Methylation of Phenyl Rings in Ester‐Stabilized Phosphorus Ylides Vastly Enhances Their Protonophoric Activity

Methylation of Phenyl Rings in Ester-Stabilized Phosphorus Ylides Vastly Enhances Their Protonophoric Activity

An ester-stabilized triphenylphosphonium ylide precursor can carry protons across artificial and natural membranes. Methylation of aryl groups together with alkyl length shortening of this protonophore preserving its lipophilicity resulted in a 20-fold increase in the flip-flop rate constant of its cationic form. Accordingly, increased proton transport across lipid membranes and enhanced uncoupling of mitochondria were observed.


Abstract

We have recently discovered that ester-stabilized phosphorus ylides, resulting from deprotonation of a phosphonium salt such as [Ph3PCH2COOR], can transfer protons across artificial and biological membranes. To create more effective cationic protonophores, we synthesized similar phosphonium salts with one ((heptyloxycarbonylmethyl)(p-tolyl)bromide) or two ((butyloxycarbonylmethyl)(3,5-xylyl)osphonium bromide) methyl substituents in the phenyl groups. The methylation enormously augmented both protonophoric activity of the ylides on planar bilayer lipid membrane (BLM) and uncoupling of mammalian mitochondria, which correlated with strongly accelerated flip-flop of their cationic precursors across the BLM.

Recent Advances of Aminopeptidases‐Responsive Small‐Molecular Probes for Bioimaging

Aminopeptidases, enzymes with critical roles in human body, are emerging as vital biomarkers for metabolic processes and diseases. Aberrant aminopeptidase levels are often associated with diseases, particularly cancer. Small-molecule probes, such as fluorescent, fluorescent/photoacoustics, bioluminescent, and chemiluminescent probes, are essential tools in the study of aminopeptidases-related diseases. The fluorescent probes provide real-time insights into protein activities, offering high sensitivity in specific locations, and precise spatiotemporal results. Additionally, photoacoustic probes offer signals that are able to penetrate deeper tissues. Bioluminescent and chemiluminescent probes can enhance in vivo imaging abilities by reducing the background. This comprehensive review is focused on small-molecule probes that respond to four key aminopeptidases: aminopeptidase N, leucine aminopeptidase, Pyroglutamate aminopeptidase 1, and Prolyl Aminopeptidase, and their utilization in imaging tumors and afflicted regions. In this review, the design strategy of small-molecule probes, the variety of designs from previous studies, and the opportunities of future bioimaging applications are discussed, serving as a roadmap for future research, sparking innovations in aminopeptidase-responsive probe development, and enhancing our understanding of these enzymes in disease diagnostics and treatment.

Design Strategy of Metal Nanoparticle Catalysis for C–H Bond Activation Reactions

C-H bond activation reactions facilitate highly efficient molecular transformations without requiring pre-activating substrates. While the majority of reported reaction systems for C-H activation rely on metal complexes, certain reactions have demonstrated unique or superior catalysis of metal nanoparticles. This Concept article seeks to delineate recent reports that examine the novel catalysis and design strategy of supported metal nanoparticles for C-H bond activation reactions. These reactions include oxidative homocoupling of arenes, dehydrogenative alkylation of benzenes, selective H/D exchange reactions, and α,β-dehydrogenation of ketones.

CO2 Hydrogenation to Hydrocarbons over Fe‐Based Catalysts: Status and Recent Developments

To control anthropogenic CO2 emissions worldwide, it is necessary not only to align the chemical industry and energy sector with renewable resources but also to implement large-scale utilization of CO2 as a feedstock. The Fe-catalyzed CO2-modified Fischer-Tropsch Synthesis (CO2-FTS) is one of the most promising options for efficient CO2 utilization, as it can be used to synthesize desired higher hydrocarbons (C2+), including lower olefins (C2=-C4=), the main building blocks of the chemical industry, and long-chain hydrocarbons (C5+), which can be used as fuels. To optimize catalyst and process design for the purpose of developing an economically viable industrial process, the reaction mechanism and the factors controlling product selectivity need to be fully understood. This article discusses the current state-of-the-art in catalyst design and approaches for making effective progress in addressing these challenges.