Electronic spectra of structurally deformed lutein.

Quantum chemical calculations have been employed for the investigation of the lowest excited electronic states of lutein, with particular reference to its function within light harvesting antenna complexes of higher plants. Through comparative analysis obtained by using different methods based on gas-phase calculations of the spectra, it was determined that variations in the lengths of the long C-C valence bonds and the dihedral angles of the polyene chain are the dominant factors in determining the spectral properties of Lut 1 and Lut 2 corresponding to the deformed lutein molecules taken from crystallographic data of the major pigment-protein complex of photosystem II. By MNDO-CAS-CI method, it was determined that the two singlet B(u) states of lutein (nominally 1B(u)(-)* and 1B(u)(+)) arise as a result of mixing of the canonical 1B(u)(-) and 1B(u)(+) states of the all-trans polyene due to the presence of the ending rings in lutein. The 1B(u)(-)* state of lutein is optically allowed, while the 1B(u)(-) of a pure all-trans polyene chain is optically forbidden. As demonstrated, the B(u) states are much more sensitive to minor distortions of the conjugated chain due to mixing of the canonical states, resulting in states of poorly defined particle-hole symmetry. Conversely, the A(g) states are relatively robust with respect to geometric distortion, and their respective inversion and particle-hole symmetries remain relatively well-defined.

[1]  J. Götze,et al.  Modeling of a violaxanthin-chlorophyll b chromophore pair in its LHCII environment using CAM-B3LYP. , 2012, Journal of photochemistry and photobiology. B, Biology.

[2]  Johannes Neugebauer,et al.  Quantum chemical description of absorption properties and excited-state processes in photosynthetic systems. , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[3]  R. van Grondelle,et al.  Identification of two emitting sites in the dissipative state of the major light harvesting antenna. , 2012, Physical chemistry chemical physics : PCCP.

[4]  Matthew P. Johnson,et al.  Photoprotection in Plants Involves a Change in Lutein 1 Binding Domain in the Major Light-harvesting Complex of Photosystem II* , 2011, The Journal of Biological Chemistry.

[5]  W. Barford,et al.  A theoretical investigation of the photophysical consequences of major plant light-harvesting complex aggregation within the photosynthetic membrane. , 2010, The journal of physical chemistry. B.

[6]  Benjamin T. Miller,et al.  A parallel implementation of the analytic nuclear gradient for time-dependent density functional theory within the Tamm–Dancoff approximation , 2010 .

[7]  T. Renger,et al.  Structure-based identification of energy sinks in plant light-harvesting complex II. , 2010, The journal of physical chemistry. B.

[8]  Nicole L. Wagner,et al.  The intramolecular charge transfer state in carbonyl-containing polyenes and carotenoids. , 2010, The journal of physical chemistry. B.

[9]  A. Holzwarth,et al.  Singlet energy dissipation in the photosystem II light-harvesting complex does not involve energy transfer to carotenoids. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[10]  A. Holzwarth,et al.  Electronic coherence provides a direct proof for energy-level crossing in photoexcited lutein and beta-carotene. , 2009, Physical review letters.

[11]  A. Ruban,et al.  Modeling of exciton quenching in photosystem II. , 2009, Physical chemistry chemical physics : PCCP.

[12]  F. Bittner,et al.  On the regulation of photosynthesis by excitonic interactions between carotenoids and chlorophylls , 2009, Proceedings of the National Academy of Sciences.

[13]  Tomáš Polívka,et al.  Dark excited states of carotenoids: Consensus and controversy , 2009 .

[14]  Tõnu Pullerits,et al.  Photon echo spectroscopy reveals structure-dynamics relationships in carotenoids , 2009 .

[15]  A. Dreuw,et al.  Excitation energy transfer and carotenoid radical cation formation in light harvesting complexes - a theoretical perspective. , 2009, Biochimica et biophysica acta.

[16]  V. Sundström,et al.  Femtosecond carotenoid to retinal energy transfer in xanthorhodopsin. , 2009, Biophysical journal.

[17]  A. Jafarpour,et al.  Carotenoid deactivation in an artificial light-harvesting complex via a vibrationally hot ground state , 2009 .

[18]  R. Cogdell,et al.  Large third-order optical nonlinearity realized in symmetric nonpolar carotenoids , 2008 .

[19]  Hong Cong,et al.  Ultrafast time-resolved spectroscopy of xanthophylls at low temperature. , 2008, The journal of physical chemistry. B.

[20]  G. Fleming,et al.  Excited State Structural Dynamics of the Charge Transfer State of Peridinin , 2007 .

