Investigation into the structural composition of hydroalcoholic solutions as basis for the development of multiple suppression pulse sequences for NMR measurement of alcoholic beverages

An eight‐fold suppression pulse sequence was recently developed to improve sensitivity in ¹H NMR measurements of alcoholic beverages [Magn. Res. Chem. 2011 (49): 734–739]. To ensure that only one combined hydroxyl peak from water and ethanol appears in the spectrum, adjustment to a certain range of ethanol concentrations was required. To explain this observation, the structure of water–ethanol solutions was studied. Hydroalcoholic solutions showed extreme behavior at 25% vol, 46% vol, and 83% vol ethanol according to ¹H NMR experiments. Near‐infrared spectroscopy confirmed the occurrence of four significant compounds (‘individual’ ethanol and water structures as well as two water–ethanol complexes of defined composition – 1 : 1 and 1 : 3). The successful multiple suppression can be achieved for every kind of alcoholic beverage with different alcoholic strengths, when the final ethanol concentration is adjusted to a range between 25% vol and 46% vol (e.g. using dilution or pure ethanol addition). In this optimum region, an individual ethanol peak was not detected, because the ‘individual’ water structure and the 1 : 1 ethanol–water complex predominate. The nature of molecular association in ethanol–water solutions is essential to elucidate NMR method development for measurement of alcoholic beverages. The presented approach can be used to optimize other NMR suppression protocols for binary water–organic solvent mixtures, where hydrogen bonding plays a dominant role. Copyright © 2014 John Wiley & Sons, Ltd.     

A backbone based TSP heuristic for large instances

We introduce a reduction technique for large instances of the traveling salesman problem (TSP). This approach is based on the observation that tours with good quality are likely to share many edges. We exploit this observation by neglecting the less important tour space defined by the shared edges, and searching the important tour subspace in more depth. More precisely, by using a basic TSP heuristic, we obtain a set of starting tours. We call the set of edges which are contained in each of these starting tours as pseudo-backbone edges. Then we compute the maximal paths consisting only of pseudo-backbone edges, and transform the TSP instance to another one with smaller size by contracting each such path to a single edge. This reduced TSP instance can be investigated more intensively, and each tour of the reduced instance can be expanded to a tour of the original instance. Combining our reduction technique with the currently leading TSP heuristic of Helsgaun, we experimentally investigate 32 difficult VLSI instances from the well-known TSP homepage. In our experimental results we set world records for seven VLSI instances, i.e., find better tours than the best tours known so far (two of these world records have since been improved upon by Keld Helsgaun and Yuichi Nagata, respectively). For the remaining instances we find tours that are equally good or only slightly worse than the world record tours.     

Cellular Fucosylation Inhibitors Based on Fluorinated Fucose-1-phosphates**

Fucosylation of glycans impacts a myriad of physiological and pathological processes. Inhibition of fucose expression emerges as a potential therapeutic avenue for example in cancer, inflammation, and infection. In this study, we found that protected 2-fluorofucose 1-phosphate efficiently inhibits cellular fucosylation with a four to seven times higher potency than known inhibitor 2FF, independently of the anomeric stereochemistry. Nucleotide sugar analysis revealed that both the α- and β-GDP-2FF anomers are formed inside the cell. In conclusion, we developed A2FF1P and B2FF1P as potent new tools for studying the role of fucosylation in health and disease and they are potential therapeutic candidates.     

Halothiation as a Method for Oxidation of Primary Halides and Terminal Olefins to Aldehydes

The richly varied reactivity of the aldehyde group frequently imparts pivotal importance to this functionality in organic synthesis. This fact has resulted in the development of several methods for the elaboration of this structural unit from a variety of precursors.² The report delineates the feasibility of two new couplementary approaches which proceed under mild conditions and demonstrate the utility of “halothiation” as applied to the oxidation of primary halides and terminal olefins. We were led to investigate this approach as a direct consequence of our interest in the Ramberg-Bäcklund rearrangement³ where the preliminary step often involves α-chlorination of the sulfide substrate.⁴ Halothiation is defined by us as a three-step transformation involving introduction of an ArS moiety, directed α-chlorination of the resulting sulfide, and hydrolysis. In principle, of course, the ArSCH₂-unit is uniquely an aldehyde synthon and attention is therefore focused specifically on it at this time.