Identification and quantification of urinary benzo[a]pyrene and its metabolites from asphalt fume exposed mice by microflow LC coupled to hybrid quadrupole time-of-flight mass spectrometry

Prolonged, extensive exposure to asphalt fume has been associated with several adverse health effects. Inhaled polycyclic aromatic hydrocarbons (PAHs) from asphalt fume exposure have been suspected of inducing such effects. In this study, a bioanalytical method was proposed and evaluated to identify and quantify benzo[a]pyrene and its hydroxy-metabolites. This method is based on coupling a microflow liquid chromatography (LC) to a hybrid quadrupole orthogonal acceleration time-of-flight mass spectrometry (Q-TOFMS). In the experiment, thirty-two B6C3FI mice were exposed to asphalt fume in a whole body inhalation chamber for 10 days (4 h day(-1)) and twelve other mice were used as controls. The asphalt fume was generated at 180 degrees C and the concentrations in the animal exposure chamber ranged 175-182 mg m(-3). Benzo[a]pyrene and its metabolites of 3-hydroxybenzo[a]pyrene, benzo[a]pyrene-7,8-dihydrodiol(+/-), benzo[a]pyrene-7,8-dihydrodiol-9,10-epoxide(+/-), and benzo[a]pyrene-7,8,9,10-tetrahydrotetrol(+/-) in the urine of asphalt fume exposed mice were identified and found at 3.18 ng 100 mL(-1), 31.36 ng 100 mL(-1), 11.56 ng 100 mL(-1), 54.92 ng 100 mL(-1), and 45.23 ng 100 mL(-1) respectively. The results revealed that the urinary benzo[a]pyrene and its hydroxy-metabolites from exposed mice were at significantly higher levels (p < 0.001) than those from the control groups. Compared with several other technologies such as HPLC-UV and HPLC-fluorescence, the new method is more sensitive and selective, and it can also provide additional useful information on the structures of the metabolites. Hence, this method can be used to perform the assessment and to study the mechanisms of the adverse health effects. The fragmentation patterns established in this study can also be used to identify and quantify PAH metabolites in other biological fluids.     

Evaluation of the impacts of gamma radiolysis on an ALSEP process solvent

Journal of Radioanalytical and Nuclear Chemistry - Separating the minor actinide elements (americium and curium) from the fission product lanthanides is an important step in closing the nuclear...     

Novel Sulfonamide Derivatives as Inhibitors of Histone Deacetylase

Inhibition of the enzyme histone deacetylase (HDAC) is emerging as a novel approach to the treatment of cancer. A series of novel sulfonamide derivatives were synthesized and evaluated for their ability to inhibit human HDAC. Compounds were identified which are potent enzyme inhibitors, with IC₅₀ values in the low nanomolar range against enzyme obtained from HeLa cell extracts, and with antiproliferative effects in cell culture. Extensive characterization of the structure–activity relationships of this series identified key requirements for activity. These include the direction of the sulfonamide bond and substitution patterns on the central phenyl ring. The alkyl spacer between the aromatic head group and the sulfonamide functionality also influenced the HDAC inhibitory activity. One of these compounds, m 11.1 , also designated PXD101, has entered clinical trials for solid tumors and haematological malignancies.     

Synthesis of novel carboxamide- and carbohydrazide-benzimidazoles as selective butyrylcholinesterase inhibitors

Molecular Diversity - Selectively inhibiting butyrylcholinesterase (BChE) is hypothesized to help in the management of Alzheimer’s disease (AD). Several studies have determined a correlation...     

Spontaneous initiation and development of hydrogen–oxygen detonation with ozone sensitization

This work studies numerically the spontaneous initiation and sustenance of a detonation wave from a hot spot with a nonuniform initial temperature embedded within an H₂O₂ mixture with and without O₃ addition. For the case with either no or just a small amount of O₃ addition, a weak reaction wave is auto-ignited at the hot spot, accelerates and then transitions to a pulsating detonation, which propagates along the temperature gradient and quenches as it runs into the cold fresh mixture. However, with increasing O₃ addition, the possibility of sustenance of a developing detonation within the gradient is significantly enhanced as it enters the cold mixture. Furthermore, the reduced induction time by O₃ addition leads to earlier appearance of the spontaneous reaction wave and detonation formation in the cold mixture, demonstrating that quenching of the detonation is largely related to the instability property of the mixture because the shortened induction time reduces substantially the instability. It is also noted that, for 5%O₃ addition, a low-temperature flame produced by the O₃ reactions is present in front of the spontaneous reaction wave, inducing a local pressure wave, which facilitates spontaneous initiation and sustains the detonation entering the cold mixture. Moreover, O₃ addition renders the critical temperature to induce the minimum spontaneous wave speed higher than the crossover temperature, while they are very close for the case without O₃.     

A fitting formula for the falloff curves of unimolecular reactions,II: Tunneling effects

By taking into account effects of tunneling on the shape of the falloff curves of unimolecular reaction rate constants based on Troe's weak collision integral, a fitting formula for these curves is developed and then examined for several tunneling‐affected reactions. It is demonstrated that, compared to the widely used Troe's formula, the present expression not only substantially enhances the accuracy in fitting for tunneling‐affected reactions, but it is also computationally more efficient in its evaluation. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 43: 31–42, 2011