Delphine Pitrat

Origin of an ancient hormone/receptor couple revealed by resurrection of an ancestral estrogen

Cladistic analysis allows inference of the structure of an ancestral steroid that acts as a ligand for the ancestral receptor. The origin of ancient ligand/receptor couples is often analyzed via reconstruction of ancient receptors and, when ligands are products of metabolic pathways, they are not supposed to evolve. However, because metabolic pathways are inherited by descent with modification, their structure can be compared using cladistic analysis. Using this approach, we studied the evolution of steroid hormones. We show that side-chain cleavage is common to most vertebrate steroids, whereas aromatization was co-opted for estrogen synthesis from a more ancient pathway. The ancestral products of aromatic activity were aromatized steroids with a side chain, which we named “paraestrols.” We synthesized paraestrol A and show that it effectively binds and activates the ancestral steroid receptor. Our study opens the way to comparative studies of biologically active small molecules.

Extremely low amplified spontaneous emission threshold and blue electroluminescence from a spin-coated octafluorene neat film

We report on the photophysical, amplified spontaneous emission (ASE), and electroluminescence properties of a blue-emitting octafluorene derivative in spin-coated films. The neat film shows an extremely low ASE threshold of 90 nJ/cm2, which is related to its high photoluminescence quantum yield of 87% and its large radiative decay rate of 1.7 × 109 s−1. Low-threshold organic distributed feedback semiconductor lasers and fluorescent organic light-emitting diodes with a maximum external quantum efficiency as high as 4.4% are then demonstrated, providing evidence that this octafluorene derivative is a promising candidate for organic laser applications.

Large-Scale Synthesis of Helicene-Like Molecules for the Design of Enantiopure Thin Films with Strong Chiroptical Activity

Helicenes are fascinating molecules owing to their unusual properties and applications in many fields from catalysis to organic electronics. Herein, we report a straightforward pathway for the synthesis of helicene-like molecules on a gram scale in an enantiopure form. Thin-film materials with good propagating optical properties and very high chiroptical responses have been grown by using pulsed laser ablation without altering the structure or the enantiopurity of the molecules. Moreover, electronic and vibrational circular dichroism spectroscopies coupled with theoretical calculations enabled some dependences of the chiroptical properties with the structure to be highlighted, for example, effects of rigidification, aromatization, or the state of matter (liquid versus solid).

Improvement of the quasi-continuous-wave lasing properties in organic semiconductor lasers using oxygen as triplet quencher

We demonstrate quasi-continuous-wave lasing in solvent-free liquid organic semiconductor distributed feedback lasers based on a blend containing a liquid 9-(2-ethylhexyl)carbazole host doped with a blue-emitting heptafluorene derivative. The liquid gain medium is bubbled with either oxygen or nitrogen in order to investigate the role of a triplet quencher such as molecular oxygen on the quasi-continuous-wave lasing properties of organic semiconductor lasers. The oxygenated laser device exhibits a low threshold of 2 μJ cm−2, which is lower than that measured in the nitrogenated device and is independent of the repetition rate in a range between 0.01 and 4 MHz.

Synthesis, Resolution, and Absolute Configuration of Chiral Tris(2-pyridylmethyl)amine-Based Hemicryptophane Molecular Cages

The synthesis, characterization, and chiroptical properties of a new class of hemicryptophane cages combining a cyclotriveratrylene unit and a tris(2-pyridylmethyl)amine (TPA) moiety are reported. Changing the linkers between these two units allows for the modification of the size and shape of the cavity. The synthesis is straightforward and efficient, providing gram-scale of cage compounds. The racemic mixture of each hemicryptophane host can be readily resolved by chiral HPLC, giving an easy access to the enantiopure molecular cages of which absolute configurations have been assigned by ECD spectroscopy. These new hemicryptophanes are available chemical platforms ready to use for various purposes due to the versatile metal complexation properties of the TPA unit. A Zn(II)@hemicryptophane complex has been obtained and used as a heteroditopic host for the selective recognition of zwitterionic guests.

Cyclotriveratrylene-BINOL-Based Host Compounds: Synthesis, Absolute Configuration Assignment, and Recognition Properties.

New host compounds combining a cyclotriveratrylene (CTV) unit and three binaphthol moieties have been synthesized enantiomerically and diastereomerically pure. The use of a chemical correlation allows for the assignment of their absolute configuration. The energy barrier of epimerization was measured, suggesting that no intramolecular hydrogen bonding occurs between the hydroxyl groups of the binaphthols. These open-shell host compounds were then tested in the recognition of carbohydrates; a preferential binding of mannose toward glucose was observed, and good diastereoselectivities were reached (up to 1:10). This recognition of sugar derivatives by open-shell CTV-based host compounds is unprecedented and opens up the way for a wider use of this easily accessible class of molecules as chiral sensors.

Accurate pH sensing via hyperpolarized

In the search for powerful non-invasive methods for pH measurement, NMR usually suffers from biases, especially for heterogeneous samples or tissues. In this Communication, using the signals of hyperpolarized 129 Xe encapsulated in a pair of water-soluble cryptophanes, we show that a differential pH measurement can be achieved, free from most of these biases, by monitoring the difference between their chemical shifts.