Modeling of fluence-dependent hole-burned spectra and hole-growth kinetics using multiple two-level system model.

Numerical formalism is presented that perfectly describes resonant low-temperature hole-burned spectra (including zero-phonon holes, ZPHs) and spectral hole-growth dynamics of Al-phthalocyanine tetrasulphonate embedded in hyperquenched glassy water films over more than seven orders of fluence magnitude (0.4 µJ/cm2-5.9 J/cm2).

Frequency-Domain Spectroscopic Study of the Photosystem I Supercomplexes, Isolated IsiA Monomers, and the Intact IsiA Ring.

The PSI-IsiA supercomplex is one of the largest and most complicated assemblies in photosynthesis. The IsiA ring, composed of 18 IsiA monomers (IsiA) surrounding the PSI trimer (PSI), forms under iron-deficient conditions in cyanobacteria and acts as a peripheral antenna. Based on the supercomplex structure recently determined via cryo-EM imaging, we model various optical spectra of the IsiA monomers and IsiA ring.

Exciton Lifetime Distributions and Population Dynamics in the FMO Protein Complex from .

Significant protein rearrangement upon excitation and energy transfer in Fenna-Matthews-Olson protein of results in a modified energy landscape, which induces more changes in pigment site energies than predicted by the "standard" hole-burning theory. The energy changes are elucidated by simulations while investigating the effects of site-dependent disorder, both static (site-energy distribution widths) and dynamic (spectral density shapes). The resulting optimized site energies and their fluctuations are consistent with relative differences observed in inhomogeneous widths calculated by recent molecular dynamic simulations.

On wavelength-dependent exciton lifetime distributions in reconstituted CP29 antenna of the photosystem II and its site-directed mutants.

To provide more insight into the excitonic structure and exciton lifetimes of the wild type (WT) CP29 complex of photosystem II, we measured high-resolution (low temperature) absorption, emission, and hole burned spectra for the A2 and B3 mutants, which lack chlorophylls a612 and b614 (Chls), respectively. Experimental and modeling results obtained for the WT CP29 and A2/B3 mutants provide new insight on the mutation-induced changes at the molecular level and shed more light on energy transfer dynamics. Simulations of the A2 and B3 optical spectra, using the second-order non-Markovian theory, and comparison with improved fits of WT CP29 optical spectra provide more insight into their excitonic structure, mutation induced changes, and frequency-dependent distributions of exciton lifetimes (T).

On uncorrelated inter-monomer Förster energy transfer in Fenna-Matthews-Olson complexes.

The Fenna-Matthews-Olson (FMO) light-harvesting antenna protein of green sulfur bacteria is a long-studied pigment-protein complex which funnels energy from the chlorosome to the reaction centre where photochemistry takes place. The structure of the FMO protein from Chlorobaculum tepidum is known as a homotrimeric complex containing eight bacteriochlorophyll a per monomer. Owing to this structure FMO has strong intra-monomer and weak inter-monomer electronic coupling constants.

Mixed Upper Exciton State of the Special Pair in Bacterial Reaction Centers.

Excitonic interactions between two closely separated bacteriochlorophyll a molecules (BChls) in the special pair of the reaction center (RC) of purple bacteria determine the positions and relative oscillator strengths of its two excitonic components. While the absorption of the lower excitonic band is well-defined, the position and the intensity of the upper excitonic band ( P) are still under debate. Recent 77 K two-dimensional electronic spectroscopy data on Rba.

Impact of Single-Point Mutations on the Excitonic Structure and Dynamics in a Fenna-Matthews-Olson Complex.

Hole burning (HB) spectroscopy and modeling studies reveal significant changes in the excitonic structure and dynamics in several mutants of the FMO trimer from the Chlorobaculum tepidum. The excited-state decay times ( T) of the high-energy excitons are significantly modified when mutation occurs near bacteriochlorophyll (BChl) 1 (V152N mutant) or BChl 6 (W184F). Longer (averaged) T times of highest-energy excitons in V152N and W184F mutants suggest that site energies of BChls 1 and 6, believed to play an important role in receiving excitation from the baseplate BChls, likely play a critical role to ensure the femtosecond (fs) energy relaxation observed in wild-type FMO.

Energy landscape of the intact and destabilized FMO antennas from C. tepidum and the L122Q mutant: Low temperature spectroscopy and modeling study.

