A novel time-resolved laser fluorescence spectroscopy system for research on complexation of uranium(IV)

To date only a small number of studies have investigated the chemical speciation of complexes and the fluorescence properties of metal ions whose emitted fluorescence lifetime is in the range of only few nanoseconds. This is due to a lack of advanced methods which allow the conduction of these measurements. In the current study we set up a new time-resolved laser fluorescence spectroscopy system with which the fluorescence properties of metal ions with very short fluorescence lifetimes such as uranium(IV) and its compounds can be investigated. By studying the fluorescence properties of uranium(IV) in perchloric acid, we showed uranium(IV) to have a detection limit of 5 × 10⁻⁷ M and a fluorescence decay time of 2.74 ± 0.36 ns. We further investigated the fluorescence properties of uranium(IV) during the reaction with fluoride and applied our novel laser system to study the complexation of uranium(IV) with fluoride.Our data revealed the formation of a 1:1 complex of uranium(IV) and fluoride. The corresponding complex formation constant of uranium(IV) fluoride UF³⁺ was found to be log β⁰ = 9.43 ± 1.94. Our results demonstrate that our novel time-resolved laser fluorescence spectroscopy system can successfully conduct speciation measurements of metal ions and their compounds with very short-lived fluorescence lifetimes. Using this laser system, it is possible to analytically investigate such elements and compounds in environmentally relevant concentration ranges.     

Re-examination of primary radical pair recombination in Rp. viridis with QA reduced

Charge recombination in the primary radical pair P⁺H⁻ of the purple photosynthetic bacterium Rp. viridis with pre-reduced secondary acceptor Q_A, has been studied by time-resolved photovoltage measurements and transient absorption spectroscopy with a time resolution of 1 ns. The lifetime of P⁺H⁻ was found to be 2.4–3 ns in intact membranes and ∼5 ns in isolated reaction centers, in contrast to a lifetime of ∼15 ns which has been widely accepted in the literature for reaction centers. The origin of the difference between lifetimes of P⁺H⁻ in membranes and isolated reaction centers is discussed.     

Determination of gross α and β activities in Ankara airborne particulate samples in 2003–2004

The complex formation of curium(III) with L2-aminobutyric acid was characterized by time-resolved laser-induced fluorescence spectroscopy (TRLFS) at trace Cm(III) concentrations (3·10⁻⁷ M). The various curium(III) species, M_pH_qL_r, identified are characterized by their individual luminescence spectra and luminescence lifetimes. The following formation constants were determined log β₁₀₁ = 5.17±0.07, log β₁₀₂ = 9.00±0.07, and log β₁₀₃ = 11.30±0.09 at ionic strength I = 0.5M. Possible structures of the curium aminobutyrate species will be discussed on the basis of the luminescence lifetime measurements and the magnitude of the formation constants.     

Triplet Lifetime Determination of Molecules in the Gas Phase by T-T Energy Transfer

It has been demonstrated that the triplet lifetime of nonemitting molecules in the dilute vapor phase - even for complex triplet decays - can be accurately determined by means of time-resolved triplet-triplet (T-T) energy transfer to a strong emitter molecule. Besides the test molecules 1-butyne-3-one and benzaldehyde the lifetime of the vibrationally relaxed nonemitting T₁(nπ*) state of cycloheptanone, τ=63 ± 5 µs at ～?0.5 Torr, together with its energy transfer rate constant to biacetyl, k_ET=(1.80±0.08) x 10⁶ s^?1 Torr^?1, have been measured.     

Time-resolved excitation spectra of xenon vapor in the 1500 Å region

Time-integrated and time-resolved excitation spectra, as well as fluorescence lifetimes, have been measured for xenon vapor as a funtion of pressure (for pure xenon as well as with different collision partners: krypton and helium), monitoring the 1700 Å second continuum afterglow. Three very different decay components have been observed: (a) A short component with lifetimes of the order of 2 ns, which is attributed to emission from the upper vibrational levels of the O⁺_u(¹Σ⁺_u) state of Xe*₂. (b) A long component with τ ≈ 60 ns, corresponding to emission from thermally relaxed vibrational levels of the 1_u,O^?_u(³Σ⁺_u) states of Xe*₂. No intervention of any Xe atomic excited species is invoked to explain the excitation and deactivation processes of Xe₂ molecules for these two components of the fluorescence. (c) A very long component with lifetimes in the 150–500 ns range, having a broad ? 1000 cm^?1 - excitation band, centered at ≈ 1470 Å and showing a striking screening and self-absorption effect as well as a strong effect when the partial pressure of a collision partner (Kr, He) is increased. The mechanism of this last excitation is not yet very well understood.     

