Voltammetry coupled to mass spectrometry in the presence of isotope O labeled water for the prediction of oxidative transformation pathways of activated aromatic ethers: Acebutolol

The coupling between an electrochemical cell (EC) and a mass spectrometer (MS) is a useful screening tool (EC-MS) to study the oxidative transformation pathways of various electroactive species. For that purpose, we showed that the EC-MS method, carried out in the presence and absence of isotope ¹⁸O labeled water leads not only to a fast identification of oxidation products but also leads to a fast elucidation of the mechanism pathway reaction. We examined herein the case of the electrochemical hydrolysis of activated aromatic ether. Acebutolol (β-blockers) was selected herein as model of activated aromatic ether, and its electrochemical oxidation was examined in both the presence and absence of isotope ¹⁸O labeled water. To elucidate electrochemical hydrolysis pathway reaction: O-dealkylation or O-dealkoxylation, our approach was used to prove its applicability. The electrochemical oxidation mechanism was then elucidated showing an O-dealkoxylation reaction. In addition, density functional theory (DFT) calculations fully support the experimental conclusions.     

Guest Covalent Capture by a Host: A Biomimetic Strategy for the Selective Functionalization of a Cavity

A biomimetic strategy for the monofunctionalization of a calix[6]arene core is described. It is based on host–guest chemistry (mimicking the Michaelis–Menten adduct in enzymes) and allows the finely tuned pre‐organization of the substrate (an alkyne) with respect to the reactant (three azido groups introduced at the calixarene large rim). It is shown that the thermal Huisgen reaction implemented in this work proceeds under very mild conditions with total regioselectivity of the cycloaddition process. The scope of the reaction was explored and the results suggest that such a supramolecular strategy is quite versatile and could be applied to the selective functionalization of other cavitands bearing different recognition patterns. A detailed structural, thermodynamic, and kinetic study is also reported, highlighting interesting biomimetic features: The importance of the host–guest adduct strength, the high sensitivity of the reaction to the pre‐organization of the reactive partners (alkyne vs. azide), and a significant impact of the embedment on the transition state. The self‐coordination of the monofunctionalized products was also studied and an “endo/exo” switch of the internal side‐chain could be triggered by adding competitive ligands.     

Mechanistic Aspects of Gas‐Phase Hydrogen‐Atom Transfer from Methane to [CO].+ and [SiO].+: Why Do They Differ?

The reactivity of the two diatomic congeneric systems [CO]^.+ and [SiO]^.+ towards methane has been investigated by means of mass spectrometry and quantum‐chemical calculations. While [CO]^.+ gives rise to three different reaction channels, [SiO]^.+ reacts only by hydrogen‐atom transfer (HAT) from methane under thermal conditions. A theoretical analysis of the respective HAT processes reveals two distinctly different mechanistic pathways for [CO]^.+ and [SiO]^.+, and a comparison to the higher metal oxides of Group 14 emphasizes the particular role of carbon as a second‐row p element.     

Enantioselective Syntheses of the Proposed Structures of Kopeolin and Kopeolone

The first total syntheses of the proposed structures of kopeolin ( 1 ) and kopeolone ( 3 ) have been achieved from a common enantiopure chiral building block obtained by a chemoenzymatic enantioconvergent methodology. The syntheses feature two key steps: a one‐pot reduction/diastereoselective protonation followed by a highly diastereoselective addition of an organocerate. The synthetic structures were fully characterized and all stereocenters were confirmed. The results show that the two previously reported structures were not assigned correctly, and suggest an initial structural misassignment during the isolation of the natural products. Thus, two revised structures, 1′ for kopeolin and 3′ for kopeolone, are proposed.     

Longitudinal Relaxation Enhancement in 1H NMR Spectroscopy of Tissue Metabolites via Spectrally Selective Excitation

Nuclear magnetic resonance spectroscopy is governed by longitudinal (T₁) relaxation. For protein and nucleic acid experiments in solutions, it is well established that apparent T₁ values can be enhanced by selective excitation of targeted resonances. The present study explores such longitudinal relaxation enhancement (LRE) effects for molecules residing in biological tissues. The longitudinal relaxation recovery of tissue resonances positioned both down‐ and upfield of the water peak were measured by spectrally selective excitation/refocusing pulses, and compared with conventional water‐suppressed, broadband‐excited counterparts at 9.4 T. Marked LRE effects with up to threefold reductions in apparent T₁ values were observed as expected for resonances in the 6–9 ppm region; remarkably, statistically significant LRE effects were also found for several non‐exchanging metabolite resonances in the 1–4 ppm region, encompassing 30–50 % decreases in apparent T₁ values. These LRE effects suggest a novel means of increasing the sensitivity of tissue‐oriented experiments, and open new vistas to investigate the nature of interactions among metabolites, water and macromolecules at a molecular level.     

