Preliminary fingerprinting of Athabasca oil sands polar organics in environmental samples using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

There is a growing need to develop analytical methods that can distinguish compounds found within industrially derived oil sands process water (OSPW) from those derived from natural weathering of oil sands deposits. This is a difficult challenge as possible leakage beyond tailings pond containments will probably be in the form of mixtures of water-soluble organics that may be similar to those leaching naturally into aquatic environments. We have evaluated the potential of negative ion electrospray ionization high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) for comparing oil sands polar organics from tailing ponds, interceptor wells, groundwater, river and lake surface waters. Principal component analysis was performed for all species observed. which included the O(2) class (often assumed to be monocarbxoylic naphthenic acids) along with a wide range of other species including humic substances in the river and lake samples: O(n) where n=1-16; NO(n) and N(2)O(n) where n=1-13; and O(n)S and O(n)S(2) where n=1-10 and 1-8, respectively. A broad range of species was investigated because classical naphthenic acids can be a small fraction of the 'organics' detected in the polar fraction of OSPW, river water and groundwater. Aquatic toxicity and environmental chemistry are attributed to the total organics (not only the classical naphthenic acids). The distributions of the oil sands polar organics, particularly the sulfur-containing species, O(n)S and O(n)S(2), may have potential for distinguishing sources of OSPW. The ratios of species containing O(n) along with nitrogen-containing species: NO(n), and N(2)O(n), were useful for differentiating organic components derived from OSPW from those found in river and lake waters. Further application of the FTICRMS technique for a diverse range of OSPW of varying ages and composition, as well as the surrounding groundwater wells, may be critical in assessing whether leakage from industrial sources to natural waters is occurring.     

Mapping blood biochemistry by Raman spectroscopy at the cellular level

We report how Raman difference imaging provides insight on cellular biochemistry in vivo as a function of sub-cellular dimensions and the cellular environment. We show that this approach offers a sensitive diagnostic to address blood biochemistry at the cellular level. We examine Raman microscopic images of the distribution of the different hemoglobins in both healthy (discocyte) and unhealthy (echinocyte) blood cells and interpret these images using pre-calculated, accurate pre-resonant Raman tensors for scattering intensities specific to hemoglobins. These tensors are developed from theoretical calculations of models of the oxy, deoxy and met forms of heme benchmarked against the experimental visible spectra of the corresponding hemoglobins. The calculations also enable assignments of the electronic transitions responsible for the colour of blood: these are mainly ligand to metal charge transfer transitions.

We assign the electronic transitions responsible for the colour of blood and present a Raman imaging diagnostic approach for individual blood cells.     

Splittability for Partially Ordered Sets

A topological space X is said to be splittable over a class P of spaces if for every AX there exists continuous f:XYP such that f(A)f(XA) is empty. A class P of topological spaces is said to be a splittability class if the spaces splittable over P are precisely the members of P. We extend the notion of splittability to partially ordered sets and consider splittability over some elementary posets. We identify precisely which subsets of a poset can be split along over an n-point chain. Using these results it is shown that the union of two splittability classes need not be a splittability class and a necessary condition for P to be a splittability class is given.     

Synthesis,Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex

We report the uranium(VI) carbene imido oxo complex [U(BIPM^TMS)(NMes)(O)(DMAP)₂] ( 5 , BIPM^TMS=C(PPh₂NSiMe₃)₂; Mes=2,4,6‐Me₃C₆H₂; DMAP=4‐(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two‐electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T‐shaped motif with respect to the carbene, which is consistent with an inverse trans‐influence. Complex 5 reacts with tert‐butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM^TMS)(O)₂(DMAP)₂] ( 6 ).     

Electronic spectral studies of molybdenyl complexes. 2. MCD spectroscopy of [MoOS4]- centers

Magnetic circular dichroism (MCD) and absorption spectroscopies have been used to probe the electronic structure of [PPh4][MoO(p-SC6H4X)4] (X = H, Cl, OMe) and [PPh4][MoO(edt)2] complexes (edt = ethane-1,2-dithiolate). The results of density functional calculations (DFT) on [MoO(SMe)4]- and [MoO(edt)2]- model complexes were used to provide a framework for the interpretation of the spectra. Our analysis shows that the lowest energy transitions in [MoVOS4] chromophores (S4 = sulfur donor ligand) result from S-->Mo charge transfer transitions from S valence orbitals that lie close to the ligand field manifold. The energies of these transitions are strongly dependent on the orientation of the S lone-pair orbitals with respect to the Mo atom that is determined by the geometry of the ligand backbone. Thus, the lowest energy transition in the MCD spectrum of [PPh4][MoO(p-SC6H4X)4] (X = H) occurs at 14,800 cm-1, while that in [PPh4][MoO(edt)2] occurs at 11,900 cm-1. The identification of three bands in the absorption spectrum of [PPh4][MoO(edt)2] arising from LMCT from S pseudo-sigma combinations to the singly occupied Mo 4d orbital in the xy plane suggests that there is considerable covalency in the ground-state electronic structures of [MoOS4] complexes. DFT calculations on [MoO(SMe)4]- reveal that the singly occupied HOMO is 53% Mo 4dxy and 35% S p for the equilibrium C4 geometry. For [MoO(edt)2]- the steric constraints imposed by the edt ligands result in the S pi orbitals being of similar energy to the Mo 4d manifold. Significant S pseudo-sigma and pi donation may also weaken the Mo identical to O bond in [MoOS4] centers, a requirement for facile active site regeneration in the catalytic cycle of the DMSO reductases. The strong dependence of the energies of the bands in the absorption and MCD spectra of [PPh4][MoO(p-SC6H4X)4] (X = H, Cl, OMe) and [PPh4][MoO(edt)2] on the ligand geometry suggests that the structural features of the active sites of the DMSO reductases may result in an electronic structure that is optimized for facile oxygen atom transfer.     

Determination of selenium in blood plasma and serum by flow injection hydride generation atomic absorption spectrometry

A flow injection hydride generation atomic absorption spectrometric (AAS) method has been used to determine the selenium concentrations of human serum and plasma samples following digestion with nitric, sulphuric and perchloric acids. In the hydride generation process, reduction was carried out by sodium tetrahydroborate to produce a hydride that was atomized in a flame-heated atomisation cell. The method had a detection limit of 1.2 ng ml-1 and a sensitivity of 2.1 ng ml-1. Within-run precisions of 5.8% at 20 ng ml-1 and 4.5% at 80 ng ml-1, and between-run precisions of 4.8% at 69 ng ml-1 and 3.4% at 80 ng ml-1 were obtained. An inter-laboratory comparison study with a graphite furnace AAS method was carried out and the results showed excellent agreement. The flow injection method of sample introduction allowed the use of a sample volume of 330 microliters with an injection rate of 90 injections per hour.     

Regioselective organocadmium alkylations of substituted quinones.

A series of substituted quinones was alkylated with diethylcadmium. Regiochemistry of addition shifted from quinol formation to conjugate addition as a function of the steric and electronic effects of the substituents.