Quantum coherent energy transport in the Fenna-Matthews-Olson complex at low temperature.

In the primary step of natural light harvesting, the solar photon energy is captured in a photoexcited electron-hole pair, or an exciton, in chlorophyll. Its conversion to chemical potential occurs in the special pair reaction center, which is reached by downhill ultrafast excited-state energy transport through a network of chromophores. Being inherently quantum, transport could in principle occur via a matter wave, with vast implications for efficiency.

Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state.

The concerted interplay between reactive nuclear and electronic motions in molecules actuates chemistry. Here, we demonstrate that out-of-plane torsional deformation and vibrational excitation of stretching motions in the electronic ground state modulate the charge-density distribution in a donor-bridge-acceptor molecule in solution. The vibrationally-induced change, visualised by transient absorption spectroscopy with a mid-infrared pump and a visible probe, is mechanistically resolved by molecular dynamics simulations.

Excited-State Vibronic Dynamics of Bacteriorhodopsin from Two-Dimensional Electronic Photon Echo Spectroscopy and Multiconfigurational Quantum Chemistry.

Owing to the ultrafast time scale of the photoinduced reaction and high degree of spectral overlap among the reactant, product, and excited electronic states in bacteriorhodopsin (bR), it has been a challenge for traditional spectroscopies to resolve the interplay between vibrational dynamics and electronic processes occurring in the retinal chromophore of bR. Here, we employ ultrafast two-dimensional electronic photon echo spectroscopy to follow the early excited-state dynamics of bR preceding the isomerization. We detect an early periodic photoinduced absorptive signal that, employing a hybrid multiconfigurational quantum/molecular mechanical model of bR, we attribute to periodic mixing of the first and second electronic excited states (S and S, respectively).

Quantum biology revisited.

Photosynthesis is a highly optimized process from which valuable lessons can be learned about the operating principles in nature. Its primary steps involve energy transport operating near theoretical quantum limits in efficiency. Recently, extensive research was motivated by the hypothesis that nature used quantum coherences to direct energy transfer.

Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran.

The ultrafast dynamics of unsubstituted spironaphthopyran (SNP) were investigated using femtosecond transient UV and visible absorption spectroscopy in three different solvents and by semi-classical nuclear dynamics simulations. The primary ring-opening of the pyran unit was found to occur in 300 fs yielding a non-planar intermediate in the first singlet excited state (S1). Subsequent planarisation and relaxation to the product ground state proceed through barrier crossing on the S1 potential energy surface (PES) and take place within 1.

Pyrene, a Test Case for Deep-Ultraviolet Molecular Photophysics.

We determined the complete relaxation dynamics of pyrene in ethanol from the second bright state, employing experimental and theoretical broadband heterodyne detected transient grating and two-dimensional photon echo (2DPE) spectroscopy, using pulses with duration of 6 fs and covering a spectral range spanning from 250 to 300 nm. Multiple lifetimes are assigned to conical intersections through a cascade of electronic states, eventually leading to a rapid population of the lowest long-living excited state and subsequent slow vibrational cooling. The lineshapes in the 2DPE spectra indicate that the efficiency of the population transfer depends on the kinetic energy deposited into modes required to reach a sloped conical intersection, which mediates the decay to the lowest electronic state.

Progressive Scoliosis and Syringomyelia - Questions of Surgical Approach.

Background: The rate of scoliosis in syringomyelia patients ranges from 25 to 74.4%. In turn, syringomyelia occurs in 1.

Primary Charge Separation in the Photosystem II Reaction Center Revealed by a Global Analysis of the Two-dimensional Electronic Spectra.

The transfer of electronic charge in the reaction center of Photosystem II is one of the key building blocks of the conversion of sunlight energy into chemical energy within the cascade of the photosynthetic reactions. Since the charge transfer dynamics is mixed with the energy transfer dynamics, an effective tool for the direct resolution of charge separation in the reaction center is still missing. Here, we use experimental two-dimensional optical photon echo spectroscopy in combination with the theoretical calculation to resolve its signature.

Simulation of photo-excited adenine in water with a hierarchy of equations of motion approach.

We present a theoretical method to simulate the electronic dynamics and two-dimensional ultraviolet spectra of the nucleobase adenine in water. The method is an extension of the hierarchy of equations of motion approach to treat a model with one or more conical intersections. The application to adenine shows that a two-level model with a direct conical intersection between the optically bright state and the ground state, generating a hot ground state, is not consistent with experimental observations.

Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer.

During the first steps of photosynthesis, the energy of impinging solar photons is transformed into electronic excitation energy of the light-harvesting biomolecular complexes. The subsequent energy transfer to the reaction center is commonly rationalized in terms of excitons moving on a grid of biomolecular chromophores on typical timescales [Formula: see text]100 fs. Today's understanding of the energy transfer includes the fact that the excitons are delocalized over a few neighboring sites, but the role of quantum coherence is considered as irrelevant for the transfer dynamics because it typically decays within a few tens of femtoseconds.

Coherent ultrafast lattice-directed reaction dynamics of triiodide anion photodissociation.

Solid-state reactions are influenced by the spatial arrangement of the reactants and the electrostatic environment of the lattice, which may enable lattice-directed chemical dynamics. Unlike the caging imposed by an inert matrix, an active lattice participates in the reaction, however, little evidence of such lattice participation has been gathered on ultrafast timescales due to the irreversibility of solid-state chemical systems. Here, by lowering the temperature to 80 K, we have been able to study the dissociative photochemistry of the triiodide anion (I) in single-crystal tetra-n-butylammonium triiodide using broadband transient absorption spectroscopy.

The Primary Photochemistry of Vision Occurs at the Molecular Speed Limit.

Ultrafast photochemical reactions are initiated by vibronic transitions from the reactant ground state to the excited potential energy surface, directly populating excited-state vibrational modes. The primary photochemical reaction of vision, the isomerization of retinal in the protein rhodopsin, is known to be a vibrationally coherent reaction, but the Franck-Condon factors responsible for initiating the process have been difficult to resolve with conventional time-resolved spectroscopies. Here we employ experimental and theoretical 2D photon echo spectroscopy to directly resolve for the first time the Franck-Condon factors that initiate isomerization on the excited potential energy surface and track the reaction dynamics.

New Insights into the Photophysics of DNA Nucleobases.

We report the results of an extended time-resolved study of DNA nucleobases in aqueous solutions conducted in the deep UV using broad-band femtosecond transient absorption and electronic two-dimensional spectroscopies. We found that the photodeactivation in all DNA nucleobases occurs in two steps: fast relaxation (500-700 fs) from the excited state ππ* to a "dark" state and its depopulation to the ground state within 1-2 ps. Our experimental observations and performed theoretical modeling allow us to conclude that this dark state can be associated with the nπ* electronic state, which is connected to the excited and ground states via conical intersections.

[ASSESSMENT OF ENERGY NEEDS AND THE ROLE OF NUTRITIONAL SUPPORT IN SENILE PATIENTS WITH INTESTINAL FAILURE IN ORTHOPEDIC SURGERY OF HIGH RISK].

The study of anamnestic, clinical, laboratory, endoscopic, morphological parallels of senile patients in knee and hip joints prosthesis shows the presence of intestinal failure while perioperative period. A direct connection between a natural intestinal and immune dysfunction and nutritional deficiency was diagnosed. The use of nutritional-metabolic correction of comorbid pathology and determination of basal metabolism in the perioperative period enabled to normalize indicators of homeostasis, microflora of the colon, indicators of immune status, and get a reduction in the number of early postoperative complications.

Reconstruction Of Glenoid Bone Deficiency With Porous Titanium Nickelide In Recurrent Anterior Shoulder Instability.

Introduction: One of the main causes of recurrent shoulder instability is a bone defect of the front edge of the glenoid. The available techniques for reconstruction of this bone defect, however, have some disadvantages.

Objective: The aim of this study was to develop a new method that can reduce the number of postoperative complications and improve the efficiency of surgical treatment of recurrent anterior shoulder instability with glenoid bone defect.

A closed-loop pump-driven wire-guided flow jet for ultrafast spectroscopy of liquid samples.

We describe the design and provide the results of the full characterization of a closed-loop pump-driven wire-guided flow jet system. The jet has excellent optical quality with a wide range of liquids spanning from alcohol to water based solutions, including phosphate buffers used for biological samples. The thickness of the jet film varies depending on the flow rate between 90 μm and 370 μm.

