Antipoxvirus Activity Evaluation of Optimized Corroles Based on Development of Autofluorescent ANCHOR Myxoma Virus.

A series of 43 antiviral corrole-based molecules have been tested on myxoma virus (Lausanne-like T1MYXV strain). An autofluorescent MYXV, with an ANCHOR cassette, has been used for the studies. A2B-fluorocorroles display various toxicities, from 40 being very toxic (CC50 = 1.7 µM) to nontoxic 38 (CC50 > 50 µM), whereas A3-fluorocorroles, with one to three fluorine atoms, are not toxic (with the exception of corroles 9, 10, and 22). In vitro, these compounds show a good selectivity index when used alone. Corrole 35 seems to be the most promising compound, which displays a high selectivity index with the lowest IC50. Interestingly, this "Hit" corrole is easy to synthesize in a two-step reaction. Upscaling production up to 25 g has been carried out for in vivo tests. In vivo studies on New Zealand white rabbits infected with myxoma virus show that symptoms are delayed and animal weight is increased upon treatment, while no acute toxicity of the corrole molecule was detected.

A3- and A2B-nitrocorroles: synthesis and antiviral activity evaluation against human cytomegalovirus infection.

Human cytomegalovirus (hCMV) is responsible for several pathologies impacting immunocompromised patients and can trigger life-threatening infection. Several antivirals are available and are used in the clinic, but hCMV resistant strains have appeared and patients have encountered therapeutic failure. Hence, there is a constant need for new best in class or first in class antiviral molecules. We have previously shown that nitrocorroles could be used as a potent anti-hCMV agent without acute toxicity in mice. They therefore represent an excellent platform to perform structure-activity relationship (SAR) studies and to increase efficiency or reduce toxicity. We have generated original A2B- and A3-substituted nitrocorroles and have discovered optimized compounds with selectivity indices above 200. These compounds are easily synthesized in only one to two-step reactions; they are up-scalable and cost efficient. They are therefore excellent candidates for hCMV therapies and they pave the way for a new generation of molecules.

A3- and A2B-fluorocorroles: synthesis, X-ray characterization and antiviral activity evaluation against human cytomegalovirus infection.

Twenty-nine fluorinated corroles were prepared, spectroscopically characterized, and studied for their antiviral activity against human cytomegalovirus infection. Six corroles were also fully characterized by X-ray crystallography giving insights on their geometrical features. The halogenated corroles reported herein exhibit significantly improved antiviral activity over their non-halogenated counterparts and over nitro-corrole analogs previously reported. Full activity of thirteen A3-corroles is achieved with four fluorine atoms present on the meso-phenyl ring reaching a selectivity index above 300. The maximum activity is achieved for A2B-corroles with selectivity indexes above 400. We thus demonstrate that the fluorocorrole is a highly potent platform to synthesize a new generation of anti hCMV molecules.

Two-Photon Absorption Properties and Structures of BODIPY and Its Dyad, Triad and Tetrad.

A series consisting of a dyad, a triad and a tetrad containing either two, three and four BODIPY units, respectively, has been synthesized and fully characterized and compared to two mono-BODIPY analogs (used as references). The one- and two-photon photophysical properties have been measured and the X-ray structures of four of the BODIPY derivatives have been determined. In the 700-900 nm range, the two-photon absorption (TPA) cross sections range from 30 GM to 160 GM for these compounds.

Porphyrin Antenna-Enriched BODIPY-Thiophene Copolymer for Efficient Solar Cells.

