The purpose of the work presented here was to evaluate the influence of solution composition and analyte characteristics on responsiveness to analysis with negative ion electrospray ionization mass spectrometry. The responses of a series of structurally diverse acidic molecules were compared in various solvents. Response was generally observed to be higher in methanol than acetonitrile and response for all analytes was poorer when water was mixed with the organic solvent. A positive correlation between negative ion ESI-MS response and log P was observed when either acetonitrile or methanol was used as the electrospray solvent. This result was expected because analytes with significant nonpolar character should be particularly responsive to ESI-MS analysis due to their higher affinity for electrospray droplet surfaces. It was also predicted that highly acidic analytes would be most responsive to analysis with negative ion ESI-MS due to their tendency to form negative ions. However, for the analytes studied here, acidity was found not to have a consistent influence on ESI-MS response. Many of the highly acidic molecules were quite polar and, consequently, were poorly responsive. Furthermore, the deprotonated molecular ion was detected for a number of molecules with very high pKa values, which would not be expected to form negative ions in the bulk solution. Ultimately, these results indicate that acidity is not a conclusive parameter for prediction of the relative magnitudes of negative ion ESI-MS response among a diverse series of analytes. Analyte polarity does; however, appear to be useful for this purpose. (J Am Soc Mass Spectrom 2005, 16, 446 -455)

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The objective of the study was to corroborate or refute the hypothesis that farmers having a high intake of organic grown commodities have a high semen quality due to their expected lower level of dietary pesticides intake. Food frequency data and semen were collected from 256 farmers (171 traditional farmers and 85 organic farmers, overall participation rate: 32%) who were selected from central registers. Each farmer delivered one semen sample before the spraying season started. The farmers were divided into three groups where the commodities from organic production contributed no (N, 0%), medium (M, 1-49%), or a high (H, 50-100%) proportion of the fruit and vegetables consumed. Farmers having a high relative intake of organically grown fruit and vegetables also had a high relative consumption of organically produced meat, milk, and bread, and differences were observed comparing the actual mean intake of single commodities, such as rice, potato, and pork meat. The current individual dietary intake of 40 pesticides was estimated using food frequencies and generalized serving size data in combination with data on pesticide concentrations in food commodities as obtained from the National Danish Food Monitoring Program. The estimated pesticide intake was significantly lower among farmers of group H, but for all three groups of farmers the average dietary intake of 40 pesticides was at or below 1% of the acceptable daily intake (ADI) except for the dithiocarbamates (max = 0.21 microg/kg day = 2.2% ADI), methidathion, (max = 0.01 microg/kg day = 1.4% ADI), and 2-phenylphenol (max = 0.21 microg/kg day = 1.1% ADI). The median sperm concentration for the three groups of farmers was not significantly different (p = 0.40, median sperm concentration was N = 62, M = 44, and H = 75 million/ml). The group of men without organic food intake had a significant lower proportion of morphologically normal spermatozoa, but in relation to 14 other semen parameters no significant differences were found between the groups. Intake of 40 individual pesticides was correlated with four semen parameters (concentration, percentage dead spermatozoa, percentage normal sperm heads, and motility [VCL]). Five significant correlations (p value 0.01) were found among the 160 comparisons in relation to percentage dead spermatozoa: azinphos-methyl, carbaryl, chlorfenson, fenitrothion, and tetradifon. For all of them a lower percentage of dead spermatozoa were found in the groups with a high dietary intake of the specific pesticide. In contrast, for all pesticides evaluated only minor differences were found between the groups when considering spermatozoa concentration, morphology, and motility. In conclusion, the estimated dietary intake of 40 pesticides did not entail a risk of impaired semen quality, but precautions should be taken when generalizing this negative result to populations with a higher dietary exposure level or an intake of other groups of pesticides.