Two-Dimensional Electronic Spectroscopy of Light-Harvesting Complex II at Ambient Temperature: A Joint Experimental and Theoretical Study.

We have performed broad-band two-dimensional (2D) electronic spectroscopy of light-harvesting complex II (LHCII) at ambient temperature. We found that electronic dephasing occurs within ∼60 fs and inhomogeneous broadening is approximately 120 cm(-1). A three-dimensional global fit analysis allows us to identify several time scales in the dynamics of the 2D spectra ranging from 100 fs to ∼10 ps and to uncover the energy-transfer pathways in LHCII.

The photocycle and ultrafast vibrational dynamics of bacteriorhodopsin in lipid nanodiscs.

The photocycle and vibrational dynamics of bacteriorhodopsin in a lipid nanodisc microenvironment have been studied by steady-state and time-resolved spectroscopies. Linear absorption and circular dichroism indicate that the nanodiscs do not perturb the structure of the retinal binding pocket, while transient absorption and flash photolysis measurements show that the photocycle which underlies proton pumping is unchanged from that in the native purple membranes. Vibrational dynamics during the initial photointermediate formation are subsequently studied by ultrafast broadband transient absorption spectroscopy, where the low scattering afforded by the lipid nanodisc microenvironment allows for unambiguous assignment of ground and excited state nuclear dynamics through Fourier filtering of frequency regions of interest and subsequent time domain analysis of the retrieved vibrational dynamics.

Vibronic and vibrational coherences in two-dimensional electronic spectra of supramolecular J-aggregates.

In J-aggregates of cyanine dyes, closely packed molecules form mesoscopic tubes with nanometer-diameter and micrometer-length. Their efficient energy transfer pathways make them suitable candidates for artificial light harvesting systems. This great potential calls for an in-depth spectroscopic analysis of the underlying energy deactivation network and coherence dynamics.

[Criteria of antibacterials choice for prophylaxis and therapy of implant-associated infections in prosthetic joints].

Prosthetic joints infection is a serious medical, social and financial problem. Significant achievements in prophylaxis of such infections are well known. In cases of primary endoprosthetics of large joints, the frequency of infection in the leading world clinics is 0.

Enhanced bandwidth noncollinear optical parametric amplification with a narrowband anamorphic pump.

Through the use of anamorphic focusing, we present a method for generating broadband noncollinear optical parametric amplification in signal regions lacking a broadband phase-matching condition that is ideally suited for narrowband pump sources, herein based on an erbium-doped fiber oscillator. With a short focal length cylindrical lens to enhance the phase-matching condition and a long focal length cylindrical lens in the orthogonal plane to limit the pump power in the amplifying beta barium borate crystal, we amplify pulses in the blue-green spectral region with over 100 THz (∼3500 cm(-1)) bandwidth. The amplified signal is subsequently compressed to 9.

Coherent control of the isomerization of retinal in bacteriorhodopsin in the high intensity regime.

Coherent control protocols provide a direct experimental determination of the relative importance of quantum interference or phase relationships of coupled states along a selected pathway. These effects are most readily observed in the high intensity regime where the field amplitude is sufficient to overcome decoherence effects. The coherent response of retinal photoisomerization in bacteriorhodopsin to the phase of the photoexcitation pulses was examined at fluences of 10(15) - 2.

Coherently-controlled two-dimensional spectroscopy: evidence for phase induced long-lived memory effects.

Using low-intensity phase-shaped excitation pulses we used two-dimensional (2D) electronic spectroscopy to follow the time dependence of the coherent correlations imposed on a solvated organic dye (Rhodamine 101 in methanol) at room temperature. Shaping of the excitation pulses strongly affects both the real and imaginary parts of the 2D-spectra, especially at small waiting times. In particular, the periodic phase modulation of the excitation pulses appears as a two-dimensional grid-like modulation in the correlation spectrum corresponding to the waiting time T = 0.

Stable UV to IR supercontinuum generation in calcium fluoride with conserved circular polarization states.

The supercontinuum generated with a linearly polarized near-IR (775 nm) pump in rotated calcium fluoride is shown to have intrinsic intensity and polarization modulations. To mask the rotation of the crystal plate, we circularly polarize the pump and find greatly improved output parameters for the generated white light: intensity fluctuations of 0.5% limited only by pump laser stability, and a circular polarization state-matching that of the pump-over the entire visible spectrum.