DELAYED MICROSECOND LUMINESCENCE OF PHYCOBILISOMES

The time-resolved luminescence spectra (in the microsecond range) of phycobilisomes and biliproteins in buffer and polymer matrix were measured in the temperature range from 8 K. to 293 K. Delayed luminescence located in the same spectral region as prompt fluorescence of investigated samples (DLF) and the long-wavelength delayed emission in the720–760 nm range (DL1) was observed. The temperature and viscosity dependencies of DLF and DL1 luminescences were different, but both do not have uniexponential decays and are not quenched by oxygen. This means that delayed luminescence could be generated without the participation of the triplet states, or the chromophores could be shielded by protein against interaction with oxygen. The linear dependence of delayed luminescence on exciting light intensity shows that delayed luminescence is monophotonically induced. It seems that both DLF and DL1 are related to electron-cation recombination, which yields excited singlet states. The DLF is emitted from the first excited singlet state of biliprotein chromophores and DL1 from the same state of the excimers or from the triplet state of some groups of chromophores. Ionization energy of chromophores can be lowered as a result of their interactions with the environment. Delay of emission is due to the trapping or solvation of electrons. Every type of biliprotein consisting of phycobilisomes possesses its own “trap” and can emit the DL. In the case of native phycobilisomes a competition between the excitation energy trapping and transfer occurs.     

Molecular weight dependence of triplet—triplet processes in poly(2-vinylnaphthalene)

Delayed fluorescence and phosphorescence spectra and decay curve measurements at 77 K are reported for samples of poly(2-vinylnaphthalene) with molecular weights determined by viscometry to be in the range 15 600 to 505 000. The intensity of delayed fluorescence relative to phosphorrescence was found to increase with molecular weight up to the highest molecular weight sample of solution polymerized material (MW ≈ 100 000) with a leveling off for the higher molecular weight bulk polymers. It is argued that these results imply a triplet exciton migration distance of up to 700 chromophore units. Decay curves imply that most mobile triplet excitons are trapped within approximately 0.3 s. The excitation dependence of the delayed emissions imply that unimolecular processes dominate the kinetics of triplet state chromophores.     

Delayed fluorescence in perhydrotriphenylene-oligothiophene inclusion compounds: evidence for molecular oxygen-related excited States

Delayed emission from α-terthiophene (3T) and α-quinquethiophene (5T) in a perhydrotriphenylene (PHTP) host is investigated. Delayed fluorescence for the lowest singlet excited state of 3T and 5T is detected at both low (80 K) and room temperatures. In addition, at low temperature, phosphorescence from 3T is observed with a lifetime of ～100 μs. Comparison of the dependence of delayed fluorescence and phosphorescence on excitation intensity and time shows that delayed fluorescence does not originate from triplet--triplet annihilation. A dependence of the delayed fluorescence on atmospheric pressure indicates that it originates, at least partially, from complexes of photoexcited oligothiophene and molecular oxygen O(2).     

Backward electron transport in photosystem 2 reaction center and temperature dependence of delayed luminescence characteristics

The temperature dependence of parameters of light-induced changes in millisecond delayed luminescence (half-width of the maximum, maximal and steady-state luminescence intensity) is studied within the temperature range from -23 to 45 degrees C in leaf segments of Chinese rose (Hibiscus rosa sinensis). Delayed luminescence (DL) is induced and registered by a homemade setup based on a Lewis-Kasha-type phosphoroscope. The temperature dependence of steady-state luminescence intensity is shown to have two maxima, at -10 and 35 degrees C. At room temperatures, the steady-state value of luminescence intensity is minimal, and its value correlates with the temperature tolerance of the plant. Depending on cooling and heating regimes, the DL steady-state value vs. temperature curves is found to be different. We suppose this effect to be caused by temperature-induced destructive changes in the structure of photosystem 2 reaction centre and probably by salting out.     

