Excited-State Proton Transfer of Fluorescein Anion as an Ionic Liquid Component

Fluorescent ionic liquids (FILs) incorporating the fluorescein anion have been prepared by anion exchange of the parent quaternary ammonium chloride (Quat⁺Cl^–) ionic liquid. By controlling the molar ratio of fluorescein to Quat⁺Cl^–, ionic liquids incorporating different prototropic forms of fluorescein were prepared. The 1:1 molar ratio ionic liquid (FIL1) is essentially composed of monoanionic fluorescein, while dianionic fluorecein is predominant in the FIL with a 1:2 molar ratio (FIL2). The fluorescence excitation spectrum of FIL2 is markedly different from its absorption spectrum. Absorption features the fluorescein dianion, while the excitation spectrum is exclusively due to the monoanion. In FIL1, the absorption and excitation spectra are both characteristic of the monoanion. In both FILs, emission of the dianion is observed upon excitation of the monoanion. This unusual behavior is interpreted in the context of a fast deprotonation of the monoanion in the excited state. The presence of residual water in the ionic liquid is important for the proton transfer process. By lowering the pH of FIL1, the transient proton transfer is inhibited, and the emission of the monoanion could be observed. The FILs have completely different spectroscopic properties from solvated fluorescein in Quat⁺Cl^–, where the prototropic equilibrium is shifted toward the neutral forms

Influence of Intracellular Membrane pH on Sphingolipid Organization and Membrane Biophysical Properties

Glucosylceramide (GlcCer) is a signaling lipid involved in the regulation of several cellular processes. It is present in different organelles, including the plasma membrane, Golgi apparatus, endoplasmic reticulum, and lysosomes. Accordingly, GlcCer is exposed to different pH environments in each organelle, which may lead to alterations in its properties and lateral organization and subsequent biological outcome. In this study, we addressed the effect of pH on the biophysical behavior of this lipid and other structurally related sphingolipids (SLs). Membranes composed of POPC (1-palmitoyl-2-oleoyl-<i>sn</i>-glycero-3-phosphocholine) and C16-GlcCer, sphingomyelin, and different acyl chain ceramides were characterized by fluorescence spectroscopy, confocal microscopy, and surface pressure–area measurements under neutral and acidic conditions. The results show that changing the pH from 7.4 to 5.5 has a larger impact on C16-GlcCer-containing membranes compared to other SLs. In addition, acidification mainly affects the organization and packing properties of the GlcCer-enriched gel phase, suggesting that the interactions established by the glucose moiety, in the GlcCer molecule, are those most affected by the increase in the acidity. These results further highlight the role of GlcCer as a modulator of membrane biophysical properties and will possibly contribute to the understanding of its biological function in different organelles

The Chemistry of Imperfections in N‑Graphene

Many propositions have been already put forth for the practical use of N-graphene in various devices, such as batteries, sensors, ultracapacitors, and next generation electronics. However, the chemistry of nitrogen imperfections in this material still remains an enigma. Here we demonstrate a method to handle N-impurities in graphene, which allows efficient conversion of pyridinic N to graphitic N and therefore precise tuning of the charge carrier concentration. By applying photoemission spectroscopy and density functional calculations, we show that the electron doping effect of graphitic N is strongly suppressed by pyridinic N. As the latter is converted into the graphitic configuration, the efficiency of doping rises up to half of electron charge per N atom