We discuss the excitonic energy landscape of the typically studied wild-type (WT) Fenna-Matthews-Olson (FMO) antenna protein from the green sulfur bacterium Chlorobaculum tepidum (referred to as WT), which is described as a mixture of intact (WT) and destabilized (WT) complexes. Optical spectra of WT and the L122Q mutant (where leucine 122 near BChl 8 is replaced with glutamine) are compared to WT FMO. We show that WT and L122Q samples are mixtures of two subpopulations of proteins, most likely induced by protein conformational changes during the isolation/purification procedures.

Toward an Understanding of the Excitonic Structure of the CP47 Antenna Protein Complex of Photosystem II Revealed via Circularly Polarized Luminescence.

Identification of the lowest energy pigments in the photosynthetic CP47 antenna protein complex of Photosystem II (PSII) is essential for understanding its excitonic structure, as well as excitation energy pathways in the PSII core complex. Unfortunately, there is no consensus concerning the nature of the low-energy state(s), nor chlorophyll (Chl) site energies in this important photosynthetic antenna. Although we raised concerns regarding the estimations of Chl site energies obtained from modeling studies of various types of CP47 optical spectra [Reinot, T; et al.

On the Conflicting Estimations of Pigment Site Energies in Photosynthetic Complexes: A Case Study of the CP47 Complex.

We focus on problems with elucidation of site energies [Formula: see text] for photosynthetic complexes (PSCs) in order to raise some genuine concern regarding the conflicting estimations propagating in the literature. As an example, we provide a stern assessment of the site energies extracted from fits to optical spectra of the widely studied CP47 antenna complex of photosystem II from spinach, though many general comments apply to other PSCs as well. Correct values of [Formula: see text] for chlorophyll (Chl) a in CP47 are essential for understanding its excitonic structure, population dynamics, and excitation energy pathway(s).

Selection of haploid maize kernels from hybrid kernels for plant breeding using near-infrared spectroscopy and SIMCA analysis.

Samples of haploid and hybrid seed from three different maize donor genotypes after maternal haploid induction were used to test the capability of automated near-infrared transmission spectroscopy to individually differentiate haploid from hybrid seeds. Using a two-step chemometric analysis in which the seeds were first classified according to genotype and then the haploid or hybrid status was determined proved to be the most successful approach. This approach allowed 11 of 13 haploid and 25 of 25 hybrid kernels to be correctly identified from a mixture that included seeds of all the genotypes.

Low-temperature protein dynamics of the B800 molecules in the LH2 light-harvesting complex: spectral hole burning study and comparison with single photosynthetic complex spectroscopy.

Previously published and new spectral hole burning (SHB) data on the B800 band of LH2 light-harvesting antenna complex of Rps. acidophila are analyzed in light of recent single photosynthetic complex spectroscopy (SPCS) results (for a review, see Berlin et al. Phys.

Hyperquenched glassy water and hyperquenched glassy ethanol probed by single molecule spectroscopy.

It is still unclear whether hyperquenched water (i.e., amorphous glassy water) heated to about 140-150 K remains glassy until it crystallizes near 154 K or whether instead it turns into a supercooled and very viscous liquid.

Terrylene in hexadecane revisited: a hole burning study.

Holes burnt into the absorption spectrum of terrylene in hexadecane have quite unusual features: spectral diffusion behavior under thermal cycles shows a narrowing regime at very low temperatures (2-5 K) followed by a plateau region (up to about 13 K) and a broadening regime (T>13 K). Thermal line broadening (quasihomogeneous linewidth) shows a nonmonotonous behavior as a function of temperature: at around 4 K there is a maximum followed by a flat minimum and the onset of strong broadening at higher temperatures. Finally, the central hole shows one-sided narrowly spaced side features.

Red antenna states of photosystem I from cyanobacteria Synechocystis PCC 6803 and Thermosynechococcus elongatus: single-complex spectroscopy and spectral hole-burning study.

Hole-burning and single photosynthetic complex spectroscopy were used to study the excitonic structure and excitation energy-transfer processes of cyanobacterial trimeric Photosystem I (PS I) complexes from Synechocystis PCC 6803 and Thermosynechococcus elongatus at low temperatures. It was shown that individual PS I complexes of Synechocystis PCC 6803 (which have two red antenna states, i.e.