Inhibition of Fenton Reaction of Glucose by Alcohols and Tetrahydrofuran in Catalytic Concentrations. Calculation of the Stability Constants of ROH/Fe2+ Complexes

Background: The Fenton reaction is of growing interest due to its primary function in bodily processes and industrial waste disposal. However, the effects of alcohol on this reaction have not been addressed. Therefore, we analyze for the first time the role that catalytic concentrations of alcohols play in the Fenton reaction. Methods: The Fenton reaction was carried out by measuring oxidation-reduction potential and pH monitoring under dark conditions to avoid photochemical reactions. The reaction end point was established using the first derivative of plotting potential versus time. This point was also checked by the dichromate test for hydrogen peroxide detection. Gas-liquid chromatography was used to measure alcohol content. The Fenton reaction of glucose was performed first, and then each alcohol, including ethanol, methanol, iso-propanol, and ter-butanol, was added separately in catalytic amounts, as well as the cyclic ether tetrahydrofuran. The reaction rate constants and the stability constants of each complex formed were measured. Results : Alcohols were shown to inhibit the Fenton reaction by forming iron-alcohol complexes. An iron-tetrahydrofuran complex was also formed. The crucial oxygen role in the functional group of alcohols and ethers is supported by a reaction with tetrahydrofuran. These results also explain the difficulties in the disposal of sugar-enriched alcoholic industrial effluents. Conclusion: Our findings show that alcohols, such as ethanol, methanol, iso-propanol, and ter-butanol at catalytic concentrations, slow down the Fenton reaction due to decreased iron availability by forming iron(II)-alcohol complexes. The method is also useful for calculating stability constants for iron-alcohol and iron-tetrahydrofuran complexes, which are not otherwise easy to assess.

C(sp3)-H alkenylation promoted by uranyl cation as a visible-light photocatalyst

The alkenylation of cyclic ethers with β-nitroalkenes using uranyl cation as a photocatalyst is reported. Previous studies revealed the feasibility of incorporating organic photocatalyst in the visible light mediated alkenylation, while the uranyl cation serves as an alternative photocatalyst candidate successfully accomplish this transformation through a different pathway. The reaction features the direct hydrogen atom transfer (HAT) process to activate alpha C(sp3)-H of cyclic ether, and consequently cyclic ether is coupled with β-nitroalkene to give the target product with F-selectivity through C-C bond formation.

Photoredox Catalyzed Ring-Opening Addition Reaction Between Benzyl Bromides and Cyclic Ethers

A novel nucleophilic reaction between cyclic ethers and benzyl bromides is achieved under photoredox catalysis. The reaction proceeds through a single electron transfer (SET) pathway rather than a common SN2 mechanism. By two steps of reduction and oxidation, a benzyl bromide heterolyzes to give a carbocation and bromide ion under mild conditions, and then a cyclic ether captures both the carbocation and bromide ion to afford the addition product.

Why Is Tetrahydrofuran a Good Solvent for Calcium Batteries? Insights From Ab Initio Molecular Dynamics Simulations

Calcium batteries are rapidly emerging as a potential, future energy storage technology; however, their advancement relies heavily on understanding of the liquid electrolyte component in terms of stability and interactions with a calcium metal anode. Tetrahydrofuran, a cyclic ether, is an experimentally common and promising solvent for the preparation of stable and efficient calcium electrolytes. However, insights into the reasons why are lacking, which could unveil key principles to electrolyte design. In this report, we provide a theoretical study employing ab initio molecular dynamics (AIMD) simulations of the interactions of Ca metal with the cyclic ether tetrahydrofuran (THF). The results show that the electrochemical breakdown and decomposition of THF at the Ca surface is highly orientation- and surface-site dependent, thereby significantly reducing the likelihood of its instability in a randomly organized bulk solvent. Likewise, in bulk electrolytes, its likelihood for breakdown is further diminished, in preference for coordination Ca2+ to form solvated structure. Hence, the finding that molecules require such strict conditions for their decomposition is an important selection and design principle for any solvent to prepare suitable calcium electrolytes. These findings are critical to the advancement of the calcium batteries.

Why Is Tetrahydrofuran a Good Solvent for Calcium Batteries? Insights From Ab Initio Molecular Dynamics Simulations

Calcium batteries are rapidly emerging as a potential, future energy storage technology; however, their advancement relies heavily on understanding of the liquid electrolyte component in terms of stability and interactions with a calcium metal anode. Tetrahydrofuran, a cyclic ether, is an experimentally common and promising solvent for the preparation of stable and efficient calcium electrolytes. However, insights into the reasons why are lacking, which could unveil key principles to electrolyte design. In this report, we provide a theoretical study employing ab initio molecular dynamics (AIMD) simulations of the interactions of Ca metal with the cyclic ether tetrahydrofuran (THF). The results show that the electrochemical breakdown and decomposition of THF at the Ca surface is highly orientation- and surface-site dependent, thereby significantly reducing the likelihood of its instability in a randomly organized bulk solvent. Likewise, in bulk electrolytes, its likelihood for breakdown is further diminished, in preference for coordination Ca2+ to form solvated structure. Hence, the finding that molecules require such strict conditions for their decomposition is an important selection and design principle for any solvent to prepare suitable calcium electrolytes. These findings are critical to the advancement of the calcium batteries.

pH-Responsive Hollow Polymeric Microspheres from Irradiated Cyclic Ether Aqueous Solution

Smart hollow polymeric microspheres have been widely applied in various fields such as controlled release, drug delivery, catalysis, and so on. Herein, a facile, green and one-step template-free method is introduced for preparing pH-responsive hollow polymeric microspheres via gamma irradiation of cyclic ether aqueous solution. The hollow polymeric microspheres are synthesized by radiation-induced polymerization and following the self-assembly and self-organization of amphiphilic polymer with cyclic ethers as monomers in water. SEM, TEM, micro-FTIR, and NMR confirmed the morphology and structures of the resultant microspheres. The confocal laser scanning microscope was used to investigate the stimuli-responsiveness and release behavior of hollow microspheres using 1-pyrene carboxaldehyde as a hydrophobic molecule model. The well-defined hollow polymeric microspheres with an average diameter of ca. 2.6 μm or 1.6 μm were prepared directly from dicyclohexal-18-crown-6 or tetraphydropyrane aqueous solution, respectively. The prepared hollow microspheres exhibit obvious pH stimuli-responsiveness and can release the encapsulated hydrophobic molecules when pH is higher than 5.0. Moreover, the reversible morphology transition between hollow microspheres and micelles makes the prepared hollow polymeric microspheres potentially suitable for a wide range of applications, including removal of dyes, oil field engineering, and biomedical fields.

Watching a hydroperoxyalkyl radical (•QOOH) dissociate

A prototypical hydroperoxyalkyl radical (•QOOH) intermediate, transiently formed in the oxidation of volatile organic compounds, was directly observed through its infrared fingerprint and energy-dependent unimolecular decay to hydroxyl radical and cyclic ether products. Direct time-domain measurements of •QOOH unimolecular dissociation rates over a wide range of energies were found to be in accord with those predicted theoretically using state-of-the-art electronic structure characterizations of the transition state barrier region. Unimolecular decay was enhanced by substantial heavy-atom tunneling involving O-O elongation and C-C-O angle contraction along the reaction pathway. Master equation modeling yielded a fully a priori prediction of the pressure-dependent thermal unimolecular dissociation rates for the •QOOH intermediate—again increased by heavy-atom tunneling—which are required for global models of atmospheric and combustion chemistry.