Long-lived quantum coherence in photosynthetic complexes at physiological temperature

Photosynthetic antenna complexes capture and concentrate solar radiation by transferring the excitation to the reaction center which stores energy from the photon in chemical bonds. This process occurs with near-perfect quantum efficiency. Recent experiments at cryogenic temperatures have revealed that coherent energy transfer - a wavelike transfer mechanism - occurs in many photosynthetic pigment-protein complexes (1-4). Using the Fenna-Matthews-Olson antenna complex (FMO) as a model system, theoretical studies incorporating both incoherent and coherent transfer as well as thermal dephasing predict that environmentally assisted quantum transfer efficiency peaks near physiological temperature; these studies further show that this process is equivalent to a quantum random walk algorithm (5-8). This theory requires long-lived quantum coherence at room temperature, which never has been observed in FMO. Here we present the first evidence that quantum coherence survives in FMO at physiological temperature for at least 300 fs, long enough to perform a rudimentary quantum computational operation. This data proves that the wave-like energy transfer process discovered at 77 K is directly relevant to biological function. Microscopically, we attribute this long coherence lifetime to correlated motions within the protein matrix encapsulating the chromophores, and we find that the degree of protection afforded by the protein appears constant between 77 K and 277 K. The protein shapes the energy landscape and mediates an efficient energy transfer despite thermal fluctuations. The persistence of quantum coherence in a dynamic, disordered system under these conditions suggests a new biomimetic strategy for designing dedicated quantum computational devices that can operate at high temperature.Comment: PDF files, 15 pages, 3 figures (included in the PDF file

Nonadiabatic derivative couplings through multiple Franck-Condon modes dictate the energy gap law for near and short-wave infrared dye molecules

Near infrared (NIR, 700 - 1,000 nm) and short-wave infrared (SWIR, 1,000 - 2,000 nm) dye molecules exhibit significant nonradiative decay rates from the first singlet excited state to the ground state. While these trends can be empirically explained by a simple energy gap law, detailed mechanisms of the nearly universal behavior have remained unsettled for many cases. Theoretical and experimental results for two representative NIR/SWIR dye molecules reported here clarify an important mechanism of such nature. It is shown that the first derivative nonadiabatic coupling terms serve as major coupling pathways for nonadiabatic decay processes exhibiting the energy gap law behavior and that vibrational modes other than the highest frequency ones also make significant contributions to the rate. This assessment is corroborated by further theoretical comparison with possible alternative mechanisms of intersystem crossing to triplet states and also by comparison with experimental data for deuterated molecules

Size Segregation of Granular Matter in Silo Discharges

We present an experimental study of segregation of granular matter in a quasi-two dimensional silo emptying out of an orifice. Size separation is observed when multi-sized particles are used with the larger particles found in the center of the silo in the region of fastest flow. We use imaging to study the flow inside the silo and quantitatively measure the concentration profiles of bi-disperse beads as a function of position and time. The angle of the surface is given by the angle of repose of the particles, and the flow occurs in a few layers only near the top of this inclined surface. The flowing region becomes deeper near the center of the silo and is confined to a parabolic region centered at the orifice which is approximately described by the kinematic model. The experimental evidence suggests that the segregation occurs on the surface and not in the flow deep inside the silo where velocity gradients also are present. We report the time development of the concentrations of the bi-disperse particles as a function of size ratios, flow rate, and the ratio of initial mixture. The qualitative aspects of the observed phenomena may be explained by a void filling model of segregation.Comment: 6 pages, 10 figures (gif format), postscript version at http://physics.clarku.edu/~akudrolli/nls.htm

