Analytical methods used in the United Kingdom Wildlife Incident Investigation Scheme for the detection of animal poisoning by pesticides

The United Kingdom Wildlife Incident Investigation Scheme (WIIS) investigates cases of suspected poisoning of wildlife, honey bees, and companion animals by pesticides. Together with field inquiries and veterinary post-mortem examinations, the analytical procedures presented here provide a comprehensive approach to the investigation of these cases. The paper covers selection of animal tissues for analysis and methods suitable for the analysis of honey bees and for various types of bait. Seven multiresidue methods cover around 130 pesticides, and methods are also described for a further 8 compounds. These methods are currently used on samples submitted to the Scheme in England and Wales.     

Conformational Dynamics Underlies Different Functions of Human KDM7 Histone Demethylases

The human KDM7 subfamily histone H3 Nϵ-methyl lysine demethylases PHF8 (KDM7B) and KIAA1718 (KDM7A) have different substrate selectivities and are linked to genetic diseases and cancer. We describe experimentally based computational studies revealing that flexibility of the region linking the PHD finger and JmjC domains in PHF8 and KIAA1718 regulates interdomain interactions, the nature of correlated motions, and ultimately H3 binding and demethylation site selectivity. F279S an X-linked mental retardation mutation in PHF8 is involved in correlated motions with the iron ligands and second sphere residues. The calculations reveal key roles of a flexible protein environment in productive formation of enzyme-substrate complexes and suggest targeting the flexible KDM7 linker region is of interest from a medicinal chemistry perspective.     

Use of SPME extraction to determine organophosphorus pesticides adsorption phenomena in water and soil matrices

Solid-phase micro extraction (SPME) coupled with GC enables rapid and simple analysis of organophosphorus pesticides in a range of complex matrices. Investigations were made into the extraction efficiencies from water of six organophosphorus insecticides (methamidophos, omethoate, dimethoate, parathion methyl, malathion, and parathion ethyl) showing a wide range of polarities. Three SPME fibres coated with different stationary phases, polydimethylsiloxane, polyacrylate, and carbowax-divinylbenzene (CW-DVB), were investigated. Water was spiked with the pesticides at concentrations from 1 to 0.01 µg mL-1, and the solutions used for optimization of the procedure. The CW-DVB fibre, with a 65 µm coating, gave the best performance. The optimized experimental conditions were sample volume 10 mL at 20°C, equilibration time 16 min, pH 5, and presence of 10% w/v NaCl. SPME analyses were performed on solutions obtained by equilibrating aqueous pesticide solutions with six certified soils with various physico-chemical characteristics. SPME data were also assessed by comparison with analyses performed by using conventional solid-phase extraction. Results indicate the suitability of SPME for analysis of pesticides in environmental water samples.     

Flophemesyl derivatives of alcohols,phenols, amines and carboxylic acids: Derivatives for mass spectrometric ion monitoring and structure determination

The flophemesyl (or pentafluorophenyldimethylsilyl) derivatives of representative alcohols, phenols, carboxylic acids and amines show rather simple spectra with a few abundant ions at high mass, characteristic of the parent compound and a few ions at low mass characteristic of the flophemesyl group. These derivatives are useful in the structure determination of simple compounds, and for the determination by single or multiple ion monitoring of known compounds at low levels.     

Solute- and temperature-responsive "smart" grafts and supported membranes formed by covalent layer-by-layer assembly

Polymers like poly(N-isopropylacrylamide) (PNIPAM) exhibit lower critical solution temperature (LCST) behavior. A variety of reports have shown that brush grafts of PNIPAM on surfaces exhibit similar temperature responsiveness. We recently described an alternative synthetic approach to such surfaces that affords surfaces with similar LCST-like behavior. We also noted how such surfaces' wettability can change in response to the identity and concentration of solutes. Here we show that this synthetic procedure can be extended to glass surfaces and to more complex surfaces present in porous glass frits. Functionalized glass surfaces exhibit solute-dependent wetting behavior analogous to that previously reported. We further show that the resulting responsive nanocomposite grafts on such frits exhibit "smart" responsive permeability with a greater than 1000-fold difference in permeability to water versus aqueous solutions of sodium sulfate. This "smart" permeability is ascribed to the solute-dependent wettability behavior of the responsive PNIPAM component of the nanocomposite graft, which is sensitive both to the identity and concentration of the solute anion and to temperature.     

Real-time imaging of nanoscale electrochemical Ni etching under thermal conditions

The ability to vary the temperature of an electrochemical cell provides opportunities to control reaction rates and pathways and to drive processes that are inaccessible at ambient temperature. Here, we explore the effect of temperature on electrochemical etching of Ni–Pt bimetallic nanoparticles. To observe the process at nanoscale resolution we use liquid cell transmission electron microscopy with a modified liquid cell that enables simultaneous heating and biasing. By controlling the cell temperature, we demonstrate that the reaction rate and dissolution potential of the electrochemical Ni etching process can be changed. The in situ measurements suggest that the destabilization of the native nickel oxide layer is the slow step prior to subsequent fast Ni removal in the electrochemical Ni dissolution process. These experiments highlight the importance of in situ structural characterization under electrochemical and thermal conditions as a strategy to provide deeper insights into nanomaterial transformations as a function of temperature and potential.

The combination of electrochemical analysis, temperature control and in situ TEM imaging directly probes the etching of Ni from bimetallic Ni–Pt nanoparticles.     

Determination of imidazole and triazole fungicide residues in honeybees using gas chromatography-mass spectrometry

An analytical method employing clean up by high-performance gel permeation chromatography (HPGPC) and solid-phase extraction (SPE) on Florisil cartridges was developed to determine residues of eleven imidazole and triazole ergosterol-biosynthesis-inhibiting (EBI) fungicides in honeybee samples. Detection was by means of gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. The method was validated by fortifying control samples at levels of 0.01 and 0.05 micro g/bee. Mean recoveries for each analyte except imazalil were between 79 and 99% with relative standard deviations of 12.3% or less. Mean recoveries of imazalil were 51% at 0.01 micro g/bee and 81% at 0.05 micro g/bee. Limits of detection for the analytes investigated ranged from 0.005 to 0.001 micro g/bee.