Fluorescence kinetics of flavin adenine dinucleotide in different microenvironments

Fluorescence kinetics of flavin adenine dinucleotide was measured in a wide time and spectral range in different media, affecting its intra- end extramolecular interactions, and analyzed by a new method based on compressed sensing

Self-phase modulation of a single-cycle THz pulse

We demonstrate self-phase modulation (SPM) of a single-cycle THz pulse in a semiconductor, using bulk n-GaAs as a model system. The SPM arises from the heating of free electrons in the electric field of the THz pulse. Electron heating leads to an ultrafast reduction of the plasma frequency, which results in a strong modification of the THz-range dielectric function of the material. THz SPM is observed directly in the time domain as a characteristic reshaping of single-cycle THz pulse. In the frequency domain, it corresponds to a strong frequency-dependent refractive index nonlinearity of n-GaAs, which is found to be both positive and negative within the broad spectrum of the THz pulse. The spectral position of zero nonlinearity is defined by the electron momentum relaxation rate. Nonlinear spectral broadening and compression of the single-cycle THz pulse was also observed

Quantum-dynamical Modeling of the Rydberg to Valence Excited-State Internal Conversion in Cyclobutanone and Cyclopentanone

In this paper we present 4-state, 5-dimensional Vibronic Coupling Hamiltonians for cyclobutanone and cyclopentanone. Wave packet calculations using these Hamiltonians reveal that for cyclobutanone the (n,3s) to (n,π*) internal conversion involves direct motion in nuclear modes coupling the two states leading to fast population transfer. For cyclopentanone, internal vibrational energy redistribution is a bottleneck for activating reactive nuclear modes leading to slower population transfer

Metamaterial-Enhanced Nonlinear Terahertz Spectroscopy

We demonstrate large nonlinear terahertz responses in the gaps of metamaterial split ring resonators in several materials and use nonlinear THz transmission and THz-pump/THz-probe spectroscopy to study the nonlinear responses and dynamics. We use the field enhancement in the SRR gaps to initiate high-field phenomena at lower incident fields. In vanadium dioxide, we drive the insulator-to-metal phase transition with high-field THz radiation. The film conductivity increases by over two orders of magnitude and the phase transition occurs on a several picosecond timescale. In gallium arsenide, we observe high-field transport phenomena, including mobility saturation and impact ionization. The carrier density increases by up to ten orders of magnitude at high fields. At the highest fields, we demonstrate THz-induced damage in both vanadium dioxide and gallium arsenide.United States. Dept. of Energy (DOE-BES, grant DE-FG02- 09ER46643)United States. Office of Naval Research (ONR Grant No. N00014-09-1-1103

Ring closing reaction in diarylethene captured by femtosecond electron crystallography

The photoinduced ring-closing reaction in diarylethene, which serves as a model system for understanding reactive crossings through conical intersections, was directly observed with atomic resolution using femtosecond electron diffraction. Complementary ab initio calculations were also performed. Immediately following photoexcitation, subpicosecond structural changes associated with the formation of an open-ring excited-state intermediate were resolved. The key motion is the rotation of the thiophene rings, which significantly decreases the distance between the reactive carbon atoms prior to ring closing. Subsequently, on the few picosecond time scale, localized torsional motions of the carbon atoms lead to the formation of the closed-ring photoproduct. These direct observations of the molecular motions driving an organic chemical reaction were only made possible through the development of an ultrabright electron source to capture the atomic motions within the limited number of sampling frames and the low data acquisition rate dictated by the intrinsically poor thermal conductivity and limited photoreversibility of organic materials

Endogenous cholinergic inputs and local circuit mechanisms govern the phasic mesolimbic dopamine response to nicotine

Nicotine exerts its reinforcing action by stimulating nicotinic acetylcholine receptors (nAChRs) and boosting dopamine (DA) output from the ventral tegmental area (VTA). Recent data have led to a debate about the principal pathway of nicotine action: direct stimulation of the DAergic cells through nAChR activation, or disinhibition mediated through desensitization of nAChRs on GABAergic interneurons. We use a computational model of the VTA circuitry and nAChR function to shed light on this issue. Our model illustrates that the α4β2-containing nAChRs either on DA or GABA cells can mediate the acute effects of nicotine. We account for in vitro as well as in vivo data, and predict the conditions necessary for either direct stimulation or disinhibition to be at the origin of DA activity increases. We propose key experiments to disentangle the contribution of both mechanisms. We show that the rate of endogenous acetylcholine input crucially determines the evoked DA response for both mechanisms. Together our results delineate the mechanisms by which the VTA mediates the acute rewarding properties of nicotine and suggest an acetylcholine dependence hypothesis for nicotine reinforcement.Peer reviewe

Aquatic Hyphomycete Species Are Screened by the Hyporheic Zone of Woodland Streams