Formation of KrCl* and ArCl* molecules and radiative lifetimes of their B states investigated with selective synchrotron radiation excitation

Monochromatic pulsed VUV excitation of Cl₂ or inert gas atoms in Cl₂ doped Kr and Ar leads to formation of KrCl^* and ArCl^*. The radiative lifetimes of the B states (KrCl^* 19 ns, ArCl^* 9 ns) and rate constants for excimer formation, quenching and collisional mixing of B and C states are given. The radiative lifetime and the quenching rate increase with vibrational excitation of the B state (KrCl^*).     

Natural radiative lifetimes in the 5snd 1 D 2 series of SrI

Natural radiative lifetimes have been measured for the 5snd ¹ D ₂ series in SrI for the previously not measuredn=10, 11 and 12 states. The measurements connect earlier measurements in lower and higher states in this heavily perturbed series. The lifetimes were determined using pulsed laser excitation and time-resolved detection.     

Solvent‐Dependent Fluorescence Lifetimes of Estrone, 17β‐Estradiol and 17α‐Ethinylestradiol

The fluorescence lifetimes of the estrogens, estrone, 17β‐estradiol and 17α‐ethinylestradiol, were studied in various solvents. The fluorescence lifetimes of 17β‐estradiol and 17α‐ethinylestradiol decreased from 4.7 to 0.9 ns as the solvent hydrogen bond accepting ability increased, in good agreement with other phenolic molecules. Estrone's two fluorescence bands had distinct lifetimes, with the 304 nm band having a lifetime shorter than 200 ps, reflecting efficient energy transfer to the carbonyl group, which had lifetimes ranging from 4.4 to 4.9 ns depending on the solvent. Solvent effects on the ¹ππ*, ¹πσ* and ¹nπ* states that are relevant to estrogen photophysics can adequately explain these trends. The solvent dependence on the excited states of these potent endocrine disruptors has significant implications for their photochemistry.     

Computer automation of polarographic analyzer PAR 384B and development of specific implementation software

The automation of Polarographic Analyzer PAR 384B by connecting it to an HP 9816S Technical Computer is presented. The connection itself transforms an analytically oriented instrument towards one which is more appropriate for research work. Specific implementation software is developed in order to enable and facilitate pseudopolarographic measurements and evaluation of heavy-metal complexation phenomena. As as example, the procedure for the simultaneous determination of the stability constants of lead and cadmium present in constant ionic strength medium of X mol/dm³ NaCl + (4 − X) mol/dm³ NaClO₄ is presented. The results obtained, for lead, β₁ = 9±1, β₂ = 92±13, β₃ = 99±21, β₄ = 27±6, and for cadmium, β₁ = 44±3, β₂ = 194±36, β₃ = 816±67, β₄ = 68±24, are in agreement with the literature data.     

Global and target analysis of time-resolved fluorescence spectra of Di-9H-fluoren-9-yldimethylsilane: dynamics and energetics for intramolecular excimer formation

Dynamics and energetics for intramolecular excimer formation of a diarylsilane, di-9H-fluoren-9-yldimethylsilane (DFYDMS) have been investigated by means of ps time-resolved fluorescence spectroscopy and ab initio calculation. Multiple fluorescence decay curves were globally deconvolved to generate time-resolved fluorescence spectra and decay-associated spectra (DAS), from which species-associated spectra (SAS) were obtained. It is shown in the global analysis that there are at least three excited states: Two states are the locally excited (LE) states (lambda(max) approximately 320 nm) having lifetimes of 0.70 +/- 0.04 and 1.75 +/- 0.02 ns, and another is the excimer state (lambda(max) approximately 400 nm) having a lifetime of 7.34 +/- 0.02 ns. The species which decays with 0.70 ns evolves into a species with a red-shifted spectrum, which in turn decays in 7.34 ns. The experimental and ab initio results indicate that the rise time of 0.70 ns corresponds to the conversion of the initial S(1) LE state having a near sandwich geometry to the S(1) excimer state adopting a true sandwich geometry.     