Excitation energy transfer in light-harvesting system: Effect of initial state

The light-harvesting is a problem of long interest. It becomes active again in recent years stimulated by suggestions of quantum effects in energy transport. Recent experiments found evidence that BChla 1 and BChla 6 are the first to be excited in the Fenna-Matthews-Olson(FMO) protein, theoretical studies, however, are mostly restricted to consider the exciton in BChla 1 initially. In this paper, we study the energy transport in the FMO complex by taking different initial states into account. Optimizations are performed for the decoherence rates as to maximal transport efficiency. Dependence of the energy transfer efficiency on the initial states is given and discussed. Effects of fluctuations in the site energies and couplings are also examined.Comment: 6 pages, 6 figures, J Phys B accepte

Increased lung volume in infants and toddlers at high compared to low altitude

Children and adults residing at high altitude (HA) compared to low altitude (LA) have larger lung volumes; however, it is unknown whether this response to chronic hypoxia begins early in life. Our objective was to determine whether infants and toddlers at HA have larger lung volumes compared to infants and toddlers at LA. Oxygen saturation (SaO2 ), functional residual capacity (FRC), as well as serum levels of vascular endothelial growth factor (VEGF) and erythropoietin (EPO) were measured in infants and toddlers from HA (N = 50; 3,440 m) and LA (N = 35; 440 m). There were no significant differences in somatic size for HA and LA subjects; however, HA subjects had significantly lower SaO2 (88.5% vs. 96.7%; P < 0.0001). Subjects at HA had significantly greater FRC compared to subjects at LA (group mean: 209 and 157 ml; P < 0.0001), adjusting for body length. Male infants at HA had a significantly greater FRC compared to males at LA (57 ml; P-value < 0.001); however, the increase in FRC for females at HA compared to LA was not significant (20 ml; P-value = 0.101). VEGF and EPO were significantly higher for subjects at HA compared to LA with no gender differences. In summary, infants and toddlers at HA have lower oxygen saturations, higher serum levels of VEGF and EPO, and higher FRC compared to subjects at LA; however, chronic hypoxia appears to generate a more robust response in lung growth in male compared to female infants early in life

Distribution of entanglement in light-harvesting complexes and their quantum efficiency

Recent evidence of electronic coherence during energy transfer in photosynthetic antenna complexes has reinvigorated the discussion of whether coherence and/or entanglement has any practical functionality for these molecular systems. Here we investigate quantitative relationships between the quantum yield of a light-harvesting complex and the distribution of entanglement among its components. Our study focusses on the entanglement yield or average entanglement surviving a time scale comparable to the average excitation trapping time. As a prototype system we consider the Fenna-Matthews-Olson (FMO) protein of green sulphur bacteria and show that there is an inverse relationship between the quantum efficiency and the average entanglement between distant donor sites. Our results suggest that longlasting electronic coherence among distant donors might help modulation of the lightharvesting function.Comment: Version accepted for publication in NJ

The effect of Zr and Sn additions on the microstructure of Ti-Nb-Fe gum metals with high elastic admissible strain

An open challenge on structural biomaterials is to obtain low-cost Ti-alloys with high elastic admissible strength (the ratio of yield strength to modulus). To reach this goal, we designed and characterized three quaternary alloys from the Ti-Nb-Fe system with additions of Zr and Sn. The samples were solution-treated and tested under two conditions: water-quenched and aged at 450 °C. Microstructures were analyzed with aid of scanning and transmission electron microscopy. Tensile tests performed at room-temperature confirmed a remarkable yield strength of 1271 MPa with an elastic modulus close to 90 GPa among aged Ti-19Nb-2.5Fe-6Sn (wt%) samples. Solution-treated Ti-19Nb-2.5Fe-10Zr samples presented a good combination of yield-strength and elastic modulus (1027 MPa and 69 GPa, respectively), displaying an elastic admissible strength close to 1.5. Although Zr and Sn are equally distributed between matrix and precipitates, the diffusion of Nb and Fe seem to be inhibited by the presence of Sn. As a result, Sn allows higher yield-strengths and more refined secondary α-phase, while Zr has a stronger effect on reducing the elastic modulus. In the end, a materials selection chart is presented to help designers to select materials for orthopedic implants considering the elastic admissible strain and cost as major guidelines16011861195CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPNão tem2014/24449-0; 2016/22714-3; 2016/24693-3Funding: This work was supported by FAPESP (São Paulo State Research Foundation, grants numbers 2014/24449-0, 2016/22714-3 and 2016/24693-3) and CNPq (National Council for Scientific and Technological Development). The authors gratefully acknowledge Prof. Hamish Fraser for the use of experimental facilities at the Center for Electron Microscopy and Analysis (CEMAS), at the Ohio State University, USA, and thank CBMM Co. for the Nb supply. The raw/processed data required to reproduce these findings cannot be shared at this time as the data also forms part of an ongoing study. Data will be made available upon reques