Aquatic hyphomycetes strongly contribute to organic matter dynamics in streams, but their abilities to colonize leaf litter buried in streambed sediments remain unexplored. Here, we conducted field and laboratory experiments (slow-filtration columns and stream-simulating microcosms) to test the following hypotheses: (i) that the hyporheic habitat acting as a physical sieve for spores filters out unsuccessful strategists from a potential species pool, (ii) that decreased pore size in sediments reduces species dispersal efficiency in the interstitial water, and (iii) that the physicochemical conditions prevailing in the hyporheic habitat will influence fungal community structure. Our field study showed that spore abundance and species diversity were consistently re- duced in the interstitial water compared with surface water within three differing streams. Significant differences occurred among aquatic hyphomycetes, with dispersal efficiency of filiform-spore species being much higher than those with compact or branched/tetraradiate spores. This pattern was remarkably consistent with those found in laboratory experiments that tested the influence of sediment pore size on spore dispersal in microcosms. Furthermore, leaves inoculated in a stream and incubated in slow-filtration columns exhibited a fungal assemblage dominated by only two species, while five species were codominant on leaves from the stream-simulating microcosms. Results of this study highlight that the hyporheic zone exerts two types of selec- tion pressure on the aquatic hyphomycete community, a physiological stress and a physical screening of the benthic spore pool, both leading to drastic changes in the structure of fungal community

Relative influence of shredders and fungi on leaf litter decomposition along a river altitudinal gradient

We compared autumn decomposition rates of European alder leaves at four sites along the Lasset–Hers River system, southern France, to test whether changes in litter decomposition rates from upstream (1,300 m elevation) to downstream (690 m) could be attributed to temperature-driven differences in microbial growth, shredder activity, or composition of the shredder community. Alder leaves lost 75–87% of original mass in 57 days, of which 46–67% could be attributed to microbial metabolism and 8–29% to shredder activity, with no trend along the river. Mass loss rates in both fine-mesh (excluding shredders) and coarse-mesh (including shredders) bags were faster at warm, downstream sites (mean daily temperature 7–8°C) than upstream (mean 1–2°C), but the differ- ence disappeared when rates were expressed in heat units to remove the temperature effect. Mycelial biomass did not correlate with mass loss rates. Faster mass loss rates upstream, after temperature correction, evidently arise from more efficient shredding by Nemourid stoneflies than by the Leuctra-dominated assemblage downstream. The influence of water temperature on decomposition rate is therefore expressed both directly, through microbial metabolism, and indirectly, through the structure of shredder commu- nities. These influences are evident even in cold water where temperature variation is small

Energy relaxation pathways between light-matter states revealed by coherent two-dimensional spectroscopy

Coupling matter excitations to electromagnetic modes inside nano-scale optical resonators leads to the formation of hybrid light-matter states, so-called polaritons, allowing the controlled manipulation of material properties. Here, we investigate the photo-induced dynamics of a prototypical strongly-coupled molecular exciton-microcavity system using broadband two-dimensional Fourier transform spectroscopy and unravel the mechanistic details of its ultrafast photo-induced dynamics. We find evidence for a direct energy relaxation pathway from the upper to the lower polariton state that initially bypasses the excitonic manifold of states, which is often assumed to act as an intermediate energy reservoir, under certain experimental conditions. This observation provides new insight into polariton photophysics and could potentially aid the development of applications that rely on controlling the energy relaxation mechanism, such as in solar energy harvesting, manipulating chemical reactivity, the creation of Bose–Einstein condensates and quantum computing

Cdk5 Is Required for Memory Function and Hippocampal Plasticity via the cAMP Signaling Pathway

Memory formation is modulated by pre- and post-synaptic signaling events in neurons. The neuronal protein kinase Cyclin-Dependent Kinase 5 (Cdk5) phosphorylates a variety of synaptic substrates and is implicated in memory formation. It has also been shown to play a role in homeostatic regulation of synaptic plasticity in cultured neurons. Surprisingly, we found that Cdk5 loss of function in hippocampal circuits results in severe impairments in memory formation and retrieval. Moreover, Cdk5 loss of function in the hippocampus disrupts cAMP signaling due to an aberrant increase in phosphodiesterase (PDE) proteins. Dysregulation of cAMP is associated with defective CREB phosphorylation and disrupted composition of synaptic proteins in Cdk5-deficient mice. Rolipram, a PDE4 inhibitor that prevents cAMP depletion, restores synaptic plasticity and memory formation in Cdk5-deficient mice. Collectively, our results demonstrate a critical role for Cdk5 in the regulation of cAMP-mediated hippocampal functions essential for synaptic plasticity and memory formation.Norman B. Leventhal FellowshipUnited States. National Institutes of Health (NIH T32 MH074249)United States. National Institutes of Health (NIH RO1 NS051874