Picosecond Component Research Articles

Integrated and dispersed photon echo studies of nitrile stretching vibration of 4-cyanophenol in methanol

By means of integrated and dispersed IR photon echo measurement methods, the vibrational dynamics of C-N stretch modes in 4-cyanophenol and 4-cyanophenoxide in methanol is investigated. The vibrational frequency-frequency correlation function (FFCF) is retrieved from the integrated photon echo signals by assuming that the FFCF is described by two exponential functions with about 400 fs and a few picosecond components. The excited state lifetimes of the C-N stretch modes of neutral and anionic 4-cyanophenols are 1.45 and 0.91 ps, respectively, and the overtone anharmonic frequency shifts are 25 and 28 cm(-1). At short waiting times, a notable underdamped oscillation, which is attributed to a low-frequency intramolecular vibration coupled to the CN stretch, in the integrated and dispersed vibrational echo as well as transient grating signals was observed. The spectral bandwidths of IR absorption and dispersed vibrational echo spectra of the 4-cyanophenoxide are significantly larger than those of its neutral form, indicating that the strong interaction between phenoxide and methanol causes large frequency fluctuation and rapid population relaxation. The resonance effects in a paradisubstituted aromatic compound would be of interest in understanding the conjugation effects and their influences on chemical reactivity of various aromatic compounds in organic solvents.

Solvation and Solvatochromism in CO2-Expanded Liquids. 3. The Dynamics of Nonspecific Preferential Solvation

Subpicosecond time-resolved fluorescence of trans-4-dimethylamino-4'-cyanostilbene (DCS) is used to measure solvation dynamics in the gas-expanded liquid (GXL) system CH(3)CN + CO(2) at 25 degrees C along the liquid-vapor coexistence curve. These measurements are supplemented by measurements of the steady-state solvatochromism of DCS and of its rotation and isomerization times. Molecular dynamics computer simulations and a semiempirical spectral model that reproduces the observed solvatochromism in this system are used to interpret the experimental results. Simulations indicate that at compositions of x(CO2) > 0.5, the cybotactic region surrounding DCS is enriched in CH(3)CN molecules, and the extent of this enrichment is greater in S(1) than that in S(0). Solvation dynamics are dominated by the CH(3)CN component. These dynamics are biphasic, consisting of a subpicosecond inertial component, followed by a slower picosecond component, related to the redistribution of CH(3)CN molecules between the cybotactic region and the bulk solvent.

Monolayers of Silver Nanoparticles Decrease Photobleaching: Application to Muscle Myofibrils

Studying single molecules in a cell has the essential advantage that kinetic information is not averaged out. However, since fluorescence is faint, such studies require that the sample be illuminated with the intense light beam. This causes photodamage of labeled proteins and rapid photobleaching of the fluorophores. Here, we show that a substantial reduction of these types of photodamage can be achieved by imaging samples on coverslips coated with monolayers of silver nanoparticles. The mechanism responsible for this effect is the interaction of localized surface plasmon polaritons excited in the metallic nanoparticles with the transition dipoles of fluorophores of a sample. This leads to a significant enhancement of fluorescence and a decrease of fluorescence lifetime of a fluorophore. Enhancement of fluorescence leads to the reduction of photodamage, because the sample can be illuminated with a dim light, and decrease of fluorescence lifetime leads to reduction of photobleaching because the fluorophore spends less time in the excited state, where it is susceptible to oxygen attack. Fluorescence enhancement and reduction of photobleaching on rough metallic surfaces are usually accompanied by a loss of optical resolution due to refraction of light by particles. In the case of monolayers of silver nanoparticles, however, the surface is smooth and glossy. The fluorescence enhancement and the reduction of photobleaching are achieved without sacrificing the optical resolution of a microscope. Skeletal muscle myofibrils were used as an example, because they contain submicron structures conveniently used to define optical resolution. Small nanoparticles (diameter ∼60 nm) did not cause loss of optical resolution, and they enhanced fluorescence ∼500-fold and caused the appearance of a major picosecond component of lifetime decay. As a result, the sample photobleached ∼20-fold more slowly than the sample on glass coverslips.