Exciton Dynamics in Photosynthetic Complexes: Excitation by Coherent and Incoherent Light

In this paper we consider dynamics of a molecular system subjected to external pumping by a light source. Within a completely quantum mechanical treatment, we derive a general formula, which enables to asses effects of different light properties on the photo-induced dynamics of a molecular system. We show that once the properties of light are known in terms of certain two-point correlation function, the only information needed to reconstruct the system dynamics is the reduced evolution superoperator. The later quantity is in principle accessible through ultrafast non-linear spectroscopy. Considering a direct excitation of a small molecular antenna by incoherent light we find that excitation of coherences is possible due to overlap of homogeneous line shapes associated with different excitonic states. In Markov and secular approximations, the amount of coherence is significant only under fast relaxation, and both the populations and coherences between exciton states become static at long time. We also study the case when the excitation of a photosynthetic complex is mediated by a mesoscopic system. We find that such case can be treated by the same formalism with a special correlation function characterizing ultrafast fluctuations of the mesoscopic system. We discuss bacterial chlorosom as an example of such a mesoscopic mediator and propose that the properties of energy transferring chromophore-protein complexes might be specially tuned for the fluctuation properties of their associated antennae.Comment: 12 page

Motional effects on the efficiency of excitation transfer

Energy transfer plays a vital role in many natural and technological processes. In this work, we study the effects of mechanical motion on the excitation transfer through a chain of interacting molecules with application to biological scenarios of transfer processes. Our investigation demonstrates that, for various types of mechanical oscillations, the transfer efficiency is significantly enhanced over that of comparable static configurations. This enhancement is a genuine quantum signature, and requires the collaborative interplay between the quantum-coherent evolution of the excitation and the mechanical motion of the molecules; it has no analogue in the classical incoherent energy transfer. This effect may not only occur naturally, but it could be exploited in artificially designed systems to optimize transport processes. As an application, we discuss a simple and hence robust control technique.Comment: 25 pages, 11 figures; completely revised; version accepted for publicatio

Full characterization of vibrational coherence in a porphyrin chromophore by two-dimensional electronic spectroscopy

In this work we present experimental and calculated two-dimensional electronic spectra for a 5,15-bisalkynyl porphyrin chromophore. The lowest energy electronic Qy transition couples mainly to a single 380 cm–1 vibrational mode. The two-dimensional electronic spectra reveal diagonal and cross peaks which oscillate as a function of population time. We analyze both the amplitude and phase distribution of this main vibronic transition as a function of excitation and detection frequencies. Even though Feynman diagrams provide a good indication of where the amplitude of the oscillating components are located in the excitation-detection plane, other factors also affect this distribution. Specifically, the oscillation corresponding to each Feynman diagram is expected to have a phase that is a function of excitation and detection frequencies. Therefore, the overall phase of the experimentally observed oscillation will reflect this phase dependence. Another consequence is that the overall oscillation amplitude can show interference patterns resulting from overlapping contributions from neighboring Feynman diagrams. These observations are consistently reproduced through simulations based on third order perturbation theory coupled to a spectral density described by a Brownian oscillator model