Hydrogen-Binding-Initiated Activation of O-H Bonds on a Nitrogen-Doped Surface for the Catalytic Oxidation of Biomass Hydroxyl Compounds.

Hydrogen binding of molecules on solid surfaces is an attractive interaction that can be used as the driving force for bond activation, material-directed assembly, protein protection, etc. However, the lack of a quantitative characterization method for hydrogen bonds (HBs) on surfaces seriously limits its application. We measured the standard Gibbs free energy change (ΔG ) of on-surface HBs using NMR.

Binding Energy as Driving Force for Controllable Reconstruction of Hydrogen Bonds with Molecular Scissors.

Hydrogen bonds are one of the most important directional intermolecular interactions and play key roles in chemical and biochemical systems, but there is still a lack of prediction and understanding of their control. Herein, hydrogen-binding energy () acted as a driving force for controllably reconstructing hydrogen bonds with molecular scissors. We related hydrogen-binding energies of the donor-acceptor couple () and the donor itself () and Δ based on Δ = + + .

Understanding and Measurement for the Binding Energy of Hydrogen bonds of Biomass-Derived Hydroxyl Compounds.

Experimental measurement for the binding energy of hydrogen-bonds (HBs) has long been an attractive and challenging topic in chemistry and biochemistry. In the present study, the binding energy of OH···O HBs can be determined by H NMR technique using a set of model biomass-derived hydroxyl compounds, including furfuryl alcohol, isosorbide, tetrahydrofurfuryl alcohol, and (S)-3-hydroxytetrahydrofuran. By performing concentration- and temperature-variation experiments, we put forward a modified Arrhenius-type equation, in which the compensated natural logarithm of the chemical shift (ln δ + Δ) is linearly correlated with 1/T.

Hydrogen bond distinction and activation upon catalytic etherification of hydroxyl compounds.

An excellent linear correlation between ln δ (OH chemical shift) and 1/T (temperature) is discovered for the first time for hydroxyl compounds. The derived slope (A) provides information as an index not only for distinguishing different types of H-bonds, but also for predicting their reactivities. This finding can be extended to other H-bond-containing molecules.

Catalytic selective etherification of hydroxyl groups in 5-hydroxymethylfurfural over H4SiW12O40/MCM-41 nanospheres for liquid fuel production.

5-Hydroxymethylfurfural (HMF) is an important biomass-derived building block, but production and sustainable utilization of HMF remain challenging due to reactions of the highly reactive functional groups of this compound. H(4)SiW(12)O(40)/MCM-41 nanospheres were developed that exhibit 84.1% selectivity to 5-ethoxymethylfurfural (EMF) when HMF conversion reaches 92.