Accessory Light-harvesting Pigments Research Articles

Subfunctionalization of D27 Isomerase Genes in Saffron.

Chromoplasts and chloroplasts contain carotenoid pigments as all-trans- and cis-isomers, which function as accessory light-harvesting pigments, antioxidant and photoprotective agents, and precursors of signaling molecules and plant hormones. The carotenoid pathway involves the participation of different carotenoid isomerases. Among them, D27 is a β-carotene isomerase showing high specificity for the C9-C10 double bond catalyzing the interconversion of all-trans- into 9-cis-β-carotene, the precursor of strigolactones. We have identified one D27 (CsD27-1) and two D27-like (CsD27-2 and CsD27-3) genes in saffron, with CsD27-1 and CsD27-3, clearly differing in their expression patterns; specifically, CsD27-1 was mainly expressed in the undeveloped stigma and roots, where it is induced by Rhizobium colonization. On the contrary, CsD27-2 and CsD27-3 were mainly expressed in leaves, with a preferential expression of CsD27-3 in this tissue. In vivo assays show that CsD27-1 catalyzes the isomerization of all-trans- to 9-cis-β-carotene, and could be involved in the isomerization of zeaxanthin, while CsD27-3 catalyzes the isomerization of all-trans- to cis-ζ-carotene and all-trans- to cis-neurosporene. Our data show that CsD27-1 and CsD27-3 enzymes are both involved in carotenoid isomerization, with CsD27-1 being specific to chromoplast/amyloplast-containing tissue, and CsD27-3 more specific to chloroplast-containing tissues. Additionally, we show that CsD27-1 is co-expressed with CCD7 and CCD8 mycorrhized roots, whereas CsD27-3 is expressed at higher levels than CRTISO and Z-ISO and showed circadian regulation in leaves. Overall, our data extend the knowledge about carotenoid isomerization and their implications in several physiological and ecological processes.

On the question of the light-harvesting role of β-carotene in photosystem II and photosystem I core complexes

β-Carotene is the only carotenoid present in the core complexes of Photosystems I and II. Its proximity to chlorophyll a molecules enables intermolecular electronic interactions, including β-carotene to chlorophyll a electronic excitation transfers. However, it has been well documented that, compared to chlorophylls and to phycobilins, the light harvesting efficiency of β-carotenes for photosynthetic O2 evolution is poor. This is more evident in cyanobacteria than in plants and algae because they lack accessory light harvesting pigments with absorptions that overlap the β-carotene absorption. In the present work we investigated the light harvesting role of β-carotenes in the cyanobacterium Synechococcus sp. PCC 7942 using selective β-carotene excitation and selective Photosystem detection of photo-induced electron transport to and from the intersystem plastoquinones (the plastoquinone pool). We report that, although selectively excited β-carotenes transfer electronic excitation to the chlorophyll a of both photosystems, they enable only the oxidation of the plastoquinone pool by Photosystem I but not its reduction by Photosystem II. This may suggest a light harvesting role for the β-carotenes of the Photosystem I core complex but not for those of the Photosystem II core complex. According to the present investigation, performed with whole cyanobacterial cells, the lower photosynthesis yields measured with β-Car-absorbed light can be attributed to the different excitation trapping efficiencies in the reaction centers of PSI and PSII.

Carotenoid oxidation products as stress signals in plants

Carotenoids are known to play important roles in plants as antioxidants, accessory light-harvesting pigments, and attractants for pollinators and seed dispersers. A new function for carotenoids has recently emerged, which relates to the response of plants to environmental stresses. Reactive oxygen species, especially singlet oxygen, produced in the chloroplasts under stress conditions, can oxidize carotenoids leading to a variety of oxidized products, including aldehydes, ketones, endoperoxides and lactones. Some of those carotenoid derivatives, such as volatile β-cyclocitral, derived from the oxidation of β-carotene, are reactive electrophile species that are bioactive and can induce changes in gene expression leading to acclimation to stress conditions. This review summarizes the current knowledge on the non-enzymatic oxidation of carotenoids, the bioactivity of the resulting cleavage compounds and their functions as stress signals in plants.

Artificial photosynthetic reaction centers coupled to light-harvesting antennas

We analyze a theoretical model for energy and electron transfer in an artificial photosynthetic system. The photosystem consists of a molecular triad (i.e., with a donor, a photosensitive unit, and an acceptor) coupled to four accessory light-harvesting-antenna pigments. The resonant energy transfer from the antennas to the artificial reaction center (the molecular triad) is described here by the Förster mechanism. We consider two different kinds of arrangements of the accessory light-harvesting pigments around the reaction center. The first arrangement allows direct excitation transfer to the reaction center from all the surrounding pigments. The second configuration transmits energy via a cascade mechanism along a chain of light-harvesting chromophores, where only one chromophore is connected to the reaction center. We show that the artificial photosynthetic system using the cascade energy transfer absorbs photons in a broader wavelength range and converts their energy into electricity with a higher efficiency than the system based on direct couplings between all the antenna chromophores and the reaction center.

Ultrafast carotenoid-to-chlorophyll singlet energy transfer in the light-harvesting complex LHCII.

