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Jürgen Köhler

Publications and source records attributed to Jürgen Köhler.

16 recordsLinked to original sources
PubMed2006

The architecture and function of the light-harvesting apparatus of purple bacteria: from single molecules to in vivo membranes.

This review describes the structures of the two major integral membrane pigment complexes, the RC-LH1 'core' and LH2 complexes, which together make up the light-harvesting system present in typical purple photosynthetic bacteria. The antenna complexes serve to absorb incident solar radiation and to transfer it to the reaction centres, where it is used to 'power' the photosynthetic redox reaction and ultimately leads to the synthesis of ATP. Our current understanding of the biosynthesis and assembly of the LH and RC complexes is described, with special emphasis on the roles of the newly described bacteriophytochromes. Using both the structural information and that obtained from a wide variety of biophysical techniques, the details of each of the different energy-transfer reactions that occur, between the absorption of a photon and the charge separation in the RC, are described. Special emphasis is given to show how the use of single-molecule spectroscopy has provided a more detailed understanding of the molecular mechanisms involved in the energy-transfer processes. We have tried, with the help of an Appendix, to make the details of the quantum mechanics that are required to appreciate these molecular mechanisms, accessible to mathematically illiterate biologists. The elegance of the purple bacterial light-harvesting system lies in the way in which it has cleverly exploited quantum mechanics.

Amino Acid Sequence↗
PubMed2006

Probing the electronic structure and conformational flexibility of individual light-harvesting 3 complexes by optical single-molecule spectroscopy.

We present fluorescence-excitation spectra of individual light-harvesting 3 (LH3 or B800-820) complexes of Rhodopseudomonas acidophila at 1.2 K. The optical single-molecule studies were employed to investigate the electronic structure as well as the conformational flexibility of the individual pigment-protein complexes. The optical spectra resemble those of individual light-harvesting 2 (LH2) complexes, in agreement with the structural similarity of both types of complexes. Although variations among the LH3 spectra are large, there is a distinct difference in the spectral features of the 800 and 820 nm region that appears in all the complexes studied. In the B800 region 4-6 narrow bands are present whereas in the B820 region a limited number of relatively broad bands are observed. These observations can generally be interpreted in terms of localized excitations in the 800 nm region and delocalized excitations in the 820 nm region. The observed heterogeneous spectral behavior, especially in the B820 band, indicates that the B820 pigments of LH3 are sensitive to light-induced local conformational changes. It is suggested that a rotation of the C(3)-acetyl chain of a BChl a pigment bound to the beta-subunit of the light-harvesting complex is the origin of the conformational flexibility and affects the optical properties of the whole pigment-protein complex.

Biophysics↗
PubMed2005

Synthesis and characterization of [PtIn6](GeO4)2O and its solid solution [PtIn6](GaO4)(2-x)(GeO4)xOx/2 (0 < or = x < or = 2): gradual color change of the solid solution from black (x = 0) to yellow (x = 2) as a consequence of quantum dot effect.

A new phase [PtIn6](GeO4)2O, a filled variant of [PtIn6](GaO4)2, and the solid solution [PtIn6](GaO4)(2-x)(GeO4)xOx/2 (0 < or = x < or = 2) were prepared and characterized. Single-crystal structure refinements show that [PtIn6](GeO4)2O is isotypic with the mineral, sulfohalite Na6FCl(SO4)2, and crystallizes in the space group Fmm (Z = 4) with a = 1006.0(1) pm. The building units of [PtIn6](GeO4)2O are isolated [PtIn6]10+ octahedra and (GeO4)4- tetrahedra, and the isolated O2- ions occupy the centers of the In6 octahedra made up of six adjacent PtIn6 octahedra. The lattice parameter of the solid solution [PtIn6](GaO4)(2-x)(GeO4)xOx/2 (0 < or = x < or = 2) varies gradually from a = 1001.3(1) pm at x = 0 to a = 1006.0(1) pm at x = 2, and the color of the solid solution changes gradually from black (x = 0) to red (x = 1) to yellow (x = 2). The cause for the gradual color change was examined by performing density functional theory electronic structure calculations for the end members [PtIn6](GaO4)2 and [PtIn6](GeO4)2O. Our analysis indicates that an oxygen atom at the center of a In6 octahedron cuts the In 5p/In 5p bonding interactions between adjacent [PtIn6]10+ octahedra thereby raising the bottom of the conduction bands, and the resulting quantum dot effect is responsible for the color change.

Color↗
PubMed2005

Multivariate analysis of single-molecule spectra: surpassing spectral diffusion.

The full exploitation of single-molecule spectroscopy in disordered systems is often hampered by spectral diffusion processes of the optical transitions due to structural fluctuations in the local environment of the probe molecule which leads to temporal averaging of the signal. Multivariate statistical pattern recognition techniques, originally developed for single-molecule cryoelectron microscopy, allow us to retrieve detailed information from optical single-molecule spectra. As an example, we present the phonon side band of the B800 excitations of the light-harvesting 2 (LH2) complex from Rhodospirillum molischianum, revealing the electron-phonon coupling strength for these transitions. The measured Debye-Waller factors, ranging from 0.4 to 0.9, fall in the regime of weak electron-phonon coupling.

