Solvent-Activated Hafnium-Containing Zeolites Enable Selective and Continuous Glucose–Fructose Isomerisation

The isomerisation of glucose to fructose is a critical step towards manufacturing petroleum-free chemicals from lignocellulosic biomass. Herein we show that Hf-containing zeolites are unique catalysts for this reaction, enabling true thermodynamic equilibrium to be achieved in a single step during intensified continuous operation, which no chemical or biological catalyst has yet been able to achieve. Unprecedented single-pass yields of 58 % are observed at a fructose selectivity of 94 %, and continuous operation for over 100 hours is demonstrated. The unexpected performance of the catalyst is realised following a period of activation within the reactor, during which time interaction with the solvent generates a state of activity that is absent in the synthesised catalyst. Mechanistic studies by X-ray absorption spectroscopy, chemisorption FTIR, operando UV/Vis and ¹H–¹³C HSQC NMR spectroscopy indicate that activity arises from isolated Hf^IV atoms with monofunctional acidic properties.     

A Stereoconvergent Tsuji–Trost Reaction in the Synthesis of Cyclohexenyl Nucleosides

A highly regio- and stereoselective route to d - and l -cyclohexenyl nucleosides has been devised, using the Tsuji–Trost reaction as the key step. Contrarily to the widely accepted mechanism (involving a net retention of configuration), the reaction proceeded in a highly stereoconvergent manner, providing cis nucleosides regardless of the relative configuration of the starting materials. DFT calculations confirmed the experimental data while suggesting the origin of the stereochemical reaction outcome.     

Molecular Engineering of Metal Alkoxides for Solution Phase Synthesis of High-Tech Metal Oxide Nanomaterials

The ‘bottom-up’ synthesis of inorganic nanomaterials with precision at the atomic/molecular level offers many opportunities for the design and improvement of the nanomaterials for various applications. Molecular engineering during soft chemical processing for the synthesis of functional nanomaterials enables the desired chemical and physical properties of the precursors, such as solubility or volatility, clean decomposition, control of stoichiometry for multimetallic species to name a few, and leads to easy control of uniform particle size distribution, stoichiometry…. This Minireview illustrates some important aspects of the molecular engineering in light of some recent developments from the molecular synthesis of nanomaterials involving non-silicon metal alkoxide systems for high-tech applications.     

Free and forced linear dynamics of a homogeneous model for beam-like structures

A homogeneous shear beam model is used here to address the free and forced dynamic behavior of a multi-story building. After a brief recall of the model, which is taken from the literature, and the hypotheses on which it is grounded, discussion on the free dynamics is carried out, highlighting the intriguing organization of the natural frequencies and modes in triplets, as functions of the wave-number. Then, the properties of the undamped and proportionally damped forced response to external loads is evaluated, and a discussion on the effects of the tip mass related to the top story is addressed. A case-study is analyzed to show the reliability of the homogeneous model, after comparing the outcomes with those provided by F.E.M. procedures applied to the corresponding multi-d.o.f. structure.

     

The multi-stage dynamic stochastic decision process with unknown distribution of the random utilities

We consider a decision maker who performs a stochastic decision process over a multiple number of stages, where the choice alternatives are characterized b     

Two Faces of the Same Coin: Coupling X-Ray Absorption and NMR Spectroscopies to Investigate the Exchange Reaction Between Prototypical Cu Coordination Complexes

The satisfactory rationalization of complex reactive pathways in solution chemistry may greatly benefit from the combined use of advanced experimental and theoretical complementary methods of analysis. In this work, we combine X-Ray Absorption and ¹H NMR spectroscopies with state-of-the-art Multivariate Curve Resolution and theoretical analyses to gain a comprehensive view on a prototypical reaction involving the variation of the oxidation state and local structure environment of a selected metal ion coordinated by organic ligands. Specifically, we investigate the 2-cyano-2-phenylpropanoic acid reduction of the octahedral complex established by the Cu²⁺ ion with terpyridine to the tetrahedral complex formed by Cu⁺ and neocuproine. Through our interdisciplinary approach we gain insights into the nature, concentration time evolution and structures of the key metal (XAS measurements) and organic (¹H NMR measurements) species under reaction. We believe our method may prove to be useful in the toolbox necessary to understand the mechanisms of reactive processes of interest in solution.     

Dissipative Dynamic Covalent Chemistry (DDCvC) Based on the Transimination Reaction

This work reports that the composition of a dynamic library (DL) of interconverting imines can be controlled over time in a dissipative fashion by the addition of an activated carboxylic acid used as a chemical fuel. When the fuel is added to the DL, which is initially under thermodynamic equilibrium, the composition of the mixture dramatically changes and a new, dissipative (out of equilibrium) state is reached that persists until fuel exhaustion. Thus, a transient dissipative dynamic library (DDL) is generated that, eventually, reverts back to the initial DL when the fuel is consumed, closing a DL→DDL→DL cycle. The larger the amount of added fuel, the longer the time spent by the system in the DDL state. The transimination reaction is shown to be an optimal candidate for the realization of a dissipative dynamic covalent chemistry (DDCvC).