Vibrational dynamics of benzoic acid in nonpolar solvents studied by subpicosecond infrared pump–probe spectroscopy

The vibrational dynamics of the OH stretching mode of the benzoic acid dimer in nonpolar solvents have been studied by subpicosecond, frequency-resolved infrared pump–probe spectroscopy. The signal consists of biexponential decay and a quantum beat, which is due to the intermolecular mode of the hydrogen bond coupled to the OH stretching mode. The subpicosecond component is suggested to be due to the vibrational relaxation of the low-frequency modes of the dimer, whereas the picosecond component is assigned to vibrational cooling. The frequency of the Fourier spectra of a quantum beat correlates with that of the OH stretching mode. The physical origin of the correlation is discussed.

PH-Induced Conformational Perturbation in Horseradish Peroxidase

The fluorescence-decay characteristics of the single tryptophan present in horseradish peroxidase (HRP) have been studied using dye laser pulses and single-photon counting techniques. The decay was found to be dominated by a picosecond-lifetime component, with small contributions from two other lifetime components in the nanosecond range. The distance of the tryptophan residue was estimated from the fluorescence-energy transfer to the heme moiety using Forster's theory. The tryptophan residue was found to be approximately 1.2 nm from the heme moiety at neutral pH. Detailed analysis of the fluorescence-decay profiles using the maximum-entropy method (MEM) has been carried out. The results of the MEM analysis also showed a maximum amplitude peak at approximately 45 ps (at pH ? 7) with a very small (< 5%) contribution from two other components. Similar results were obtained with the cyanide derivative of the enzyme (HRPCN) where the major lifetime component was found to be 58 ps at neutral pH. The picosecond component of fluorescence lifetimes of native HRP as well as of HRPCN were found to increase with decrease in pH in the range pH 6–3.5. Moreover, the native enzyme showed significant increase in the magnitude of this fast lifetime component at pH above 8. Such increase in the major lifetime component possibly indicated a conformational perturbation caused by pH change in the enzyme. However, the pH dependence of HRPCN, which is devoid of alkaline transition, showed that the shortest lifetime component remains almost unchanged over the pH range 6–11. This result showed that the alkaline transition in native HRP is associated with a structural change in the distal region of the heme center, which is absent in the cyanide-ligated enzyme. The results have been discussed with respect to understanding the pH-induced effects associated with salt bridge and hydrogen-bonding network in HRP.

Femtosecond Kinetics of Photoconversion of the Higher Plant Photoreceptor Phytochrome Carrying Native and Modified Chromophores

The photoprocesses of native (phyA of oat), and of C-terminally truncated recombinant phytochromes, assembled instead of the native phytochromobilin with phycocyanobilin (PCB-65 kDa-phy) and iso-phycocyanobilin (iso-PCB-65 kDa-phy) chromophores, have been studied by femtosecond transient absorption spectroscopy in both their red absorbing phytochrome (P r) and far-red absorbing phytochrome (P fr) forms. Native P r phytochrome shows an excitation wavelength dependence of the kinetics with three main picosecond components. The formation kinetics of the first ground-state intermediate I 700, absorbing at ∼690 nm, is mainly described by 28 ps or 40 ps components in native and PCB phytochrome, respectively, whereas additional ∼15 and 50 ps components describe conformational dynamics and equilibria among different local minima on the excited-state hypersurface. No significant amount of I 700 formation can be observed on our timescale for iso-PCB phytochrome. We suggest that iso-PCB-65 kDa-phy either interacts with the protein differently leading to a more twisted and/or less protonated configuration, or undergoes P r to P fr isomerization primarily via a different configurational pathway, largely circumventing I 700 as an intermediate. The isomerization process is accompanied by strong coherent oscillations due to wavepacket motion on the excited-state surface for both phytochrome forms. The femto- to (sub-)nanosecond kinetics of the P fr forms is again quite similar for the native and the PCB phytochromes. After an ultrafast excited-state relaxation within ∼150 fs, the chromophores return to the first ground-state intermediate in 400–800 fs followed by two additional ground-state intermediates which are formed with 2–3 ps and ∼400 ps lifetimes. We call the first ground-state intermediate in native phytochrome I fr·750, due to its pronounced absorption at that wavelength. The other intermediates are termed I fr·675 and pseudo-P r. The absorption spectrum of the latter already closely resembles the absorption of the P r chromophore. PCB-65 kDa-phy shows a very similar kinetics, although many of the detailed spectral features in the transients seen in native phy are blurred, presumably due to wider inhomogeneous distribution of the chromophore conformation. Iso-PCB-65 kDa-phy shows similar features to the PCB-65 kDa-phy, with some additional blue-shift of the transient spectra of ∼10 nm. The sub-200 fs component is, however, absent, and the picosecond lifetimes are somewhat longer than in 124 kDa phytochrome or in PCB-65 kDa-phy. We interpret the data within the framework of two- and three-dimensional potential energy surface diagrams for the photoisomerization processes and the ground-state intermediates involved in the two photoconversions.

