Natural radioactivity in groundwater--a review

The issue of natural radioactivity in groundwater is reviewed, with emphasis on those radioisotopes which contribute in a significant way to the overall effective dose received by members of the public due to the intake of drinking water originating from groundwater systems. The term 'natural radioactivity' is used in this context to cover all radioactivity present in the environment, including man-made (anthropogenic) radioactivity. Comprehensive discussion of radiological aspects of the presence of natural radionuclides in groundwater, including an overview of current regulations dealing with radioactivity in drinking water, is provided. The presented data indicate that thorough assessments of the committed doses resulting from the presence of natural radioactivity in groundwater are needed, particularly when such water is envisaged for regular intake by infants. They should be based on a precise determination of radioactivity concentration levels of the whole suite of radionuclides, including characterisation of their temporal variability. Equally important is a realistic assessment of water intake values for specific age groups. Only such an evaluation may provide the basis for possible remedial actions.     

Determination of antioxidant activity using oxidative damage to plasmid DNA — pursuit of solvent optimization

Oxidative stress plays a key role in the pathophysiology of many diseases. Hydroxyl radical is the oxidative species most commonly causing damage to cells. The aim of this work was to optimize the method for antioxidant activity determination on a model lipophilic geranylated flavanone, diplacone. This method uses protection of plasmid DNA from oxidation by a hydroxyl radical generated by the Fenton reaction involving oxidation of metal ions using H₂O₂ and ascorbate. The method was optimized for lipophilic compounds using several solvents and co-solvents. It was found that (2-hydroxypropyl)-β-cyclodextrin (0.1 mass % aq. sol.) is the best co-solvent for our model lipophilic compound to measure the antioxidant activity by the method presented. Other solvents, namely dimethyl sulfoxide, Cremophor EL® (0.1 mass % aq. sol.), ethanol, and methanol, were not suitable for the determination of the antioxidant activity by the method described. Tween 80 (0.1 mass % aq. sol.) and a mixture of 10 vol. % ethanol and 9 mass % bovine serum albumin (aq. sol.) significantly decreased the antioxidant activity of the model lipophilic compound and thus were not suitable for this method.     

Identification of the New Metabolite of Nebivolol Using Liquid Chromatography Coupled with High-Resolution Mass Spectrometry and Chemometrics

In this study, the phase I hepatic metabolism pathway of a cardiovascular drug nebivolol was proposed on the basis of a human liver microsomes assay with the use of LC-HR-MS coupled with the chemometric method. Six biotransformation products were found with the assistance of chemometric analysis. Five of them were identified as the previously reported products of alicyclic hydroxylation and dihydroxylation, aromatic hydroxylation, as well as alicyclic oxidation of the parent compound. Moreover, one metabolite, not reported so far, was found to be a product of N-dealkylation of nebivolol—2-amino-1-(6-fluoro-3,4-dihydro-2H-1-benzopyran-2-yl)ethan-1-ol. The novel metabolite was submitted to an in silico toxicity analysis to assess its biological properties. The applied computational methods indicated a significantly elevated risk of its mutagenic activity, compared to the parent molecule. Several metabolites of the nebivolol described in the literature were not detected in this study, indicating their non-hepatic origin.     

Nucleophilic Substitution at Heteroatoms—Identity Substitution Reactions at Phosphorus and Sulfur Centers: Do They Proceed in a Concerted (SN2) or Stepwise (A–E) Way?

The mechanisms of three selected identity substitution reactions at phosphorus and sulfur occurring with stereospecific inversion have been investigated using density functional theory (DFT). The first identity reaction between methoxyl anion and methyl ethylphenylphosphinate 1 reported in 1963 has been shown to proceed in a stepwise fashion according to the addition–elimination (A–E) mechanism involving formation of a pentacoordinate phosphorus intermediate (TBI-1). In contrast, the results of DFT studies of the identity chloride exchange reaction in (ethoxy)ethylphosphonochloridothionate 3 in acetone solution provided evidence that it proceeds synchronously according to the classical Ingold’s S_N2-P mechanism. DFT calculations of the methoxyl–methoxy exchange reaction at sulfur in methyl p-toluenesulfinate 4 catalyzed by trifluoroacetic acid in methanol revealed that it proceeds stepwise (A–E mechanism), involving the formation of the high-coordinate sulfurane intermediate. In both identity transesterification reactions, 1 and 4, the transiently formed trigonal bipyramidal intermediates with the two methoxyl groups occupying apical positions (TBI-1 and TBI-4) have higher free energy barriers for the Berry-type pseudorotation than those for direct decomposition to starting phosphinate and sulfinate ensuring stereospecific inversion of configuration at the phosphinyl and sulfinyl centers. Thus, the DFT method proved its usefulness in the distinction between both mechanisms that are often indistinguishable by kinetic measurements.     

Bounding the distance among longest paths in a connected graph

It is easy to see that in a connected graph any $2$ longest paths have a vertex in common. For $k\ge 7$, Skupień in 1966 obtained a connected graph in which some $k$ longest paths have no common vertex, but every $k?1$ longest paths have a common vertex. It is not known whether every $3$ longest paths in a connected graph have a common vertex and similarly for 4, 5, and $6$ longest path. Fujita et al. in 2015 give an upper bound on distance among $3$ longest paths in a connected graph. In this paper we give a similar upper bound on distance between $4$ longest paths and also for $k$ longest paths, in general.     

Taylor’s Modularity Conjecture and Related Problems for Idempotent Varieties

We provide a partial result on Taylor’s modularity conjecture, and several related problems. Namely, we show that the interpretability join of two idempotent varieties that are not congruence modular is not congruence modular either, and we prove an analog for idempotent varieties with a cube term. Also, similar results are proved for linear varieties and the properties of congruence modularity, having a cube term, congruence n-permutability for a fixed n, and satisfying a non-trivial congruence identity.     

Helicenophyrins: Expanded Carbaporphyrins Incorporating Aza[5]helicene and Heptacyclic S‐Shaped Aza[5]helicene Motifs

Incorporation of phenanthrene into a hexaphyrin(1.1.1.1.1.0) frame resulted in intramolecular ring fusion, thus giving rise to chiral helicenophyrins. These molecules contain helicene and porphyrin features by incorporating either an aza[5]helicene or heptacyclic S‐shaped aza[5]helicene.     

Unlocking the Hydrolytic Mechanism of GH92 α-1,2-Mannosidases: Computation Inspires the use of C-Glycosides as Michaelis Complex Mimics

The conformational changes in a sugar moiety along the hydrolytic pathway are key to understand the mechanism of glycoside hydrolases (GHs) and to design new inhibitors. The two predominant itineraries for mannosidases go via ^OS₂→B_2,5→¹S₅ and ³S₁→³H₄→¹C₄. For the CAZy family 92, the conformational itinerary was unknown. Published complexes of Bacteroides thetaiotaomicron GH92 catalyst with a S-glycoside and mannoimidazole indicate a ⁴C₁→⁴H₅/¹S₅→¹S₅ mechanism. However, as observed with the GH125 family, S-glycosides may not act always as good mimics of GH's natural substrate. Here we present a cooperative study between computations and experiments where our results predict the E₅→B_2,5/¹S₅→¹S₅ pathway for GH92 enzymes. Furthermore, we demonstrate the Michaelis complex mimicry of a new kind of C-disaccharides, whose biochemical applicability was still a chimera.