Decarboxylation efficiency of carboxylic acids as ligands of metal oxide nanocluster resists upon γ-ray irradiation

Metal oxide nanocluster resists have recently attracted considerable attention for use in extreme ultraviolet (EUV) lithography. To obtain sophisticated guidelines for material design, it is necessary to understand well the radiation-induced chemical reaction scheme including the insolubilization mechanism. In this study, the production of CO2, which is considered to be one of the end products of treatment with an ionizing radiation, was investigated for eight types of carboxylic acid under various conditions using -rays (60Co) as a radiation source. The amount of CO2 produced was measured by gas chromatography (GC). GCO2 (/100 eV), which indicates decarboxylation efficiency, was evaluated. CO2 was generated through electron addition, hole transfer, and hydroxyl radical addition to the molecular and ionic forms of carboxylic acids. The dependences of GCO2 on reaction partners were clarified. The dependences of GCO2 on the molecular structure and dissociative state of carboxylic acids were also clarified.

Fourier Transform Infrared Spectroscopy and Vibrational Circular Dichroism Assisted Elucidation of the Solution-State Supramolecular Speciation in Racemic and Enantiopure Ketoprofen

The molecular structure and solution-state molecular interactions in the popular non-steroidal anti-inflammatory drug, ketoprofen, are extensively studied with the aim of gaining a better understanding of the chemical behavior of its solution state and its connection to its nucleation pathway and crystallization outcome. Using as reference solid-state X-ray structures of enantiomeric and racemic forms of ketoprofen, a set of self-assembly models underpinned by density functional theory calculations has been considered for the analysis of spectroscopic data, infrared (IR) and vibrational circular dichroism (VCD), obtained for solutions of the samples as a function of composition and solvent. From our results it can be concluded that, contrary to the general belief for generic carboxylic acids, there are no cyclic dimeric structures of ketoprofen present in solution, but rather linear arrays made up of two (in high polar or diluted media) or more units (in low polar or low dilution media). This observation is in line with the idea that the weak contacts (other than H-bonding) would hold the key to molecular self-assembly, in agreement with recent studies on other aromatic carboxylic acids.

Differential mosquito attraction to humans is associated with skin-derived carboxylic acid levels

Female Aedes aegypti mosquitoes feed on human blood, which they use to develop their eggs. It has been widely noted that some people are more attractive to mosquitoes than others, but the mechanistic basis of this phenomenon is poorly understood. Here we tested mosquito attraction to skin odor collected from human subjects and identified people who are exceptionally attractive or unattractive to mosquitoes. Notably, these preferences were stable over several years, indicating consistent longitudinal differences in skin odor between subjects. We carried out gas chromatography/quadrupole time of flight-mass spectrometry to analyze the chemical composition of human skin odor in these subjects and discovered that highly attractive people produce significantly increased levels of carboxylic acids. Consistent with the hypothesis that odor concentration is a major driver of differential attraction, mosquitoes could reliably distinguish a highly attractive human from their weakly attractive counterparts unless we substantially diluted the odor of the most attractive subject. Our work suggests that an increased abundance of mosquito attractants on the preferred subject explains differential attraction, rather than the non-preferred skin odor blend being repellent. Mosquitoes detect carboxylic acids with a large family of odor-gated ion channels encoded by the Ionotropic Receptor gene superfamily. Mutant mosquitoes lacking any of the Ionotropic Receptor (IR) co-receptors Ir8a, Ir25a, and Ir76b, were severely impaired in attraction to human scent but retained the ability to differentiate highly and weakly attractive people. The link between elevated carboxylic acids in mosquito-magnet human skin odor and phenotypes of genetic mutations in carboxylic acid receptors suggests that such compounds contribute to differential mosquito attraction. Understanding why some humans are more attractive than others will provide insights into what skin odorants are most important to the mosquito and could inform the development of more effective repellents.

Pyrylium Salts Acting as Both Energy Transfer and Electron Transfer Photocatalysts for E→Z Isomerization of Activated Alkenes and Cyclization of Cinnamic or Biaryl Carboxylic Acids

2,4,6-Triarylpyrylium salts are stable, easily available and cheap. However, only their elec-tron transfer oxidation ability was explored. We herein report that they could perform both energy transfer and electron transfer...