Conformational Landscape of α-Halopropiophenones Determined by NMR Reveals Unexpected Patterns and Geometric Constraints.

The conformational features of α-halopropiophenones were investigated to understand the influence of α-halogens on conformation through hyperconjugative interactions, electrostatics, and steric factors. Using NMR, C-H scalar coupling constants were measured in different solvents, revealing a pattern in the conformational equilibria, which we validated by computational means. This behavior arises largely from hyperconjugative effects with the exception of the fluoro-derivatives, which are also influenced by steric and electrostatic interactions.

Next-Generation Tags for Fluorine Nuclear Magnetic Resonance: Designing Amplification of Chemical Shift Sensitivity.

Fluorine NMR is a highly sensitive technique for delineating the conformational states of biomolecules and has shown great utility in drug screening and in understanding protein function. Current fluorinated protein tags leverage the intrinsic chemical shift sensitivity of the F nucleus to detect subtle changes in protein conformation and topology. This chemical shift sensitivity can be amplified by embedding the fluorine or trifluoromethyl reporter within a pyridone.

Controlled Pyrazole-Hydrazone Annulation: Regiodivergent Synthesis of 1- and 2-Pyrazolo[3,4-]pyridazinones.

An efficient and controlled site-selective annulation of 3,5-diethoxycarbonyl 4-hydrazonyl pyrazoles is described. The relative proportion of the products is affected by hydrazone intermediate configuration, reaction temperature, and Lewis acid employed. At a temperature of 110-120 °C, the reaction preferentially afforded 1-pyrazolo[3,4-]pyridazin-7(6)-ones, whereas using Yb(OTf) in MeCN reflux, 2-pyrazolo[3,4-]pyridazin-7(6)-ones were favored.

Conformational Isomerism of 3-Chalcogenomethyl--Methyl-2-Pyrrolidinones: Insights from NMR Spectroscopy and Molecular Modeling.

A conformational analysis of -methyl-2-pyrrolidinone 3-substituted by methoxyl, thiomethoxyl, and selenomethoxyl is reported by means of H nuclear magnetic resonance spectroscopy and electronic structure calculations. The five-membered ring has an envelope conformation with the α-carbonyl substituent being able to assume two positions: pseudo-axial and pseudo-equatorial. In vacuum, the calculations pointed to the pseudo-axial conformer as the most stable one, and this preference increases with the size of the substituent and a decrease in its electronegativity.

Shelf-life of guavas coated with biodegradable starch and cellulose-based films.

Guava is a perishable fruit susceptible to post-harvest losses. So, the development of biodegradable films based on acetylated cassava starch (ACS) and hydroxyethyl cellulose (HEC) could be an alternative to increase guavas (Psidium guajava L.) shelf life.