Mercury determination by cold vapor atomic absorption spectrometry utilizing UV photoreduction

A method for the determination of mercury via UV photoreduction has been investigated. Mercury vapor was generated by the reduction of mercury species in an acetic acid solution using UV radiation. Detection of the volatile mercury was accomplished by atomic absorption spectrometry. An optimized system was found to provide a detection limit (defined as the concentration giving a signal equal to three times the standard deviation of the blank) of 2.1 μg L⁻¹ with a precision of 2.9% relative standard deviation (n = 8) for a 500 μg L⁻¹ mercury standard. The effect of various metal ions on the mercury signal was investigated and the method validated with a NRCC certified dogfish liver material (DOLT-3) using the method of standard additions. A reaction pathway is hypothesized for UV photoreduction.     

Mapping tertiary interactions in protein folding reactions: a novel mass spectrometry- and chemical synthesis-based approach

A novel mass spectrometry- and chemical synthesis-based approach for studying protein folding reactions is described, and its initial application to study the folding/unfolding reaction of a homo-hexameric enzyme 4-oxalocrotonate (4OT) is reported. This new approach involves the application of total chemical synthesis to prepare protein analogues that contain a photoreactive amino acid site-specifically incorporated into their primary amino acid sequence. To this end, a photoreactive amino acid-containing analogue of 4OT in which Pro-1 was replaced with p-benzoyl-l-phenylalanine (Bpa) was prepared. This analogue can be used to map structurally specific protein-protein interactions in 4OT’s native folded state. These photocrosslinking studies and peptide mapping results with (P1Bpa)4OT indicate that this construct is potentially useful for probing the structural properties of equilibrium and kinetic intermediates in 4OT’s folding reaction.     

The one-electron oxidation of [HCCOCC]- to form neutral HCCOCC, and the subsequent rearrangement of HCCOCC to form HCCCCO. An experimental and computational study

The singlet anion [HCCOCC]- may be made in the source of a VG ZAB 2HF mass spectrometer by the reaction between F- (from SF6) and H-C[triple chemical bond]C-O-C[triple chemical bond]C-TMS. Vertical (Franck-Condon) one-electron oxidation of [HCCOCC]- in the first collision cell produces doublet neutral HCCOCC. A combination of experiment and molecular modelling [at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31 + G(d) level of theory] provides data which are consistent with some HCCOCC neutrals being stable for the duration of the neutralisation reionisation experiment, while others rearrange to form the decomposing doublet neutral HCCCCO.     

Determination of volatile mercury species at the picogram level by low-temperature gas chromatography with cold-vapour atomic fluorescence detection

Alkylmercury compounds were preconcentrated from air on a Carbotrap (graphitized carbon black) column at room temperature. The species were then transferred by thermal desorption to a U-tube chromatographic column packed with 15% OV-3 on Chromosorb WAW-DMSC, held at ?196°C in liquid nitrogen. The compounds were clearly separated and eluted in order of increasing polarity using a simple, ramped heating step to 180°C over 20 min. After thermal decomposition of the eluant, the resultant mercury vapour was detected by cold-vapour atomic fluorescence spectrometry. The detection limits (as Hg) for the system were approximately 0.3 pg for mercury and dimethylmercury, 0.4 pg for diethylmercury, and 2.0 pg for methylmercury chloride. A study of the Long Island Sound atmosphere showed Hg⁰ to account for 95–100% of the total mercury present, with the remainder being monomethylmercury.     

Protecting-group-free synthesis of a dual CCK1/CCK2 receptor antagonist

In our pursuit of an efficient, protecting-group-free synthesis of the dual CCK1/CCK2 receptor antagonist 1, we have developed chemoselective conditions for sulfonamide formation reaction in pure water and a PhNMe(2) mediated carboxamide formation, both in the presence of a carboxylic acid. Practical synthesis of an unnatural, chiral β-aryl-α-amino acid is also described.     

Anisotropic ferromagnetism in substituted zinc oxide

Room-temperature ferromagnetism is observed in (110) oriented ZnO films made from targets containing 5 at. % of Sc, Ti, V, Fe, Co, or Ni, but not Cr, Mn, or Cu ions. There are large moments, 2.6 micro(B) and 0.5 micro(B)/dopant atom for Co- and Ti-containing oxides, respectively. There is also a moment of 0.3 micro(B)/Sc. Magnetization is very anisotropic, with variations of up to a factor of 3 depending on the orientation of the applied field relative to the substrate. Results are interpreted in terms of a spin-split donor impurity-band model, which can account for ferromagnetism in insulating or conducting high-k oxides with concentrations of magnetic ions that lie far below the percolation threshold. Magnetic moments are associated with two-electron defects in the films as well as unpaired electrons of the 3d ions.     

Strength of the 18F(p,alpha)15O resonance at Ec.m. = 330 keV

Production of the radioisotope 18F in novae is severely constrained by the rate of the 18F(p,alpha)15O reaction. A resonance at E(c.m.)=330 keV may strongly enhance the 18F(p,alpha)15O reaction rate, but its strength has been very uncertain. We have determined the strength of this important resonance by measuring the 18F(p,alpha)15O cross section on and off resonance using a radioactive 18F beam at the ORNL Holifield Radioactive Ion Beam Facility. We find that its resonance strength is 1.48+/-0.46 eV, and that it dominates the 18F(p,alpha)15O reaction rate over a significant range of temperatures characteristic of ONeMg novae.     

Synthesis, spectroscopy and electronic structure of the vinylidene and alkynyl complexes [W(C=CHR)(dppe)(η-C₇H₇)](+) and [W(C≡CR)(dppe)(η-C₇H₇](n+) (n = 0 or 1)

The first examples of vinylidene complexes of the cycloheptatrienyl tungsten system [W(C=CHR)(dppe)(η-C?H?)](+) (dppe = Ph?PCH?CH?PPh?; R = H, 3; Ph, 4; C?H?-4-Me, 5) have been synthesised by reaction of [WBr(dppe)(η-C?H?)], 1, with terminal alkynes HC≡CR; a one-pot synthesis of 1 from [WBr(CO)?(η-C?H?)] facilitates its use as a precursor. The X-ray structure of 4[PF?] reveals that the vinylidene ligand substituents lie in the pseudo mirror plane of the W(dppe)(η-C?H?) auxiliary (vertical orientation) with the phenyl group located syn to the cycloheptatrienyl ring. Variable temperature 1H NMR investigations on [W(C=CH?)(dppe)(η-C?H?)][PF?], 3, estimate the energy barrier to rotation about the W=C(α) bond as 62.5 ± 2 kJ mol?1; approximately 10 kJ mol?1 greater than for the molybdenum analogue. Deprotonation of 4 and 5 with KOBu(t) yields the alkynyls [W(C≡CR)(dppe)(η-C?H?)] (R = Ph, 6; C?H?-4-Me, 7) which undergo a reversible one-electron oxidation at a glassy carbon electrode in CH?Cl? with E(?) values approximately 0.12 V negative of Mo analogues. The 17-electron radicals [6](+) and [7](+) have been investigated by spectroelectrochemical IR, UV-visible and EPR methods. The electronic structures of representative vinylidene (3) and alkynyl (6) complexes have been investigated at the B3LYP/Def2-SVP level. In both cases, electronic structure is characterised by a frontier orbital with significant metal d(z2)character and this dominates the structural and spectroscopic properties of the system.