Fluorescence Up-Conversion Study of Excitation Energy Transport Dynamics in Oligothiophene−Fullerene Linked Dyads

Photoinduced excitation energy transport dynamics in oligothiophene-fullerene linked dyads, nT-C60 (n = 4, 8, and 12), have been investigated by femtosecond fluorescence up-conversion. In 8T-C60 and 12T-C60, each time profile of the fluorescence due to the 1nT* moiety consists of two components. The sub-picosecond component and a few picosecond components were experimentally evaluated depending on the lengths of oligothiophenes (n =8 and 12) and on the analyzing wavelength of the fluorescence. However, the time trace of the fluorescence due to 14T*-C60 decayed with a single short component in approximately 300 fs due to direct excited energy transfer (EET) from the 14T* moiety to the C60 moiety. On the basis of the kinetic models considering the short and long locally pi-conjugative thiophene segments in 8T-C60 and 12T-C60, the rate parameters of the elemental processes were evaluated. Sub-picosecond time constants of nT-C60 were found to be EET from the thiophene segment vicinal to the C60 moiety and intrachain energy transfer. Slower picosecond dynamics mainly corresponds to EET from the thiophene segments apart from the C60 moiety.

Femtosecond time-resolved dynamics in electron-doped high-Tc superconductor La2-xCexCuO4

The quasiparticle dynamics in the electron-doped high-Tc superconductor La2-xCexCuO4 (LCCO) was investigated by ultrafast time-resolved optical pump-probe technique. We present results in three temperature regions: namely the low temperature (TTc) region, that around Tc(0.7Tc≤T≤Tc) and the high temperature (T&gt;Tc) region. In general, there was a slowdown of the relaxation as the temperature decreases. However, the quasiparticle lifetime was found to exhibit a quasi-divergence as the temperature approached Tc from below. The relaxation time in normal state was much longer than what was expected for metallic relaxation, indicating the presence of a T-independent pseudogap. We have also observed picosecond rise component of photoinduced change in reflectivity ΔR/R in the electron-doped LCCO, which is attributed to the Cooper pair-breaking dynamics. The rise time became shorter as the temperature increased. The experimental results are analyzed by Rothwarf-Taylor model.

Ultrafast hole burning in intersubband absorption lines of GaN∕AlN superlattices

The authors present evidence for a distinct optical phonon progression in the nonlinear intersubband absorption spectra of electrons in a GaN∕AlN superlattice. Femtosecond two-color pump-probe experiments in the near infrared show spectral holes separated by the longitudinal optical (LO) phonon frequency and a homogeneous line broadening of approximately 50meV. The nonlinear bleaching signal decays with a time constant of 160fs due to intersubband scattering of delocalized electrons, followed by a weak picosecond component attributed to the relaxation of electrons from longer-lived localized states.

Complexity of excited-state dynamics in DNA

Absorption of ultraviolet light by DNA is known to lead to carcinogenic mutations, but the processes between photon absorption and the photochemical reactions are poorly understood. In their study of the excited-stated dynamics of model DNA helices using femtosecond transient absorption spectroscopy, Crespo-Hernández et al. observe that the picosecond component of the transient signals recorded for the adenine-thymine oligonucleotide (dA)18.(dT)18 is close to that for (dA)18, but quite different from that for (dAdT)9.(dAdT)9; from this observation, they conclude that excimer formation limits excitation energy to one strand at a time. Here we use time-resolved fluorescence spectroscopy to probe the excited-state dynamics, which reveals the complexity of these systems and indicates that the interpretation of Crespo-Hernández et al. is an oversimplification. We also comment on the pertinence of separating base stacking and base pairing in excited-state dynamics of double helices and question the authors' assignment of the long-lived signal component found for (dA)18.(dT)18 to adenine excimers.