[21]  J. Kennis,et al.  Identification of a mechanism of photoprotective energy dissipation in higher plants , 2007, Nature.

[22]  Jeremy F. Koscielecki,et al.  Ultrafast dynamics and excited state spectra of open-chain carotenoids at room and low temperatures. , 2007, The journal of physical chemistry. B.

[23]  Hans-Joachim Werner,et al.  Matrix-formulated direct multiconfiguration self-consistent field and multiconfiguration reference configuration-interaction methods , 2007 .

[24]  W. Wohlleben,et al.  Pump-probe and pump-deplete-probe spectroscopies on carotenoids with N=9-15 conjugated bonds. , 2006, The Journal of chemical physics.

[25]  Andreas Dreuw,et al.  How much double excitation character do the lowest excited states of linear polyenes have , 2006 .

[26]  R. Birge,et al.  Femtosecond time-resolved transient absorption spectroscopy of xanthophylls. , 2006, The journal of physical chemistry. B.

[27]  A. Dreuw.  Influence of geometry relaxation on the energies of the S1 and S2 states of violaxanthin, zeaxanthin, and lutein. , 2006, The journal of physical chemistry. A.

[28]  Mikas Vengris,et al.  Excited-state dynamics of carotenoids in light-harvesting complexes. 1. Exploring the relationship between the S1 and S* states. , 2006, The journal of physical chemistry. B.

[29]  I. V. van Stokkum,et al.  Use of ultrafast dispersed pump-dump-probe and pump-repump-probe spectroscopies to explore the light-induced dynamics of peridinin in solution. , 2006, The journal of physical chemistry. B.

[30]  Andreas Dreuw,et al.  Single-reference ab initio methods for the calculation of excited states of large molecules. , 2005, Chemical reviews.

[31]  M. Head‐Gordon,et al.  Role of electron-transfer quenching of chlorophyll fluorescence by carotenoids in non-photochemical quenching of green plants. , 2005, Biochemical Society transactions.

[32]  Bruno Robert,et al.  Molecular basis of photoprotection and control of photosynthetic light-harvesting , 2005, Nature.

[33]  Leonas Valkunas,et al.  Carotenoid Cation Formation and the Regulation of Photosynthetic Light Harvesting , 2005, Science.

[34]  K. Hirao,et al.  The π → π* excited states of long linear polyenes studied by the CASCI-MRMP method , 2004 .

[35]  Mikas Vengris,et al.  Resolving the excited state equilibrium of peridinin in solution. , 2004, Biochemistry.

[36]  G. Fleming,et al.  Transient Absorption Study of Peridinin and Peridinin-Chlorophyll a-Protein after Two-Photon Excitation † , 2004 .

[37]  Zhenfeng Liu,et al.  Crystal structure of spinach major light-harvesting complex at 2.72 Å resolution , 2004, Nature.

[38]  V. Sundström,et al.  Ultrafast dynamics of carotenoid excited States-from solution to natural and artificial systems. , 2004, Chemical reviews.

[39]  P. Horton,et al.  The functional significance of the monomeric and trimeric states of the photosystem II light harvesting complexes. , 2004, Biochemistry.

[40]  C. Gradinaru,et al.  Stark spectroscopy of the light-harvesting complex II in different oligomerisation states. , 2003, Biochimica et biophysica acta.

[41]  M. Head‐Gordon,et al.  Quantum Chemical Evidence for an Intramolecular Charge-Transfer State in the Carotenoid Peridinin of Peridinin-Chlorophyll-Protein , 2003 .

[42]  Ivo H. M. van Stokkum,et al.  Light harvesting by carotenoids incorporated into the B850 light-harvesting complex from Rhodobacter sphaeroides R-26.1: Excited-state relaxation, ultrafast triplet formation, and energy transfer to bacteriochlorophyll , 2003 .

[43]  Tomáš Polívka,et al.  Dynamics of Excited States of the Carotenoid Peridinin in Polar Solvents: Dependence on Excitation Wavelength, Viscosity, and Temperature. , 2003 .

[44]  Robert R. Birge,et al.  Two-Photon and Fluorescence Spectroscopy and the Effect of Environment on the Photochemical Properties of Peridinin in Solution and in the Peridinin-Chlorophyll-Protein from Amphidinium carterae† , 2003 .

[45]  Pam Lee,et al.  Molecular Configuration of Xanthophyll Cycle Carotenoids in Photosystem II Antenna Complexes* , 2002, The Journal of Biological Chemistry.

