Alaa Abdul-Sada

Neonicotinoid Residues in Wildflowers, a Potential Route of Chronic Exposure for Bees

In recent years, an intense debate about the environmental risks posed by neonicotinoids, a group of widely used, neurotoxic insecticides, has been joined. When these systemic compounds are applied to seeds, low concentrations are subsequently found in the nectar and pollen of the crop, which are then collected and consumed by bees. Here we demonstrate that the current focus on exposure to pesticides via the crop overlooks an important factor: throughout spring and summer, mixtures of neonicotinoids are also found in the pollen and nectar of wildflowers growing in arable field margins, at concentrations that are sometimes even higher than those found in the crop. Indeed, the large majority (97%) of neonicotinoids brought back in pollen to honey bee hives in arable landscapes was from wildflowers, not crops. Both previous and ongoing field studies have been based on the premise that exposure to neonicotinoids would occur only during the blooming period of flowering crops and that it may be diluted by bees also foraging on untreated wildflowers. Here, we show that exposure is likely to be higher and more prolonged than currently recognized because of widespread contamination of wild plants growing near treated crops.

Widespread contamination of wildflower and bee-collected pollen with complex mixtures of neonicotinoids and fungicides commonly applied to crops

There is considerable and ongoing debate as to the harm inflicted on bees by exposure to agricultural pesticides. In part, the lack of consensus reflects a shortage of information on field-realistic levels of exposure. Here, we quantify concentrations of neonicotinoid insecticides and fungicides in the pollen of oilseed rape, and in pollen of wildflowers growing near arable fields. We then compare this to concentrations of these pesticides found in pollen collected by honey bees and in pollen and adult bees sampled from bumble bee colonies placed on arable farms. We also compared this with levels found in bumble bee colonies placed in urban areas. Pollen of oilseed rape was heavily contaminated with a broad range of pesticides, as was the pollen of wildflowers growing nearby. Consequently, pollen collected by both bee species also contained a wide range of pesticides, notably including the fungicides carbendazim, boscalid, flusilazole, metconazole, tebuconazole and trifloxystrobin and the neonicotinoids thiamethoxam, thiacloprid and imidacloprid. In bumble bees, the fungicides carbendazim, boscalid, tebuconazole, flusilazole and metconazole were present at concentrations up to 73nanogram/gram (ng/g). It is notable that pollen collected by bumble bees in rural areas contained high levels of the neonicotinoids thiamethoxam (mean 18ng/g) and thiacloprid (mean 2.9ng/g), along with a range of fungicides, some of which are known to act synergistically with neonicotinoids. Pesticide exposure of bumble bee colonies in urban areas was much lower than in rural areas. Understanding the effects of simultaneous exposure of bees to complex mixtures of pesticides remains a major challenge.

Mutations in SLC39A14 disrupt manganese homeostasis and cause childhood-onset parkinsonism–dystonia

Although manganese is an essential trace metal, little is known about its transport and homeostatic regulation. Here we have identified a cohort of patients with a novel autosomal recessive manganese transporter defect caused by mutations in SLC39A14. Excessive accumulation of manganese in these patients results in rapidly progressive childhood-onset parkinsonism–dystonia with distinctive brain magnetic resonance imaging appearances and neurodegenerative features on post-mortem examination. We show that mutations in SLC39A14 impair manganese transport in vitro and lead to manganese dyshomeostasis and altered locomotor activity in zebrafish with CRISPR-induced slc39a14 null mutations. Chelation with disodium calcium edetate lowers blood manganese levels in patients and can lead to striking clinical improvement. Our results demonstrate that SLC39A14 functions as a pivotal manganese transporter in vertebrates.

Heteronuclear 3 d/DyIII Coordination Clusters as Catalysts in a Domino Reaction

Three isoskeletal tetranuclear coordination clusters with general formula [M(II) 2 Dy(III) 2 L4 (EtOH)6 ](ClO4 )2 ⋅2 EtOH, (M=Co, 1; M=Ni, 2) and [Ni(II) 2 Dy(III) 2 L4 Cl2 (CH3 CN)2 ]⋅2 CH3 CN (3), have been synthesized and characterized. These air-stable compounds, and in particular 3, display efficient homogeneous catalytic behavior in the room-temperature synthesis of trans-4,5-diaminocyclopent-2-enones from 2-furaldehyde and primary or secondary amines under a non-inert atmosphere.

There are no fullerenes in the K-T boundary layer

Abstract Careful re-examination of the Cretacous-Tertiary boundary layer material that was reported earlier to contain C60, confirms that there is a peak in the HPLC of the extract having a retention time similar to that of C60 (the basis of the earlier claim). However, mass spectrometric analysis shows this to be merely a mixture of hydrocarbons. No traces of either C60 or C70 are present under conditions capable of detecting as little as 50 pg (0.001 part per billion in the original material), this sensitivity being four times greater than that given in the earlier report. These findings are entirely consistent with the known high oxidative instability of fullerenes.

Upon the hydrogen-bonding ability of the H4 and H5 protons of the imidazolium cation

The crystal and molecular structures of [Me2Etim]Cl, [Me2Etim]2[CoCl4], and [Me2Etim]2[NiCl4] ([Me2Etim]+ = 1,2-dimethyl-3-ethylimidazolium cation) all contain evidence that the H4 and H5 protons of the imidazolium cation enter into hydrogen bonds; the implications of this observation for the interactions in room-temperature chloroaluminate(III) ionic liquids are considered.

