Synchrotron speciation of umbilical cord mercury and selenium after environmental exposure in Niigata.

The insidious and deadly nature of mercury's organometallic compounds is informed by two large scale poisonings due to industrial mercury pollution that occurred decades ago in Minamata and Niigata, Japan. The present study examined chemical speciation for both mercury and selenium in a historic umbilical cord sample from a child born to a mother who lived near the Agano River in Niigata. The mother had experienced mercury exposure leading to more than 50 ppm mercury measured in her hair and was symptomatic 9 years prior to the birth. We sought to determine the mercury and selenium speciation in the child's cord using Hg Lα1 and Se Kα1 high-energy resolution fluorescence detected X-ray absorption spectroscopy, the chemical speciation of mercury was found to be predominantly organometallic and coordinated to a thiolate. The selenium was found to be primarily in an organic form and at levels higher than those of mercury, with no evidence of mercury-selenium chemical species. Our results are consistent with mercury exposure at Niigata being due to exposure to organometallic mercury species.

Synchrotron X-ray methods in the study of mercury neurotoxicology.

In situ methods are valuable in all fields of research. In toxicology, the importance of dose is well known, elevating the need for in situ techniques to measure levels of toxicants and their byproducts in precise anatomically identifiable locations. More recently, additional emphasis has been placed on the value of techniques which can detect chemical form or speciation, which is equally important in the toxicology of a chemical compound. Many important but conventional methods risk losing valuable information due to extractions, digestions, or the general reliance on mobile phases. Few analytical tools possess the power and diversity of X-ray methods as in-situ methods. Here we present an overview, intended for toxicologists and pathologists, of a variety of synchrotron X-ray methods for determining in situ chemical form and distribution of heavier elements. The versatility and range of these synchrotron techniques, which are both established and emerging, is demonstrated in the context of the study of neurotoxicology of mercury, a global pollutant with the ability to harm both human health and the environment.

Isolation, bonding and reactivity of a monomeric stibine oxide.

In contrast to phosphine oxides and arsine oxides, which are common and exist as stable monomeric species featuring the corresponding pnictoryl functional group (Pn=O/Pn+-O-; Pn = P, As), stibine oxides are generally polymeric, and the properties of the unperturbed stiboryl group (Sb=O/Sb+-O-) remain unexplored. We now report the isolation of the monomeric stibine oxide, Dipp3SbO (where Dipp = 2,6-diisopropylphenyl). Spectroscopic, crystallographic and computational studies provide insight into the nature of the Sb=O/Sb+-O- bond. Moreover, isolation of Dipp3SbO allows the chemistry of the stiboryl group to be explored. Here we show that Dipp3SbO can act as a Brønsted base, a hydrogen-bond acceptor and a transition-metal ligand, in addition engaging in 1,2-addition, O-for-F2 exchange and O-atom transfer. In all cases, the reactivity of Dipp3SbO differed from that of the lighter congeners Dipp3AsO and Dipp3PO.

Abridged spectral matrix inversion: parametric fitting of X-ray fluorescence spectra following integrative data reduction.

Recent improvements in both X-ray detectors and readout speeds have led to a substantial increase in the volume of X-ray fluorescence data being produced at synchrotron facilities. This in turn results in increased challenges associated with processing and fitting such data, both temporally and computationally. Herein an abridging approach is described that both reduces and partially integrates X-ray fluorescence (XRF) data sets to obtain a fivefold total improvement in processing time with negligible decrease in quality of fitting. The approach is demonstrated using linear least-squares matrix inversion on XRF data with strongly overlapping fluorescent peaks. This approach is applicable to any type of linear algebra based fitting algorithm to fit spectra containing overlapping signals wherein the spectra also contain unimportant (non-characteristic) regions which add little (or no) weight to fitted values, e.g. energy regions in XRF spectra that contain little or no peak information.

Geometry of Pentaphenylantimony in Solution: Support for a Trigonal Bipyramidal Assignment from X-ray Absorption Spectroscopy and Vibrational Spectroscopic Data.

Pentaphenylantimony (SbPh5) has been previously crystallized in either a square pyramidal or trigonal bipyramidal geometry. Investigation of the solution-state structure of SbPh5 has been hampered by the extreme fluxionality of this compound, but previous vibrational spectroscopic studies concluded that it maintains a square pyramidal geometry in solution. This non-VSEPR-compliant geometry, which is also assumed by BiPh5 in the solid state, stands in contrast to the trigonal bipyramidal geometries of PPh5 and AsPh5. A range of phenomena have been invoked to explain this discrepancy, most notably, the increased importance of relativistic effects as group 15 is descended. We present crystallographic, spectroscopic, and computational data revealing that SbPh5 in fact assumes the VSEPR-compliant trigonal bipyramidal geometry in solution. In particular, Sb X-ray absorption spectroscopy (XAS) was used to obtain geometry-sensitive spectra that do not suffer from the slow spectroscopic time scale that has prevented NMR studies from elucidating the structure of this fluxional molecule. Sb K-edge and LIII-edge XAS spectra of crystalline solids featuring SbPh5 in either a square pyramidal (nonsolvate) or trigonal bipyramidal (cyclohexane hemisolvate or THF hemisolvate) form were compared to spectra of SbPh5 in solution. The solution-state spectra agree with those from solids containing trigonal bipyramidal SbPh5. The most diagnostic spectroscopic feature was the distribution of intensity in the Sb LIII pre-edge features. These distributions were rationalized using time-dependent density functional theory calculations that take into account spin-orbit coupling. Our use of Sb XAS not only resolves a long-standing physical inorganic question but also demonstrates more widely the utility of XAS in establishing the structures of fluxional main-group compounds. This conclusion was further supported by solid- and solution-state Raman data. Finally, we note that the present high-resolution diffraction data allow τ for nonsolvated SbPh5 to be revised to 0.216.