An experimental and computational study on the dissociation behavior of hydroxypyridine N‐oxides in atmospheric pressure ionization mass spectrometry

A tandem mass spectrometric study of protonated isomeric hydroxypyridine N‐oxides was carried out with a hybrid quadrupole/time‐of‐flight mass spectrometer coupled with different atmospheric pressure ionization sources. The behavior observed in the collision‐induced dissociation (CID) mass spectra of the parent cations, was similar irrespective of the source employed. However, there were intrinsic differences in the intensities of the two fragments observed for each isomer. The major fragment because of elimination of a hydroxyl radical, dominated the CID spectra (in contrast with weaker water loss) at different energy thresholds. Therefore, it was possible to differentiate both isomers at collision energies above 13 eV by comparing the ratio of intensities of the major fragment relative to the precursor cation. In addition, quantum chemical calculations at the B3LYP/6‐31 + + G(d,p) level of theory were performed for the protonated isomers of hydroxypyridine N‐oxide and their radical cation products in order to gain insight into the major routes of dissociation. The results suggest that dissociation from the lowest triplet excited state of the protonated species would provide a reasonable rationalization for the difference in behavior of both isomers. Copyright © 2010 John Wiley & Sons, Ltd.     

SYNTHESIS OF METAL OXIDE PARTICLES FROM AQUEOUS MEDIA: THE HOMOGENEOUS ALKALIN1ZAT1ON METHOD

An analysis of the urea method as a way to synthesize uniform colloidal particles is presented. Various selected cases of precipitation and coprecipitation are reviewed to illustrate the inherent complexities of the method. The importance of the kinetics of urea hydrolysis is recognized. The concept of trajectory is used to rationalized the evolution of the systems upon aging. The influence of thermodynamic and kinetic factors in the definition of the nature of the precipitating solid phases is analyzed; the overriding role of the latter is stressed. The factors that influence particle morphology are also addressed.     

New way to quantify multiple steroidal compounds in wastewater by comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry

The applicability of comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry to the screening of steroidal compounds in wastewater is demonstrated. Advanced software was utilized to identify unknown compounds in complex two-dimensional chromatograms exploiting retention indices and two different mass spectral databases. Response factors calculated as a function of the individual mass spectra of six commercial standards at different concentrations were used to develop a model allowing the quantitation of all steroidal compounds identified in the sample. The model, based on partial least squares regression equations, provided good accuracy (prediction error < 16%) in the quantitation of steroidal compounds, so offering a valuable alternative to conventional quantitation methods where reference compounds are required for the verification of analytical measurements. Special attention was paid to the development of an exhaustive sample preparation method for the separate analysis of conjugated and free steroids in both water phase and suspended solid particles. The method, including the exploitation of chemometrics, was successfully applied to the determination of steroidal compounds in effluent and influent waters collected at a local wastewater treatment plant.     

On stars and links of shellable polytopal complexes

The vertex stars of shellable polytopal complexes are shown to be shellable. The link of a vertex v of a shellable polytopal complex is also shown to be shellable, provided that all facets of the star of v are simple polytopes, or (more generally) if there exists a shelling F₁,…,F_n of the star of v such that, for every 1<j?n, the intersection of F_j with the previous facets is an initial segment of a line shelling of the boundary complex of F_j.     

