On the relation of protein dynamics and exciton relaxation in pigment–protein complexes: An estimation of the spectral density and a theory for the calculation of optical spectra

A theory for calculating time– and frequency–domain optical spectra of pigment–protein complexes is presented using a density matrix approach. Non-Markovian effects in the exciton–vibrational coupling are included. A correlation function is deduced from the simulation of 1.6 K fluorescence line narrowing spectra of a monomer pigment–protein complex (B777), and then used to calculate fluorescence line narrowing spectra of a dimer complex (B820). A vibrational sideband of an excitonic transition is obtained, a distinct non-Markovian feature, and agrees well with experiment on B820 complexes. The theory and the above correlation function are used elsewhere to make predictions and compare with data on time–domain pump–probe spectra and frequency–domain linear absorption, circular dichroism and fluorescence spectra of Photosystem II reaction centers

The DLR Complex Irradiation Facility (CIF)

The DLR Institute of Space Systems in Bremen has built a new facility to study the behavior of materials under complex irradiation and to estimate their degradation in a space environment. It is named Complex Irradiation Facility (CIF). CIF allows simultaneously irradiating samples with three light sources for the simulation of the spectrum of solar electromagnetic radiation. The light sources are a solar simulator with a Xe-lamp (wavelength range 300-1200nm), a deuterium-UV-source (112-200nm), and an Argon-gas-jet-VUV-simulator. The latter allows irradiating samples with shorter wavelengths below the limitation of any window material. The VUV-simulator has been validated at the PTB (Physikalisch Technische Bundesanstalt) in Berlin by calibration that uses synchrotron radiation in the wavelength range between 40 and 400nm. Beside the different light sources CIF provides also electron and proton sources. Electrons and protons are generated in a low energy range from 1 to 10 keV with currents from 1 to 100 nA and in a higher range from 10 to 100 keV with 0.1 to 100 µA. Both particle sources can be operated simultaneously. In order to model temperature variations as appear in free space, the sample can be cooled down to liquid Nitrogen and heated up to about 450 K during irradiation. The complete facility has been manufactured in UHV-technology with metal sealing. It is free of organic compounds to avoid self-contamination. The different pumping systems achieve a final pressure of 1*1010 mbar (empty sample chamber) Besides the installed radiation sensors that control the stability of the various radiation sources and an attached mass spectrometer for analyzing the outgassing processes in the chamber, the construction of CIF allows adding other in-situ measurement systems to measure parameters that are of the user’s interest. We are currently planning to develop an in-situ measurement system in order to determine changes in the optical properties of the samples caused by irradiation. Within this paper we will show the design of CIF in more detail and discuss the performance of the various radiation sources

Design and performance of a vacuum-UV simulator for material testing under space conditions

This paper describes the construction and performance of a VUV-simulator that has been designed to study degradation of materials under space conditions. It is part of the Complex Irradiation Facility at DLR in Bremen, Germany, that has been built for testing of material under irradiation in the complete UV-range as well as under proton and electron irradiation. Presently available UV-sources used for material tests do not allow the irradiation with wavelengths smaller than about $115$ nm where common Deuterium lamps show an intensity cut-off. The VUV-simulator generates radiation by excitation of a gas-flow with an electron beam. The intensity of the radiation can be varied by manipulating the gas-flow and/or the electron beam. The VUV simulator has been calibrated at three different gas-flow settings in the range from $40$ nm to $410$ nm. The calibration has been made by the Physikalisch-Technische Bundesanstalt (PTB) in Berlin. The measured spectra show total irradiance intensities from $24$ to $58$ mW$\rm{m^{-2}}$ (see Table 4.2) in the VUV-range, i.e. for wavelengths smaller than $200$ nm. They exhibit a large number of spectral lines generated either by the gas-flow constituents or by metal atoms in the residual gas which come from metals used in the source construction. In the range from $40$ nm to $120$ nm where Deuterium lamps are not usable, acceleration factors of $3$ to $26.3$ Solar Constants are reached depending on the gas-flow setting. The VUV-simulator allows studies of general degradation effects caused by photoionization and photodissociation as well as accelerated degradation tests by use of intensities that are significantly higher compared to that of the Sun at $1$ AU

The Complex Irradiation Facility at DLR-Bremen

All material exposed to interplanetary space conditions are subject to degradation processes. For obvious reasons there is a great interest to study these processes for materials that are used in satellite construction. However, also the influence of particle and electromagnetic radiation on the weathering of extraterrestrial rocks and on organic and biological tissues is the research topic of various scientific disciplines. To strengthen the comprehensive and systematic investigation of degradation processes a new laboratory, the complex irradiation facility (CIF), has been designed, set up, tested, and put into operation at the DLR-Institute of Space Systems in Bremen (Germany). The CIF allows the simultaneous irradiation with three light sources and with a dual beam irradiation system for the bombardment of materials with electrons and protons having energies up to 100 keV. It is eminently suitable to perform a large variety of irradiation procedures that are similar to those which appear at different distances to the Sun. This paper is devoted to potential users in order to inform them about the capabilities of the CIF

