Spectral hole burning: examples from photosynthesis

The optical spectra of photosynthetic pigment–protein complexes usually show broad absorption bands, often consisting of a number of overlapping, ‘hidden’ bands belonging to different species. Spectral hole burning is an ideal technique to unravel the optical and dynamic properties of such hidden species. Here, the principles of spectral hole burning (HB) and the experimental set-up used in its continuous wave (CW) and time-resolved versions are described. Examples from photosynthesis studied with hole burning, obtained in our laboratory, are then presented. These examples have been classified into three groups according to the parameters that were measured: (1) hole widths as a function of temperature, (2) hole widths as a function of delay time and (3) hole depths as a function of wavelength. Two examples from light-harvesting (LH) 2 complexes of purple bacteria are given within the first group: (a) the determination of energy-transfer times from the chromophores in the B800 ring to the B850 ring, and (b) optical dephasing in the B850 absorption band. One example from photosystem II (PSII) sub-core complexes of higher plants is given within the second group: it shows that the size of the complex determines the amount of spectral diffusion measured. Within the third group, two examples from (green) plants and purple bacteria have been chosen for: (a) the identification of ‘traps’ for energy transfer in PSII sub-core complexes of green plants, and (b) the uncovering of the lowest k = 0 exciton-state distribution within the B850 band of LH2 complexes of purple bacteria. The results prove the potential of spectral hole burning measurements for getting quantitative insight into dynamic processes in photosynthetic systems at low temperature, in particular, when individual bands are hidden within broad absorption bands. Because of its high-resolution wavelength selectivity, HB is a technique that is complementary to ultrafast pump–probe methods. In this review, we have provided an extensive bibliography for the benefit of scientists who plan to make use of this valuable technique in their future research

Effects of sodium citrate ingestion before exercise on endurance performance in well trained college runners

Objective: To test the hypothesis that sodium citrate administered two hours before exercise improves performance in a 5 km running time trial. Methods: A total of 17 male well trained college runners (mean (SD) [Image: see text] O(2)MAX 61.3 (4.9) ml/kg/min) performed a 5 km treadmill run with and without sodium citrate ingestion in a random, double blind, crossover design. In the citrate trial, subjects consumed 1 litre of solution containing 0.5 g of sodium citrate/kg body mass two hours before the run. In the placebo trial, the same amount of flavoured mineral water was consumed. Results: The time required to complete the run was faster in the citrate trial than the placebo trial (1153.2 (74.1) and 1183.8 (91.4) seconds respectively; p = 0.01). Lower packed cell volume and haemoglobin levels were found in venous blood samples taken before and after the run in the citrate compared with the placebo trial. Lactate concentration in the blood sample taken after the run was higher in the citrate than the placebo trial (11.9 (3.0) v 9.8 (2.8) mmol/l; p<0.001), and glucose concentration was lower (8.3 (1.9) v 8.8 (1.7) mmol/l; p = 0.02). Conclusion: The ingestion of 0.5 g of sodium citrate/kg body mass shortly before a 5 km running time trial improves performance in well trained college runners

Energy transfer in the inhomogeneously broadened core antenna of purple bacteria: a simultaneous fit of low-intensity picosecond absorption and fluorescence kinetics

The excited state decay kinetics of chromatophores of the purple photosynthetic bacterium Rhodospirillum rubrum have been recorded at 77 K using picosecond absorption difference spectroscopy under strict annihilation free conditions. The kinetics are shown to be strongly detection wavelength dependent. A simultaneous kinetic modeling of these experiments together with earlier fluorescence kinetics by numerical integration of the appropriate master equation is performed. This model, which accounts for the spectral inhomogeneity of the core light-harvesting antenna of photosynthetic purple bacteria, reveals three qualitatively distinct stages of excitation transfer with different time scales. At first a fast transfer to a local energy minimum takes place (approximately 1 ps). This is followed by a much slower transfer between different energy minima (10–30 ps). The third component corresponds to the excitation transfer to the reaction center, which depends on its state (60 and 200 ps for open and closed, respectively) and seems also to be the bottleneck in the overall trapping time. An acceptable correspondence between theoretical and experimental decay kinetics is achieved at 77 K and at room temperature by assuming that the width of the inhomogeneous broadening is 10–15 nm and the mean residence time of the excitation in the antenna lattice site is 2–3 ps

Fluorescence-excitation and emission spectra from LH2 antenna complexes of rhodopseudomonas acidophila as a function of the sample preparation conditions

The high sensitivity of optical spectra of pigment–protein complexes to temperature and pressure is well known. In the present study, we have demonstrated the significant influence of the environments commonly used in bulk and single-molecule spectroscopic studies at low temperatures on the LH2 photosynthetic antenna complex from Rhodopseudomonas acidophila. A transfer of this LH2 complex from a bulk-buffer solution into a spin-coated polymer film results in a 189 cm–1 blue shift of the B850 excitonic absorption band at 5 K. Within the molecular exciton model, the origin of this shift could be disentangled into three parts, namely to an increase of the local site energies, a contraction of the exciton band, and a decrease of the displacement energy