Vibrational coherence and quantum yield of retinal-chromophore-inspired molecular switches.

UV-Vis transient absorption (TA) spectroscopy is used to carry out a systematic investigation of the ultrafast C[double bond, length as m-dash]C double photoisomerization dynamics and quantum yield of each isomer of a set of six chromophores based on the same retinal-inspired, indanylidene pyrrolinium (IP) molecular framework. All compounds undergo a sub-picosecond photoisomerization, and can be categorized within two photoisomerization scenarios. Scenario I corresponds to compounds which display the signatures of a vibrationally coherent reactive motion through the conical intersection, with different degrees of vibrational coherence. Qualitatively distinct TA signatures are observed for other compounds which are therefore proposed to obey scenario II, referring to an intermediate regime between scenario I and a thermally-equilibrated, fully stochastic photoreaction. Remarkably, the photoisomerization scenario is observed to correlate with the computed distortion from planarity of the ground state equilibrium geometry, reflecting the torsional strain that would be released after photoexcitation. The most planar compounds - i.e. those having a C[double bond, length as m-dash]C double bond pre-twist of less than 10° - obey scenario II, while compounds obeying scenario I have larger pre-twists. The most pre-twisted compounds (>15°) show pronounced oscillatory signatures of a reaction-induced, low-frequency vibrational wavepacket observed in the S0 photoproduct and assigned to the torsion mode of the reaction coordinate, thus mimicking the vibrationally coherent photoisomerization dynamics of the rhodopsin protein. Importantly, the systematic comparison of all photoisomerization quantum yields does however not reveal any correlation with observables such as excited state life time, vibrational coherence, absorption wavelengths or degree of pre-twisting.

Synthesis, spectroscopy and QM/MM simulations of a biomimetic ultrafast light-driven molecular motor.

A molecular motor potentially performing a continuous unidirectional rotation is studied by a multidisciplinary approach including organic synthesis, transient spectroscopy and excited state trajectory calculations. A stereogenic center was introduced in the N-alkylated indanylidene-pyrroline Schiff base framework of a previously investigated light-driven molecular switch in order to achieve the unidirectional C[double bond, length as m-dash]C rotary motion typical of Feringa's motor. Here we report that the specific substitution pattern of the designed chiral molecule must critically determine the unidirectional efficiency of the light-induced rotary motion. More specifically, we find that a stereogenic center containing a methyl group and a hydrogen atom as substituents does not create a differential steric effect large enough to fully direct the motion in either the clockwise or counterclockwise direction especially along the E→Z coordinate. However, due to the documented ultrafast character and electronic circular dichroism activity of the investigated system, we find that it provides the basis for development of a novel generation of rotary motors with a biomimetic framework and operating on a picosecond time scale.

Design, Synthesis, and Dynamics of a Green Fluorescent Protein Fluorophore Mimic with an Ultrafast Switching Function.

While rotary molecular switches based on neutral and cationic organic π-systems have been reported, structurally homologous anionic switches providing complementary properties have not been prepared so far. Here we report the design and preparation of a molecular switch mimicking the anionic p-HBDI chromophore of the green fluorescent protein. The investigation of the mechanism and dynamics of the E/Z switching function is carried out both computationally and experimentally. The data consistently support axial rotary motion occurring on a sub-picosecond time scale. Transient spectroscopy and trajectory simulations show that the nonadiabatic decay process occurs in the vicinity of a conical intersection (CInt) between a charge transfer state and a covalent/diradical state. Comparison of our anionic p-HBDI-like switch with the previously reported cationic N-alkyl indanylidene pyrrolinium switch mimicking visual pigments reveals that these similar systems translocate, upon vertical excitation, a similar net charge in the same axial direction.

A biomimetic molecular switch at work: coupling photoisomerization dynamics to peptide structural rearrangement.

In spite of considerable interest in the design of molecular switches towards photo-controllable (bio)materials, few studies focused on the major influence of the surrounding environment on the switch photoreactivities. We present a combined experimental and computational study of a retinal-like molecular switch linked to a peptide, elucidating the effects on the photoreactivity and on the α-helix secondary structure. Temperature-dependent, femtosecond UV-vis transient absorption spectroscopy and high-level hybrid quantum mechanics/molecular mechanics methods were applied to describe the photoisomerization process and the subsequent peptide rearrangement. It was found that the conformational heterogeneity of the ground state peptide controls the excited state potential energy surface and the thermally activated population decay. Still, a reversible α-helix to α-hairpin conformational change is predicted, paving the way for a fine photocontrol of different secondary structure elements, hence (bio)molecular functions, using retinal-inspired molecular switches.

