Understanding complex supramolecular landscapes: non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer.

As molecular self-assembled systems increase in complexity, due to a large number of participating entities and/or the establishment of multiple competing equilibria, their full understanding becomes likewise more complicated, and the use of diverse analytical techniques that can afford complementary information is required. We demonstrate in this work that resonance excitation energy transfer phenomena, measured by fluorescence spectroscopy in combination with other optical spectroscopies, can be a valuable tool to obtain supplementary thermodynamic data about complex supramolecular landscapes that other methods fail to provide. In particular, noncovalent macrocyclization processes of lipophilic dinucleosides are studied here by setting up a competition between intra- and intermolecular association processes of Watson-Crick H-bonding pairs. Multiwavelength analysis of the monomer emission changes allowed us to determine cyclotetramerization constants and to quantify chelate cooperativity, which was confirmed to be substantially larger for the G-C than for the A-U pair. Furthermore, when bithiophene-BODIPY donor-acceptor energy transfer probes are employed in these competition experiments, fluorescence and circular dichroism spectroscopy measurements in different regions of the visible spectrum additionally reveal intermolecular interactions occurring simultaneously at both sides of the macrocyclization reaction: the cyclic product, acting as a host for the competitor, and the monomer reactant, ultimately leading to macrocycle denaturation.

Following a photoinduced reconstructive phase transformation and its influence on the crystal integrity: powder diffraction and theoretical study.

In the course of solid-state photoreactions, a single crystal (SC) of the reactant can be transformed into an SC of the product or it can lose crystallinity and become amorphous. In-between these two scenarios exist the reconstructive phase transformations, where upon irradiation, the reactant SC becomes a powder or an SC with increased mosaicity. We present a detailed description of reconstructive photodimerization, where the structural changes are directly correlated with the disintegration process. The kinetics of the reaction is explained by two kinetic regimes, forming an autocatalytic autoinhibition photoreaction set with high quantum yield. In addition, the photoreaction pathways were studied theoretically.

Benzylidene-oxazolones as molecular photoswitches.

The synthesis and photochemical study of a family of molecular switches inspired by the green fluorescent protein (GFP) chromophore is presented. These compounds can be easily synthesized, and their photophysical properties may be tuned. Due to their efficient photoisomerization and high stability, these compounds can be switched on/off by using light and heat or light with different wavelengths.

Reversible photocontrol of peptide conformation with a rhodopsin-like photoswitch.

Reversible photocontrol of biomolecules requires chromophores that can efficiently undergo large conformational changes upon exposure to wavelengths of light that are compatible with living systems. We designed a benzylidene-pyrroline chromophore that mimics the Schiff base of rhodopsin and can be used to introduce light-switchable intramolecular cross-links in peptides and proteins. This new class of photoswitch undergoes an ~10 Å change in end-to-end distance upon isomerization and can be used to control the conformation of a target peptide efficiently and reversibly using, alternately, violet (400 nm) and blue (446 nm) light.