pheophytin-a and diadinoxanthin

Carotenoids (Cars) exhibit two functions in photosynthesis, light-harvesting and photoprotective functions, which are performed through the excited states of Cars. Therefore, increasing our knowledge on excitation relaxation dynamics of Cars is important for understanding of the functions of Cars. In light-harvesting complexes, there exist Cars functioning by converting the π-conjugation number in response to light conditions. It is well known that some microalgae have a mechanism controlling the conjugation number of Cars, called as the diadinoxanthin cycle; diadinoxanthin (10 conjugations) is accumulated under low light, whereas diatoxanthin (11 conjugations) appears under high light. However, the excitation relaxation dynamics of these two Cars have not been clarified. In the present study, we investigated excitation relaxation dynamics of diadinoxanthin and diatoxanthin in relation to their functions, by the ultrafast fluorescence spectroscopy. After an excitation to the S

Topics: Acetone; Carotenoids; Chlorophyll; Chlorophyll A; Ethanol; Ether; Light-Harvesting Protein Complexes; Xanthophylls

The importance of diadinoxanthin (Ddx) de-epoxidation in the short-term modulation of the temperature effect on photosynthetic membranes of the diatom Phaeodactylum tricornutum was demonstrated by electron paramagnetic resonance (EPR), Laurdan fluorescence spectroscopy, and high-performance liquid chromatography. The 5-SASL spin probe employed for the EPR measurements and Laurdan provided information about the membrane area close to the polar head groups of the membrane lipids, whereas with the 16-SASL spin probe, the hydrophobic core, where the fatty acid residues are located, was probed. The obtained results indicate that Ddx de-epoxidation induces a two component mechanism in the short-term regulation of the membrane fluidity of diatom thylakoids during changing temperatures. One component has been termed the "dynamic effect" and the second the "stable effect" of Ddx de-epoxidation. The "dynamic effect" includes changes of the membrane during the time course of de-epoxidation whereas the "stable effect" is based on the rigidifying properties of Dtx. The combination of both effects results in a temporary increase of the rigidity of both peripheral and internal parts of the membrane whereas the persistent increase of the rigidity of the hydrophobic core of the membrane is solely based on the "stable effect."

Topics: Chlorophyll A; Chromatography, High Pressure Liquid; Diatoms; Electron Spin Resonance Spectroscopy; Epoxy Compounds; Photosynthesis; Spectrometry, Fluorescence; Temperature; Thylakoids; Xanthophylls

Diatoms are abundant photosynthetic organisms in aquatic environments and contribute 40% of its primary productivity. An important factor that contributes to the success of diatoms is their fucoxanthin chlorophyll a/c-binding proteins (FCPs), which have exceptional light-harvesting and photoprotection capabilities. Here, we report the crystal structure of an FCP from the marine diatom

Topics: Chlorophyll; Chlorophyll A; Chlorophyll Binding Proteins; Diatoms; Energy Transfer; Light; Photosynthesis; Protein Structure, Quaternary; Thylakoids; Xanthophylls

Fucoxanthin chlorophyll (Chl) a/ c-binding proteins (FCPs) are unique light-harvesting antennas in diatoms. Recent time-resolved fluorescence analysis of photosystem I with FCP associated (PSI-FCPI) has mainly shown excitation energy transfer among Chls a from FCPI to PSI in tens of picoseconds. However, it remains unclear how each pigment, especially carotenoids and Chl c, in the FCPI is functionally related to the energy transfer in a femtosecond time range. Here, we reveal ultrafast excitation energy transfer mechanism in the PSI-FCPI preparations isolated from a diatom, Chaetoceros gracilis, by means of femtosecond time-resolved fluorescence spectroscopy with an upconversion system. Compared with the fluorescence lifetime components of PSI core-like complexes, the energy transfer of Chl c → Chl a in the FCPI was observed within hundreds of femtoseconds, and the energy in the FCPI was transferred to PSI in ∼2 ps. The comparative fluorescence analyses provide physical insights into the energy transfer machinery within FCPI and from FCPI to PSI.

