Chelated fluoroboron cations : synthesis and multinuclear nmr studies

The preparation of chelated difluoroboron cations (DD)BF2+, where DD is a saturated polydentate tertiary-amine or polydentate aromatic ligand, has been systematically studied by using multinuclear solution and solid state nuclear magnetic resonance spectroscopy and fast atom bombardment mass spectrometry. Three new methods of synthesis of (DD)BF2+ cations are reported, and compared with the previous method of reacting a chelating donor with Et20.BF3. The methods most effective for aromatic donors such as 1,1O-phenanthroline are ineffective for saturated polydentate tertiary-amines like N,N,N' ,Nil ,Nil-pentamethyldiethylenetriamine. Polydentate tertiary-amine donors that form 5-membered rings upon bidentate chelation were found to chelate effectively when the BF2 source contained two leaving groups (a heavy halide and a Lewis base such as pyridine =pyr or isoxazole =ISOX), i.e., pyr.BF2X (X = CI or Br), ISOX.BF2X and (pyr)2BF2+. Those that would form 6membered rings upon chelation do not chelate by any of the four methods. Polydentate aromatic ligands chelate effectively when the BF2 source contained a weak Lewis base, e.g., ISOX.BF3, ISOX.BF2X and Et20.BF3. Bidentate chelation by polydentate tertiaryamine and aromatic donors leads to nmr parameters that are significantly different then their (D)2BF2+ relatives (D =monod~ntate t-amines or pyridines). The chelated haloboron cations (DD)BFCI+, and (DD)BFBr+ were generated from D.BFX2 adducts for all ligands that form BF2+ cations above. In addition, the (DD)BCI2+ and (DD)BBr2+ cations were formed from D.BX3 adducts by the chelating aromatic ligands, except for the aromatic ligand 1,8-bis(dimethylamino)naphthalene, which formed only the (DD)BF2+ cation, apparently due to its extreme steric hindrance. Chelation by a donor is a two-step reaction. For polydentate tertiary-amine ligands, the two rates appear to be very dependent on the two possible leaving groups on the central boron atom. The order of increasing ease of displacement for the donors was: pyr < Cl < Br < ISOX. The rate of chelation by polydentate aromatic ligands appears to be dependent on the displacement of the first ligand from the boron. The order of increasing ease of displacement for the donors was: pyr < CI < ISOX ~ Br < Et20.

Soil-Transmitted Helminth Infections and Nutritional Status in School-age Children from Rural Communities in Honduras

Background: Soil-transmitted helminth (STH) infections are endemic in Honduras and efforts are underway to decrease their transmission. However, current evidence is lacking in regards to their prevalence, intensity and their impact on children’s health. Objectives: To evaluate the prevalence and intensity of STH infections and their association with nutritional status in a sample of Honduran children. Methodology: A cross-sectional study was done among school-age children residing in rural communities in Honduras, in 2011. Demographic data was obtained, hemoglobin and protein concentrations were determined in blood samples and STH infections investigated in single-stool samples by Kato-Katz. Anthropometric measurements were taken to calculate heightfor- age (HAZ), BMI-for-age (BAZ) and weight-for-age (WAZ) to determine stunting, thinness and underweight, respectively. Results: Among 320 children studied (48% girls, aged 7–14 years, mean 9.7661.4) an overall STH prevalence of 72.5% was found. Children .10 years of age were generally more infected than 7–10 year-olds (p = 0.015). Prevalence was 30%, 67% and 16% for Ascaris, Trichuris and hookworms, respectively. Moderate-to-heavy infections as well as polyparasitism were common among the infected children (36% and 44%, respectively). Polyparasitism was four times more likely to occur in children attending schools with absent or annual deworming schedules than in pupils attending schools deworming twice a year (p,0.001). Stunting was observed in 5.6% of children and it was associated with increasing age. Also, 2.2% of studied children were thin, 1.3% underweight and 2.2% had anemia. Moderate-to-heavy infections and polyparasitism were significantly associated with decreased values in WAZ and marginally associated with decreased values in HAZ. Conclusions: STH infections remain a public health concern in Honduras and despite current efforts were highly prevalent in the studied community. The role of multiparasite STH infections in undermining children’s nutritional status warrants more research.