Delayed Fluorescent Emission from Pyrene Doped Phenanthrene Nanoparticles Based on Triplet-triplet Energy Transfer

Doped nanoparticles were prepared from pyrene and phenanthrene using a facile reprecipitation method. The doped nanoparticles presented unique delayed fluorescent emissions of pyrene under the unprotected condition. The ratio of the intensity of delayed fluorescence (I_DF) to that of phosphorescence (I_P) is about 4:1, which almost keeps unchanged with the decrease of pyrene content at room temperature. The intensity of the delayed fluorescence emissions is dependent on the relative content of pyrene, as well as the aggregation degree of nanoparticles. The delayed emissions are contributed to efficient triplet‐triplet energy transfer from phenanthrene (donor) to pyrene (acceptor). Steady fluorescence measurement have proved that the singlet‐singlet energy transfer process was also existent dominated by the radiation energy transfer mechanism.     

CHLOROPHYLL a FLUORESCENCE OF GONYAULAX POLYEDRA GROWN ON A LIGHT-DARK CYCLE AND AFTER TRANSFER TO CONSTANT LIGHT

Abstract— The chlorophyll a fluorescence properties of Gonyaulax polyedra cells before and after transfer from a lightdark cycle (LD) to constant dim light (LL) were investigated. The latter display a faster fluorescence transient from the level ‘I’ (intermediary peak) to ‘D’ (dip) to ‘P’ (peak) than the former (3 s as compared to 10 s), and a different pattern of decline in fluorescence from ‘I’ to ‘D’ and from ‘P’ to the steady state level with no clearly separable second wave of slow fluorescence change, referred to as ‘s' (quasi steady state)→‘M’ (maximum) →‘T’ (terminal steady state). The above differences are constant features of cells in LD and LL, and are not dependent on the time of day. They are interpreted as evidence for a greater ratio of photosystem II/photosystem I activity in cells in LL. After an initial photoadaptive response following transfer from LD to LL, the cell absorbance at room temperature and fluorescence emission spectra at 77 K for cells in LL and LD are comparable. The major emission peak is at 685–688 nm (from an antenna Chl a 680, perhaps Chl a-c complex), but, unlike higher plants and other algae, the emission bands at 696–698 nm (from Chl a_II complex, Chl a 685, close to reaction center II) and 710–720 nm (from Chl a₁, complexes, Chl a 695, close to reaction center I) are very minor and could be observed only in the fluorescence emission difference spectra of LL minus LD cells and in the ratio spectra of DCMU-treated to non-treated cells. Comparison of emission spectra of cells in LL and LD suggested that, in LL, there is a slightly greater net excitation energy transfer from the light-harvesting peridinin-Chl a (Chl a 670) complex, fluorescing at 675 nm, to the other antenna chlorophyll a complex fluorescing at 685–688 nm, and from the Chl a., complex to the reaction center II. Comparison of excitation spectra of fluorescence of LL and LD cells, in the presence of DCMU, confirmed that cells in LL transfer energy more extensively from the peridinin-Chl a complex to other Chl a complexes than do cells in LD.     

Photochemistry on surfaces: Fluorescence emission of monomers and dimers and triplet state absorption of acridine orange adsorbed on microcrystalline cellulose

Prompt fluorescence as well as delayed fluorescence emission of acridine orange was detected at room temperature from samples where this dye is adsorbed on microcrystalline cellulose. Ground state absorption studies provided evidence for dimer formation of the dye when adsorbed on cellulose, and the equilibrium constant for dimerisation was determined as 1.6±0.1 × 10⁶mol⁻¹g. At low loadings of acridine orange on cellulose (<1 μmol g⁻¹) the fluorescence emission is mainly due to the monomer and is similar to that observed in ethanolic solutions where little aggregation occurs, and peaks at 530 nm. A linear dependence of the fluorescence intensity on the amount of light absorbed by the dye was established for these “diluted” samples. However, at higher loadings (>20 μmol g⁻¹), the fluorescence intensity decreases, and the emission is broad with its maximum at 620 nm, and is mainly due to the dimer. By assuming that the excited monomer and dimer of acridine orange are the only emitting species, it was possible to determine the fluorescence quantum yields for these two species when adsorbed on microcrystalline cellulose as 0.95±0.05 and 0.40±0.10, respectively. Pulsed emission studies at room temperature in the millisecond time-range also revealed monomer and dimer emissions on this longer time-scale. These are shown to be due to thermally activated delayed fluorescence arising from the triplet states of monomer and dimer acridine orange as confirmed by diffuse reflectance transient absorption studies.     

