Olena Ponomarenko

Selenium Preferentially Accumulates in the Eye Lens Following Embryonic Exposure: A Confocal X-ray Fluorescence Imaging Study

Maternal transfer of elevated selenium (Se) to offspring is an important route of Se exposure for fish in the natural environment. However, there is a lack of information on the tissue specific spatial distribution and speciation of Se in the early developmental stages of fish, which provide important information about Se toxicokinetics. The effect of maternal transfer of Se was studied by feeding adult zebrafish a Se-elevated or a control diet followed by collection of larvae from both groups. Novel confocal synchrotron-based techniques were used to investigate Se within intact preserved larvae. Confocal X-ray fluorescence imaging was used to compare Se distributions within specific planes of an intact larva from each of the two groups. The elevated Se treatment showed substantially higher Se levels than the control; Se preferentially accumulated to highest levels in the eye lens, with lower levels in the retina, yolk and other tissues. Confocal X-ray absorption spectroscopy was used to determine that the speciation of Se within the eye lens of the intact larva was a selenomethionine-like species. Preferential accumulation of Se in the eye lens may suggest a direct cause-and-effect relationship between exposure to elevated Se and Se-induced ocular impairments reported previously. This study illustrates the effectiveness of confocal X-ray fluorescence methods for investigating trace element distribution and speciation in intact biological specimens.

The solution structure of the copper clioquinol complex

Clioquinol (5-chloro-7-iodo-8-hydroxyquinoline) recently has shown promising results in the treatment of Alzheimers disease and in cancer therapy, both of which also are thought to be due to clioquinols ability as a lipophilic copper chelator. Previously, clioquinol was used as an anti-fungal and anti-protozoal drug that was responsible for an epidemic of subacute myelo-optic neuropathy (SMON) in Japan during the 1960s, probably a myeloneuropathy arising from a clioquinol-induced copper deficiency. Previous X-ray absorption spectroscopy of solutions of copper chelates of clioquinol suggested unusual coordination chemistry. Here we use a combination of electron paramagnetic, UV-visible and X-ray absorption spectroscopies to provide clarification of the chelation chemistry between clioquinol and copper. We find that the solution structures for the copper complexes formed with stoichiometric and excess clioquinol are conventional 8-hydroxyquinolate chelates. Thus, the promise of clioquinol in new treatments for Alzheimers disease and in cancer therapy is not likely to be due to any novel chelation chemistry, but rather due to other factors including the high lipophilicity of the free ligand and chelate complexes.

Observation of the seleno bis-(S-glutathionyl) arsinium anion in rat bile.

Certain arsenic and selenium compounds show a remarkable mutual cancelation of toxicities, where a lethal dose of one can be voided by an equimolar and otherwise lethal dose of the other. It is now well established that the molecular basis of this antagonism is the formation and biliary excretion of seleno bis-(S-glutathionyl) arsinium anion [(GS)2AsSe](-). Previous work has definitively demonstrated the presence of [(GS)2AsSe](-) in rabbit bile, but only in the presence of other arsenic and selenium species. Rabbits have a gall bladder, which concentrates bile and lowers its pH; it seems likely that this may be responsible for the breakdown of biliary [(GS)2AsSe](-). Since rats have no gall bladder, the bile proceeds directly through the bile duct from the hepatobiliary tree. In the present work we have shown that the primary product of biliary co-excretion of arsenic and selenium in rats is [(GS)2AsSe](-), with essentially 100% of the arsenic and selenium present as this species. The chemical plausibility of the X-ray absorption spectroscopy-derived structural conclusions of this novel arsenic and selenium co-excretion product is supported by density functional theory calculations. These results establish the biomolecular basis to further explore the use of selenium dietary supplements as a possible palliative for chronic low-level arsenic poisoning of human populations.

Synchrotron X-ray absorption spectroscopy analysis of arsenic chemical speciation in human nail clippings

Environmental context Chronic ingestion of arsenic leads to its accumulation in keratinous tissues, which can represent a risk factor for developing cancer. We use synchrotron X-ray absorption spectroscopy to investigate chemical bonding of arsenic in the keratins from nail clippings of volunteers from areas in Atlantic Canada with low-to-moderate arsenic contamination of drinking water. The study helps our understanding of arsenic metabolism and its role in cancer development. Abstract Drinking water aquifers in many areas of the world have naturally elevated levels of inorganic arsenic exceeding the World Health Organization limit. Arsenic concentrations in human nail clippings are commonly used as a biomarker of exposure to this toxic element. However, the chemical form of arsenic accumulated in nail tissues is not well determined. We employed synchrotron microprobe and bulk X-ray absorption spectroscopy techniques to analyse the concentration and chemical speciation of arsenic in the finger- and toenail clippings of volunteers living in the vicinity of Sackville, New Brunswick, Canada. This area is known to have low-to-moderately elevated levels of arsenic in ground water. Arsenic species in clippings were represented by three main groups, distinguished by the As-K near-edge X-ray absorption fine structure spectra: (1) AsIII type, which can be fitted as a mixture of As bound to thiols, and also to oxygen or methyl groups, with a small contribution from AsV species, (2) AsV type, best represented by fitting arsenate in aqueous solution and (3) The AsIII+AsV mixture type. The high proportion (%) of sulfur-bound arsenic species most likely corresponds to binding between arsenic (in its trivalent and, to a lesser extent, pentavalent forms) and cysteine residues in the sulfur-rich fraction of keratin and keratin-associated proteins. Further work is needed to explore whether these chemical species could be used as toxicity biomarkers of human exposure to elevated levels of As in drinking water.

Interaction of acetone with the Ge(001) surface

The adsorption of acetone on the Ge(001) surface has been investigated using density functional theory (DFT). We have considered a number of different possible adsorbate configurations corresponding to the dative bonded, α-hydrogen cleavage, [2 + 2] cycloaddition, end-bridging and dimer-bridging structures. Analysis of the associated energetics has resulted in a comprehensive description of the overall reaction processes of acetone on the Ge(001) surface. The preferred structure at low temperature is found to be the dative structure, whilst at higher temperature the predominant structure is predicted to be a dimer-bridge dissociated configuration. Both of these predictions are consistent with the available experimental data. Comparison with earlier work of acetone on Si(001) reveals significantly weaker bonding in the case of Ge(001), and highlights fundamental differences between the chemical properties of these two surfaces.

X-ray spectroscopy and imaging of selenium in living systems

BACKGROUND Selenium is an essential element with a rich and varied chemistry in living organisms. It plays a variety of important roles ranging from being essential in enzymes that are critical for redox homeostasis to acting as a deterrent for herbivory in hyperaccumulating plants. Despite its importance there are many open questions, especially related to its chemistry in situ within living organisms. SCOPE OF REVIEW This review discusses X-ray spectroscopy and imaging of selenium in biological samples, with an emphasis on the methods, and in particular the techniques of X-ray absorption spectroscopy (XAS) and X-ray fluorescence imaging (XFI). We discuss the experimental methods and capabilities of XAS and XFI, and review their advantages and their limitations. A perspective on future possibilities and next-generation of experiments is also provided. MAJOR CONCLUSIONS XAS and XFI provide powerful probes of selenium chemistry, together with unique in situ capabilities. The opportunities and capabilities of the next generation of advanced X-ray spectroscopy experiments are particularly exciting. GENERAL SIGNIFICANCE XAS and XFI provide versatile tools that are generally applicable to any element with a convenient X-ray absorption edge, suitable for investigating complex systems essentially without pre-treatment.