Rigid-rod push–pull naphthalenediimide photosystems

Design, synthesis and evaluation of advanced rigid-rod π-stack photosystems with asymmetric scaffolds are reported. The influence of push–pull rods on self-organization, photoinduced charge separation and photosynthetic activity is investigated and turns out to be surprisingly small overall

Zipper Assembly of Vectorial Rigid-Rod π-Stack Architectures with Red and Blue Naphthalenediimides: Toward Supramolecular Cascade n/p-Heterojunctions

Zipped up: Supramolecular 3D organization on gold with interdigitating intra- and interlayer recognition motifs (see picure, black p-oligophenyl rods; red, blue naphthalenediimide (NDI) stacks) is designed to access supramolecular cascade n/p-heterojunctions or the adaptable directionality needed to control fill factors in current–voltage curves

Ultrafast Photoinduced Charge Separation in Naphthalene Diimide Based Multichromophoric Systems in Liquid Solutions and in a Lipid Membrane

The photophysical properties of multichromophoric systems consisting of eight red or blue naphthalene diimides (NDIs) covalently attached to a p-octiphenyl scaffold, as well as a blue bichromophoric system with a biphenyl scaffold, have been investigated in detail using femtosecond time-resolved spectroscopy. The blue octachromophoric systems have been recently shown to self-assemble as supramolecular tetramers in lipid bilayer membranes and to enable generation of a transmembrane proton gradient upon photoexcitation (Bhosale, S.; Sisson, A. L.; Talukdar, P.; Fürstenberg, A.; Banerji, N.; Vauthey, E.; Bollot, G.; Mareda, J.; Röger, C.; Würthner, F.; Sakai, N.; Matile, S. Science2006, 313, 84). A strong reduction of the fluorescence quantum yield was observed when going from the single NDI units to the multichromophoric systems in methanol, the effect being even stronger in a vesicular lipid membrane. Fluorescence up-conversion measurements reveal ultrafast self-quenching in the multichromophoric systems, whereas the formation of the NDI radical anion, evidenced by transient absorption measurements, points to the occurrence of photoinduced charge separation. The location of the positive charge could not be established unambiguously from the transient absorption measurements, but energetic considerations indicate that charge separation should occur between two NDI units in the blue systems, whereas both an NDI unit and the p-octiphenyl scaffold could act as electron donor in the red system. The lifetime of the charge-separated state was found to increase from 22 to 45 ps by going from the bi- to the octachromophoric blue systems in methanol, while a 400 ps decay component was observed in the lipid membrane. This lifetime lengthening is explained in terms of charge migration that is most efficient when the octachromophoric systems are assembled as supramolecular tetramers in the lipid membrane. Furthermore, the average charge-separated state lifetime of the red system in methanol is even larger and amounts to 750 ps. This effect cannot be simply explained in terms of Marcus inverted regime as the driving force for charge recombination in the red system is only slightly larger than in the blue one. A better spatial separation of the charges in the red system stemming from the localization of the hole on the p-octiphenyl scaffold could additionally contribute to the slowing down of charge recombination

Coordinate-based co-localization-mediated analysis of arrestin clustering upon stimulation of the C-C chemokine receptor 5 with RANTES/CCL5 analogues

G protein-coupled receptor activation and desensitization leads to recruitment of arrestin proteins from cytosolic pools to the cell membrane where they form clusters difficult to characterize due to their small size and further mediate receptor internalization. We quantitatively investigated clustering of arrestin 3 induced by potent anti-HIV analogues of the chemokine RANTES after stimulation of the C-C chemokine receptor 5 using single-molecule localization-based super-resolution microscopy. We determined arrestin 3 cluster sizes and relative fractions of arrestin 3 molecules in each cluster through image-based analysis of the localization data by adapting a method originally developed for co-localization analysis from molecular coordinates. We found that only classical agonists in the set of tested ligands were able to efficiently recruit arrestin 3 to clusters mostly larger than 150nm in size and compare our results with existing data on arrestin 2 clustering induced by the same chemokine analogues