Journal Article↗
PubMed2005

Bonding and oxidation state of a transition metal atom encapsulated in an isolated octahedral cluster cation of main group elements: synthesis, crystal structure, and electronic structure of Pt2In14Ga3(O)8F15 containing highly positive 18-electron complex [PtIn6]10+ and low-valent In+ ions.

Colorless transparent single crystals and white polycrystalline powder samples of Pt2In14Ga3(O)8F15 were obtained by heating a mixture of stoichiometric amounts of Pt, In, InF3, and Ga2(O)3, in a Pt crucible under Ar at 600 degrees C. The new oxyfluoride crystallizes in a new structure type in the trigonal space group Rm (No. 166) with a = 709.0(6) pm, c = 4556.4(3) pm, and Z = 6 with characteristic building units of PtIn6 octahedra (Pt-In = 255-257 pm), GaF6 octahedra (Ga-F = 189 pm), and GaO(4) tetrahedra (Ga-O = 186-187 pm). This oxyfluoride consists of a highly positive 18-electron complex [PtIn6]10+ as well as low-valent In+ ions. Electronic band structure calculations for Pt2In14(Ga3)O(8)F15 and molecular orbital (MO) calculations for [PtIn6]10+ were carried out to analyze the electronic structure of [PtIn6]10+ and estimate the oxidation state of Pt. Our analysis indicates that the oxidation state of the Pt atom in [PtIn6]10+ is negative rather than positive. For other octahedral cluster cations of main group elements stuffed with a transition metal atom (e.g., [RuSn6]14+ and "[IrBi6]11+") as well, we showed that the oxidation state of the transition metal atom is most probably negative by studying their electronic structures.

Journal Article↗
PubMed2005

Photophysical properties of a tetraphenoxy-substituted perylene bisimide derivative characterized by single-molecule spectroscopy.

We present a detailed study of the photophysical properties of a tetraphenoxy-substituted perylene bisimide derivative. The probe molecules were immobilized in a Shpol'skii matrix of hexadecane and investigated by single-molecule spectroscopy at cryogenic temperatures. By using single-molecule spectroscopic techniques we reveal the triplet substate kinetics and the fluorescence quantum yield, and we provide an estimate for the S1-S0 transition dipole moment.

Journal Article↗
PubMed2003

Direct observation of tiers in the energy landscape of a chromoprotein: a single-molecule study.

Single-molecule spectroscopic techniques were applied to individual pigments embedded in a chromoprotein. A sensitive tool to monitor structural fluctuations of the protein backbone in the local environment of the chromophore is provided by recording the changes of the spectral positions of the pigment absorptions as a function of time. The data provide information about the organization of the energy landscape of the protein in tiers that can be characterized by an average barrier height. Additionally, a correlation between the average barrier height within a distinct tier and the time scale of the structural fluctuations is observed.

Bacterial Proteins↗
PubMed2003

Energy transfer in a single self-aggregated photosynthetic unit.

The primary events of bacterial photosynthesis rely on the interplay of various specialized protein complexes organized in a supramolecular structure commonly termed the photosynthetic unit (PSU), which consists of the photochemical reaction center and of an associated antenna network. Employing single-molecule spectroscopic techniques we have been able to observe the excitation-energy transfer within a single PSU. From these findings we conclude that the building blocks of the PSU spontaneously form stable, functional aggregates in a non-membrane environment.

Energy Transfer↗
PubMed2003

Single-molecule study of the electronic couplings in a circular array of molecules: light-harvesting-2 complex from Rhodospirillum molischianum.

Applying single-molecule spectroscopic techniques allowed us to determine the mutual angles between the transition-dipole moments associated with optical transitions of the eight bacteriochlorophyll a molecules which form the so-called B800 ring of the light-harvesting-2 complex from Rhodospirillum molischianum. The orientation of the transition-dipole moment is a sensitive probe for the strength of the local intermolecular interactions because of the well-defined arrangement of the individual molecules within the B800 ring. Our data reveal that the strength of the electronic coupling between individual molecules in the ring is subjected to spatial as well as temporal variations.

Bacteriochlorophyll A↗
PubMed2002

Chemical bonding variations and electron-phonon interactions.

A new functional, Psib(Phi), of an electronic state in solids based on the bonding indicator B(tau,tau') in terms of Mulliken's electron partitioning approach has been introduced. Using Psib(Phi), the bonding variations of an electronic state caused by electron-phonon coupling can be studied. With this proposed approach, the differences between the "flat band" states for Hg in coupling to the phonons and the peaklike structure of electron-phonon coupling constants in the q space are well explained.

Journal Article↗
PubMed2002

Spectroscopy on individual light-harvesting 1 complexes of Rhodopseudomonas acidophila.

In this paper the fluorescence-excitation spectra of individual LH1-RC complexes (Rhodopseudomonas acidophila) at 1.2 K are presented. All spectra show a limited number of broad bands with a characteristic polarization behavior, indicating that the excitations are delocalized over a large number of pigments. A significant variation in the number of bands, their bandwidths, and polarization behavior is observed. Only 30% of the spectra carry a clear signature of delocalized excited states of a circular structure of the pigments. The large spectral variety suggests that besides site heterogeneity also structural heterogeneity determines the optical spectrum of the individual LH1-RC complexes. Further research should reveal if such heterogeneity is a native property of the complex or induced during the experimental procedures.

Bacterial Proteins↗