Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries

The superoxide disproportionation reaction is a key step in the chemistry of aprotic metal oxygen batteries that controls the peroxide formation upon discharge and opens the way for singlet oxygen release. Here we clarify the energy landscape of the disproportionation of superoxide in aprotic media catalyzed by group 1A cations. Our analysis is based on ab initio multireference computational methods and unveils the competition between the expected reactive path leading to peroxide and an unexpected reaction channel that involves the reduction of the alkaline ion. Both channels lead to the release of triplet and singlet O2. The existence of this reduction channel not only facilitates singlet oxygen release but leads to a reactive neutral solvated species that can onset parasitic chemistries due to their well-known reducing properties. Overall, we show that the application of moderate overpotentials makes both these channels accessible in aprotic batteries.

5-[(1,3-Dimethyl-5-oxo-2-sulfanylideneimidazolidin-4-ylidene)amino]-2-methylisoindoline-1,3-dione

The title N,N-dimethylthiohydantoin containing an N-methylated pthalimide group, C14H12N4O3S, arose from an unexpected reaction in a deep eutectic dimethylthiourea–tartaric acid solvent system. The mean planes of the ring systems are twisted at an angle of 73.84 (17)°. In the crystal, weak C—H...O hydrogen bonds connect the molecules.

Aberrant Behavior of Employees at Workplace: Conceivable Reasons, Effects and Remedies in Teachings of Qur’ān

Organizations are always concerned with the behavior of employees. The loyal and positive behavior of employees results in maximum output. It is generally observed that sometimes unwanted response from the employer nourishes the internal anger to the employee.The researchers have conclusively described that such unexpected reaction directly impacts the thinking of an individual causing anxiety and uneasiness in behavior. It gradually becomes a reason for many unwanted incidences by violation of legal and ethical policies.It also affects his interaction with his employer, colleagues, and the property at work place accordingly. Unfortunately, it cannot be denied that extensive research has been done in Psychiatry on finding numerous therapies to treat such kinds of behaviors. However, it is also evident that religion has always had strong effects on human psychology.The faith is directly connected with the will of an individual. Therefore, if an anxious employee is recommended to take guidance from the teachings of the Holy Qur’ān, it will certainly help him to overcome his psychological issues. This research is based upon the possible reasons of irregular behavior, its effects on the workplace environment, and how the teachings of the Holy Qur’ān can be used to rehabilitate affected employees.

An Unexpected Reaction of Isodehydracetic Acid with Amines in the Presence of 1-Ethyl-3-(3-dimethylaminopropyl) Carbodiimide Hydrochloride Yields a New Type of β-Enaminones

The reaction of isodehydracetic acid with amines was serendipitously found to afford β-enaminones in the presence of the coupling agent 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC). Under the optimal reaction condition, 23 examples of α-aminomethylene glutaconic anhydride were obtained at approximately 30−80% yields. This is a concise, operationally simple method to expediently synthesize a new type of β-enaminone-containing compound.

In the Mists of a Fungal Metabolite: An Unexpected Reaction of 2,4,5-Trimethoxyphenylglyoxylic Acid

The reactions of phenylglyoxylic acids during the synthesis and biological evaluation of fungal metabolites led to the discovery of hitherto unknown compounds with a p-quinone methide (p-QM) structure. The formation of these p-QMs using 13C-labelled starting materials revealed a key-step of this reaction being a retro-Friedel–Crafts alkylation.

Unexpected Reaction Pathway of the Alpha-Aminoalkyl Radical Derived from One-Electron Oxidation of S-Alkylglutathiones

Laser flash photolysis and high-resolution mass spectrometry were used to investigate the mechanism of one-electron oxidation of two S-alkylglutathiones using 3-carboxybenzophenone (3CB) as a photosensitizer. This report indicates an unexpected reaction pathway of the α-aminoalkyl radical cation (αN+) derived from the oxidation of S-alkylglutathiones. Instead of a common hydrolysis reaction of αN+ reported earlier for methionine and other sulfur-containing aminoacids and peptides, an intramolecular ring-closure reaction was found for S-alkylglutathiones.

Radical rearrangement and transfer reactions in proteins

Radical rearrangement and transfer reactions play an important role in the chemical modifications of proteins in vivo and in vitro. These reactions depend on protein sequence, as well as structure and dynamics. Frequently, these reactions have well-defined precedents in the organic chemistry literature, but their occurrence in proteins provides a stage for a number of novel and, perhaps, unexpected reaction products. This essay will provide an overview over a few representative examples of radical rearrangement and transfer reactions.