Alkylation of inorganic oxo compounds and insights on preventing DNA damage

Metabolism of food- and tobacco-borne procarcinogens results in the exposure of DNA to toxic alkylating agents. These assaults can bring about DNA alkylation damage, mutations, and cancer. Dietary inorganic compounds such as selenium and vanadium are known to prevent cancer, possibly by reacting directly with alkylating agents, thereby preventing DNA damage. To understand potential interactions between oxo species and alkylating toxins, we reacted a series of alkylating agents with varied classes of oxo compounds (i.e., vanadates, selenate, phosphate, sulfate, acetate, nitrate, and nitrite). A new organic-soluble selenate, [(C6H5)4P]3(O3SeOCH2OSeO3)(HSeO4), was synthesized and characterized for these studies. Vanadates were found to convert ethylating agents into ethanol, whereas other anions formed esters upon alkylation. General trends show that oxo anions of the greatest charge density were the most reactive. These studies suggest that the design of new compounds for cancer prevention should incorporate reactive oxo groups with high anionic charge density.     

Comparison of four mass analyzers for determining carbosulfan and its metabolites in citrus by liquid chromatography/mass spectrometry

Four liquid chromatography/mass spectrometry (LC/MS) systems, equipped with single quadrupole, triple quadrupole (QqQ), quadrupole ion trap (QIT) and quadrupole time-of-flight (QqTOF) mass analyzers, were evaluated for the analysis of carbosulfan and its main transformation products. The comparison of quantitative aspects (sensitivity, precision and accuracy) was emphasized. Results showed that the triple quadrupole instrument reaches at least 20-fold higher sensitivity (LOD from 0.04 to 0.4 microg kg(-1)) compared to the single quadrupole (4-70 microg kg(-1)), the QIT (4-25 microg kg(-1)) and the QqTOF (4-23 microg kg(-1)) instruments. Recoveries were over 70% for all the analytes, except dibutylamine and 7-phenolcarbofuran. Repeatabilities (within-day) were slightly better by the single quadrupole (5-10%) and the QqQ (5-9%) than by the QIT (12-16%) and the QqTOF (9-16%). Both the QqTOF and QIT offer a linear dynamic range of two orders of magnitude whereas the single quadrupole and QqQ of, at least, three orders of magnitude. The method was applied to analyze carbosulfan field-treated orange samples, in which carbosulfan, carbofuran, 3-hydroxycarbofuran, and dibutylamine were found. As an example, the mean carbosulfan concentration was 20 +/- 0.6 microg kg(-1) measured by the QqQ, 22 +/- 1.2 microg kg(-1) by the single quadrupole, 25 +/- 2.8 microg kg(-1) by the QIT, and 20 +/- 1.8 microg kg(-1) by the QqTOF. Although the QqQ is more sensitive and precise, the mean values obtained by the four instruments are acceptable and comparable. The potential of each technique for the verification of the identity of residues detected in oranges is discussed using the concept of identification points.     

On the conformal systoles of four-manifolds

We extend a result of M. Katz on conformal systoles to all four-manifolds with which have odd intersection form. The same result holds for all four-manifolds with with even intersection form and which are symplectic or satisfy the so-called -conjecture.     

Green's functions for a volume source in an elastic half-space

Green's functions are derived for elastic waves generated by a volume source in a homogeneous isotropic half-space. The context is sources at shallow burial depths, for which surface (Rayleigh) and bulk waves, both longitudinal and transverse, can be generated with comparable magnitudes. Two approaches are followed. First, the Green's function is expanded with respect to eigenmodes that correspond to Rayleigh waves. While bulk waves are thus ignored, this approximation is valid on the surface far from the source, where the Rayleigh wave modes dominate. The second approach employs an angular spectrum that accounts for the bulk waves and yields a solution that may be separated into two terms. One is associated with bulk waves, the other with Rayleigh waves. The latter is proved to be identical to the Green's function obtained following the first approach. The Green's function obtained via angular spectrum decomposition is analyzed numerically in the time domain for different burial depths and distances to the receiver, and for parameters relevant to seismo-acoustic detection of land mines and other buried objects.     

Model for bubble pulsation in liquid between parallel viscoelastic layers

A model is presented for a pulsating spherical bubble positioned at a fixed location in a viscous, compressible liquid between parallel viscoelastic layers of finite thickness. The Green's function for particle displacement is found and utilized to derive an expression for the radiation load imposed on the bubble by the layers. Although the radiation load is derived for linear harmonic motion it may be incorporated into an equation for the nonlinear radial dynamics of the bubble. This expression is valid if the strain magnitudes in the viscoelastic layer remain small. Dependence of bubble pulsation on the viscoelastic and geometric parameters of the layers is demonstrated through numerical simulations.     

Reconfigurations and diffusion of trivacancy in silicon

Disappearance of the divacancy (V₂) and trivacancy (V₃) complexes upon isochronal and isothermal annealing of electron irradiated Si:O crystals has been studied by means of deep level transient spectroscopy. The annealing studies have shown that the V₂ and V₃ defects are mobile in Si at T>200 °C and in oxygen-rich material are trapped by interstitial oxygen atoms so resulting in the appearance of V₂O and V₃O defects. The activation energies for diffusion of the V₂ and V₃ centers have been determined. Density functional modeling calculations have been carried out to investigate the migration and reorientation mechanisms of V₃ in large silicon supercells. It is proposed that these comprise a sequence of transformations between V₃(D₃) and V₃(C_2v) configurations.