Excited state properties of β-carotene analogs incorporating a lactone ring.

Carotenoids possessing a carbonyl group along their polyene backbone exhibit unique excited state properties due to the occurrence of intramolecular charge transfer (ICT) in the excited state. In fact, the ICT characteristics of naturally occurring carbonyl carotenoids play an essential role in the highly efficient energy transfer that proceeds in aquatic photosynthetic antenna systems. In the present study, we synthesized two short-chain polyene carotenoids incorporating a lactone ring, denoted as BL-7 and BL-8, having seven and eight conjugated double bonds (n = 7 and 8), respectively.

Excited state properties of a short π-electron conjugated peridinin analogue.

C-peridinin is a synthetic analogue of the important, naturally-occurring carotenoid, peridinin, found in several marine algal species. C-peridinin has five conjugated carbon-carbon double bonds compared to eight possessed by peridinin and also lacks the methyl group functionalities typically present along the polyene chain of carotenoids. These structural modifications lead to unique excited state properties and important insights regarding the factors controlling the photophysics of peridinin and other carbonyl-containing carotenoids, which are critical components of the light-harvesting systems of many photosynthetic organisms.

Elucidation and Control of an Intramolecular Charge Transfer Property of Fucoxanthin by a Modification of Its Polyene Chain Length.

Fucoxanthin is an essential pigment for the highly efficient light-harvesting function of marine algal photosynthesis. It exhibits excited state properties attributed to intramolecular charge transfer (ICT) in polar environments due to the presence of the carbonyl group in its polyene backbone. This report describes the excited state properties of fucoxanthin homologues with four to eight conjugated double bonds in various solvents using the femtosecond pump-probe technique.

Excited states energies and dynamics of peridinin analogues and the nature of the intramolecular charge transfer state in carbonyl-containing carotenoids.

The lifetime of the lowest excited singlet state of carbonyl-containing carotenoids typically depends on the polarity of the solvent, an effect that has been attributed to the presence of an intramolecular charge transfer (ICT) state. The nature of this ICT state has yet to be clarified. In the present work, steady-state and ultrafast time-resolved optical spectroscopic experiments have been performed on peridinin and three synthetic analogues, C33-peridinin, C35-peridinin, and C39-peridinin, which have different extents of π-electron conjugation.

Effect of Molecular Symmetry on the Spectra and Dynamics of the Intramolecular Charge Transfer (ICT) state of peridinin.

The spectroscopic properties and dynamics of the excited states of two different synthetic analogues of peridinin were investigated as a function of solvent polarity using steady-state absorption, fluorescence, and ultrafast time-resolved optical spectroscopy. The analogues are denoted S-1- and S-2-peridinin and differ from naturally occurring peridinin in the location of the lactone ring and its associated carbonyl group, known to be obligatory for the observation of a solvent dependence of the lifetime of the S(1) state of carotenoids. Relative to peridinin, S-1- and S-2-peridinin have their lactone rings two and four carbons more toward the center of the π-electron system of conjugated carbon-carbon double bonds, respectively.

Stereocontrolled total synthesis of fucoxanthin and its polyene chain-modified derivative.

Fucoxanthin exhibits high energy transfer efficiencies to Chlorophyll a (Chl a) in photosynthesis in the sea. In order to reveal how each characteristic functional group, such as the length of the polyene chain, allene, and conjugated carbonyl groups, of this marine natural product are responsible for its remarkably efficient ability, the total synthesis of fucoxanthin by controlling the stereochemistry was achieved. The method established for fucoxanthin synthesis was successfully applied to the synthesis of the C42 longer chain analogue.

Singlet and triplet state spectra and dynamics of structurally modified peridinins.

The peridinin-chlorophyll a-protein (PCP) is a light-harvesting pigment-protein complex found in many species of marine algae. It contains the highly substituted carotenoid peridinin and chlorophyll a, which together facilitate the transfer of absorbed solar energy to the photosynthetic reaction center. Photoexcited peridinin exhibits unorthodox spectroscopic and kinetic behavior for a carotenoid, including a strong dependence of the S(1) excited singlet state lifetime on solvent environment.

