Building on these stoichiometric studies, the frustrated Lewis pair (FLP) reactivity observed for the GaR3/ItBu combination with HBPin could then be upgraded to catalytic regimes, allowing the efficient hydroboration of a range of aldehydes and ketones under mild reaction conditions. Mechanistic insights into the possible reaction pathway involved in this process have been gained by combining kinetic investigations with a comparative study of the catalytic capabilities of several gallium and borenium species related to 2. Disclosing a new cooperative partnership, reactions are proposed to occur via the formation of a highly reactive monomeric hydride gallate, [ItBu-BPin+GaR3(H)-] (I). Each anionic and cationic component of I plays a key role for success of the hydroboration, with the nucleophilic monomeric gallate anion favoring the transfer of its hydride to the C═O bond of the organic substate, which in turn is activated by coordination to the borenium cation.Measuring and monitoring the electrical signals transmitted between neurons is key to understanding the communication between neurons that underlies human perception, information processing, and decision-making. While electrode-based electrophysiology has been the gold standard, optical electrophysiology has opened up a new area in the past decade. Voltage-dependent fluorescent reporters enable voltage imaging with high spatial resolution and flexibility to choose recording locations. However, they exhibit photobleaching as well as phototoxicity and may perturb the physiology of the cell. Label-free optical electrophysiology seeks to overcome these hurdles by detecting electrical activities optically, without the incorporation of exogenous fluorophores in cells.  https://www.selleckchem.com/products/amg510.html  For example, electrochromic optical recording detects neuroelectrical signals via a voltage-dependent color change of extracellular materials, and interferometric optical recording monitors membrane deformations that accompany electrical activities. Label-free optical electrophysiology, however, is in an early stage, and often has limited sensitivity and temporal resolution. In this Perspective, we review the recent progress to overcome these hurdles. We hope this Perspective will inspire developments of label-free optical electrophysiology techniques with high recording sensitivity and temporal resolution in the near future.Methylmalonic acidemia is a rare metabolic disorder caused by the deficient activity of l-methylmalonyl-CoA mutase or its cofactor 5-deoxyadenosylcobalamin and is characterized by accumulation of methylmalonic acid (MMA) and alternative metabolites. The brain is one of the most affected tissues and neurologic symptoms, characterized by seizures, mental retardation, psychomotor abnormalities, and coma, commonly appear in newborns. The molecular mechanisms of neuropathogenesis in methylmalonic acidemia are still poorly understood, specifically regarding the impairments in neuronal development, maturation, and differentiation. In this study, we investigated the effects of MMA in both undifferentiated and differentiated phenotypes of SH-SY5Y human neuroblastoma cells. We observed an increase in glucose consumption and reduction in respiratory parameters of both undifferentiated and differentiated cells after exposition to MMA, suggesting that differentiated cells are slightly more prone to perturbations in respiratory parameters by MMA than undifferentiated cells. Next, we performed qPCR of mature neuronal-specific gene markers and measured mitochondrial functioning to evaluate the role of MMA during differentiation. Our results showed that MMA impairs the respiratory parameters only at the late stage of differentiation and downregulates the transcriptional gene profile of mature neuronal markers neuron-specific enolase (ENO2) and synaptophysin (SYP). Altogether, our findings point out important changes observed during neuronal maturation and energetic stress vulnerability that can play a role in the neurological clinical symptoms at the newborn period and reveal important molecular mechanisms that could help the screening of targets to new approaches in the therapies of this disease.The reaction mechanism and the origin of the selectivity for the photocatalytic intermolecular anti-Markovnikov hydroamination of unactivated alkenes with primary amines to furnish secondary amines have been revealed by time-resolved laser kinetics measurements of the key reaction intermediates. We show that back-electron transfer (BET) between the photogenerated aminium radical cation (ARC) and reduced photocatalyst complex (Ir(II)) is nearly absent due to rapid deprotonation of the ARC on the sub-100 ns time scale. The selectivity for primary amine alkylation is derived from the faster addition of the primary ARCs (as compared to secondary ARCs) to alkenes. The turnover of the photocatalyst occurs via the reaction between Ir(II) and a thiyl radical; the in situ formation of an off-cycle disulfide from thiyl radicals suppresses this turnover, diminishing the efficiency of the reaction. With these detailed mechanistic insights, the turnover of the photocatalyst has been optimized, resulting in a >10-fold improvement in the quantum yield. These improvements enabled the development of a scalable flow protocol, demonstrating a potential strategy for practical applications with improved energy efficiency and cost-effectiveness.Most of the cadmium (Cd) accumulated in rice grains is derived from its remobilization in soils during the grain filling period when paddy water is drained. The factors affecting Cd remobilization upon drainage remain poorly understood. Here, we show that the free radical effect produced from the oxidation of ferrous sulfides is an important mechanism affecting the oxidative remobilization of Cd during soil drainage. When soils were flooded, microbial sulfate reduction results in the formation of various metal sulfides including CdS and FeS. Upon soil drainage, the oxidation of FeS produced considerable amounts of hydroxyl free radicals (OH•), which could oxidize CdS directly and thereby promote the oxidative dissolution of CdS and increase Cd mobilization in soils. FeS and CdS could also form a within-sulfide voltaic cell, with FeS protecting the oxidative dissolution of CdS due to the lower electrochemical potential of the former. However, this voltaic effect was short-lived and was surpassed by the free radical effect.