The Heavy-Atom Effect on the Photophysics of Aromatic Hydrocarbons in the Presence of Solid Clays

The exchange of the original cation present on a Laponite clay (usually Na⁺) for heavy atoms such as Rb⁺, Cs⁺, and Tl⁺ significantly alters the emission characteristics of some aromatic hydrocarbons (p-terphenyl, naphthalene, pyrene, and biphenyl). The increase of the atomic mass of the cation induces a decrease of the fluorescence emission simultaneous with an increase of the emission in the region of lower energies of the spectra, ascribed to the phosphorescence of those hydrocarbons. Time-resolved experiments for the pyrene–clay system showed a decrease of singlet lifetimes for the heavier atoms. Hydrocarbon aggregates were also detected from both the emission spectra and the time-resolved studies. The “excimer-like” emission showed longer lifetimes (10–25 ns) than the monomolecular hydrocarbons (1–3 ns), as already found for other similar systems. The amount of aggregates increased for the heavier cations due to the smaller surface available on the clay particles. Experiments increasing the amount of Tl⁺ in samples containing a constant concentration of naphthalene allowed evaluation of the distance between the heavy atoms and the probe on the clay surface. The Perrin model treatment was used and resulted in approximately R₀=9.2 Å.     

Lifetime determination of fluorescence and phosphorescence of a series of oligofluorenes

The photoluminescence (PL) properties of oligofluorenes with 2-ethylhexyl group in 9, 9' position in solution and as thin films were investigated by time-resolved techniques at both room temperature and 77 K. The fluorescence lifetimes of the oligomers decrease with chain length. The lifetimes tau follow the relation tau=386+808(1/n) (ps) where n is the number of fluorene units in the oligomer. Concentration and laser excitation energy dependences of PL spectra of the oligofluorenes are also given. Phosphorescence was observed for oligofluorenes in the frozen matrix of MTHF at 77 K. The lifetime of phosphorescence increases with increasing molecular length. Similar emission bands were observed for oligofluorenes with a central ketogroup. A lifetime analysis clearly reveals that the "green emission" of the oligomers free of ketogroups results from a phosphorescence with lifetime tau of 3 ms while the green emission from the keto-oligomer is a fluorescence from a charge transfer pi-pi* level of tau=8 ns.     

The radiative lifetime of the A1II state of BH

Second-order polarization propagator calculations of the X¹Σ⁺ → A¹II transition moment as well as the radiative lifetime of the A¹II state of BH are reported. The calculated vibrational lifetimes are τ(v′ = 0) = 121 ns, τ(v′ = 1) = 129 ns, and τ(v′ = 2) = 137 ns. The τ(v′ = 0 lifetime agrees with the most recent experiment of τ(v′ = 0) = 125 ± 5 ns. We show that the electronic oscillator strength computed at the ground state equilibrium is rather different from the band absorption oscillator strength f₀₀, which demonstrates that theoretical electronic oscillator strengths should not be expected to agree with experimentally determined band oscillator strengths.     

Insight into the drastically different triplet lifetimes of BODIPY obtained by optical/magnetic spectroscopy and theoretical computations

