On-Surface Alcohol Oxidation Monitored by Paper Spray Mass Spectrometry: The Role of Ruthenium as Catalyst.

Paper spray ionization mass spectrometry (PS-MS) is employed herein as a convenient platform to investigate an on-surface catalytic process, that is, the oxidation of alcohols induced by ruthenium salts. The tag-charged benzyl alcohol 1 (m/z 166), used as a suitable prototype starting substrate, is quickly oxidized by tert-butyl hydroperoxide (TBHP) in an on-surface process catalyzed by ruthenium trichloride (RuCl3). The PS(+)-MS revealed the formation of products from the oxidation of alcohol 1. RuCl3 and TBHP played a crucial role in this process since when salts of other metals (platinum, palladium, and iron) and another oxidizing agent (hydrogen peroxide) are employed, no reaction is observed. Moreover, UV radiation and heating accelerate the on-surface alcohol 1 oxidation. Finally, an exciting possibility is to employ PS-MS to investigate similar organic catalytic reactions to accelerate them and detect unstable intermediates, indiscernible in the condensed phase.

Organocatalysis in the three-component Povarov reaction and investigation by mass spectrometry.

A diastereoselective three-component cascade reaction, catalyzed by p-sulfonic acid calix[4]arene, provides a unique method to access diverse julolidine derivatives in high yields. Additionally, the reaction was also monitored by mass spectrometry and the mechanistic pathway uncovered.

Calixarenes as new platforms for drug design.

Calixarenes, macrocyclic compounds of phenolic units linked by methylene groups at the 2,6-positions, present some of the requirements to serve as platforms for the design and synthesis of biological active compounds. They are also interesting host molecules for chemical biology study purposes. Their basic molecular scaffold has potential ability for molecule recognition; it is promptly synthesized in large amounts, and might be easily modified for maximizing molecular interactions toward relevant guest molecules. Calixarenes present well-defined conformational properties and cavities with molecular dimensions that enable to encapsulate guest drugs. Calixarenes have been shown to have antiviral, antibacterial, antifungal, and anticancer activities (including HIV as target). We provide here an overview of the use of calixarenes either as new chemical entity of distinct biological activities or as host for bioactive guest molecules. The importance of calixarenes for drugs development is discussed. The use of Nuclear Magnetic Resonance (NMR) and Mass Spectrometry (MS) techniques for the study of calixarenes as biological molecule hosts is also described.