Topics: Carotenoids; Chlorophyll; Chlorophyll A; Chlorophyll Binding Proteins; Diatoms; Energy Transfer; Fluorescence; Photosystem I Protein Complex; Spectrometry, Fluorescence; Xanthophylls

Diatoms contain a highly flexible capacity to dissipate excessively absorbed light by nonphotochemical fluorescence quenching (NPQ) based on the light-induced conversion of diadinoxanthin (Dd) into diatoxanthin (Dt) and the presence of Lhcx proteins. Their NPQ fine regulation on the molecular level upon a shift to dynamic light conditions is unknown. We investigated the regulation of Dd + Dt amount, Lhcx gene and protein synthesis and NPQ capacity in the diatom Phaeodactylum tricornutum after a change from continuous low light to 3 d of sine (SL) or fluctuating (FL) light conditions. Four P. tricornutum strains with different NPQ capacities due to different expression of Lhcx1 were included. All strains responded to dynamic light comparably, independently of initial NPQ capacity. During SL, NPQ capacity was strongly enhanced due to a gradual increase of Lhcx2 and Dd + Dt amount. During FL, cells enhanced their NPQ capacity on the first day due to increased Dd + Dt, Lhcx2 and Lhcx3; already by the second day light acclimation was accomplished. While quenching efficiency of Dt was strongly lowered during SL conditions, it remained high throughout the whole FL exposure. Our results highlight a more balanced and cost-effective photoacclimation strategy of P. tricornutum under FL than under SL conditions.

Topics: Chlorophyll; Chlorophyll A; Diatoms; Fluorescence; Gene Expression Regulation, Bacterial; Light; Light-Harvesting Protein Complexes; Photosynthesis; Protein Biosynthesis; RNA, Messenger; Xanthophylls

The major light-harvesting pigment protein complex (fucoxanthin-chlorophyll-binding protein complex; FCP) was purified from a marine centric diatom, Chaetoceros gracilis, by mild solubilization followed by sucrose density gradient centrifugation, and then characterized. The dynamic light scattering measurement showed unimodality, indicating that the complex was highly purified. The amount of chlorophyll a (Chl a) bound to the purified FCP accounted for more than 60 % of total cellular Chl a. The complex was composed of three abundant polypeptides, although there are nearly 30 FCP-related genes. The two major components were identified as Fcp3 (Lhcf3)- and Fcp4 (Lhcf4)-equivalent proteins based on their internal amino acid sequences and a two-dimensional isoelectric focusing electrophoresis analysis developed in this work. Compared with the thylakoids, the FCP complex showed higher contents of fucoxanthin and chlorophyll c but lower contents of the xanthophyll cycle pigments diadinoxanthin and diatoxanthin. Fluorescence excitation spectra analyses indicated that light harvesting, rather than photosystem protection, is the major function of the purified FCP complex, which is associated with more than 60 % of total cellular Chl a. These findings suggest that the huge amount of Chl bound to the FCP complex composed of Lhcf3, Lhcf4, and an unidentified minor protein has a light-harvesting function to allow efficient photosynthesis under the dim-light conditions in the ocean.

Topics: Carrier Proteins; Chlorophyll; Chlorophyll A; Diatoms; Light; Light-Harvesting Protein Complexes; Photosystem II Protein Complex; Spectrometry, Fluorescence; Thylakoids; Xanthophylls

Phytoplankton dominant species and their light absorption properties during the blooms occurred in August 2013 in adjacent waters of the Changjiang Estuary were analyzed. The results showed that phytoplankton blooms broke out in 10 out of 34 investigation stations, among which diatom blooms occurred in 6 stations while 3 stations were predominated by dinoflagellate. Phytoplankton absorption coefficients of both bloom and non-bloom waters exhibited large variations, with respective ranges of 0.199-0.832 m(-1) and 0.012-0.109 m(-1), while phytoplankton specific absorption coefficients spanned much narrower range, with the average values of bloom and non-bloom waters being 0.023 and 0.035 m2 x mg(-1), respectively. When transitioned from bloom to non-bloom waters, the proportion of phytoplankton with larger cell size lowered while that of smaller phytoplankton elevated, causing a less extent of package effect and thus higher specific absorption coefficients. Distinctive absorption spectra were observed between different types of bloom (such as diatom and dinoflagellate blooms) with similar phytoplankton cell size, mostly attributed to distinctive accessory pigment composition. The ratios of diadinoxanthin and chlorophyll-c2 concentrations to chlorophyll-a concentration in dinoflagellate blooms were higher than those in diatom blooms, which largely contributed to the shoulder peaks at 465 nm in dinoflagellate blooms.