Carotenoids serve as accessory light-harvesting pigments in photosynthesis absorbing light in the blue-green spectral region and efficiently transferring energy to neighbouring chlorophylls. In the light-harvesting complex LHCII of higher plants there are a large number of possible pathways between the lowest excited singlet states of the different carotenoids and chlorophylls a and b. We have made fluorescence upconversion measurements of the excited S2 state decay lifetimes of both lutein and the mixture of xanthophylls extracted from LHCII and dissolved in simple solvents. In benzyl alcohol, chosen as a model of the protein environment, the carotenoid emission shows a major decay component of ~120 fs. In contrast, the carotenoid emission observed upon excitation of the LHCII trimers at 501 nm was only ~26 fs. The same measurement made after addition of the detergent TX100, which disrupts energy transfer from both chlorophyll b and the xanthophylls to chlorophyll a, resulted in a decay time constant of 116 fs. These results suggest an ultrafast energy transfer pathway from the S2 state of lutein to the chlorophylls with a ~78% efficiency. The emission wavelength dependence of the chlorophyll rise kinetics was also studied after excitation of LHCII at 501 nm, or 470 nm, and the observation of an ultrafast component in the rise kinetics is consistent with energy transfer from the carotenoid S2 state.

Biological functions of carotenoids--diversity and evolution.

Carotenoids first emerged in archaebacteria as lipids reinforcing cell membranes. To serve this function their long molecules have extremely rigid backbone due to the linear chain of usually 10 to 11 conjugated C=C bonds in transconfiguration--the length corresponding the thickness of hydrophobic zone of membrane which they penetrate as "molecular rivets". Carotenoids retain their membrane-reinforcing function in some fungi and animals. The general structure of carotenoid molecule, originally having evolved for mechanical functions in membranes, possess a number of other properties that were later used for independent functions. The most striking fact is that these properties proved to fit some new functions to perfection. The polyene chain of 9-11 double bonds absorbs light precisely in the gap of chlorophyll absorption--function as accessory light-harvesting pigments in all plants; Unique arrangement of electronic levels owing to the by polyene chain structure makes carotenoids the only natural compounds capable of excitation energy transfer both (i) from carotenoid excited state to chlorophyll in the light-harvesting complex and (ii) from triplet chlorophyll or singlet oxygen to carotenoid in photosynthetic reaction centers--protection of RC from photodamage. The linear system of conjugated C=C bonds provides high reducing potential of carotenoid molecules making them potent antioxidants in lipid formations. Still, there is a lack of evidence of the chemical antioxidant function of carotenoids, especially in higher organisms; most data demonstrate an antioxidant ability rather than a function. Carotenoids have many other independent biological functions, including: specific coloration patterns in plants and animals, screening from excessive light and spectral filtering, defense of egg proteins from proteases in some invertebrates; the direct carotenoid derivative--retinal--acts as visual pigment in all animals and as chromophore in bacteriorhodopsin photosynthesis, retinoic acid in animals and abscisic acid in plants serve as hormones. All these functions utilize various properties (mechanical, electronic, stereospecific) of a single structure evolved in bacteria for a single membrane-reinforcing function, thus demonstrating an example of pure evolutionary preadaptation. One of the practical conclusions that can be reached by reviewing uniquely diverse properties and functions of carotenoids is that, when considering possible mechanisms of their effects in organisms (e.g., anticarcinogenic action), all their functional traits should be taken into account.

Carotenoids in photosynthesis.

Carotenoids are usually considered to perform two major functions in photosynthesis. They serve as accessory light harvesting pigments, extending the range of wavelengths over which light can drive photosynthesis, and they act to protect the chlorophyllous pigments from the harmful photodestructive reaction which occurs in the presence of oxygen. Drawing upon recent work with photosynthetic bacteria, evidence is presented as to how the carotenoids are organized within both portions of the photosynthetic unit (the light harvesting antenna and the reaction centre) and how they discharge both their functions. The accessory pigment role is a singlet-singlet energy transfer from the carotenoid to the bacteriochlorophyll, while the protective role is a triplet-triplet energy transfer from the bacteriochlorophyll to the carotenoid.

Carotenoids as accessory light-harvesting pigments

Abstract

Carotenoids in photosynthesis

Abstract

Carotenoids in photosynthesis

Carotenoids are usually considered to perform two major functions in photosynthesis. They serve as accessory light harvesting pigments, extending the range of wavelengths over which light can drive photosynthesis, and they act to protect the chlorophyllous pigments from the harmful photodestructive reaction which occurs in the presence of oxygen. Drawing upon recent work with photosynthetic bacteria, evidence is presented as to how the carotenoids are organized within both portions of the photosynthetic unit (the light harvesting antenna and the reaction centre) and how they discharge both their functions. The accessory pigment role is a singlet-singlet energy transfer from the carotenoid to the bacteriochlorophyll, while the protective role is a triplet-triplet energy transfer from the bacteriochlorophyll to the carotenoid.

Carotenoid and merocyanine probes in chromatophore membranes.

Increasing awareness of the vast amount of information that can be obtained from intrinsic and extrinsic probes of membrane phenomena has led to a wide-ranging survey of the properties of both types of probe. Intrinsic probes of photosynthetic membranes are provided by the carotenoid pigments. The carotenoids are assumed to be located in the lipid phase of the membrane close to chlorophyll, since they act as accessory light-harvesting pigments. Isolated reaction center preparations from photosynthetic bacteria usually contain tightly bound carotenoids, which further supports the concept of a close association between them and the photosynthetic unit. The spectral and kinetic properties of these pigments respond to several parameters: light, oxygen, ATP, and inorganic pyrophosphate (PPi). In single-flash illumination experiments, the rate of decay of the membrane charge is assumed to depict the degree of coupling of the chromatophore or chloroplast membrane. The origin of the carotenoid absorbance change has been much debated and recently it has been shown to coincide with the formation of a diffusion potential in chromatophore membranes from Rhodopseudomonas spheroides (Jackson and Crofts, 1969, 1971; Crofts, 1974). In plant chloroplasts, the corresponding absorbance change at 518 nm has been stated by Witt (1972) to indicate the formation of a transmembrane electric field. When induced in the dark by energizing conditions, or by illumination, the steady state response of the pigments is abolished by uncouplers but the response to a single flash is unaltered in rise time and extent, even though the decay time is accelerated.