Modeling of oligomeric-state dependent spectral heterogeneity in the B875 light-harvesting complex of Rhodobacter sphaeroides by numerical simulation

A series of detergent-isolated light-harvesting 1 (LH1, B875) complexes from Rhodobacter sphaeroides, estimated to range in size from (RâBChl2)4 to (RâBChl2)13, was used to study the combined effects of spectral disorder and excitonic interactions on oligomeric-state dependent optical properties. Numerical simulations of absorption and fluorescence emission, excitation, and polarization spectra, based on the structure of the related LH2 complex, were compared to spectra measured experimentally at 77 K (Westerhuis and Niederman, in preparation). The aggregation-state dependence of the polarization spectra was found to be particularly sensitive to the choice of parameters, and vibronic components were included to obtain satisfactory simulations. Good agreement with most experimental features, including the oligomeric-state dependence of the absorption and emission maxima, was obtained only when the inter- and intradimer coupling strengths for adjacent BChls were similar (200-260 cm-1), and the width for the inhomogeneous distribution function (300-400 cm-1) was comparable. The relevance of these findings to existing controversies on the physical origin of spectral heterogeneity observed for the LH1 complex is discussed

Understanding the Changes in the Circular Dichroism of Light Harvesting Complex II upon Varying Its Pigment Composition and Organization

In this work we modeled the circular dichroism (CD) spectrum of LHCII, the main light harvesting antenna of photosystem II of higher plants. Excitonic calculations are performed for a monomeric subunit, taken from the crystal structure of trimeric LHCII from spinach. All of the major features of the CD spectrum above 450 nm are satisfactorily reproduced, and possible orientations of the Chl and carotenoid transition dipole moments are identified. The obtained modeling parameters are used to simulate the CD spectra of two complexes with altered pigment composition: a mutant lacking Chls a 611-612 and a complex lacking the carotenoid neoxanthin. By removing the relevant pigment(s) from the structure, we are able to reproduce their spectra, which implies that the alteration does not disturb the overall structure. The CD spectrum of trimeric LHCII shows a reversed relative intensity of the two negative bands around 470 and 490 nm as compared to monomeric LHCII. The simulations reproduce this reversal, indicating that it is mainly due to interactions between chromophores in different monomeric subunits, and the trimerization does not induce observable changes in the monomeric structure. Our simulated spectrum resembles one of two different trimeric CD spectra reported in literature. We argue that the differences in the experimental trimeric CD spectra are caused by changes in the strength of the monomer-monomer interactions due to the differences in detergents used for the purification of the complexes.

Interplay of disorder and delocalization in photosynthetic light harvesting

Photosystems, the machines of photosynthesis, are highly complex and energetically disordered pigment–protein structures. Yet, they perform their function, be it highly efficient energy transfer and charge separation or the ability to switch between light-harvesting and photoprotective states, extremely well. In this opinioned review we describe the interplay of disorder and exciton delocalization in photosynthetic light harvesting. By discussing recent research advances on grounds of well-established concepts, we demonstrate that not only is the excitation delocalization a robust phenomenon, but that it in fact enables the light-harvesting function in the disordered environment

Structural information on the light-harvesting complex II of green plants that can be depichered from polarized absorption characteristics.

The atomic model of light-harvesting complex II of green plants (LHCII) reveals a densely packed arrangement of 12 chlorophylls and two carotenoids. At the current resolution of 3.4 Angstrom chlorophylls can only be modeled as ''naked'' tetrapyrrole rings. Consequently, definitive assignments of the identities of the chlorophylls (chlorophyll a or chlorophyll b) and the directions of the transition dipole moments are obstructed. These uncertainties lead to a large number of possible configurations, and a detailed understanding of the structure-function relationship is obscured. It is demonstrated that a large reduction in the number of possible configurations and a considerable amount of additional structural information can be obtained by deciphering global features of the polarized absorption spectra within the context of exciton calculations. It is shown that only a limited number of configurations are able to explain the global features of the linear and circular dichroism spectra of LHCII. Assuming that the preliminary assignment of the identities of the 12 chlorophylls by Kuhlbrandt and co-workers is correct, it is possible to deduce the most likely orientations for most of the chlorophylls. The information presented in this study on the most likely orientations will be important for a detailed understanding of the relation between the structure and spectroscopy

