RESUMEN

The origin of the stability of bulk Nanobubbles (NBs) has been the object of scrutiny in recent years. The interplay between the surface charge on the NBs and the Laplace pressure resulting from the surface tension at the solvent-NB interface has often been evoked to explain the stability of the dispersed NBs. While the Laplace pressure is well understood in the community, the nature of the surface charge on the NBs has remained obscure. In this work, we aim to show that the solvent and the present ions can effectively polarize the NB surface by inducing a dipole moment, which in turn controls the NB stability. We show that the polarizability of the dispersed gas and the polarity of the dispersing solvent control the dipole-induced dipole interactions between the solvent and the NBs, and that, in turn, determines their stability in solution.

RESUMEN

Rapid and selective detection of biomarkers at trace levels is a highly coveted objective in the early diagnosis of cancer. Herein, we disclose the design and synthesis of a polyhedral oligomeric silsesquioxane (POSS) substituted perylene diimide. This compound is fully characterized in solution by multi nuclear NMR, as well as in gas state by ESI-MS. Surprisingly, solid-state characterization revealed an unusual cubic morphology with particle dimensions of 80-160 nm. Fluorescence studies indicate that the bulky POSS units effectively prevent perylene's aggregation caused quenching, yielding quantum yields as high as 92%. Exposing the sensor droplet-cast on quartz to anline and o-toluidine, two important biomarkers for lung cancer, results in very highly reproducible, reversible and selective fluorescence quenching responses, with LODs as low as 19 and 8 ng L-1, and linear ranges of 65-350 and 25-450 ng L-1 respectively. Mechanistic investigations point to photoinduced electron transfer (PET) as the operative pathway responsible for fluorescence quenching.

Asunto(s)

RESUMEN

With the discovery of late transition metal platforms that support clean photoreductive halogen eliminations, we now describe an indazol-3-ylidene gold trichloride complex ([7]+ ) decorated at the 4-position by a xanthylium unit. This orange complex features a low energy band in the visible part of the spectrum, assigned to the charge transfer excitation of the indazol-3-ylidene/xanthylium donor/acceptor dyad. Green-light irradiation of this complex in the presence of a chlorine trap elicits the clean photoelimination of chlorine radicals, producing the corresponding gold(I) complex. This visible-light-induced photoreduction is very efficient, reaching quantum yields close to 10 %. A neutral analog of [7]+ featuring an anthryl group rather than a xanthylium unit proved to be perfectly photostable, supporting the importance of the xanthylium-based photoredox unit present in [7]+ .

RESUMEN

Searching for a connection between the two-electron redox behavior of Group-14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o-(Ph2 P)C6 H4 )2 GeIV Cl2 ]PtII Cl2 and [(o-(Ph2 P)C6 H4 )2 ClGeIII ]PtIII Cl3 , two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o-(Ph2 P)C6 H4 )2 ClGeIII ]PtI Cl with quantum yields of 1.7 % and 3.2 % for the GeIV -PtII and GeIII -PtIII isomers, respectively. Conversion of the GeIV -PtII isomer into the platinum germyl complex is a rare example of a light-induced transition-metal/main-group-element bond-forming process. Finally, transient-absorption-spectroscopy studies carried out on the GeIII -PtIII isomer point to a ligand arene-Cl. charge-transfer complex as an intermediate.

RESUMEN

The development of catalysts for the oxygen reduction reaction is a coveted objective of relevance to energy research. This study describes a metal-free approach to catalyzing the reduction of O2 into H2O2, based on the use of redox-active carbenium species. The most active catalysts uncovered by these studies are the bifunctional dications 1,8-bis(xanthylium)-biphenylene ([3]2+) and 4,5-bis(xanthylium)-9,9-dimethylxanthene ([4]2+) which promote the reaction when in the presence of decamethylferrocene and methanesulfonic acid. Electrochemical studies carried out with [4]2+ suggest the intermediacy of an organic peroxide that, upon protonation, converts back into the starting dication while also releasing H2O2. Kinetic studies point to the second protonation event as being rate-determining.