Spectroscopy of Auramine Fluorescent Probes Free and Bound to Poly(Methacrylic Acid)

Auramines containing a vinyl group with strong electron-withdrawing substituent exhibit a pi-conjugated extended effect that gives a red shift in their absorption and emission bands. The new fluorochromic dyes were bound to poly(methacrylic acid) (PMA), and their photophysical dynamics in methanol and in aqueous solution were studied. These derivatives were also used as optical probes for copolymerization process. The process was monitored by the changes in electronic absorption with a concomitant fading of the free vinyl auramine absorption band in the red and an appearance of a UV band ascribed to dye bound to the polymer chain. The conformational transition of PMA with solvent and pH was clearly observed by the drastic changes in the photophysical properties of these auramine derivatives attached to the polymer chain. Time-resolved experiments revealed an unusual long-lived decay component of about 2.2-2.6 ns in aqueous solution at low pH together with two picosecond components (50 and 570 ps). Such long decay was only reported in the literature for auramine adsorbed in solid matrices. It was ascribed to the fraction of bound auramine in a region of compact coil of PMA.

Femtosecond Fluorescence Dynamics of Porphyrin in Solution and Solid Films: The Effects of Aggregation and Interfacial Electron Transfer between Porphyrin and TiO2

The excited-state relaxation dynamics of a synthetic porphyrin, ZnCAPEBPP, in solution, coated on a glass substrate as solid films, mixed with PMMA and coated on a glass substrate as solid films, and sensitized on nanocrystalline TiO2 films were investigated by using femtosecond fluorescence up-conversion spectroscopy with excitation in the Soret band, S2. We found that the S2--> S1 electronic relaxation of ZnCAPEBPP in solution and on PMMA films occurs in 910 and 690 fs, respectively, but it becomes extremely rapid, <100 fs, in solid films and TiO2 films due to formation of porphyrin aggregates. When probed in the S1 state of porphyrin, the fluorescence transients of the solid films show a biphasic kinetic feature with the rapid and slow components decaying in 1.9-2.4 and 19-26 ps, respectively. The transients in ZnCAPEBPP/TiO2 films also feature two relaxation processes but they occur on different time scales, 100-300 fs and 0.8-4.1 ps, and contain a small offset. According to the variation of relaxation period as a function of molecular density on a TiO2 surface, we assigned the femtosecond component of the TiO2 films as due to indirect interfacial electron transfer through a phenylethynyl bridge attached to one of four meso positions of the porphyrin ring, and the picosecond component arising from intermolecular energy transfer among porphyrins. The observed variation of aggregate-induced relaxation periods between solid and TiO2 films is due mainly to aggregation of two types: J-type aggregation is dominant in the former case whereas H-type aggregation prevails in the latter case.

Femtosecond Fluorescence Studies of Self-Assembled Helical Aggregates in Solution

For the diamino-bipyridine based C(3)-symmetrical disk molecule, TAB, (sub)picosecond fluorescence transients have been observed by means of femtosecond fluorescence upconversion and picosecond time-correlated photon counting techniques. The dodecyl peripheral side chains of the synthetic compound are large enough to allow, in apolar solvents, self-assembling of the discotic molecules to helical aggregates. In polar solvents, the hydrogen bonding and pi-pi interactions pertaining to the chiral aggregation are compensated by solvation and self-assembling of the disklike molecules is disrupted. For comparison, time-resolved fluorescence measurements have been performed for the subgroup molecule, DAC, which is the (asymmetric) building block for TAB. It is concluded that, after pulsed photoexcitation, TAB and DAC exhibit excited-state intramolecular double proton transfer (ESIDPT) with a typical time of approximately 200-300 fs, irrespective of the degree of aggregation. Picosecond components in the fluorescence of TAB and DAC, ranging from 3 to 25 ps, are representative of vibrational cooling effects in the excited product state. Only aggregated TAB shows a rapid ( approximately 1 ps) decay of its fluorescence anisotropy. This component is attributed to excited-state energy transfer within the aggregate. Finally, the excited-state lifetime of TAB in the aggregated form is found to be an order of magnitude longer than that for TAB in its nonaggregated form. It is inferred that aggregation diminishes the influence of low-frequency twisting motions in the radiationless decay of the excited state.