Topics: Chlorophyll; Chlorophyll A; Diatoms; Dinoflagellida; Estuaries; Eutrophication; Light; Phytoplankton; Xanthophylls

The physiological response of the scleractinian coral Turbinaria reniformis to ammonium enrichment (3 μmol l(-1)) was examined at 26°C as well as during a 7 day increase in temperature to 31°C (thermal stress). At 26°C, ammonium supplementation had little effect on the coral physiology. It induced a decrease in symbiont density, compensated by an increase in chlorophyll content per symbiont cell. Organic carbon release was reduced, likely because of a better utilization of the photosynthesized carbon (i.e. incorporation into proteins, kept in the coral tissue). The δ(15)N signatures of the ammonium-enriched symbionts and host tissue were also significantly decreased, by 4 and 2‰, respectively, compared with the non-enriched conditions, suggesting a significant uptake of inorganic nitrogen by the holobiont. Under thermal stress, coral colonies that were not nitrogen enriched experienced a drastic decrease in photosynthetic and photoprotective pigments (chlorophyll a, β-carotene, diadinoxanthin, diatoxanthin and peridinin), followed by a decrease in the rates of photosynthesis and calcification. Organic carbon release was not affected by this thermal stress. Conversely, nitrogen-enriched corals showed an increase in their pigment concentrations, and maintained rates of photosynthesis and calcification at ca. 60% and 100% of those measured under control conditions, respectively. However, these corals lost more organic carbon into the environment. Overall, these results indicate that inorganic nitrogen availability can be important to determining the resilience of some scleractinian coral species to thermal stress, and can have a function equivalent to that of heterotrophic feeding concerning the maintenance of coral metabolism under stress conditions.

Topics: Ammonium Compounds; Analysis of Variance; Animals; Anthozoa; beta Carotene; Calcification, Physiologic; Carotenoids; Chlorophyll; Chlorophyll A; Dinoflagellida; Fluorescence; Hot Temperature; Indian Ocean; Nitrogen; Photosynthesis; Stress, Physiological; Symbiosis; Xanthophylls

Bleaching of corals by loss of symbiotic dinoflagellate algae and/or photosynthetic pigments is commonly triggered by elevated temperatures coupled with high irradiance, and is a first-order threat to coral reef communities. In this study, a high-resolution high-performance liquid chromatography method integrated with mass spectrometry was applied to obtain the first definitive identification of chlorophyll and carotenoid pigments of three clades of symbiotic dinoflagellate algae (Symbiodinium) in corals, and their response to experimentally elevated temperature and irradiance. The carotenoids peridinin, dinoxanthin, diadinoxanthin (Dn), diatoxanthin (Dt) and beta-carotene were detected, together with chlorophylls a and c2, and phaeophytin a, in all three algal clades in unstressed corals. On exposure to elevated temperature and irradiance, three coral species (Montastrea franksi and Favia fragum with clade B algae, and Montastrea cavernosa with clade C) bleached by loss of 50-80% of their algal cells, with no significant impact to chlorophyll a or c2, or peridinin in retained algal cells. One species (Agaricia sp. with clade C) showed no significant reduction in algal cells at elevated temperature and irradiance, but lost substantial amounts of chlorophyll a and carotenoid pigments, presumably through photo-oxidative processes. Two coral species (Porites astreoides and Porites porites both bearing clade A algae) did not bleach. The impact of elevated temperature and irradiance on the levels of the photoprotective xanthophylls (Dn + Dt) and beta-carotene varied among the corals, both in pool size and xanthophyll cycling, and was not correlated to coral bleaching resistance.

Topics: Animals; Anthozoa; Cell Count; Chlorophyll; Chromatography, High Pressure Liquid; Eukaryota; Light; Mass Spectrometry; Phylogeny; Pigments, Biological; Symbiosis; Temperature; Xanthophylls

The lifetimes of the first excited singlet states (2(1)A(g)) of diadinoxanthin and diatoxanthin, carotenoids involved in the xanthophyll cycle in some genera of algae, have been measured by femtosecond time-resolved optical spectroscopy to be 22.8 +/- 0.1 ps and 13.3 +/- 0.1 ps, respectively. Using the energy gap law for radiationless transitions set forth by Englman and Jortner (Mol. Phys. 18 (1970) 145-164), these lifetimes correspond to S1 excited state energies of 15210 cm-1 for diadinoxanthin and 14620 cm-1 for diatoxanthin. The lowest excited singlet state energy of Chl a has an energy of 14700 cm-1. The fact that the S1 state energy of diadinoxanthin lies above that of Chl a, whereas the S1 state energy of diatoxanthin lies below that of Chl a, suggests that the xanthophyll cycle involving the enzymatic interconversion of diadinoxanthin and diatoxanthin may play a role in regulating energy flow between these molecules and Chl a in many species of algae, essentially fulfilling a role identical to that proposed for violaxanthin and zeaxanthin in higher plants and green algae (Frank et al. (1994) Photosyn. Res. 41, 389-395).

Topics: Carotenoids; Chlorophyll; Chlorophyll A; Energy Metabolism; Eukaryota; Hydrogen-Ion Concentration; Spectrometry, Fluorescence; Spectrophotometry; Thermodynamics; Xanthophylls