The xenometabolome and novel contaminant markers in fish exposed to a wastewater treatment works effluent.

Organisms exposed to wastewater treatment works (WwTW) effluents accumulate complex mixtures of xenobiotics but there is a scarcity of information on the nature and impacts of these chemical mixtures. We applied metabolomics techniques as a novel approach to identify xenobiotics and their metabolites (the xenometabolome) that bioconcentrate in fish exposed to a WwTW effluent. Exposed juvenile rainbow trout (Oncorhynchus mykiss) accumulated surfactants, naphthols, chlorinated xylenols, and phenoxyphenols, chlorophenes, resin acids, mefenamic acid, oxybenzone, and steroidal alkaloids in the bile or plasma, and there were perturbations in the plasma concentrations of bile acids and lipids. Exposure of adult roach (Rutilus rutilus) to 50% or 100% concentrations of the same effluent resulted in dose-dependent increases in plasma concentrations of xenometabolites as well as cyprinol sulfate and taurocholic acid, lysophospholipids, and a decrease in sphingosine levels (a key component of cell membrane lipids). Our findings reveal the highly complex nature of xenobiotics accumulating in effluent-exposed fish, and the great potential of metabolomics for both identifying plasma marker (bio)chemicals for monitoring exposure to wastewater effluents, and for targeting studies on potential consequent impacts on fish health.

Upon the structure of room temperature halogenoaluminate ionic liquids

The X-ray structure of a monoclinic crystal of 1-methyl-3-ethylimidazolium iodide, [MeEtim]l, reveals the presence of discrete hydrogen-bonded ion-pairs [r{C(2)H ⋯ l–}= 0.293 nm]: the structural implications of the presence of hydrogen-bonding in ionic liquids based upon [MeEtim]X–AlX3(X = Cl or Br) mixtures are discussed.

A new approach for plasma (xeno)metabolomics based on solid-phase extraction and nanoflow liquid chromatography-nanoelectrospray ionisation mass spectrometry

Current metabolite profiling methods based on liquid chromatography-mass spectrometry (LC-MS) platforms do not detect many of the components present at trace concentrations in extracts of plasma due to their low ionisation efficiency or to interference from highly abundant compounds. Nanoflow LC-nanospray MS platforms, which are commonly used in proteomics, could overcome these limitations and significantly increase analytical sensitivity and coverage of the plasma (xeno)metabolome (i.e., metabolites and xenobiotics), but require small injection volumes (<0.5μL). In this study, we developed sample preparation methods to remove ion suppressive phospholipids and concentrate remaining components of the plasma (xeno)metabolome in order to analyse sub-microliter volumes of plasma extracts for nanoflow ultra-high-performance liquid chromatography-nanoelectrospray ionisation-time-of-flight mass spectrometry (nUHPLC-nESI-TOFMS). These methods use phospholipid filtration plates in combination with polymeric or mixed mode exchange solid-phase extraction (SPE). The phospholipid filtration plates removed >94% of the predominant phospholipid/lysophospholipid species from plasma, whilst absolute recoveries of 63 selected (xeno)metabolites from spiked plasma were generally between 60 and 104%. After a further SPE step, recoveries of test compounds were between 50 and 81%. Studies revealed that both the sample preparation methodology and nUHPLC-nESI-TOFMS analyses gave acceptable repeatability. A qualitative comparison of SPE methods revealed that sample concentration by either polymer or mixed mode ion-exchange SPE gave comprehensive metabolite coverage of plasma extracts, but the use of cation exchange SPE significantly increased detection of many cationic compounds in the sample extracts. Method detection limits for steroid, eicosanoid and bile metabolites were <1.0ng/mL plasma and for pharmaceutical contaminants were between 0.01 and 30ng/mL plasma. Comparison of the phospholipid removal/cation exchange SPE and the classical protein precipitation (PPT) sample preparation methodologies revealed that both methods detected the same range of (xeno)metabolites. However, unlike PPT extracts, the SPE preparations allowed direct injection of more concentrated plasma extracts onto the nUHPLC-nESI-TOFMS platform without blockage of the nanocolumn or nanospray, thus resulting in a wider coverage of the (xeno)metabolome. This is the first work to demonstrate the significantly enhanced sensitivity arising from the use of concentrated SPE sample preparations and direct nUHPLC-nESI-TOFMS analysis for untargeted profiling of plasma samples and constitutes a step forward for identifying mixtures of chemical stressors accumulated in blood as well as the disruption of key metabolite pathways in the same sample.

Polyhydrogenation of [60]- and [70]fullerenes with Zn/HCl and Zn/DCl

Abstract Previous work on polyhydrogenation of fullerenes leading to C 60 H 36 and C 70 H 36 as the main products is reviewed. The most probable structures of these species, based on their aromaticities, are presented. Zinc/concentrated HCl is shown to be an excellent and rapid reducing agent for benzene or toluene solutions of fullerenes at room temperature. The polyhydrogenated species are unstable towards light and undergo oxidative degradation, with, in the case of C 60 H 36 , formation of C 60 H 18 as an intermediate. Reduction of these fullerenes by zinc/concentrated DCl gives C 60 H 44 and C 70 H 48 as the highest hydrogenated products; the greater incorporation of deuterium is attributed to the greater C-D bond energy. In the absence of light and oxygen, C 60 H 36 exhibits high thermal stability. Attempted further reduction of C 60 H 36 leads to formation of trimethylene adducts; these are also formed on reduction of [84] fullerenes which gives C 84 H 48 as the main product.