Time-resolved Difference Absorption Spectra Research Articles

A functional compartmental model of the Synechocystis PCC 6803 phycobilisome

In the light-harvesting antenna of the Synechocystis PCC 6803 phycobilisome (PB), the core consists of three cylinders, each composed of four disks, whereas each of the six rods consists of up to three hexamers (Arteni et al., Biochim Biophys Acta 1787(4):272–279, 2009). The rods and core contain phycocyanin and allophycocyanin pigments, respectively. Together these pigments absorb light between 400 and 650 nm. Time-resolved difference absorption spectra from wild-type PB and rod mutants have been measured in different quenching and annihilation conditions. Based upon a global analysis of these data and of published time-resolved emission spectra, a functional compartmental model of the phycobilisome is proposed. The model describes all experiments with a common set of parameters. Three annihilation time constants are estimated, 3, 25, and 147 ps, which represent, respectively, intradisk, interdisk/intracylinder, and intercylinder annihilation. The species-associated difference absorption and emission spectra of two phycocyanin and two allophycocyanin pigments are consistently estimated, as well as all the excitation energy transfer rates. Thus, the wild-type PB containing 396 pigments can be described by a functional compartmental model of 22 compartments. When the interhexamer equilibration within a rod is not taken into account, this can be further simplified to ten compartments, which is the minimal model. In this model, the slowest excitation energy transfer rates are between the core cylinders (time constants 115–145 ps), and between the rods and the core (time constants 68–115 ps).

Tuning the emissive triplet excited states of platinum(ii) Schiff base complexes with pyrene, and application for luminescent oxygen sensing and triplet–triplet-annihilation based upconversions

Pt(II) Schiff base complexes containing pyrene subunits were prepared using the chemistry-on-complex approach. This is the first time that supramolecular photochemical approach has been used to tune the photophysical properties of Schiff base Pt(II) complexes, such as emission wavelength and lifetimes. The complexes show intense absorption in the visible region (ε = 13100 M(-1) cm(-1) at 534 nm) and red phosphorescence at room temperature. Notably, much longer triplet excited state lifetimes (τ = 21.0 μs) were observed, compared to the model complexes (τ = 4.4 μs). The extension of triplet excited state lifetimes is attributed to the establishment of equilibrium between the metal-to-ligand charge-transfer ((3)MLCT) state (coordination centre localized) and the intraligand ((3)IL) state (pyrene localized), or population of the long-lived (3)IL triplet excited state. These assignments were fully rationalized by nanosecond time-resolved difference absorption spectra, 77 K emission spectra and density functional theory calculations. The complexes were used as triplet sensitizers for triplet-triplet-energy-tranfer (TTET) processes, i.e. luminescent O(2) sensing and triplet-triplet annihilation (TTA) based upconversion. The O(2) sensitivity (Stern-Volmer quenching constant) of the complexes was quantitatively evaluated in polymer films. The results show that the O(2) sensing sensitivity of the pyrene containing complex (K(SV) = 0.04623 Torr(-1)) is 15-fold of the model complex (K(SV) = 0.00313 Torr(-1)). Furthermore, significant TTA upconversion (upconversion quantum yield Φ(UC) = 17.7% and the anti-Stokes shift is 0.77 eV) was observed with pyrene containing complexes being used as triplet sensitizers. Our approach to tune the triplet excited states of Pt(II) Schiff base complexes will be useful for the design of phosphorescent transition metal complexes and their applications in light-harvesting, photovoltaics, luminescent O(2) sensing and upconversion, etc.

Ultrafast Spectroscopy of Oxyhemoglobin during Photodissociation

Ultrafast time-resolved pump-probe spectroscopy was studied to clarify the detailed mechanism in the photodissociation process of oxyhemoglobin in the visible spectral range. The photodissociation had not been time-resolved and only the upper limit of the time needed for the dissociation process was claimed to be faster than 50 fs; it was time-resolved to be 45 +/- 5 fs with 10 fs time resolution. The broadband spectrum of the visible laser pulses enabled us to observe the signal over a broad spectral range. A broadband multichannel detector array was used to simultaneously obtain the pump-probe signal at all probe frequencies. Thus, we obtained for the first time the spectra of the ultrashort lifetime electronic excited state of HbO(2) in the visible range from 523 nm (19 109 cm(-1)) to 719 nm (13 914 cm(-1)). After the photodissociation, subpicosecond time constant was found and attributed to the dynamics of the photolyzed Hb. Time-resolved difference absorption spectra in 0-100 fs showed oscillatory motion reflecting wavepacket motion in the potential energy surface of the photoexcited HbO(2) during the ultrafast photolysis.

Sub-μ-second Time-Resolved Absorption Spectroscopy of a Polar Carotenoid Analogue, 2-(All-trans-retinylidene)indan-1,3-dione; Formation of the Dication by Direct Triplet-Excited Sensitization

Sub-micro-second time-resolved difference absorption spectra of a polar carotenoid analogue, 2-(all-trans-retinylidene)indan-1,3-dione (hereafter, we will call RetInd), were recorded in tetrahydrofuran at room temperature upon anthracene-sensitized triplet excitation. In addition to the typical Tn <-- T1 absorption spectrum of anthracene followed by that of RetInd, a novel transient species, which peaked at 670 nm, was detected. The lifetime and the population of the 670 nm species was not affected by the presence of oxygen but was quenched by the cation scavenger, triethylamine. Therefore, we have identified this species as a "cation". The transient 670 nm species was not generated by direct photoexcitation of RetInd in the absence of a triplet sensitizer. Therefore, this species was not generated via the T1 species of RetInd but rather via an "invisible state" of RetInd, which is generated by direct energy or electron transfer from T1 anthracene. This proposed pathway was confirmed by a singular-value decomposition followed by a global fitting analysis. The "cation" of RetInd shows vibrational structure in its absorption spectrum, and its lifetime was determined to be 15 micros. Chemical oxidation of RetInd in 2,2,2-trifluoroethanol (dichloromethane) produced a broad absorption band around 880 (1013) nm, which could be transformed into a shoulder around 640 (675) nm upon addition of increasing amounts of the oxidant, FeCl3. The former absorption band can be assigned to a radical cation, while the latter to a dication. Because of the spectral similarity, the 670 nm species can be assigned to the dication, and the "invisible state" is ascribed to the radical cation of RetInd. This is the first direct evidence for the production of a dication of a biological polyene moiety generated in non-halogenated solution following anthracene-sensitized excitation.