Effect of lectins from Diocleinae subtribe against oral Streptococci

Surface colonization is an essential step in biofilm development. The ability of oral pathogens to adhere to tooth surfaces is directly linked with the presence of specific molecules at the bacterial surface that can interact with enamel acquired pellicle ligands. In light of this, the aim of this study was to verify inhibitory and antibiofilm action of lectins from the Diocleinaesubtribe against Streptococcus mutans and Streptococcus oralis. The inhibitory action against planctonic cells was assessed using lectins from Canavaliaensi formis (ConA), Canavalia brasiliensis (ConBr), Canavalia maritima (ConM), Canavalia gladiata (CGL) and Canavalia boliviana (ConBol). ConBol, ConBr and ConM showed inhibitory activity on S. mutans growth. All lectins, except ConA, stimulated significantly the growth of S. oralis. To evaluate the effect on biofilm formation, clarified saliva was added to 96-well, flat-bottomed polystyrene plates, followed by the addition of solutions containing 100 or 200 μg/mL of the selected lectins. ConBol, ConM and ConA inhibited the S. mutans biofilms. No effects were found on S. oralis biofilms. Structure/function analysis were carried out using bioinformatics tools. The aperture and deepness of the CRD (Carbohydrate Recognition Domain) permit us to distinguish the two groups of Canavalia lectins in accordance to their actions against S. mutans and S. oralis. The results found provide a basis for encouraging the use of plant lectins as biotechnological tools in ecological control and prevention of caries disease.     

Electron interaction with nitromethane embedded in helium droplets: attachment and ionization measurements

Results of a detailed study on electron interactions with nitromethane (CH(3)NO(2)) embedded in helium nanodroplets are reported. Anionic and cationic products formed are analysed by mass spectrometry. When the doped helium droplets are irradiated with low-energy electrons of about 2 eV kinetic energy, exclusively parent cluster anions (CH(3)NO(2))(n)(-) are formed. At 8.5 eV, three anion cluster series are observed, i.e., (CH(3)NO(2))(n)(-), [(CH(3)NO(2))(n)-H](-), and (CH(3)NO(2))(n)NO(2)(-), the latter being the most abundant. The results obtained for anions are compared with previous electron attachment studies with bare nitromethane and nitromethane condensed on a surface. The cation chemistry (induced by electron ionization of the helium matrix at 70 eV and subsequent charge transfer from He(+) to the dopant cluster) is dominated by production of methylated and protonated nitromethane clusters, (CH(3)NO(2))(n)CH(3)(+) and (CH(3)NO(2))(n)H(+).     

Low-level laser therapy promotes vascular endothelial growth factor receptor-1 expression in endothelial and nonendothelial cells of mice gastrocnemius exposed to snake venom

Crotalinae snake venoms cause severe local myonecrosis and microvasculature failure at the bite site. We evaluated whether low-level laser therapy (LLLT) could accelerate angiogenesis and myoregeneration in male Swiss mice injected with Bothrops moojeni venom through immunohistochemistry of the vascular endothelial growth factor receptor-1 (VEGFR-1). Envenomed gastrocnemius was either unirradiated (V) or irradiated with HeNe (VHN, 632.8 nm) or GaAs (VGA, 904 nm, 10000 Hz). Animals sacrificed at 3 and 12 h were irradiated once (4 J cm(-2)), at 24 h (twice) and at 3, 7, 21 days (4, 8, 22 times, respectively). At 3 days, LLLT increased angiogenesis (80%:HeNe vs 40%:GaAs), decreased neutrophils and increased proliferation of regenerating cells. However, after 21 days, myoregeneration observed in the VHN group appeared delayed compared with the V group. As LLLT improved revascularization, the suggestive delay in myoregeneration could be a dose-response inhibitory effect caused by multiple irradiations in myogenesis. The immunodetection of VEGFR-1 in neutrophils, macrophages, satellite cells, fibroblasts, Schwann cells and skeletal and smooth muscle fibers (not seen in saline-controls) at only the acute stages of envenoming suggests a mediator role for VEGFR-1 in local alterations. This is the first time that VEGFR-1 expression, and its modulation by photostimulation, has been demonstrated in endothelial and nonendothelial cells of snake envenomed skeletal muscle.     

A finite element dynamical nonlinear subscale approximation for the low Mach number flow equations

In this work we propose a variational multiscale finite element approximation of thermally coupled low speed flows. The physical model is described by the low Mach number equations, which are obtained as a limit of the compressible Navier–Stokes equations in the small Mach number regime. In contrast to the commonly used Boussinesq approximation, this model permits to take volumetric deformation into account. Although the former is more general than the latter, both systems have similar mathematical structure and their numerical approximation can suffer from the same type of instabilities.