Spectroscopic Properties of Reaction Center Pigments in Photosystem II Core Complexes: Revision of the Multimer Model

AbstractAbsorbance difference spectra associated with the light-induced formation of functional states in photosystem II core complexes from Thermosynechococcus elongatus and Synechocystis sp. PCC 6803 (e.g., P+Pheo−,P+QA−,3P) are described quantitatively in the framework of exciton theory. In addition, effects are analyzed of site-directed mutations of D1-His198, the axial ligand of the special-pair chlorophyll PD1, and D1-Thr179, an amino-acid residue nearest to the accessory chlorophyll ChlD1, on the spectral properties of the reaction center pigments. Using pigment transition energies (site energies) determined previously from independent experiments on D1-D2-cytb559 complexes, good agreement between calculated and experimental spectra is obtained. The only difference in site energies of the reaction center pigments in D1-D2-cytb559 and photosystem II core complexes concerns ChlD1. Compared to isolated reaction centers, the site energy of ChlD1 is red-shifted by 4nm and less inhomogeneously distributed in core complexes. The site energies cause primary electron transfer at cryogenic temperatures to be initiated by an excited state that is strongly localized on ChlD1 rather than from a delocalized state as assumed in the previously described multimer model. This result is consistent with earlier experimental data on special-pair mutants and with our previous calculations on D1-D2-cytb559 complexes. The calculations show that at 5K the lowest excited state of the reaction center is lower by ∼10nm than the low-energy exciton state of the two special-pair chlorophylls PD1 and PD2 which form an excitonic dimer. The experimental temperature dependence of the wild-type difference spectra can only be understood in this model if temperature-dependent site energies are assumed for ChlD1 and PD1, reducing the above energy gap from 10 to 6 nm upon increasing the temperature from 5 to 300K. At physiological temperature, there are considerable contributions from all pigments to the equilibrated excited state P*. The contribution of ChlD1 is twice that of PD1 at ambient temperature, making it likely that the primary charge separation will be initiated by ChlD1 under these conditions. The calculations of absorbance difference spectra provide independent evidence that after primary electron transfer the hole stabilizes at PD1, and that the physiologically dangerous charge recombination triplets, which may form under light stress, equilibrate between ChlD1 and PD1

Towards a structure-based exciton Hamiltonian for the CP29 antenna of photosystem II

The exciton Hamiltonian pertaining to the first excited states of chlorophyll (Chl) a and b pigments in the minor light-harvesting complex CP29 of plant photosystem II is determined based on the recent crystal structure at 2.8 Å resolution applying a combined quantum chemical/electrostatic approach as used earlier for the major light-harvesting complex LHCII. Two electrostatic methods for the calculation of the local transition energies (site energies), referred to as the Poisson–Boltzmann/quantum chemical (PBQC) and charge density coupling (CDC) method, which differ in the way the polarizable environment of the pigments is described, are compared and found to yield comparable results, when tested against fits of measured optical spectra (linear absorption, linear dichroism, circular dichroism, and fluorescence). The crystal structure shows a Chl a/b ratio of 2.25, whereas a ratio between 2.25 and 3.0 can be estimated from the simulation of experimental spectra. Thus, it is possible that up to one Chl b is lost in CP29 samples. The lowest site energy is found to be located at Chl a604 close to neoxanthin. This assignment is confirmed by the simulation of wild-type-minus-mutant difference spectra of reconstituted CP29, where a tyrosine residue next to Chl a604 is modified in the mutant. Nonetheless, the terminal emitter domain (TED), i.e. the pigments contributing mostly to the lowest exciton state, is found at the Chl a611–a612–a615 trimer due to strong excitonic coupling between these pigments, with the largest contributions from Chls a611 and a612. A major difference between CP29 and LHCII is that Chl a610 is not the energy sink in CP29, which is presumably to a large extent due to the replacement of a lysine residue with alanine close to the TED

Towards an ab initio description of the optical spectra of light-harvesting antennae: application to the CP29 complex of photosystem II.

Only going beyond the static crystal picture through molecular dynamics simulations can a realistic excitonic picture of the light-harvesting complex CP29 be obtained using a multiscale polarizable QM/MM approach

Thermo-Optical Property Degradation of ITO-Coated Aluminized Polyimide Thin Films Under VUV and Low-Energy Proton Radiation

We studied thermo-optical property degradation of indium tin oxide (ITO)-coated aluminized polyimide thin films under exposure to vacuum ultraviolet radiation and low-energy (3 and 5 keV) protons during ground tests using the Complex Irradiation Facility at the DLR site in Bremen. Changes in solar absorption and thermal emission coefficients caused by the irradiation were analyzed. We report a significant increase in solar absorptance of the samples irradiated by protons. We also attempted to identify any defects on the surface of the samples. The study was motivated by a unique opportunity that is provided by the Complex Irradiation Facility to study the degradation effects induced by exposure to protons with an energy below 10 keV and short-wavelength light below 115 nm