Femtosecond time-resolved difference absorption spectroscopy of all-trans-b-Apo-8'-carotenal

The femtosecond time-resolved difference absorption spectra of all-trans-β-Apo-8′-carotenal have been recorded and analyzed by the singular-value decomposition (SVD) method followed by global fitting using a sequential model for the excited-state energy relaxation. With this model, we have obtained the excited-state absorption spectra and the lifetimes of the corresponding excited states both in nonpolar solvent n-hexane and polar solvent methanol. Three excited states, namely S 3 (170fs), S 2 (2.32ps) and S 1 (26ps) in n-hexane, and two excited states S 2 (190fs) and S 1 (9.4ps) in methanol have been observed. The excited-state absorption spectra of all-trans-β-Apo-8'-carotenal in methanol display a red shift and broadeness, while the lifetime of S 1 state becomes shorter. It is proposed that these effects are related to the presence of a carbonyl functional group that leads to the solvent effect on the excited-state energy level. At the same time, it is shown that the SVD method is a useful tool in resolving the time-resolved absorption spectra.

Ultrafast Optical Responses of the Squarylium Dye J-Aggregates Films

ABSTRACTUltrafast optical responses of the organic films containing squaryliurn dye J-aggregates prepared by simple spincoating method were investigated. Some SQ films exhibited a sharp absorption peak originated from J-aggregates and especially the SQ derivative which has dibutylamino bases at the end of benzene rings forms good J-aggregates in the films without any extra treatment. Time-resolved difference absorption spectra were measured about the SQ44 film. Clear bleached absorption peak and its fast recovery were observed. The decay time was determined to be about 220 fs at 50 MW/cm2 excitation intensity. Sample preparations and all the measurements were performed in air at room temperature.

Relaxation dynamics of photoexcitations in C 60 films

Time-resolved difference absorption spectra of polycrystalline thin films of C 60 were measured by femtosecond pump–probe spectroscopy. The decay dynamics of the excited state can be explained in terms of a model of localized excitations. Self-trapped excitons (STEs) are formed after photoexcitation and then converted to polarons. The polarons mainly recombine when they encounter each other after intersite hopping. The decay times of the STEs and polarons are estimated to be 570±120 fs and 54±7 ps, respectively.

Energy transfer in spectrally inhomogeneous light-harvesting pigment-protein complexes of purple bacteria

Energy transfer within the peripheral light-harvesting antenna of the purple bacteria Rhodobacter sphaeroides and Rhodopseudomonas palustris was studied by one- and two-color pump-probe absorption spectroscopy with approximately 100-fs tunable pulses at room temperature and at 77 K. The energy transfer from B800 to B850 occurs with a time constant of 0.7 +/- 0.05 ps at room temperature and 1.8 +/- 0.2 ps at 77 K and is similar in both species. Anisotropy measurements suggest a limited but fast B800 <--> B800 transfer time (tau approximately 0.3 ps). This is analyzed as incoherent hopping of the excitation in a system of spectrally inhomogeneous antenna pigment-protein complexes, by a master equation approach. The simulations show that the measured B800 dynamics is well described as energy transfer with a characteristic average nearest-neighbor pairwise transfer time of 0.35 ps among approximately 10 Bchl molecules in a circular arrangement, in good agreement with the recent high-resolution structure of LH2. The possible presence of fast intramolecular relaxation processes within the Bchl a molecule was investigated by measurement of time-resolved difference absorption spectra and kinetics of Bchl a in solution and in low-temperature glasses. From these measurements it is concluded that fast transients observed at room temperature are due mainly to solvation processes, whereas at 77 K predominantly slower (> 10-ps) relaxation occurs.

Femtosecond nonlinear optical dynamics of excitons in J-aggregates

Time-resolved difference absorption spectra of J-aggregates were measured by femtosecond pump-probe spectroscopy. The induced absorption near the J-band at 20 K was assigned to the transitions from n-exciton states to ( n + 1)-exciton states ( n⩾1). The decay time of the n(⩾2)-exciton states is determined to be about 200 fs. The ultrafast dynamics of the exciton states is explained by a confined exciton model in individual coherent aggregates, which incoherently constitute the whole structural aggregate. The average size of the exciton system defined for each coherent aggregate is estimated to be about 20 molecules.

Raman-absorption simultaneous measurements for cytochrome oxidase compound A at room temperature with a novel flow apparatus

A novel flow apparatus for continuously producing reaction intermediates of cytochrome oxidase was constructed and applied successfully to observe the transient absorption and resonance Raman spectra in its reaction with oxygen. Time-resolved difference absorption spectra in 500-650-nm region clearly indicated the formation of compound A upon photolysis of the fully reduced CO-bound form at 5 degrees C, and at this stage electrons were not transferred from cytochrome c to cytochrome oxidase. However, at the stage of formation of compound B, cytochrome c was oxidized. Resonance Raman spectra of these intermediates measured simultaneously with the absorption spectra are also reported.