Mixing of exciton and charge-transfer states in Photosystem II reaction centers: Modeling of stark spectra with modified redfield theory

AbstractWe propose an exciton model for the Photosystem II reaction center (RC) based on a quantitative simultaneous fit of the absorption, linear dichroism, circular dichroism, steady-state fluorescence, triplet-minus-singlet, and Stark spectra together with the spectra of pheophytin-modified RCs, and so-called RC5 complexes that lack one of the peripheral chlorophylls. In this model, the excited state manifold includes a primary charge-transfer (CT) state that is supposed to be strongly mixed with the pure exciton states. We generalize the exciton theory of Stark spectra by 1), taking into account the coupling to a CT state (whose static dipole cannot be treated as a small parameter in contrast to usual excited states); and 2), expressing the line shape functions in terms of the modified Redfield approach (the same as used for modeling of the linear responses). This allows a consistent modeling of the whole set of experimental data using a unified physical picture. We show that the fluorescence and Stark spectra are extremely sensitive to the assignment of the primary CT state, its energy, and coupling to the excited states. The best fit of the data is obtained supposing that the initial charge separation occurs within the special-pair PD1PD2. Additionally, the scheme with primary electron transfer from the accessory chlorophyll to pheophytin gave a reasonable quantitative fit. We show that the effectiveness of these two pathways is strongly dependent on the realization of the energetic disorder. Supposing a mixed scheme of primary charge separation with a disorder-controlled competition of the two channels, we can explain the coexistence of fast sub-ps and slow ps components of the Phe-anion formation as revealed by different ultrafast spectroscopic techniques

Spectral broadening of interacting pigments: Polarized absorption by photosynthetic proteins.

Excitonic interaction between pigment molecules is largely responsible for the static and dynamic spectroscopic properties of photosynthetic pigment-proteins. This paper provides a new description of its effect on polarized absorption spectroscopy, in particular on circular dichroism (CD). We investigate excitonic spectra of finite width and use "spectral moments" to compare 1) inhomogeneously broadened excitonic spectra, 2) spectra that are (homogeneously broadened by vibrations or electron-phonon interaction, and 3) spectra that are simulated by applying convolution after the interaction has been evaluated. Two cases are distinguished. If the excitonic splitting is smaller than the width of the interacting absorption bands, the broadening of the excitonic spectrum can be approximated by a convolution approach, although a correction is necessary for CD spectra. If the excitonic splitting exceeds the bandwidth, the well-known exchange narrowing occurs. We demonstrate that this is accompanied by redistribution of dipole strength and spectral shifts. The magnitude of a CD spectrum is conveniently expressed by its first spectral moment. As will be shown, this is independent of spectral broadening as well as dispersive shifts induced by pigment-protein interactions. Consequently, it provides a simple tool to relate the experimental CD spectrum of a pigment complex to the excitonic interactions from which it originates. To illustrate the potential of the presented framework, the spectroscopy of the LH2 pigment-protein complex from purple bacteria is analyzed and compared for dimer-like and ring-like structures. Furthermore, it is demonstrated that the variability of the CD of chlorosomes from green bacteria can be explained by small changes in the structure of their cylindrical bacteriochlorophyll c subunits

Towards Business Process Management in Networked Ecosystems

Managing and supporting the collaboration between different actors is key in any organizational context, whether of a hierarchical or a networked nature. In the networked context of ecosystems of service providers and other stakeholders, BPM is faced with different challenges than in a conventional hierarchical model, based on up front consolidation and consensus on the process flows used in collaboration. In networked ecosystems of potential business partners, designing collaboration upfront is not feasible. Coalitions are formed situationally, and sometimes even ad-hoc. This paper presents a number of challenges for conventional BPM in such environments, and explores how declarative process management technology could address them, indicating topics for further research