The synthesis of 2,3-dideoxy-2,3-difluoro-D-glucose and 2,3-dideoxy-3-fluoro-D-glucose is reported in respectively 5 and 6 steps from D-glucal, using a fluorination strategy.

The effect of fluorination on the conformational and hydrogen-bond (HB)-donating properties of a series of benzyl alcohols has been investigated experimentally by IR spectroscopy and theoretically with quantum chemical methods (ab initio (MP2) and DFT (MPWB1K)). It was found that o-fluorination generally resulted in an increase in the HB acidity of the hydroxyl group, whereas a decrease was observed upon o,o′-difluorination. Computational analysis showed that the conformational landscapes of the title compounds are strongly influenced by the presence of o-fluorine atoms. Intramolecular interaction descriptors based on AIM, NCI and NBO analyses reveal that, in addition to an intramolecular OH⋅⋅⋅F interaction, secondary CH⋅⋅⋅F and/or CH⋅⋅⋅O interactions also occur, contributing to the stabilisation of the various conformations, and influencing the overall HB properties of the alcohol group. The benzyl alcohol HB-donating capacity trends are properly described by an electrostatic potential based descriptor calculated at the MPWB1K/6-31+G(d,p) level of theory, provided solvation effects are taken into account for these flexible HB donors.

Rational modulations of molecular interactions are of significant importance in compound properties optimization. We have previously shown that fluorination of conformationally rigid cyclohexanols leads to attenuation of their hydrogen-bond (H-bond) donating capacity (pKAHY) when OH•••F intramolecular hydrogenbond (IMHB) interactions occur, as opposed to an increase in pKAHY due to the fluorine electronegativity. This work has now been extended to a wider range of aliphatic β-fluorohydrins with increasing degrees of conformational flexibility. We show that the -sometimes unexpected-observed differences in pKAHY between closely related diastereomers can be fully rationalized by subtle variations in populations of conformers able to engage in OH•••F IMHB, as well as by the strength of these IMHBs. We also show that the Kenny theoretical Vα(r) descriptor of H-bond acidity accurately reflects the observed variations and a calibration equation extended to fluorohydrins is proposed. This work clearly underlines the importance of the weak OH•••F IMHB in the modulation of alcohol Hbond donating capacity.

Carbohydrate-aromatic interactions are highly relevant for many biological processes.Nevertheless, experimental data in aqueous solution relating structure and energetics for sugararene stacking interactions are very scarce. Here, we evaluate how structural variations in a monosaccharide including carboxyl, N-acetyl, fluorine and methyl groups affect stacking interactions with aromatic DNA bases. We find small differences on stacking interaction among the natural carbohydrates examined. The presence of fluorine atoms within the pyranose ring slightly increases the interaction with the C-G DNA base pair. Carbohydrate hydrophobicity is the most determinant factor. However, gradual increase in hydrophobicity of the carbohydrate does not translate directly into a steady growth in stacking interaction. The energetics correlates better with the amount of apolar surface buried upon sugar stacking on top of the aromatic DNA base pair.

Assessment of levels of pesticide residues in vegetables was carried out in some villages in the Western Usambara and Uluguru Mountains of Tanzania where varieties of vegetables are grown. Tomatoes and cabbages were the most popular enterprise grown all year round and therefore were selected as the model crops for this study. Analysis of the cleaned sample extracts on a gas chromatography with electron capture detector (GC-ECD) and confirmation on the Gas chromatography-mass spectrometry (GC-MS) revealed dominance of organochlorine pesticides. Organophosphorous pesticides (parathion and marathion) were only detected in some samples, however, in most cases with higher concentrations compared to organochlorine pesticides. Levels of pesticide residues detected in vegetables were up to: parathion 5.07 μg/Kg, marathion 3.73 μg/Kg, α-endosulfan 0.32 μg/Kg, β-endosulfan 0.53 μg/Kg, dieldrin 1.36 μg/Kg, γ-HCH 0.25 μg/Kg, α-HCH 0.09 μg/Kg, and p, p'-DDT 0.64 μg/Kg. These results clearly show that vegetables are contaminated with different pesticide residues. However, the total levels of pesticide residues in both tomatoes and cabbages are lower than their respective codex alimentarius maximum residue levels (MRLs). This means that the vegetables produced in the area are suitable for human consumption.

Fluorination induces significant modulations of molecular properties. The focus herein is on quantifying its influence on the hydrogen‐bond (H‐bond) donating capacity of a vicinal OH group. Using β‐fluorohydrin probes, changes in H‐bond acidity are rationalized by subtle differences in the conformational landscape. The OH⋅⋅⋅F intramolecular H‐bonds form five‐membered rings, symbolized here by the “Anneaux de Buren” (Nantes, France), and imply a decrease of the OH H‐bond acidity in monofluorinated compounds. In contrast, di‐ and trifluorination of β‐fluorohydrins lead to a successive increase of H‐bond acidity. More information can be found in the Full Paper by J. Graton, J.‐Y. Le Questel, B. Linclau et al. on page 2811 ff.

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