AN ANALYSIS OF A TRIPLET EXCITON MODEL FOR THE DELAYED LIGHT IN CHLORELLA*

Abstract— The time dependence of the delayed light in the green alga Chlorella pyrenoidosa has been examined quantitatively in the 1 to 12 msec range after excitation with light pulses (A = 6328 Å) of 100 μsec and 4.5 msec duration. We have confirmed the data of Tollin, Ruby, and Bertsch et al., on the time course of the delayed light in the msec range. New experiments, with 100 μsec flash excitation, on the time dependence of the delayed light emitted by Chlorella treated with 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DMU), hydroxylamine, methyl violgen, and various combinations of these chemicals are presented. Also, data on the dependence of the delayed light intensity on the intensity of the excitation light in the 1.5 and 5.0 msec range are reported. The square law dependence, reported by Jones, in the 140 and 250 msec range is confirmed in the 1.5 and 5.0 msec range at very low light levels. The experimental data on delayed light has been analyzed in terms of a model which incorporates triplet exciton fusion. The following major points result from this analysis: (1) A triplet exciton kinetic model can explain both the time dependence and the excitation intensity dependence of the delayed light emitted by Chlorella. (2) The density of triplet excitons predicted by the model from the observed delayed light intensity is much less than that which can be detected by flash photolysis measurements. Therefore, the failure of such measurements to detect triplet states in vivo does not disprove the model. (3) The possibility of changes in the rate of electron transfer reactions of photosynthesis is included in the kinetic model. The predictions from the model are compared with the effects of chemical additives on the time dependence of the delayed light decay. (4) The proposed triplet exciton model predicts that the delayed light intensity may, under certain specific conditions, be affected by a magnetic field. The negative result of an attempt to observe this effect is reported and discussed. (5) It is concluded that the proposed triplet ‘fusion’ model is a valid alternative to the electron-hole recombination model.     

DELAYED FLUORESCENCE AND SOME PROPERTIES OF THE CHLOROPHYLL TRIPLETS

–P-Type delayed fluorescence and sensitised P-Type delayed fluorescence have been observed from solutions of chlorophylls a and b in ethanol. E-Type delayed fluorescence has been observed from solutions in propylene glycol. The measurements in propylene glycol have yielded approximate values for the triplet energies of chlorophylls a and b. Measurements of the emissions from the ethanolic solutions have been used to calculate approximate values of the triplet formation efficiencies in this solvent. The sums of the fluorescence and triplet formation efficiencies in ethanol fall far short of unity and the triplet formation efficiencies therefore need to be confirmed by an independent method before they can be accepted with confidence.     

STUDIES OF CHLOROPHYLL-CHLOROPHYLL AND CHLOROPHYLL-LIGAND INTERACTIONS BY VISIBLE ABSORPTION AND INFRARED SPECTROSCOPY AT LOW TEMPERATURES

Abstract— A comparison of the visible absorption and infrared spectra of various chlorophyll-chlorophyll (Chl) and Chi-nucleophile aggregates at room temperature and at low temperatures has been made. The IR data provide structural information indispensable for the interpretation of the visible spectra. As a necessary preliminary, it is shown that Chl a solutions in nonpolar solvents can be prepared by appropriate drying techniques that contain at a conservative estimate ≤ 3 mol % of water (i.e. Chl a/H₂O > 30:1). Very dry solutions of Chl a or Pyrochl a(≥ 10 mM) in toluene or methylcyclohexane-isopentane solution show only slight changes in visible spectra on cooling to 77 K. From IR, additional Chl-Chl aggregation occurs on cooling in methylcyclohexane-isopentane but not to a significant extent in toluene. Dilute (10 μM) solutions of Chl a or Pyrochl a in nonpolar solvents form a new absorption peak near 700 nm at low temperatures, which we attribute to traces of water in the solvent or other residual nucleophiles not removed during the Chl purification. Addition of stoichiometric amounts of water increases the size of the ?700 nm peak even in dilute Chl solutions. Chlorophyll a, Pyrochl a, but not pheophytin a are shown to interact with nucleophiles of the general type RXH (where R= H or alkyl, and X = O, N, or S). Such nucleophiles can coordinate to the Mg atom of one Chl molecule by lone pairs on O, N, or S, and hydrogen bond to oxygen donor functions in another Chl molecule. A ?0.1 M solution of Chl a or Pyrochl a in toluene containing 1.5 equivalents of ethanol is converted almost entirely to a species absorbing at ?700 nm at 77 K. Infrared spectroscopy shows conclusively that it is the keto C=O function that is involved in the cross-linking by hydrogen bonding, a conclusion supported by the observation that Pyrochl a forms a very similar red-shifted species at low temperatures, despite the absence of a carbomethoxy C=O function. n-Butylamine and ethanethiol interact in much the same way as does ethanol to form species red shifted to ?700 nm. A variety of possible structures for the low temperature forms is discussed, and the use of these red shifted species as paradigms for photoreaction center Chl is described.     