Low bandgap A-π-D copolymer, P(BdP-DEHT), consisting of alternating BOronDIPYrromethene (BODIPY) and thiophene units bridged by ethynyl linkers, and its porphyrin-enriched analogue, P(BdP/Por-DEHT), were prepared, and their optical and electrochemical properties were studied. P(BdP-DEHT) exhibits strong absorption in the 500-800 nm range with an optical bandgap of 1.74 eV. On the basis of cyclic voltammetry, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels are evaluated to be -5.40 and -3.66 eV, respectively. After the anchoring of zinc(II) porphyrin on the BODIPY unit, P(BdP/Por-DEHT) displays broadened absorption, thanks to porphyrins, and the optical bandgap decreases to 1.59 eV because of extension of BODIPY conjugation. The resulting estimated HOMO and LUMO energy levels, respectively, move to -5.32 and -3.73 eV. After optimization of the P(BdP-DEHT) or P(BdP/Por-DEHT) to PC71BM weight ratio to 1:2 in dichlorobenzene solution, the bulk heterojunction polymer solar cells show overall power conversion efficiencies (PCEs) of 3.03 and 3.86%, respectively. After solvent vapor annealing (SVA) treatment in CH2Cl2 for 40 s, the PCEs increased to 7.40% [Voc of 0.95 V, Jsc of 12.77 mA/cm2, and fill factor (FF) of 0.61 with energy loss of 0.79 eV] and 8.79% (Voc of 0.92 V, Jsc of 14.48 mA/cm2, and FF of 0.66 with energy loss of 0.67 eV). The increase in the PCE for P(BdP/Por-DEHT)-based devices is mainly attributed to the enhancement in Jsc and FF, which may be related to the broader absorption spectra, lower band gap, and better charge transport of P(BdP/Por-DEHT) compared to P(BdP-DEHT). This could also be related to the optimized nanoscale morphology of the active layer for both efficient exciton dissociation and charge transport toward the electrodes and a balanced charge transport in the device, induced by the SVA treatment of the active layer.

A Very Low Band Gap Diketopyrrolopyrrole-Porphyrin Conjugated Polymer.

A porphyrin-diketopyrrolopyrrole-containing polymer (poly(porphyrin-diketopyrrolopyrrole) (PPDPP)) shows impressive molar absorption coefficients from λ=300 to 1000 nm. The photophysical and structural properties of PPDPP have been studied. With PPDPP as the electron donor and [6,6]-phenyl C71 butyric acid methyl ester (PC71 BM) as the electron acceptor, the bulk heterojunction polymer solar cell showed overall power conversion efficiencies of 4.18 and 6.44 % for as-cast and two-step annealing processed PPDPP:PC71 BM (1:2) active layers, respectively. These results are quite impressive for porphyrin-containing polymers, especially when directly included in the π-conjugated backbone, and offer interesting perspectives for the design of new materials based on this chromophore.

Cyclotriveratrylene-Containing Porphyrins.

The C3-symmetric cyclotriveratrylene (CTV) was covalently bonded via click chemistry to 1, 2, 3, and 6 zinc(II) porphyrin units to various host for C60. The binding constants, Ka, were measured from the quenching of the porphyrin fluorescence by C60. These constants vary between 400 and 4000 M(-1) and are considered weak. Computer modeling demonstrated that the zinc(II) porphyrin units, [Zn], exhibit a strong tendency to occupy the CTV cavity, hence blocking the access for C60 to land on this site. Instead, the pincer of the type [Zn]----[Zn] and in one case [Zn]----CTV, were found to be the most probable geometry to promote host-guest associations in these systems.

Synthesis, Electrochemistry, and Photophysics of Aza-BODIPY Porphyrin Dyes.

The synthesis of dyad and triad aza-BODIPY-porphyrin systems in two steps starting from an aryl-substituted aza-BODIPY chromophore is described. The properties of the resulting aza-BODIPY-porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination.

Synthesis and Characterization of Carbazole-Linked Porphyrin Tweezers.

Herein the synthesis, spectroscopic characterization, two-photon absorption and electrochemical properties of 3,6-disubstituted carbazole tweezers is reported. A dimer resulting from a Glaser homocoupling was isolated during a Sonogashira coupling reaction between a diethynyl-carbazole spacer and a 5-bromo-triarylporphyrin and the properties of this original compound were compared with the 3,6-disubstituted carbazole bisporphyrin tweezers. The dyads reported herein present a two-photon absorption maximum at 920 nm with two-photon absorption cross-section in the 1200 GM range. Despite a strong linear absorption in the Soret region and moderate fluorescence quantum yield, they both lead to a high brightness reaching 30 000 M(-1) cm(-1) .