Excited-state annihilation reduces power dependence of single-molecule FRET experiments.

Single-molecule Förster resonance energy transfer (FRET) experiments are an important method for probing biomolecular structure and dynamics. The results from such experiments appear to be surprisingly independent of the excitation power used, in contradiction to the simple photophysical mechanism usually invoked for FRET. Here we show that excited-state annihilation processes are an essential cause of this behavior. Singlet-singlet annihilation (SSA) is a mechanism of fluorescence quenching induced by Förster-type energy transfer between two fluorophores while they are both in their first excited singlet states (S1S1), which is usually neglected in the interpretation of FRET experiments. However, this approximation is only justified in the limit of low excitation rates. We demonstrate that SSA is evident in fluorescence correlation measurements for the commonly used FRET pair Alexa 488/Alexa 594, with a rate comparable to the rate of energy transfer between the donor excited state and the acceptor ground state (S1S0) that is exploited in FRET experiments. Transient absorption spectroscopy shows that SSA occurs exclusively via energy transfer from Alexa 488 to Alexa 594. Excitation-power dependent microsecond correlation experiments support the conclusion based on previously reported absorption spectra of triplet states that singlet-triplet annihilation (STA) analogously mediates energy transfer if the acceptor is in the triplet state. The results indicate that both SSA and STA have a pronounced effect on the overall FRET process and reduce the power dependence of the observed FRET efficiencies. The existence of annihilation processes thus seems to be essential for using FRET as a reliable spectroscopic ruler at the high excitation rates commonly employed in single-molecule spectroscopy.

WRF 1960-2014 Winter Season Simulations of Particulate Matter in the Sahel: Implications for Air Quality and Respiratory Health.

We use the Weather Research and Forecast model using the Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) dust module (WRF-CHEM) to simulate the particulate matter (PM) variations in the Sahel during the winter seasons (January-March) of 1960-2014. Two simulations are undertaken where the direct aerosol feedback is turned off, and only transport is considered and where the direct aerosol feedback is turned on. We find that simulated Sahelian PM10 and PM2.5 concentrations were lower in the 1960s and after 2003 and higher during the period between 1988 and 2002. Higher Sahelian PM10 concentrations are due to stronger winds between the surface and 925 hPa over the Sahara, which transport dust into the Sahel. Negative PM10 concentration anomalies are found over the Bodele Depression and associated with weaker 925 wind anomalies after 1997 through 2014. Further west, positive PM10 concentration anomalies are found across the Adrar Plateau in the Sahara and responsible for dust transport to the Western Sahel. The North Atlantic Oscillation (NAO) is positively correlated to Sahelian dust concentrations especially during the periods of 1960-1970 and 1988-2002. The temporal/spatial patterns of PM10 concentrations have significant respiratory health implications for inhabitants of the Sahel.

Engineering the vibrational coherence of vision into a synthetic molecular device.

The light-induced double-bond isomerization of the visual pigment rhodopsin operates a molecular-level optomechanical energy transduction, which triggers a crucial protein structure change. In fact, rhodopsin isomerization occurs according to a unique, ultrafast mechanism that preserves mode-specific vibrational coherence all the way from the reactant excited state to the primary photoproduct ground state. The engineering of such an energy-funnelling function in synthetic compounds would pave the way towards biomimetic molecular machines capable of achieving optimum light-to-mechanical energy conversion. Here we use resonance and off-resonance vibrational coherence spectroscopy to demonstrate that a rhodopsin-like isomerization operates in a biomimetic molecular switch in solution. Furthermore, by using quantum chemical simulations, we show why the observed coherent nuclear motion critically depends on minor chemical modifications capable to induce specific geometric and electronic effects. This finding provides a strategy for engineering vibrationally coherent motions in other synthetic systems.

Broadband UV-Vis vibrational coherence spectrometer based on a hollow fiber compressor.

