Anharmonic Molecular Motion Drives Resonance Energy Transfer in peri-Arylene Dyads

Spectral and dynamical properties of molecular donor-acceptor systems strongly depend on the steric arrangement of the constituents with exciton coupling J as a key control parameter. In the present work we study two peri-arylene based dyads with orthogonal and parallel transition dipoles for donor and acceptor moieties, respectively. We show that the anharmonic multi-well character of the orthogonal dyad's intramolecular potential explains findings from both stationary and time-resolved absorption experiments. While for a parallel dyad, standard quantum chemical estimates of J at 0 K are in good agreement with experimental observations, J becomes vanishingly small for the orthogonal dyad, in contrast to its ultrafast experimental transfer times. This discrepancy is not resolved even by accounting for harmonic fluctuations along normal coordinates. We resolve this problem by supplementing quantum chemical approaches with dynamical sampling of fluctuating geometries. In contrast to the moderate Gaussian fluctuations of J for the parallel dyad, fluctuations for the orthogonal dyad are found to follow non-Gaussian statistics leading to significantly higher effective J in good agreement with experimental observations. In effort to apply a unified framework for treating the dynamics of optical coherence and excitonic populations of both dyads, we employ a vibronic approach treating electronic and selected vibrational degrees on an equal footing. This vibronic model is used to model absorption and fluorescence spectra as well as donor-acceptor transport dynamics and covers the more traditional categories of Förster and Redfield transport as limiting cases

Molecular characterization of Geitleria appalachiana sp. nov. (Nostocales, Cyanobacteria) and formation of Geitleriaceae fam. nov.

Geitleria was described from a limestone cave in Israel, and subsequently reported from caves of France, Romania, Spain, Florida, Costa Rica, and Cook Islands. It is morphologically unusual in that it has true branching, but no heterocytes. A morphologically distinct species of Geitleria was recently collected from a limestone cave in Great Smoky Mountains National Park, Tennessee, and is herein described as G. appalachiana sp. nov. Sequence data for 16S rRNA and rpoC1 loci for the species were obtained from field material using single filament PCR. Phylogenetic evidence indicates that Geitleria does not belong to any family in the Nostocales containing true–branching genera, i.e. Hapalosiphonaceae, Chlorogloeopsidaceae, and Symphyonemataceae, and consequently Geitleriaceae fam. nov. is established to contain this unique genus

Geometric dependencies of vibronically mediated excitation transfer in rylene dyads

We study the excitation transfer in various geometric arrangements of rylene dimers using absorption, fluorescence and transient absorption spectra. Polarization and detection frequency dependencies of transient absorption track the interplay of transfer and vibrational relaxation within the dyads. We have resolved microscopic parametrization of intermolecular coupling between rylenes and reproduced transport data. Dynamical sampling of molecular geometries captures thermal fluctuations for Quantum Chemical estimate of couplings for orthogonally arranged dyad, where static estimates vanish and normal mode analysis of fluctuations underestimates them by an order of magnitude. Nonperturbative accounts for the modulation of transport by strongly coupled anharmonic vibrational modes is provided by a vibronic dimer model. Vibronic dynamics is demonstrated to cover both the F\"{o}rster transport regime of orthogonally arranged dyads and the strong coupling regime of parallel chromophores and allows us to model signal variations along the detection frequency

Ultrafast Photo-Induced Charge Transfer Unveiled by Two-Dimensional Electronic Spectroscopy

The interaction of exciton and charge transfer (CT) states plays a central role in photo-induced CT processes in chemistry, biology and physics. In this work, we use a combination of two-dimensional electronic spectroscopy (2D-ES), pump-probe measurements and quantum chemistry to investigate the ultrafast CT dynamics in a lutetium bisphthalocyanine dimer in different oxidation states. It is found that in the anionic form, the combination of strong CT-exciton interaction and electronic asymmetry induced by a counter-ion enables CT between the two macrocycles of the complex on a 30 fs timescale. Following optical excitation, a chain of electron and hole transfer steps gives rise to characteristic cross-peak dynamics in the electronic 2D spectra, and we monitor how the excited state charge density ultimately localizes on the macrocycle closest to the counter-ion within 100 fs. A comparison with the dynamics in the radical species further elucidates how CT states modulate the electronic structure and tune fs-reaction dynamics. Our experiments demonstrate the unique capability of 2D-ES in combination with other methods to decipher ultrafast CT dynamics.Comment: 14 pages, 11 figures, and Supporting informatio

Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters

The initial energy transfer in photosynthesis occurs between the light-harvesting pigments and on ultrafast timescales. We analyze the carotenoid to bacteriochlorophyll energy transfer in LH2 Marichromatium purpuratum as well as in an artificial light-harvesting dyad system by using transient grating and two-dimensional electronic spectroscopy with 10 fs time resolution. We find that F\"orster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which leads to a disagreement with both linear absorption and electronic 2D-spectra. We show that a vibronic model, which treats carotenoid vibrations on both electronic ground and excited state as part of the system's Hamiltonian, reproduces all measured quantities. Importantly, the vibronic model presented here can explain the fast energy transfer rates with only moderate coupling constants, which are in agreement with structure based calculations. Counterintuitively, the vibrational levels on the carotenoid electronic ground state play a central role in the excited state population transfer to bacteriochlorophyll as the resonance between the donor-acceptor energy gap and vibrational ground state energies is the physical basis of the ultrafast energy transfer rates in these systems

Utility of fatty acid profile and in vitro immune cell activation for chemical and biological standardization of Arthrospira/Limnospira

Corresponding author (NCNPR): Jin Zhang, [email protected]://egrove.olemiss.edu/pharm_annual_posters_2022/1021/thumbnail.jp

Nunduva, a new marine genus of Rivulariaceae (Nostocales, Cyanobacteria) from marine rocky shores

Several populations of a non–tapering and tapering, fasciculated, single and geminate false branch- ing heterocytous cyanobacterium were collected from rocky shores in the Pacific Ocean and Gulf of Mexico. The populations were provisionally placed in Brasilonema based on morphology, but upon sequencing of both environmental and culture material it was discovered that the populations/cultures belonged to the Rivulariaceae, in a marine subclade of the family containing Kyrtuthrix huatulcensis. In culture, the taxon exhibited tapering in isopolar filaments, providing further evidence that it was a member of the rivulariacean clade. Based on molecular data for other cyanobacteria within the rivulariacean clade, we identified at least three more species morphologically distinguishable from the Brasilonema–like material, all of which show more pronounced ta- pering. These cyanobacteria include not only tropical marine strains, but also a strain isolated from the English coastline in the Atlantic Ocean. We propose a new genus and four species for members of this distinctive clade, Nunduva fasciculata gen. nov., sp. nov., N. kania sp. nov., N. biania sp. nov., and N. britannica sp. nov. Other strains that others and we have isolated are sister to Nunduva and may eventually be placed within this genus, but at present, we consider the evidence for inclusion in Nunduva to be insufficient

Speed, wealth and power

In many of his texts French cultural critic, city planner and philosopher Paul Virilio emphasises that speed is not a phenomenon, but a relation between phenomena. The difference between contemporary society and societies of the past consists in the fact that earlier speed used to be mainly connected with transport, now it concerns relations within information. The question of speed is central. Speed and wealth go hand in hand. To give a philosophical definition of speed, we can say that it is not a phenomenon, but rather the relationship between phenomena. In other words, it is relativity itself. Virilio's influential books analyses new problems resulting from the fact that the development of industrial capitalism has reached the stage in which wealth and power in society have been interconnected with ever increasing speed. In view of Virilio's statement that wealth is an aspect of speed it has become necessary to consider speed and all its aspects and consequences through a prism of a new discipline - dromology. Dromology originates from the Greek word dromos. Hence dromology is the science of the ride, the journey, the drive, the way. This means that speed and riches are totally linked concepts. And that the history of the world is not only about the political economy of riches, that is, wealth, money, capital, but also about political economy of speed. Text analyzes the two main themes. Firstly, the treatise attempts at an philosophical analysis of - dromology. Dromologic revolutions cause artificial acceleration of speed in the form of steam or combustion engine, or, nowadays, nuclear energy and they immediately form both e.g. waging wars and kinds of communication. The second part of the study discusses the difference between contemporary society and societies of the past. Vehicles of speed create new dromospheric chronology, new tracks and nodal points (ports, roads, airports, telecommunications etc.) through which things, goods, money, weapons, people or information will start flowing within a different structure.Web of Science54215515