Abstract:Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of earth-abundant elements and are non-toxic, non-flammable, and safe for use in residential and commercial environments. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy. Main Text:The cost of photovoltaic (PV) and wind electricity has dropped so much that one of the largest barriers to getting the vast majority of our electricity from these renewable sources is their intermittency (1-3). Batteries provide a means to store electrical energy; however, traditional, enclosed batteries maintain discharge at peak power for far too short a duration to adequately regulate wind or solar power output (1, 2). In contrast, flow batteries can independently scale the power and energy components of the system by storing the electro-active species outside the battery container itself (3)(4)(5). In a flow battery, the power is generated in a device resembling a fuel cell, which contains electrodes separated by an ion-permeable membrane. Liquid solutions of redox-active species are pumped into the cell where they can be charged and discharged, before being returned to storage in an external storage tank. Scaling the amount of energy to be stored thus involves simply making larger tanks ( Fig 1A). Existing flow batteries are based on metal ions in acidic solution but there are challenges with corrosivity, hydrogen evolution, kinetics, material cost and abundance, and efficiency that thus far have prevented large-scale commercialization. The use of anthraquinones in an acidic aqueous flow battery can dramatically reduce battery costs (6, 7); however, the use of bromine in the other half of the system precludes deployment in residential communities due to toxicity concerns.We demonstrate that quinone-based flow batteries can be adapted to alkaline solutions, where hydroxylated anthraquinones are highly soluble and bromine can be replaced with the non-toxic ferricyanide ion (8, 9) -a food additive (10). Functionalization of 9,10-anthraquinone (AQ) with electron-donating groups such as OH has been shown to lower the reduction potential and expand the battery voltage (6). In alkaline solution, these OH groups are deprotonated to provide solubility and greater electron donation capability, which results in an increase in the open circuit voltage of 47% over the previously reported system. Because functionalization away from the ketone group provides molecules with the highest solubility...

Quinones are important organic oxidants in a variety of synthetic and biological contexts, and they are susceptible to activation toward electron transfer through hydrogen bonding. While this effect of hydrogen bond donors (HBDs) has been observed for Lewis basic, weakly oxidizing quinones, comparable activation is not readily achieved when more reactive and synthetically useful electron-deficient quinones are used. We have successfully employed HBD-coupled electron transfer as a strategy to activate electron-deficient quinones. A systematic investigation of HBDs has led to the discovery that certain dicationic HBDs have an exceptionally large effect on the rate and thermodynamics of electron transfer. We further demonstrate that these HBDs can be used as catalysts in a quinone-mediated model synthetic transformation.

The first example of aromatic cation-activated nucleophilic acyl substitution has been achieved. The conversion of carboxylic acids to their corresponding acid chlorides occurs rapidly in the presence of 3,3-dichlorocyclopropenes via the intermediacy of cyclopropenium carboxylate complexes. The effect of cyclopropene substituents on the rate of conversion is examined. The addition of tertiary amine base is found to dramatically accelerate reaction, and conditions were developed for the preparation of acid sensitive acid chlorides. Preparative scale peptide couplings of two N-Boc amino acids were achieved with this method.

The dirhodium tetracarboxylate-catalysed asymmetric cyclopropanation has been applied to the enantioselective syntheses of pharmaceutically relevant 1-aryl-2-heteroaryl- and 1,2-diheteroarylcyclopropane-1-carboxylates.

The coronavirus disease 2019 (COVID-19) pandemic is caused by the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), a recently emerged human coronavirus. COVID-19 vaccines have proven to be successful in protecting the vaccinated from infection, reducing the severity of disease, and deterring the transmission of infection. However, COVID-19 vaccination faces many challenges, such as the decline in vaccine-induced immunity over time, and the decrease in potency against some SARS-CoV-2 variants including the recently emerged Omicron variant, resulting in breakthrough infections. The challenges that COVID-19 vaccination is facing highlight the importance of the discovery of antivirals to serve as another means to tackle the pandemic. To date, neutralizing antibodies that block viral entry by targeting the viral spike protein make up the largest class of antivirals that has received US FDA emergency use authorization (EUA) for COVID-19 treatment. In addition to the spike protein, other key targets for the discovery of direct-acting antivirals include viral enzymes that are essential for SARS-CoV-2 replication, such as RNA-dependent RNA polymerase and proteases, as judged by US FDA approval for remdesivir, and EUA for Paxlovid (nirmatrelvir + ritonavir) for treating COVID-19 infections. This review presents an overview of the current status and future direction of antiviral drug discovery for treating SARS-CoV-2 infections, covering important antiviral targets such as the viral spike protein, non-structural protein (nsp) 3 papain-like protease, nsp5 main protease, and the nsp12/nsp7/nsp8 RNA-dependent RNA polymerase complex.