activity, soil formation and acidic weathering
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