Pulse Electrolysis Turns on CO2 Methanation through N-Confused Cupric Porphyrin.

Breaking the D4h symmetry in the square-planar M-N4 configuration of macrocycle molecular catalysts has witnessed enhanced electrocatalytic activity, but at the expense of electrochemical stability. Herein, we hypothesize that the lability of the active Cu-N3 motifs in the N-confused copper (II) tetraphenylporphyrin (CuNCP) could be overcome by applying pulsed potential electrolysis (PPE) during electrocatalytic carbon dioxide reduction. We find that applying PPE can indeed enhance the CH4 selectivity on CuNCP by 3 folds to reach the partial current density of 170 mA cm-2 at >60 % Faradaic efficiency (FE) in flow cell. However, combined ex situ X-ray diffraction (XRD), transmission electron microscope (TEM), and in situ X-ray absorption spectroscopy (XAS), infrared (IR), Raman, scanning electrochemical microscopy (SECM) characterizations reveal that, in a prolonged time scale, the decomplexation of CuNCP is unavoidable, and the promoted water dissociation under high anodic bias with lowered pH and enriched protons facilitates successive hydrogenation of *CO on the irreversibly reduced Cu nanoparticles, leading to the improved CH4 selectivity. As a key note, this study signifies the adaption of electrolytic protocol to the catalyst structure for tailoring local chemical environment towards efficient CO2 reduction.

Neutrophil: A New Player in Metastatic Cancers.

The interaction between cancer cells and immune cells is important for the cancer development. However, much attention has been given to T cells and macrophages. Being the most abundant leukocytes in the blood, the functions of neutrophils in cancer have been underdetermined. They have long been considered an "audience" in the development of cancer. However, emerging evidence indicate that neutrophils are a heterogeneous population with plasticity, and subpopulation of neutrophils (such as low density neutrophils, polymorphonuclear-myeloid-derived suppressor cells) are actively involved in cancer growth and metastasis. Here, we review the current understanding of the role of neutrophils in cancer development, with a specific focus on their pro-metastatic functions. We also discuss the potential and challenges of neutrophils as therapeutic targets. A better understanding the role of neutrophils in cancer will discover new mechanisms of metastasis and develop new immunotherapies by targeting neutrophils.

α-Pinene-Derived Organic Coatings on Acidic Sulfate Aerosol Impacts Secondary Organic Aerosol Formation from Isoprene in a Box Model.

Fine particulate matter (PM2.5) is known to have an adverse impact on public health and is an important climate forcer. Secondary organic aerosol (SOA) contributes up to 80% of PM2.5 worldwide and multiphase reactions are an important pathway to form SOA. Aerosol-phase state is thought to influence the reactive uptake of gas-phase precursors to aerosol particles by altering diffusion rates within particles. Current air quality models do not include the impact of diffusion-limiting organic coatings on SOA formation. This work examines how α-pinene-derived organic coatings change the predicted formation of SOA from the acid-catalyzed multiphase reactions of isoprene epoxydiols (IEPOX). A box model, with inputs provided from field measurements taken at the Look Rock (LRK) site in Great Smokey Mountains National Park during the 2013 Southern Oxidant and Aerosol Study (SOAS), was modified to incorporate the latest laboratory-based kinetic data accounting for organic coating influences. Including an organic coating influence reduced the modeled reactive uptake when relative humidity was in the 55-80% range, with predicted IEPOX-derived SOA being reduced by up to 33%. Only sensitivity cases with a large increase in Henry's Law values of an order of magnitude or more or in particle reaction rates resulted in the large statistically significant differences form base model performance. These results suggest an organic coating layer could have an impact on IEPOX-derived SOA formation and warrant consideration in regional and global scale models.