Triplet state spectra and dynamics of peridinin analogs having different extents of pi-electron conjugation.

The Peridinin-Chlorophyll a-Protein (PCP) complex has both an exceptionally efficient light-harvesting ability and a highly effective protective capacity against photodynamic reactions involving singlet oxygen. These functions can be attributed to presence of a substantial amount of the highly-substituted and complex carotenoid, peridinin, in the protein and the facts that the low-lying singlet states of peridinin are higher in energy than those of chlorophyll (Chl) a, but the lowest-lying triplet state of peridinin is below that of Chl a. Thus, singlet energy can be transferred from peridinin to Chl a, but the Chl a triplet state is quenched before it can sensitize the formation of singlet oxygen.

Olefin metathesis in carotenoid synthesis.

Olefin metathesis is a powerful and widely applicable synthetic method for carbon-carbon double bond formation. However, its application to the synthesis of conjugating polyene chains has been very limited because of possible undesired side reactions. We attempted to apply this method to the synthesis of symmetrical carotenoids.

Syntheses of C33-, C35-, and C39-peridinin and their spectral characteristics.

Peridinin, a nor-carotenoid, exhibits an exceptionally high energy transfer efficiency to chlorophyll a in photosynthesis in the sea. This efficiency would be related to the unique structure of peridinin. To answer the question of why peridinin possesses the irregular C37 skeleton, we have achieved the synthesis of three peridinin derivatives.

Effect of pi-electron conjugation length on the solvent-dependent S(1) lifetime of peridinin.

Peridinin exhibits an anomalous solvent dependence of its S(1) excited state lifetime attributed to the presence of an intramolecular charge transfer (ICT) state. The nature of this state has yet to be elucidated. Ultrafast time-resolved optical spectroscopy has been performed on a synthetic analog, C(35)-peridinin, having one less conjugated double bond than peridinin.

Spectroscopic investigation of peridinin analogues having different pi-electron conjugated chain lengths: exploring the nature of the intramolecular charge transfer state.

The lifetime of the lowest excited singlet (S(1)) state of peridinin and many other carbonyl-containing carotenoids and polyenes has been reported to depend on the polarity of the solvent. This effect has been attributed to the presence of an intramolecular charge transfer (ICT) state in the manifold of excited states for these molecules. The nature of this ICT state has yet to be elucidated.

Syntheses of allene-modified derivatives of peridinin toward elucidation of the effective role of the allene function in high energy transfer efficiencies in photosynthesis.

Peridinin is known as the main light-harvesting pigment in photosynthesis in the sea and exhibits exceptionally high energy transfer efficiencies to chlorophyll a. This energy transfer efficiency is thought to be related to the intricate structure of peridinin, which possesses allene and ylidenbutenolide functions in the polyene backbone. There are, however, no studies on the relationship between the structural features of peridinin and its super ability for energy transfer.

Effect of structural modifications on the spectroscopic properties and dynamics of the excited states of peridinin.

The spectroscopic properties and dynamics of the lowest excited singlet states of peridinin and two derivatives have been studied by steady-state absorption and fast-transient optical spectroscopic techniques. One derivative denoted PerOlEs, possesses a double bond and a methyl ester group instead of the r-ylidenebutenolide of peridinin. Another derivative denoted PerAcEs, is the biosynthetic precursor of peridinin and possesses a triple bond and a methyl ester group corresponding to the r-ylidenbutenolide function.

Stark Absorption Spectroscopy of Peridinin and Allene-Modified Analogues.

Stark absorption spectra of peridinin (Per) and five allene-modified analogues and their angular dependence as a function of an externally applied electric field were measured in methyl methacrylate polymer at 77K. In all cases, the energetically lowest absorption band has a significant change of static dipole moment upon photoexcitation (Δμ). In particular, Per has the largest value of |Δμ|.