Artificial tongues and leaves

The objective with synthetic multifunctional nanoarchitecture is to create large suprastructures with interesting functions. For this purpose, lipid bilayer membranes or conducting surfaces have been used as platforms and rigid-rod molecules as shape-persistent scaffolds. Examples for functions obtained by this approach include pores that can act as multicomponent sensors in complex matrices or rigid-rod π-stack architecture for artificial photosynthesis and photovoltaic

Ultrafast excited-state dynamics in biological and in organised environments

La dynamique d'états excités de sondes fluorescentes placées dans des environnements biologiques et organisés a été étudiée par spectroscopie optique stationnaire et par spectroscopie laser femtoseconde. En particulier, l'influence de tels environnements sur des processus ultrarapides tels que la solvatation, la relaxation vibrationnelle, l'inhibition de fluorescence et la dépolarisation de fluorescence a été suivie. Les systèmes étudiés sont : ( 1) les protéines avidine et streptavidine au ligand naturel desquels, la biotine, différentes sondes fluorescentes ont été attachées ; (2) des intercalateurs d'acides nucléiques fluorescents en présence de différentes séquences d'ADN et d'ARN ; (3) des systèmes photosynthétiques artificiels composés de 32 chromophores identiques qui s'autoassemblent dans des membranes lipidiques. Les nombreux exemples expérimentaux permettent de démontrer la puissance de la spectroscopie de fluorescence femtoseconde en tant qu'outil pour obtenir des informations sur l'environnement local de sondes fluorescentes et ainsi des informations structurales sur des macromolécules d'intérêt biologique

Water in Biomolecular Fluorescence Spectroscopy and Imaging: Side Effects and Remedies

Historically, many of the classical organic fluorescent dyes were developed as laser dyes and characterized and optimized in organic solvents. Since then, fluorescence has, however, found a vast range of applications in the life sciences in which the fluorophores are usually surrounded by water and not by organic solvents. The omnipresence of water in biomolecular fluorescence spectroscopy and imaging leads to some unwanted but nonetheless unavoidable consequences on the photophysical properties of the dyes, which may impact the quality and complicate quantitative interpretation of the experiments. This paper discusses and illustrates with examples two such water-induced phenomena, namely chromophore aggregation in water and fluorescence quenching by water, as well as some ways to overcome them

Ultrafast Excited-State Dynamics of Oxazole Yellow DNA Intercalators

The excited-state dynamics of the DNA intercalator YO-PRO-1 and of three derivatives has been investigated in water and in DNA using ultrafast fluorescence spectroscopy. In the free form, the singly charged dyes exist both as monomers and as H-dimers, while the doubly charged dyes exist predominantly as monomers. Both forms are very weakly fluorescent: the monomers because of ultrafast nonradiative deactivation, with a time constant on the order of 3-4 ps, associated with large amplitude motion around the methine bridge, and the H-dimers because of excitonic interaction. Upon intercalation into DNA, large amplitude motion is inhibited, H-dimers are disrupted, and the molecules become highly fluorescent. The early fluorescence dynamics of these dyes in DNA exhibits substantial differences compared with that measured with their homodimeric YOYO analogues, which are ascribed to dissimilarities in their local environment. Finally, the decay of the fluorescence polarization anisotropy reveals ultrafast hopping of the excitation energy between the intercalated dyes. In one case, a marked change of the depolarization dynamics upon increasing the dye concentration is observed and explained in terms of a different binding mode

SCS Photochemistry Section Meeting Fribourg, June 14, 2019: Conference Report

On June 14, 2019, nearly 50 photochemists from all over Switzerland and beyond gathered together at the Haute Ecole d'Ingénierie et d'Architecture in Fribourg (HEIA-FR) for the annual SCS Photochemistry Section meeting to discuss their latest findings in the field. The organizing committee consisting of the board of the SCS Photochemistry Section put together a program consisting of 3 invited talks, 9 oral communications and a poster session with 24 posters to revive this event which, they hope, will take place annually. In addition, the general assembly of the Section was held at the premise during the day