Fluorescence studies in environmentally benign solvents: solvation dynamics of Coumarin 102 in [BMIM][BF4

The steady-state and time-resolved fluorescence behavior of Coumarin 102 (C-102) has been investigated in a ionic liquid at room temperature, 1-buty1-3-methylimidazolium tetrafluoroborate, abbreviated here as [BMIM][BF4]. From the steady-state fluorescence maximum of C-102 in [BMIM][BF4], the polarity of this ionic liquid has been estimated to be 50.4 in the ET (30) scale, suggesting that [BMIM][BF4] is more polar than acetonitrile but less polar than methanol. In contrast to its time-resolved behavior in conventional polar solvents, C-102 exhibits wavelength-dependent fluorescence decay behavior in [BMIM][BF4] because of slow solvation dynamics in this viscous medium. The solvation dynamics has been found to be biphasic in nature consisting of picosecond and nanosecond components. In addition to these slow resolvable components, evidence is found for a very fast component of solvation, which occurs within the time resolution of the set-up (25 ps).

Evidence for Rigid Binding of Rhodamine 6G to Silica Surfaces in Aqueous Solution Based on Fluorescence Anisotropy Decay Analysis

Strong ionic binding of the cationic probe rhodamine 6G (R6G) to the anionic surface of silica particles in water provides a convenient labeling procedure to study both particle growth kinetics and surface modification by time-resolved fluorescence anisotropy (TRFA). The decays for R6G dispersed in diluted Ludox silica sols usually fit to a sum of picosecond and nanosecond decay components, along with a significant residual anisotropy component. The origin of the nanosecond decay component (phi2) is not fully understood, and has been ascribed to wobbling of the probe on the silica surface, the presence of a subpopulation of small nanoparticles in the Ludox sol, or rapid exchange between free and bound R6G. To elucidate the physical meaning of phi2, measurements were performed in various silica-based colloidal systems using different concentrations of silica. We found that the fraction of phi2 was generally higher in Ludox than in aqueous sodium silicate and decreased with increasing silica concentration; phi2 vanished upon gelation of sodium silicate at pH 7 leading to a total loss of R6G depolarization (r(t) = const). These results rule out the presence of local R6G wobbling when bound ionically to colloidal silica and support the rigid sphere model to describe the TRFA decays for R6G-Ludox. This conclusion is entirely supported by steady-state anisotropy data and structural considerations for the R6G molecule and the silica surface.

Femtosecond Fluorescence Dynamics of Rotation-Restricted Azobenzenophanes: New Evidence on the Mechanism of trans → cis Photoisomerization of Azobenzene

The ultrafast relaxation dynamics of two rotation-restricted (azobenzeno-2S-phane and azobenzeno-4S-phane) and one rotation-free (4,4'-dimethylazobenzene) azobenzene derivatives were investigated using femtosecond fluorescence up-conversion on both S(1)(n,pi) and S(2)(pi,pi) excitations. On S(2) excitation, pulse-limited kinetics with a decay coefficient of approximately 100 fs corresponding to ultrafast S(2) --> S(1) relaxation is found to be common for all molecules under investigation regardless of the molecular structure. This indicates that a direct rotational relaxation on the S(2) surface is unfavorable. On S(1) excitation, we observed biphasic fluorescence decay with a femtosecond component attributed to the decay of the Franck-Condon state prepared by excitation and a picosecond component attributed to the deactivation of the relaxed molecule on the S(1) surface. This picosecond component is slowed by at least a factor of 2 for the rotation-restricted 2S-bridged molecule compared to that of the rotation-free molecule; for the even stronger rotation-restricted azobenzeno-4S-phane, the decrease is by a factor of 10. These differences in deactivation suggest that the relaxed states and probably the trajectories for rotation-free and rotation-restricted molecules are different on the S(1) surface, which should be important for the quantum yield of photoisomerization.