Phosphorescence characteristics of acetophenone, benzophenone, p-aminobenzophenone and Michler's ketone in various environments

The phosphorescence characteristics (excitation and emission spectra and lifetimes) of acetophenone (AP), benzophenone (BP), p-aminobenzophenone (PABP) and Michler's ketone (MK) adsorbed on Whatman No. 1 filter paper were measured at various temperatures, and compared with the phosphorescence characteristics in different solvent glasses at 77 K. Both AP and BP phosphoresce on filter paper only at low temperature (208 K). The phosphorescence lifetimes of AP and BP are < 1 msec, indicating a (3)(n,pi(*)) lower triplet level for paper substrates. With PABP, the low lying triplet state in polar solvents is (3)(CT) and in non-polar solvents is (3)(n, pi(*)); PABP on filter paper results in spectral characteristics similar to those of PABP in polar solvents at 77 K. The lifetime of PABP is longer than that of BP, indicating a (3)(CT) low-lying triplet state. MK, like PABP, has strongly environment-dependent photophysical properties. MK, when adsorbed on filter paper, has an intense long-lived luminescence at room temperature, resulting in a limit of detection of 3 ng ml or 3 pg, and a linear dynamic range of over 3 orders of magnitude. MK appears to be strongly hydrogen-bonded to the filter paper. In studies in ethanol and other solvents, MK adsorbed on filter paper shows a dramatic change in its phosphorescence spectrum when the temperature is lowered from 298 K to 208 K; the phosphorescence peak moves to longer wavelengths and the intensity decreases. The temperature effect could arise from the presence of several conformers of MK or be due to different environmental sites or E-type delayed fluorescence. The low-lying triplet state of MK on filter paper is most likely a (3)(CT) state. Lowering the temperature appears to increase the phosphorescence intensity for ketones which phosphoresce in the (3)(n,pi(*)) triplet state, but affects it only slightly for analytes which phosphoresce in the (3)(pi,pi(*)) triplet state. Room-temperature phosphorescence seems to arise for aromatic ketones and aldehydes with low-lying (3)(pi, pi(*)) or (3)(CT) triplet states.     

Triplet–Triplet Energy Transfer from a UV‐A Absorber Butylmethoxydibenzoylmethane to UV‐B Absorbers

The phosphorescence decay of a UV‐A absorber, 4‐tert‐butyl‐4′‐methoxydibenzolymethane (BMDBM) has been observed following a 355 nm laser excitation in the absence and presence of UV‐B absorbers, 2‐ethylhexyl 4‐methoxycinnamate (octyl methoxycinnamate, OMC) and octocrylene (OCR) in ethanol at 77 K. The lifetime of the lowest excited triplet (T₁) state of BMDBM is significantly reduced in the presence of OMC and OCR. The observed quenching of BMDBM triplet by OMC and OCR suggests that the intermolecular triplet–triplet energy transfer occurs from BMDBM to OMC and OCR. The T₁ state of OCR is nonphosphorescent or very weakly phosphorescent. However, we have shown that the energy level of the T₁ state of OCR is lower than that of the enol form of BMDBM. Our methodology of energy‐donor phosphorescence decay measurements can be applied to the study of the triplet–triplet energy transfer between UV absorbers even if the energy acceptor is nonphosphorescent. In addition, the delayed fluorescence of BMDBM due to triplet–triplet annihilation was observed in the BMDBM–OMC and BMDBM–OCR mixtures in ethanol at 77 K. Delayed fluorescence is one of the deactivation processes of the excited states of BMDBM under our experimental conditions.     

