A novel cacalolide from Psacalium decompositum

A new cacalolide sesquiterpenoid, named as Romo-A, was isolated from the roots of Psacalium decompositum, Asteraceae, a Mexican medicinal shrub with antidiabetic properties. Its structure was elucidated by NMR, MS, IR, UV, and confirmed by X-ray diffraction studies.     

Novel acid-catalyzed rearrangement of tetrahydro-1,2,3,4-tetrazines: unexpected formation of glycosazones

The present contribution discloses a simple and unexpected acid-catalyzed cleavage of tetrahydrotetrazines leading to 1,2-bis(hydrazones). Incorporation of a chiral fragment derived from carbohydrates enables the rapid preparation of glycosazones, a family of compounds employed by Emil Fischer to elucidate the configuration of sugars. In addition, a mechanistic proposal accounts for experimental observations.     

Conformational selection of glycomimetics at enzyme catalytic sites: experimental demonstration of the binding of distinct high-energy distorted conformations of C-, S-, and O-glycosides by E. Coli beta-galactosidases

We show that the conformational features of the molecular complexes of E. coli beta-galactosidase and O-glycosides may differ from those formed with closely related compounds in their chemical nature, such as C- and S-glycosyl analogues. In the particular case presented here, NMR and ab initio quantum mechanical results show that the 3D-shapes of the ligand/inhibitor within the enzyme binding site depend on the chemical nature of the compounds. In fact, they depend on the relative size of the stereoelectronic barriers for chair deformation or for rotation around Phi glycosidic linkage.     

Conformational differences between O- and C-glycosides: the alpha-O-man-(1-->1)-beta-Gal/alpha-C-Man-(1-->1)-beta-Gal case--a decisive demonstration of the importance of the exo-anomeric effect on the conformation of glycosides

The conformational behavior of alpha-O-Man-(1-->1)-beta-Gal (1) and its C-analogue (2) has been studied using J/NOE NMR data, molecular mechanics, molecular dynamics, and ab initio calculations. The population distribution around the glycosidic linkages of 1 and 2 is rather different, especially for the alpha-Man linkage. A lower limit for the exo-anomeric effect in water has been experimentally determined.     

Isotope exchange and separation factor of238U/235U for the system U(III)/U(IV) in aqueous/organic phases

A study of the isotope exchange reaction U(III)_org/U(IV)_aq in the extraction system: 7M HCl — tributyl phosphate (TBP) — toluene has been performed. For 20 s of contact the results show a separation factor²³⁵U/²³⁸U of 1.014. This large separation factor is explained by the oxidation reaction of²³⁵U(III) and²³⁸U(III).     

13C direct detected experiments: optimization for paramagnetic signals

To optimize 13C direct detected experiments for the observation of signals close to a paramagnetic center, we have assessed the sensitivity of different sequences based on CO-Cali coherence transfer. Features of CACO experiments were tested for Calbindin D9k, in which one of the two native Ca2+ ions is replaced by the paramagnetic Ce3+ ion. We have studied the comparison of single vs multiple quantum coherence transfer evolution as well as the influence of in-phase vs anti-phase detection of 13CO signals and finally the comparison of a coherence transfer step based on a CyO in plane with respect to a Cy ali in plane. The acquisition of the anti-phase component of the signal, accomplished by the removal of the last refocusing steps, allowed the identification of some signals unobserved with other pathways. The structural dependency of paramagnetism-induced nuclear relaxation is such that the identification of the most suitable coherence transfer pathway is not known "a priori" but it is driven by the relative proximity of Cali and CO to the paramagnetic center.