Conformational states of HRPA1 induced by thermal unfolding: effect of low molecular weight solutes.

Fluorescence, CD, and activity measurements were used to characterize the different conformational states of horseradish peroxidase A1 induced by thermal unfolding. Picosecond time-resolved fluorescence studies showed a three-exponential decay dominated by a picosecond lifetime component resulting from energy transfer from tryptophan to heme. Upon thermal unfolding a decrease in the preexponential factor of the picosecond lifetime and an increase in the quantum yield were observed approaching the characteristics observed for apoHRPA1. The fraction of heme-quenched fluorophore decreased to 0.4 after unfolding as shown by acrylamide quenching. A new unfolding pathway for HRPA1 was proposed and the effect of the low molecular weight solutes trehalose, sorbitol, and melezitose on this pathway was analyzed. Native HRPA1 unfolds with an intermediate between the native and the unfolded conformation. The unfolded conformation can refold to the native state or to a native-like conformation with no calcium ions upon cooling or can give an irreversible denatured state. The refolded conformation with no calcium ions was clearly identified in a second thermal scan in the presence of EDTA and shows secondary and tertiary structures, heme reincorporation in the cavity, and at least 59% of activity. Melezitose stabilized the refolded Ca2+-depleted protein and induced a more complex mechanism for heme disruption. The effect of sorbitol and trehalose were mainly characterized by an increase in the temperature of unfolding.

Femtosecond fluorescence upconversion studies of excited-state proton-transfer dynamics in 2-(2 ′-hydroxyphenyl)benzoxazole (HBO) in liquid solution and DNA

A femtosecond fluorescence upconversion study is reported for HBO in solution, as well as for HBO incorporated in DNA. The typical time for the excited-state intramolecular proton-transfer reaction of the syn-enol tautomer in solution and in DNA has been determined to be 150 fs. In addition, the lifetimes of the keto, the anti-enol and the ‘solvated enol’ tautomer forms were determined in protic solvents, aprotic solvents and DNA. Picosecond rise and decay components in the fluorescence transients with characteristic times between 3 and 25 ps are also observed and attributed to the effects of vibrational cooling.

Transient Absorption Spectroscopy of Ruthenium and Osmium Polypyridyl Complexes Adsorbed onto Nanocrystalline TiO2 Photoelectrodes

Transient absorption spectroscopy has been used to probe the electron injection dynamics of transition metal polypyridyl complexes adsorbed onto nanocrystalline TiO2 photoelectrodes. Experiments were performed on photoelectrodes coated with Ru(H2L‘)2(CN)2, Os(H2L‘)2(CN)2, Ru(H2L‘)2(NCS)2, or Os(H2L‘)2(NCS)2, where H2L‘ is 4,4‘-dicarboxylic acid-2,2‘-bipyridine, to study how the excited-state energetics and the nature of the metal center affect the injection kinetics. All of these complexes exhibited electron injection dynamics on both the femtosecond and picosecond time scales. The femtosecond components were instrument-limited (<200 fs), whereas the picosecond components ranged from 3.3 ± 0.3 ps to 14 ± 4 ps (electron injection rate constants k2‘ = (7.1−30) × 1010 s-1). The picosecond decay component became more rapid as the formal excited-state reduction potential of the complex became more negative. Variable excitation wavelength studies suggest that femtosecond injection is characteristic of the nonth...

Transient absorption studies of the Ru(dcbpy) 2(NCS) 2 excited state and the dye cation on nanocrystalline TiO 2 film

We have measured dynamics of the Ru(dcbpy) 2(NCS) 2 [dcbpy = 4,4 ′-dicarboxy-2,2 ′-bipyridine] excited state and the dye cation on nanocrystalline TiO 2 film in the wavelength region 700–900 nm. The dye in ethanol solution and Ru(dcbpy) 2(NCS) 2 sensitized nanocrystalline Al 2O 3 films were used as non-injecting reference samples for excited state identification. For TiO 2/Ru(dcbpy) 2(NCS) 2 film the `reactant' decay and `product' formation kinetics observed at different probe wavelengths showed that the resolved transient absorption picosecond components (1.1±0.2), (12±2) and (100±5) ps are related to electron injection from the excited states of the dye to the semiconductor TiO 2.