[46]  V. Sundström,et al.  The carotenoid S-1 state in LH2 complexes from purple bacteria Rhodobacter sphaeroides and Rhodopseudomonas acidophila: S-1 energies, dynamics, and carotenoid radical formation , 2002 .

[47]  A. Hoff,et al.  Aggregation of LHCII Leads to a Redistribution of the Triplets over the Central Xanthophylls in LHCII. , 2002, Biochemistry.

[48]  Rienk van Grondelle,et al.  An alternative carotenoid-to-bacteriochlorophyll energy transfer pathway in photosynthetic light harvesting , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[49]  P. Horton,et al.  Activation of Zeaxanthin Is an Obligatory Event in the Regulation of Photosynthetic Light Harvesting* , 2002, The Journal of Biological Chemistry.

[50]  P. Horton,et al.  Configuration and Dynamics of Xanthophylls in Light-harvesting Antennae of Higher Plants , 2001, The Journal of Biological Chemistry.

[51]  K. Niyogi,et al.  Non-photochemical quenching. A response to excess light energy. , 2001, Plant physiology.

[52]  E. Gantt,et al.  One ring or two? Determination of ring number in carotenoids by lycopene ɛ-cyclases , 2001, Proceedings of the National Academy of Sciences of the United States of America.

[53]  G. Fleming,et al.  An unusual pathway of excitation energy deactivation in carotenoids: Singlet-to-triplet conversion on an ultrafast timescale in a photosynthetic antenna , 2001, Proceedings of the National Academy of Sciences of the United States of America.

[54]  Sason Shaik,et al.  Using valence bond theory to understand electronic excited states: Application to the hidden excited state (2(1)A(g)) of C2nH2n+2 (n=2-14) polyenes , 2000 .

[55]  K. Müllen,et al.  Adiabatic One- and Two-Photon Excited States in Phenylene-Based Conjugated Oligomers: A Quantum-Chemical Study , 2000 .

[56]  R. van Grondelle,et al.  Generation of fluorescence quenchers from the triplet states of chlorophylls in the major light-harvesting complex II from green plants. , 2000, Biochemistry.

[57]  A. Ruban,et al.  Xanthophylls of the major photosynthetic light‐harvesting complex of plants: identification, conformation and dynamics , 2000, FEBS letters.

[58]  David J. Gosztola,et al.  Effect of the Solvent Environment on the Spectroscopic Properties and Dynamics of the Lowest Excited States of Carotenoids , 2000 .

[59]  David J. Gosztola,et al.  Excited state properties of peridinin: Observation of a solvent dependence of the lowest excited singlet state lifetime and spectral behavior unique among carotenoids , 1999 .

[60]  Vidmantas Gulbinas,et al.  Charge Transfer Induced Excited State Twisting of N,N-Dimethylaminobenzylidene-1,3-indandione in Solution , 1999 .

[61]  P. Horton,et al.  REGULATION OF LIGHT HARVESTING IN GREEN PLANTS. , 1996, Annual review of plant physiology and plant molecular biology.

[62]  M. E. Casida.  Time-Dependent Density Functional Response Theory for Molecules , 1995 .

[63]  G. Köhler,et al.  Excited state properties and deactivation pathways of 7-aminocoumarins , 1994 .

[64]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[65]  F. Zerbetto,et al.  Theoretical analysis of spectra of short polyenes , 1991 .

[66]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[67]  K. Winter,et al.  Zeaxanthin and the Heat Dissipation of Excess Light Energy in Nerium oleander Exposed to a Combination of High Light and Water Stress. , 1988, Plant physiology.

[68]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[69]  Klaus Schulten,et al.  The low‐lying electronic excitations in long polyenes: A PPP‐MRD‐CI study , 1986 .

[70]  W. Rettig.  Charge Separation in Excited States of Decoupled Systems—TICT Compounds and Implications Regarding the Development of New Laser Dyes and the Primary Process of Vision and Photosynthesis , 1986 .

[71]  Hans-Joachim Werner,et al.  The self‐consistent electron pairs method for multiconfiguration reference state functions , 1982 .

[72]  Rudolph Pariser,et al.  Theory of the Electronic Spectra and Structure of the Polyacenes and of Alternant Hydrocarbons , 1956 .

[73]  Matthew P. Johnson,et al.  Light-harvesting antenna composition controls the macrostructure and dynamics of thylakoid membranes in Arabidopsis. , 2012, The Plant journal : for cell and molecular biology.

[74]  M. Head‐Gordon,et al.  Excitation Energies from Time-Dependent Density Functional Theory for Linear Polyene Oligomers: Butadiene to Decapentaene , 2001 .