We describe a broadband transient absorption (TA) spectrometer devised to excite and probe, in the blue to UV range, vibrational coherence dynamics in organic molecules in condensed phase. A 800-nm Ti:Sa amplifier and a hollow fiber compressor are used to generate a 6-fs short pulse at 1 kHz. Broadband sum frequency generation with the fundamental pulse is implemented to produce a 400-nm, 8-fs Fourier limited short pulse. A UV-Vis white-light supercontinuum is implemented as a probe with intensity self-referencing to achieve a shot-noise-limited sensitivity. Rapid scanning of the pump-probe delay is shown very efficient in suppressing the noise resulting from low-frequency pump intensity fluctuations. Using either of the 800-nm or 400-nm broadband pulses as the pump for TA spectroscopy of organic molecules in solution, we resolve oscillatory signals down to the 320 nm probing wavelength with a 3200 cm-1 FWHM bandwidth. Their Fourier transformation reveals the corresponding molecular vibrational spectra. Finally, we demonstrate the use of this setup as a vibrational coherence spectrometer for the investigation of the vibrational dynamics accompanying the sub-ps C=C photoisomerization of a retinal-like molecular switch through a conical intersection.

The impact of environmental degradation on reproduction of the black-chinned tilapia Sarotherodon melanotheron from various coastal marine, estuarine and freshwater habitats.

There is growing evidence that climate change has greatly altered environmental conditions in many aquatic ecosystems over the last decades, leading to changes in fish distribution and life history traits. Recent works conducted in Senegalese and Gambian coastal marine, estuarine and freshwater ecosystems have shown important changes in the intensity, frequency and breeding timing of wild population of Sarotherodon melanotheron in response to changes in salinity regimes. In addition to salinity, this study investigates the potential influences of other environmental factors that have received less attention on the reproduction of S. melanotheron from three different aquatic ecosystems in Senegal. The results demonstrate that day-length and temperature affect sexual maturity in both males and females from Guiers Lake and Hann Bay, but no such effects were found in upstream of the Saloum Estuary, where the spawning activity seems to be under the synergetic control of rainfall and salinity that apparently predominate over all the other ambient factors. This study demonstrated for the first time that aside from photoperiod and temperature, rainfall also influences fish reproduction in Hann Bay probably through its effects on water quality. Furthermore, our results confirm previous findings that changes in salinity regimes resulting from seasonal variations in precipitation and evaporation are the ultimate causes of temporal changes in the reproductive activity of the species in this estuary.

Comparative analysis of reproductive traits in black-chinned tilapia females from various coastal marine, estuarine and freshwater ecosystems.

The black-chinned tilapia Sarotherodon melanotheron is a marine teleost characterised by an extreme euryhalinity. However, beyond a certain threshold at very high salinity, the species exhibits impaired growth and precocious reproduction. In this study, the relationships between reproductive parameters, environmental salinity and condition factor were investigated in wild populations of this species that were sampled in two consecutive years (2003 and 2004) from three locations in Senegal with different salinities: Guiers lake (freshwater, 0 psu), Hann bay (seawater, 37 psu) and Saloum estuary (hypersaline water, 66-127 psu). The highest absolute fecundity and spawning weight were recorded in seawater by comparison to either freshwater or hypersaline water whereas the poorest condition factors were observed in the most saline sampling site. These results reflect higher resource allocation to the reproduction due to the lowest costs of adaptation to salinity in seawater (the natural environment of this species) rather than differences in food resources at sites and/or efficiency at foraging and prey availability. Fecundities, oocyte size as well as spawning weight were consistent from year to year. However, the relative fecundity in the Saloum estuary varied significantly between the dry and rainy raisons with higher values in the wet season, which seems to reflect seasonal variations in environmental salinity. Such a reproductive tactic of producing large amounts of eggs in the rainy season when the salinity in the estuary was lower, would give the fry a better chance at survival and therefore assures a high larval recruitment. An inverse correlation was found between relative fecundity and oocyte size at the two extreme salinity locations, indicating that S. melanotheron has different reproductive strategies in these ecosystems. The adaptive significance of these two reproductive modes is discussed in regard to the heavy osmotic constraint imposed by extreme salinities and high inter-specific competition.