Alternating Copolymers Consisting of Arylalkyl Methacrylates III: Phosphorescence of Poly(arylalkyl methacrylate-alt-styrene) in a Rigid Solution

Delayed emission was observed for alternating and random copolymers of 9-phenanthrylmethyl methacrylate and 2-(9-carbazolyl)ethyl methacrylate with styrene in a rigid solution at 77 K. All the copolymers showed monomeric phosphorescence and delayed fluorescence, indicating the absence of deep trap sites in either the excited singlet or triplet states. The delayed fluorescence was more pronounced for the random copolymers with higher chromophore contents than that for the alternating copolymers. Hence, the interchromophore distance is crucial for efficient triplet-state energy migration. © 1997 John Wiley & Sons, Ltd.     

On the origin of long-lived emission in some charge-transfer crystals

Temperature dependence of emission spectra, decay times and intensity of emission, for molecular (1:1) crystals of charge-transfer (CT) complexes of tetrachloro- and tetrabromophthalic anhydride with penta- and hexamethylbenzene, have been investigated over a wide temperature range (1.7–300 K). A long-lived emission, observed in those crystals, has been identified as CT phosphorescence from CT triplet traps. No delayed emission, controlled by triplet—triplet annihilation (P-type), has been found. An explanation of observations connected with the fact that these complexes belong to the class where the lowest triplet state is of charge-transfer character is offered.     

Thermally Activated Delayed Fluorescence in a Y3N@C80 Endohedral Fullerene: Time‐Resolved Luminescence and EPR Studies

The endohedral fullerene Y₃N@C₈₀ exhibits luminescence with reasonable quantum yield and extraordinary long lifetime. By variable‐temperature steady‐state and time‐resolved luminescence spectroscopy, it is demonstrated that above 60 K the Y₃N@C₈₀ exhibits thermally activated delayed fluorescence with maximum emission at 120 K and a negligible prompt fluorescence. Below 60 K, a phosphorescence with a lifetime of 192±1 ms is observed. Spin distribution and dynamics in the triplet excited state is investigated with X‐ and W‐band EPR and ENDOR spectroscopies and DFT computations. Finally, electroluminescence of the Y₃N@C₈₀/PFO film is demonstrated opening the possibility for red‐emitting fullerene‐based organic light‐emitting diodes (OLEDs).     

Intramolecular excimer formation and delayed fluorescence in sterically constrained pyrene dimers

The synthesis is described for a series of five molecular dyads comprising pyrene-based terminals covalently linked through a 1,3-disubstituted phenylene spacer. The extent of through-space communication between the pyrene units is modulated by steric interactions imposed by bulky moieties attached at the 6,8-positions of each pyrene unit. For the control compound, only hydrogen atoms occupy the 6,8 positions (DP1), whereas the remaining compounds incorporate ethynylene groups terminated with either triisopropylsilyl (DP2), 1-tert-butylbenzene (DP3), 2,6-di-tert-butylbenzene (DP4) or 1-tert-butyl-3,5-dimethylbenzene (DP5) units. Each compound shows a mixture of monomer and excimer fluorescence in fluid solution at room temperature, but only monomer emission in a glassy matrix at 77 K. The ratio of monomer to excimer fluorescence depends markedly on the molecular structure; DP1 is heavily biased in favour of the excimer and DP4 is enriched with monomer fluorescence. Photophysical properties, including laser induced and delayed fluorescence data, are reported for each compound. Delayed fluorescence occurs by both intramolecular and bimolecular steps, but these events take place on different timescales. The possibility is raised for using intramolecular triplet-triplet annihilation as a means of molecular imaging.     