The triplet state lifetimes of organic chromophores are crucial for fundamental photochemistry studies as well as applications as photosensitizers in photocatalysis, photovoltaics, photodynamic therapy and photon upconversion. It is noteworthy that the triplet state lifetime of a chromophore can vary significantly for its analogues, while the exact reason was rarely studied. Herein with a few exemplars of typical BODIPY derivatives, which show triplet lifetimes varying up to 110-fold (1.4–160 μs), we found that for these derivatives with short triplet state lifetimes (ca. 1–3 μs), the electron spin polarization (ESP) pattern of the time-resolved electron paramagnetic resonance (TREPR) spectra of the triplet state is inverted at a longer delay time after laser pulse excitation, as a consequence of a strong anisotropy in the decay rates of the zero-field state sublevel of the triplet state. For the derivatives showing longer triplet state lifetimes (>50 μs), no such ESP inversion was observed. The observed fast decay of one sublevel is responsible for the short triplet state lifetime; theoretical computations indicate that it is due to a strong coupling between the T_z sublevel and the ground state mediated by the spin–orbit interaction. Another finding is that the heavy atom effect on the shortening of the triplet state lifetime is more significant for the T₁ states with lower energy. To the best of our knowledge, this is the first systematic study to rationalize the short triplet state lifetime of visible-light-harvesting organic chromophores. Our results are useful for fundamental photochemistry and the design of photosensitizers showing long-lived triplet states.

The electron spin polarization inversion and anisotropic decay of triplet substates explain the short triplet state lifetime of BODIPY derivatives.     

Chemical control of competing electron transfer pathways in iron tetracyano-polypyridyl photosensitizers

Photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN)₄(2,2′-bipyridine)]²⁻ (1), [Fe(CN)₄(2,3-bis(2-pyridyl)pyrazine)]²⁻ (2) and [Fe(CN)₄(2,2′-bipyrimidine)]²⁻ (3) were investigated in various solvents with static and time-resolved UV-Visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering (RIXS). This series of polypyridyl ligands, combined with the strong solvatochromism of the complexes, enables the ¹MLCT vertical energy to be varied from 1.64 eV to 2.64 eV and the ³MLCT lifetime to range from 180 fs to 67 ps. The ³MLCT lifetimes in 1 and 2 decrease exponentially as the MLCT energy increases, consistent with electron transfer to the lowest energy triplet metal-centred (³MC) excited state, as established by the Tanabe–Sugano analysis of the Fe 2p3d RIXS data. In contrast, the ³MLCT lifetime in 3 changes non-monotonically with MLCT energy, exhibiting a maximum. This qualitatively distinct behaviour results from a competing ³MLCT → ground state (GS) electron transfer pathway that exhibits energy gap law behaviour. The ³MLCT → GS pathway involves nuclear tunnelling for the high-frequency polypyridyl breathing mode (hν = 1530 cm⁻¹), which is most displaced for complex 3, making this pathway significantly more efficient. Our study demonstrates that the excited state relaxation mechanism of Fe polypyridyl photosensitizers can be readily tuned by ligand and solvent environment. Furthermore, our study reveals that extending charge transfer lifetimes requires control of the relative energies of the ³MLCT and the ³MC states and suppression of the intramolecular distortion of the acceptor ligand in the ³MLCT excited state.

Photoinduced intramolecular electron transfer in Fe tetracyano-polypyridyl complexes was investigated with static and time-resolved UV-visible absorption and resonant inelastic X-ray scattering which revealed a competition of two relaxation pathways.     

Fluorescence of sanguinarine: fundamental characteristics and analysis of interconversion between various forms

The quaternary isoquinoline alkaloid, sanguinarine (SG) plays an important role in both traditional and modern medicine, exhibiting a wide range of biological activities. Under physiological conditions, there is an equilibrium between the quaternary cation (SG⁺) and a pseudobase (SGOH) forms of SG. In the gastrointestinal tract, SG is converted to dihydrosanguinarine (DHSG). All forms exhibit bright fluorescence. However, their spectra overlap, which limited the use of powerful techniques based on fluorescence spectroscopy/microscopy. Our experiments using a combination of steady-state and time-resolved techniques enabled the separation of individual components. The results revealed that (a) the equilibrium constant between SG⁺ and SGOH is pK _a = 8.06, while fluorescence of DHSG exhibited no changes in the pH range 5–12, (b) the SGOH has excitation/emission spectra with maxima at 327/418 nm and excited-state lifetime 3.2 ns, the spectra of the SG⁺ have maxima at 475/590 nm and excited-state lifetime 2.4 ns. The DHSG spectra have maxima at 327/446 nm and 2-exponential decay with components 4.2 and 2.0 ns, (c) NADH is able to convert SG to DHSG, while there is no apparent interaction between NADH and DHSG. These techniques are applicable for monitoring the SG to DHSG conversion in hepatocytes.     

