487 research outputs found
How carotenoid distortions may determine optical properties: lessons from the Orange Carotenoid Protein
Trivial Excitation Energy Transfer to Carotenoids Is an Unlikely Mechanism for Non-photochemical Quenching in LHCII
Higher plants defend themselves from bursts of intense light via the mechanism of Non-Photochemical Quenching (NPQ). It involves the Photosystem II (PSII) antenna protein (LHCII) adopting a conformation that favors excitation quenching. In recent years several structural models have suggested that quenching proceeds via energy transfer to the optically forbidden and short-lived S(1) states of a carotenoid. It was proposed that this pathway was controlled by subtle changes in the relative orientation of a small number of pigments. However, quantum chemical calculations of S(1) properties are not trivial and therefore its energy, oscillator strength and lifetime are treated as rather loose parameters. Moreover, the models were based either on a single LHCII crystal structure or Molecular Dynamics (MD) trajectories about a single minimum. Here we try and address these limitations by parameterizing the vibronic structure and relaxation dynamics of lutein in terms of observable quantities, namely its linear absorption (LA), transient absorption (TA) and two-photon excitation (TPE) spectra. We also analyze a number of minima taken from an exhaustive meta-dynamical search of the LHCII free energy surface. We show that trivial, Coulomb-mediated energy transfer to S(1) is an unlikely quenching mechanism, with pigment movements insufficiently pronounced to switch the system between quenched and unquenched states. Modulation of S(1) energy level as a quenching switch is similarly unlikely. Moreover, the quenching predicted by previous models is possibly an artifact of quantum chemical over-estimation of S(1) oscillator strength and the real mechanism likely involves short-range interaction and/or non-trivial inter-molecular states
Challenges in the Analysis of Historic Concrete:Understanding the Limitations of Techniques, the Variability of the Material and the Importance of Representative Samples
Investigation of β-carotene–gelatin composite particles with a multiwavelength UV/vis detector for the analytical ultracentrifuge
A multiwavelength UV/vis detector for the analytical ultracentrifuge (MWL-AUC) has been developed recently. In this work, β-carotene–gelatin composite particles are investigated with MWL-AUC. Band centrifugation with a Vinograd cell is used to ensure maximum sample separation. Spectral changes of the system are observed in dependence of the sedimentation coefficient and are attributed to a previously unknown inhomogeneity of the β-carotene chemical composition with both H- and J-aggregates coexisting in a mixture. In addition, our data suggest that pure H- and J-aggregates exist in a particle while their relative concentrations in a mixture determine the color characteristics of the sample. The unique abilities and properties of MWL-AUC include sedimentation coefficient distributions for all possible wavelengths, full UV/vis spectra of each different species in the mixture and 3D movies of the sedimentation process. These properties significantly extend the scope of the analytical ultracentrifuge technique and show that complex biopolymer multicomponent mixtures can be resolved into their individual species
Tests of the Equivalence Principle with Neutral Kaons
We test the Principle of Equivalence for particles and antiparticles, using
CPLEAR data on tagged K0 and K0bar decays into pi^+ pi^-. For the first time,
we search for possible annual, monthly and diurnal modulations of the
observables |eta_{+-}| and phi_{+-}, that could be correlated with variations
in astrophysical potentials. Within the accuracy of CPLEAR, the measured values
of |eta_{+-}| and phi_{+-} are found not to be correlated with changes of the
gravitational potential. We analyze data assuming effective scalar, vector and
tensor interactions, and we conclude that the Principle of Equivalence between
particles and antiparticles holds to a level of 6.5, 4.3 and 1.8 x 10^{-9},
respectively, for scalar, vector and tensor potentials originating from the Sun
with a range much greater than the distance Earth-Sun. We also study
energy-dependent effects that might arise from vector or tensor interactions.
Finally, we compile upper limits on the gravitational coupling difference
between K0 and K0bar as a function of the scalar, vector and tensor interaction
range.Comment: 15 pages latex 2e, five figures, one style file (cernart.csl)
incorporate
New insights into the photochemistry of carotenoid spheroidenone in light-harvesting complex 2 from the purple bacterium Rhodobacter sphaeroides
Light-harvesting complex 2 (LH2) from the
semi-aerobically grown purple phototrophic bacterium
Rhodobacter sphaeroides was studied using optical (static
and time-resolved) and resonance Raman spectroscopies.
This antenna complex comprises bacteriochlorophyll
(BChl) a and the carotenoid spheroidenone, a ketolated
derivative of spheroidene. The results indicate that the
spheroidenone-LH2 complex contains two spectral forms
of the carotenoid: (1) a minor, ‘‘blue’’ form with an S2
(11
Bu
?) spectral origin band at 522 nm, shifted from the
position in organic media simply by the high polarizability
of the binding site, and (2) the major, ‘‘red’’ form with the
origin band at 562 nm that is associated with a pool of
pigments that more strongly interact with protein residues,
most likely via hydrogen bonding. Application of targeted
modeling of excited-state decay pathways after carotenoid
excitation suggests that the high (92%) carotenoid-to-BChl
energy transfer efficiency in this LH2 system, relative to
LH2 complexes binding carotenoids with comparable
double-bond conjugation lengths, derives mainly from
resonance energy transfer from spheroidenone S2 (11
Bu
?)
state to BChl a via the Qx state of the latter, accounting for
60% of the total transfer. The elevated S2 (11
Bu
?) ? Qx
transfer efficiency is apparently associated with substantially
decreased energy gap (increased spectral overlap)
between the virtual S2 (11
Bu
?) ? S0 (11
Ag
-) carotenoid
emission and Qx absorption of BChl a. This reduced
energetic gap is the ultimate consequence of strong carotenoid–protein
interactions, including the inferred hydrogen
bondin
Test of CPT Symmetry and Quantum Mechanics with Experimental data from CPLEAR
We use fits to recent published CPLEAR data on neutral kaon decays to
and to constrain the CPT--violation parameters
appearing in a formulation of the neutral kaon system as an open
quantum-mechanical system. The obtained upper limits of the CPT--violation
parameters are approaching the range suggested by certain ideas concerning
quantum gravity.Comment: 9 pages of uuencoded postscript (includes 3 figures
Nanoscale Confinement and Fluorescence Effects of Bacterial Light Harvesting Complex LH2 in Mesoporous Silicas
Many key chemical and biochemical reactions, particularly in living cells, take place in confined space at the mesoscopic scale. Toward understanding of physicochemical nature of biomacromolecules confined in nanoscale space, in this work we have elucidated fluorescence effects of a light harvesting complex LH2 in nanoscale chemical environments. Mesoporous silicas (SBA-15 family) with different shapes and pore sizes were synthesized and used to create nanoscale biomimetic environments for molecular confinement of LH2. A combination of UV-vis absorption, wide-field fluorescence microscopy, and in situ ellipsometry supports that the LH2 complexes are located inside the silica nanopores. Systematic fluorescence effects were observed and depend on degree of space confinement. In particular, the temperature dependence of the steady-state fluorescence spectra was analyzed in detail using condensed matter band shape theories. Systematic electronic-vibrational coupling differences in the LH2 transitions between the free and confined states are found, most likely responsible for the fluorescence effects experimentally observed
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