ASSOCIATION OF CHLOROPHYLL WITH AMIDES ON PLASTICIZED POLYETHYLENE PARTICLES—I. N,N-DIMETH YLM YRISTAMIDE*

Abstract— Model systems have been prepared in which chlorophyll a (Chl a) and N.N-dimethylmyristamide (DMMA) are adsorbed together in various ratios to particles of polyethylene swollen with undecane. The adsorption is performed by equilibrating the particles with methanol-water solutions of increasing water content. Absorption spectra of the coated particles in viscous suspenions show sharp well-marked bands over much of the composition range examined. With the aid of second derivative spectra. the red absorption band has been resolved into three components. at 661.5. 674 and 680 nm. Fluoresccnce spectra have also been resolved into their principal components with some assistance from comparison with spectra of Chl in undecane solution containing DMMA. At room temperature (295 K) the resolvable components are of monomeric Chl at 670 nm. and of associated species at 681 and 725 nm. Fluorescence at 77 Kis of similar intensity but is distributed differently. in favor of longer-wave components. Corresponding to the 295 K components are emission bands at 675, 683–5 and 735 nm. Othcr components appear under certain conditions: at 695–700 nm when the Chl and DMMA conccntrations are both high, and at 705 nm whcn the ratio of DMMA to Chl is low. If DMMA is absent or at low concentration, much of the Chl exists as an aggregated form absorbing near 741 nm and fluorescing weakly near 760 nm at 77 K. Adsorption isotherms indicate some degree of cooperativity in the binding of Chl and DMMA to the particles. The photoreduction of p-dinitrobenzene by hvdrazobenzene. scnsitized by these particles, has been demonstrated     

荧光双重敏感响应型水溶聚合物的合成及其发光性能研究

将丙烯酰氯与荧光素反应,合成出丙烯酸酯单体3-丙烯酰氧基荧光素(Ac-Flu),然后采用自由基溶液聚合法将Ac-Flu与丙烯酰胺(AM)共聚,制备得到含有荧光素生色团的水溶性荧光共聚物poly(Ac-Flu-co-AM).合成单体Ac-Flu和共聚物poly(Ac-Flu-co-AM)采用核磁(NMR),质谱(HR-MS),红外光谱(FTIR),示差扫描量热法(DSC),可见紫外分光光度仪(UV-Vis)等方法进行了结构表征,同时采用荧光光谱对共聚物poly(Ac-Flu-co-AM)的荧光极其荧光对温度和pH敏感响应性进行了测定研究.结果表明,poly(Ac-Flu-co-AM)的水溶液和薄膜在520 nm附近均具有较强的荧光发射.其中,水溶液荧光强度在0～60℃范围内随着温度的升高呈线性下降,表现出较好的温度敏感响应性质.同时,水溶液荧光强度在pH=4～10范围内随着碱性的增强而升高,表现出较好的pH敏感响应性质.     

THE CHLOROPHYLL a AGGREGATE ABSORBING NEAR 685 nm IS SELECTIVELY FORMED IN AQUEOUS TETRAHYDROFURAN*

An aqueous solution of 2–12% (vol/vol) tetrahydrofuran (THF) induced the selective aggregation of chlorophyll a (Chl a) to form a novel species, A-685, absorbing near 685 nm. The formation of A-685 was closely correlated with a decrease in water activity of the solution. A Raman spectrum of the Chl a species formed in the presence of 6% THF suggests a unique interaction among Chl a, solvent THF and water molecules to give a stacked aggregate (Chl a.THF.H₂O.THF.Chl a). The circular dichroic spectrum of the Chl a species formed in the 6% THF aqueous solution showed an intense signal that had negative and positive wings with about 100-fold larger molar ellipticity for the A-685 than for monomer. However, Chl a', the C10 epimer of Chl a, and chlorophyllide, with a phytyl chain replaced by an ethyl group, did not form A-685 in 6% THF. These clearly indicate that 10-methylcarboxylate and the phytyl chain have a significant role in stabilizing A-685. A possible structure for A-685 is proposed as a novel in vitro model for the P-680 Chl a dimer.     

Boron photochemistry : XI. A study of the unusual luminescence and spectral properties of anilinodimesitylboranes

Anilinodimesitylboranes fluoresce showing the largest Stokes shifts yet reported, which correspond to energy losses of 35.3–61.8 kcal/mole. The dependence of wavelengths of fluorescence on the polarity of the solvent indicates that the first excited singlet state is highly dipolar in nature. A scheme involving an excited-state dipolar

species is used to explain the large loss of energy corresponding to the Stokes shifts for the anilinodimesitylboranes. Delayed emission found at 77 K corresponding to fluorescence is attributed to electron ejection—recombination-type luminescence. No emission was found at longer wavelengths corresponding to triplet emission. It is proposed that the photochemical rearrangements of anilinodimesitylboranes in the presence of iodine occur by interception of an excited singlet or excited charge-transfer state.