Interplay between Cellular Uptake, Intracellular Localization and the Cell Death Mechanism in Triphenylamine-Mediated Photoinduced Cell Death.

Triphenylamines (TPAs) were previously shown to trigger cell death under prolonged one- or two-photon illumination. Their initial subcellular localization, before prolonged illumination, is exclusively cytoplasmic and they translocate to the nucleus upon photoactivation. However, depending on their structure, they display significant differences in terms of precise initial localization and subsequent photoinduced cell death mechanism.

EPR spectroelectrochemical investigation of guanine radical formation and environment effects.

Guanine radical detection was carried out by a new convenient and efficient method coupling electron paramagnetic resonance spectroscopy and indirect electrooxidation of guanine in different biological environments, from the free nucleotide to several types of DNA substrates. Compared to the widely used photoirradiation method, this method appeared more selective in the choice of the electrochemical mediator. Carried out in presence of a ruthenium mediator and PBN as spin trap, this method revealed two types of EPR spectra depending of the environment of the guanine radical.

DNA switches on the two-photon efficiency of an ultrabright triphenylamine fluorescent probe specific of AT regions.

We report on the design and synthesis of two-photon fluorescent triphenylamines bearing two or three vinyl branches terminated by a N-methyl benzimidazolium moiety. The new compounds (TP-2Bzim, TP-3Bzim) are light-up fluorescent DNA probes with a long wavelength emission (>580 nm). Compared to their pyridinium models, the TP-Bzim dyes exhibit a remarkable improvement of both their DNA affinity and fluorescence quantum yield, especially for the two-branch derivative (TP-2Bzim: ΦF = 0.

Vinyl-triphenylamine dyes, a new family of switchable fluorescent probes for targeted two-photon cellular imaging: from DNA to protein labeling.

On the basis of our previous work on vinyl-triphenylamine derived DNA fluorophores we explored the structure space around this core by coupling it to diverse cationic, anionic and zwitterionic groups in the aim of targeting different classes of biomolecules. In parallel core modifications were performed to optimize the photophysical properties (quantum yield, two-photon absorption). The resulting water soluble π-conjugated molecules are called TP dyes and display an exceptional combination of optical properties: high two-photon absorption cross-section, high photostability, no self-quenching, and switchable fluorescence emission when bound to a biopolymer matrix.

Trinaphthylamines as robust organic materials for two-photon-induced fluorescence.

The synthesis of a novel pi-conjugated trinaphthylamines series is described. These original push-pull octupolar systems exhibit large two-photon action cross section (sigma phi up to 510 GM) increased by a factor of 2-3 as compared to their triphenylamines analogues. This substantial improvement of the two-photon absorption properties is attributed to the stronger donor character of the trinaphthyl core.

Synthetic strategies to derivatizable triphenylamines displaying high two-photon absorption.

A versatile synthetic strategy to access a set of highly fluorescent pi-conjugated triphenylamines bearing a functional linker at various positions on one phenyl ring is described. These compounds were designed for large two-photon absorption (2PA) and in particular for labeling of biomolecules. The monoderivatized trisformylated or trisiodinated intermediates described herein allow introduction of a large variety of electron-withdrawing groups required for large 2PA as well as a panel of chemical functions suitable for coupling to biomolecules.

Vinyl-pyridinium triphenylamines: novel far-red emitters with high photostability and two-photon absorption properties for staining DNA.

A series of mono-, bis- and trisvinyl-pyridinium triphenylamines (TP-py) has been synthesised and evaluated for its one- and two-photon absorption (2PA) induced-fluorescence properties under biological conditions. Interestingly, these compounds are only weakly fluorescent in water, whereas their fluorescence emissions are strongly restored (exaltation factors of 20-100) upon binding to double-stranded DNA. Additional measurements in glycerol indicate that the fluorescence increases are the result of immobilisation of the dyes in the DNA matrix, which inhibits rotational de-excitation modes.

Total synthesis of (+)-cyanthiwigin AC.

A 13-step synthesis of (+)-cyanthiwigin-AC (2) from (+)-Hajos-Parrish ketone derivative 8b and dimesylate 9c employing deconjugative spiro-bis-alkylation strategy is described. [reaction: see text].