Geochemistry and mineralogical association of heavy metal contaminants in fine grained sediment, Welland River, Southern Ontario /

This investigation of geochemistry and mineralogy of heavy metals in fine grained (<63^m) sediment of the Welland River was imdertaken to: 1) describe metal dispersion patterns relative to a source, identify minerals forming and existing at the outfall region and relate sediment particle size to chemistry; 2) to delineate sample handling, preparation and evaluate, modify and develop analytical methods for heavy metal analysis of complex environmental samples. Ajoint project between Brock University and Geoscience Laboratories was initiated to test a contaminated site of the Welland River at the base of Atlas Speciality Steels Co. Methods were developed and utilized for particle size separation and two acid extraction techniques: 1) Partial extraction; 2) Total extraction. The mineralogical assessment identified calcite, dolomite, quartz and clays. These minerals are typical of the carbonate-shale rock basement of the Niagara Peninsula. Minerals such as, mullite and ferrocolumbite were found at the outfall region. These are not typical of the local geology and are generally associated with industrial pollutants. Partial and total extraction techniques were used to characterize the sediments based on chemical distribution, elemental behaviour and analytical differences. The majority of elements were lower in concentration in the partial extraction technique; suggesting these elements are bound in an acid extractable phase (exchangeable, organic and carbonate phases). The total extraction technique yielded higher elemental concentrations taking difficult oxides and silicates into solution. Geochemical analyses of grain size separates revealed that heavy metal (Co, Ni, V, Mn, Fe, Ba) concentrations did not increase with decreasing grain size. This is a function of the anthropogenic mill scale input into the river. The background elements (Sc, Y, Sr, Mg, Al and Ti) showed an increase in concentration to the finest grain size suggesting that it is directly related to the local mineralogy and geology. Dispersion patterns ofmetals fall into two distinct categories: 1) the heavy metals (Co, Cu, Ni, Zn, V and Cr), and 2) the background elements (Be, Sc, Y, Sr, Al and Ti). The heavy metals show a marked increase in the outfall region, while the background elements show a significant decrease at the outfall. This pattern is attributed to a "dilution effect" ofthe natural sediments by the anthropogenic mill scale sediments. Multivariant statistical analysis and correlation coefficient matrix results clearly support these results and conclusions. These results indicate the outfall region ofthe Welland River is highly contaminated with to heavy metals from the industrialized area of Welland. A short distance downstream, the metal concentrations return to baseline geochemical levels. It appears, contaminants rapidly come out of suspension and are deposited in close proximity to the source. Therefore, it is likely that dredging the sediment from the river may cause resuspension of contaminated sediments, but may not distribute the sediment as far as initially anticipated.

Sample preparation and heavy metal determination by atomic spectrometry /

Microwave digestions of mercury in Standards Reference Material (SRM) coal samples with nitric acid and hydrogen peroxide in quartz vessels were compared with Teflon® vessel digestion by using flow injection cold vapor atomic absorption spectrometry. Teflon® vessels gave poor reproducibiUty and tended to deliver high values, while the digestion results from quartz vessel show good agreement with certificate values and better standard deviations. Trace level elements (Ag, Ba, Cd, Cr, Co, Cu, Fe, Mg, Mn, Mo, Pb, Sn, Ti, V and Zn) in used oil and residual oil samples were determined by inductively coupled plasma-optical emission spectrometry. Different microwave digestion programs were developed for each sample and most of the results are in good agreement with certified values. The disagreement with values for Ag was due to the precipitation of Ag in sample; while Sn, V and Zn values had good recoveries from the spike test, which suggests that these certified values might need to be reconsidered. Gold, silver, copper, cadmium, cobalt, nickel and zinc were determined by continuous hydride generation inductively coupled plasma-optical emission spectrometry. The performance of two sample introduction systems: MSIS™ and gas-liquid separator were compared. Under the respective optimum conditions, MSIS^"^ showed better sensitivity and lower detection limits for Ag, Cd, Cu, Co and similar values for Au, Ni and Zn to those for the gas-liquid separator.

Socio-demographic factors, smoking, symptoms, morbidities and pulmonary function and quality of life in individuals with a heavy smoking history

Objective: To determine which socio-demographic, exposure, morbidity and symptom variables are associated with health-related quality of life among former and current heavy smokers. Methods: Cross sectional data from 2537 participants were studied. All participants were at ≥2% risk of developing lung cancer within 6 years. Linear and logistic regression models utilizing a multivariable fractional polynomial selection process identified variables associated with health-related quality of life, measured by the EQ-5D. Results: Upstream and downstream associations between smoking cessation and higher health-related quality of life were evident. Significant upstream associations, such as education level and current working status and were explained by the addition of morbidities and symptoms to regression models. Having arthritis, decreased forced expiratory volume in one second, fatigue, poor appetite or dyspnea were most highly and commonly associated with decreased HRQoL. Discussion: Upstream factors such as educational attainment, employment status and smoking cessation should be targeted to prevent decreased health-related quality of life. Practitioners should focus treatment on downstream factors, especially symptoms, to improve health-related quality of life.