Cellulose chiral induction during the synthesis of cellulose N-phthaloyl-amino acid esters

Cellulose was acylated by N-phthaloyl amino acid chlorides in the presence of pyridine to prepare an original library of cellulose N-phthaloyl-amino acid esters as chiral solid supports for enantioselective adsorption of racemates. Cellulose esters derived from N-phthaloyl glycine, alanine, valine, leucine, phenylalanine, phenylglycine and isoleucine were isolated in high yields and with degrees of substitution approaching 3. Interestingly, the use of an optically pure (d or l) or a rac-amino acid led to the same cellulose ester according to (1) the measured optical rotation, (2) the enantiomeric excesses of the amino acids resulting from a non-racemising and total hydrolysis and (3) the enantioselective adsorptions of rac-benzoin, rac-Pirkle’s alcohol and rac-Tröger’s base. This suggests that either the formation of a prochiral ketene intermediate which was diastereoselectively attacked by the cellulose alcohols or, alternatively (or concomitantly), the occurrence of a chiral induction in the formed triesters during prolonged contact with the pyridine base in the reaction medium. Enantiomeric excesses in favour of the (S) form ranged from 8 % to 50 % depending on the N-phthaloyl amino acid. The memory of the chirality of the starting material was lost and new chirality was imprinted by the cellulose backbone on the amino acid residues.     

Where is the Oxygen? Structural Analysis of α‐Humulene Oxidation Products by the Crystalline Sponge Method

Crystal structures of α‐humulene, a cyclic sesquiterpene, and its oxidized subproducts, were analyzed by the crystalline sponge method. Regio‐ and stereochemistry, including absolute configuration when a chiral oxidant was applied, and the stable conformations of all the scaffold‐related compounds were successfully determined for samples on a 5–50 μg scale.     

Uncommon suffix tries

Common assumptions on the source producing the words inserted in a suffix trie with n leaves lead to a height and saturation level. We provide an example of a suffix trie whose height increases faster than a power of n and another one whose saturation level is negligible with respect to . Both are built from VLMC (Variable Length Markov Chain) probabilistic sources and are easily extended to families of tries having the same properties. The first example corresponds to a “logarithmic infinite comb” and enjoys a non uniform polynomial mixing. The second one corresponds to a “factorial infinite comb” for which mixing is uniform and exponential. © 2013 Wiley Periodicals, Inc. Random Struct. Alg., 46, 117–141, 2015     

Carbon‐Coated LiTi2(PO4)3: An Ideal Insertion Host for Lithium‐Ion and Sodium‐Ion Batteries

We report the extraordinary performance of carbon‐coated sodium super ion conductor (NASICON)‐type LiTi₂(PO₄)₃ as an ideal host matrix for reversible insertion of both Li and Na ions. The NASICON‐type compound was prepared by means of a Pechini‐type polymerizable complex method and was subsequently carbon coated. Several characterization techniques such as XRD, thermogravimetric analysis (TGA), field‐emission (FE) SEM, TEM, and Raman analysis were used to study the physicochemical properties. Both guest species underwent a two‐phase insertion mechanism during the charge/discharge process that was clearly evidenced from galvanostatic and cyclic voltammetric studies. Unlike that of Li (≈1.5 moles of Li), Na insertion exhibits better reversibility (≈1.59 moles of Na) while experiencing a slightly higher capacity fade (≈8 % higher than Li) and polarization (780 mV) than Li. However, excellent rate capability profiles were noted for Na insertion relative to its counterpart Li. Overall, the Na insertion properties were found to be superior relative to Li insertion, which makes carbon‐coated NASICON‐type LiTi₂(PO₄)₃ hosts attractive for the development of next‐generation batteries.     

Structure of the calcium pyrophosphate monohydrate phase (Ca2P2O7·H2O): towards understanding the dehydration process in calcium pyrophosphate hydrates

Calcium pyrophosphate hydrate (CPP, Ca₂P₂O₇·nH₂O) and calcium orthophosphate compounds (including apatite, octacalcium phosphate etc.) are among the most prevalent pathological calcifications in joints. Even though only two dihydrated forms of CPP (CPPD) have been detected in vivo (monoclinic and triclinic CPPD), investigations of other hydrated forms such as tetrahydrated or amorphous CPP are relevant to a further understanding of the physicochemistry of those phases of biological interest. The synthesis of single crystals of calcium pyrophosphate monohydrate (CPPM; Ca₂P₂O₇·H₂O) by diffusion in silica gel at ambient temperature and the structural analysis of this phase are reported in this paper. Complementarily, data from synchrotron X‐ray diffraction on a CPPM powder sample have been fitted to the crystal parameters. Finally, the relationship between the resolved structure for the CPPM phase and the structure of the tetrahydrated calcium pyrophosphate β phase (CPPT‐β) is discussed.