On xenon molecule excited state lifetimes

Time-resolved excitation spectra of xenon vapor in the 150 nm region are analysed in terms of four main fluorescence lifetimes corresponding to decays of four stable excited electronic states of the Xe dimer. The two shortest decay times, ≈ 2 ns and ≈ 60 ns, are assigned to the direct radiative relaxation of the two lowest excited ungerade states, (¹Σ⁺_u)0⁺_u and (³Σ⁺_u))1 u respectively. The two longest decay times, ≈ 150 ns and ≈ 500 ns, must correspond to the overall depopulation rates of the two lowest excited gerade states, (³Σ⁺_g)1g and (¹Σ⁺_g)0⁺_g, decaying into the gerade ground state by cascading down through the intermediate ungerade states.     

MEASURING SUBNANOSECOND FLUORESCENT LIFETIMES USING PHOTON COUNTING

An evaluation is made of a typical time-correlated single photon counting apparatus using a D₂-filled gated flash lamp. The aim is to determine: (1) the valid flash lamp profile, and (2) the reliability and sensitivity of subnanosecond lifetime measurements. As model systems for very short-lived fluorescence possessing single exponential decay, concentrated JV-methylpiperidine (NMP) solutions in n-hexane were used. Stern-Volmer self-quenching kinetics were observed over a concentration range of 0.508 M to 1.00 × 10^-4M. Solutions having known subnanosecond lifetimes were accordingly prepared. The flash lamp profile was altered so that the tail-portion (time > 3.6 ns after maximum) was reduced by a factor of 0.80. This altered profile provided the best convoluted functions as compared with the observed fluorescence decay curves. For lifetimes less than about 1 ns, the full-width-tenth-maximum values of the convoluted and observed decay functions were used as the criterion for best fit. Using highly concentrated NMP solutions, lifetimes of 0.30, 0.50, and 0.70 ns could be clearly distinguished; a lower limit for reliable measurement is placed at ca 0.2 ns for a flash lamp having a FWHM of 2.6 ns and a 1/e value of 0.8 ns.     

MULTI-SITE PHOSPHORESCENCE OF α, β-ENONES:LEVEL INVERSION IN 6β, 19-EPOXYCHOLEST-4-EN-3-ONE BY SOLVATION AND AGGREGATION

Millisecond time-resolved emission spectroscopy was used to probe the phosphorescence kinetics of the α-β-enone 6β, 19-epoxycholest-4-en-3-one (1) as a function of concentration in several paraffinic and hydroxylic glasses at 77 K. Only in methylcyclohexane/methylcyclopentane glass at low concentration (10^?4M) does the phosphorescence decay exponentially. It is interpreted as emission from the ³n* state. Upon increasing the concentration a second emission grows which is characterized by a longer lifetime, a decreased fine structure and a hypsochromically shifted S₀→¹nπ* excitation spectrum. This phosphorescence is ascribed to ³ππ* emission of aggregates of 1. In hydroxylic glasses the phosphorescence decay is multiexponential, even at 10^?4M concentration; from emission band shapes and lifetimes it follows that both ³nπ* and ³ππ* type emissions are present, the latter increasing with the alcohol concentration in the solvent. The two types of phosphorescence have different excitation spectra: that of the structureless and long-lived ³ππ* emission is shifted to the blue in the S₀→¹nπ* region and to the red in the S⁰→¹ππ* region. This emission is ascribed to complexes of 1 with the alcoholic solvent. The results of time-resolved measurements of the circular polarization of the luminescence are consistent with the assignments given above and indicate that in the H-bonded and possibly also in the free species ³ππ* and ³nπ* states are intermixed to a considerable extent.     

Laser-induced fluorescence of benzyl radicals in the gas phase

The excitation spectrum of the laser-induced fluorescence of benzyl has been observed in the gas phase. Fluorescence lifetimes of 880 ± 10 ns at zero pressure were obtained for the s, t and 6a¹₀ bands of the (1 ²A₂—1 ²B₂, 2 ²B₂—1 ²B₂) transitions of benzyl-h₇. The fluorescence lifetime of the t band in the corresponding transition of benzyl-d₇ was 1340 ns.