Synthesis of Highly Fluoroalkyl‐Functionalized Oligoporphyrin Systems

Abstract

Four different multiporphyrin systems have been synthesized and characterized. Highly fluoroalkyl‐functionalized porphyrins are the most complex objects so far to have exhibited quantum wave nature. We have functionalized larger oligoporphyrin systems with fluoroalkyl chains to increase their mass and minimize their intermolecular interactions. The to‐some‐extent random substitution of fluorine atoms at the periphery of the oligoporphyrins results in libraries consisting of molecules varying in both the number and spatial distribution of substituents. The mass‐selected individual members of these libraries were designed for quantum interference experiments. To investigate the volatilization nature of the molecules within the library, laser desorption and post‐ionization studies were performed. These studies demonstrated that molecular beams of suitable velocity and ionization cross‐section can be obtained from these libraries. In particular, we present these features for two libraries, based on either a tetrahedrally arranged central porphyrin tetramer or a more planar porphyrin pentamer.

Matter–wave interference and deflection of tripeptides decorated with fluorinated alkyl chains

“…Despite their fragility, thermal beams of nucleotides 24 and individual amino acids 25 have been prepared successfully for mass spectrometry before. It has also been recently demonstrated 26–28 that highly fluorinated alkyl tags can facilitate molecular volatilization. It is interesting to note that fluorination of biomolecules is a frequently used technique to enhance the stability of proteins against chemical and thermal denaturation, while maintaining the molecule's structure and biological activity 29 .…”

Stability of high-mass molecular libraries: the role of the oligoporphyrin core

“…[3,4] At a fixed molecular beam velocity, mass variation implies a controlled tuning of de Broglie wavelengths (λ dB = h/mv). We compare two molecular libraries [27] as shown in Fig. 1: a tetrahedral arrangement of four zinc-coordinated porphyrins arranged around one tetraphenylmethane core and a planar pentaporphyrin.…”

Tailoring the volatility and stability of oligopeptides

“…In our present work, we focus on the question how to derivatize biomolecular structures such that their sublimation enthalpy is reduced and their thermal stability increased. Perfluoroalkyl functionalization of individual molecules is expected to reduce the binding to neighbouring particles and surfaces because earlier studies have shown that it enhances the volatility of large organic compounds . Here, we apply this strategy for the first time to oligopeptides and study its influence on their volatility.…”

“…Perfluoroalkyl functionalization of individual molecules is expected to reduce the binding to neighbouring particles and surfaces because earlier studies have shown that it enhances the volatility of large organic compounds. [17,[59][60][61] Here, we apply this strategy for the first time to oligopeptides and study its influence on their volatility.…”