Time-resolved Luminescence Spectroscopy Research Articles

The Influence of Concentrations of Sensitizers and Activators on Luminescence Kinetics Parameters of Up-Conversion Nanocomplexes NaYF4:Yb3+/Tm3+

For colloids of NaYF4:Yb3+/Tm3+ nanoparticles in DMSO, by the method of time-resolved luminescence spectroscopy with nanosecond pulsed excitation at a wavelength of 975 nm, the photophysical processes that determine the course of kinetic curves have been revealed. It has been found that the luminescence rise time decreases with an increase in the concentration of activators and sensitizers due to the increase in the efficiency of energy transfer from sensitizers to activators. The cross-relaxation of the excited states of activators provides a decrease in the luminescence decay time with an increase in the concentration of activators and a constant concentration of the sensitizer. There is no correlation between the time of luminescence decay with the change in the concentration of sensitizers and the constant concentration of activators due to the competition of the processes of energy back transfer from activators to sensitizers and the “feeding” of activators by excitations coming from remote sensitizer ions.

Photophysical analysis and Judd–Ofelt calculation of Eu (III) complexes: Influence of various neutral ligands on luminescent properties

This article presents the preparation and characterization of a series of four tris-β-diketonate Eu(III) complexes with formulation of [Eu(tfaa)3(L)n], tfaa denotes the 1,1,1-trifluoroacetylacetone, L to monodentate or bidentate neutral ligand with nitrogen and oxygen as donor atom and n can be 1 and 2. The characterization of synthesized complexes was done using infrared spectroscopy, thermo-gravimetric analysis and proton NMR spectroscopy. UV–vis absorption, photoluminescence as well as time-resolved luminescence spectroscopies were also employed to examine the spectroscopic features of ternary complexes. The proton NMR and IR spectral information has suggested the bonding of organic moieties to the Eu(III) ion. The chemical shift obtained for the protons of primary and secondary moieties are shifted in an opposite direction. The band gap values (optical and electronic) suggest the semiconducting nature of prepared europium complexes. The trivalent ion centered emission is shown by all the prepared complexes on excitation under UV-light. The hypersensitive peak situated at about 612 nm responsible for red emission is corresponding to 5D0→7F2 transition and found to be sensitive to the chelating environment present at around emissive ion. Red emanating europium materials have acquired significant utilization in OLEDs, flat panel displays and solid state electronics.

Aromatic systems with two and three pyridine-2,6-dicarbazolyl-3,5-dicarbonitrile fragments as electron-transporting organic semiconductors exhibiting long-lived emissions.

The pyridine-3,5-dicarbonitrile moiety has gained significant attention in the field of materials chemistry, particularly in the development of heavy-metal-free pure organic light-emitting diodes (OLEDs). Extensive research on organic compounds exhibiting thermally activated delayed fluorescence (TADF) has led to numerous patents and research articles. This study focuses on the synthesis and investigation of the semiconducting properties of polyaromatic π-systems containing two and three fragments of pyridine-2,6-dicarbazolyl-3,5-dicarbonitrile. The compounds are synthesized by Sonogashira coupling reactions and characterized by steady-state and time-resolved luminescence spectroscopy. The compounds show efficient intramolecular charge transfer (ICT) from the donor to the acceptor. The photoluminescence (PL) spectra of the solutions of the compounds showed non-structured emission peaks in the visible region, which are attributed to ICT emission. The PL intensities of the solutions of the compounds are enhanced after deoxygenation, which is indicative of TADF. The photoluminescence quantum yields and TADF properties of the compounds are sensitive to the medium. Cyclic voltammetry measurements indicate good hole-blocking and electron-injecting properties due to their high ionization potentials. Photoelectron spectroscopy and time-of-flight measurements reveal good electron-transporting properties for one of the compounds. In general, polyaromatic π-systems with pyridine-3,5-dicarbonitrile fragments demonstrate promising potential for use in organic electronic devices, such as OLEDs.

Exciplex luminescence of difluoroboron meta- and para-Nitrodibenzoylmethanates in solutions and polymer matrix

Molecular systems with intense exciplex luminescence are promising for the creation of OLEDs and light-transforming materials. The luminescent properties of difluoroboron meta- and para-nitrodibenzoylmethanates (1 and 2) were studied by the steady-state and time-resolved luminescence spectroscopy methods and quantum chemistry simulation. The influence of the position of the nitro group on the spectral properties of the complexes was revealed. The nitro group withdraws the electron density upon photoexcitation in the para-isomer in contrast to the meta-isomer. The bond order of the CC bond between the phenyl and chelate rings decreases in the excited relaxed state of 2, which leads to rotation of the substituent and a low quantum yield. Formation of exciplexes of 1 and 2 in benzene, toluene and polystyrene was found. The formation of the ground and excited-state electron donor–acceptor complexes based on difluoroboron nitrodibenzoylmethanates and benzene was revealed. The TDDFT method showed that the complexes are characterized by the presence of short contacts between the fluorine atom of the dye molecule and the hydrogen atoms of the aromatic hydrocarbon molecule. These contacts shorten during the transition from the ground state to the excited state. Polymeric compositions based on polystyrene (PS) and poly(methyl methacrylate) (PMMA) doped with 1 and 2 were obtained. The luminescence intensity of dyes 1 and 2 increases during the transition from PMMA to PS. A significant bathochromic shift of the luminescence maximum of 1 is observed, which is associated with the formation of exciplexes and triplexes. The obtained polymeric materials are promising for the development of optical smart materials.

Luminescence of tris (8-hydroxyquinoline) aluminium thin films under synchrotron radiation excitation

The work is dedicated to the investigation of the luminescent properties of Tris (8-hydroxyquinoline) aluminium (Alq3) thin layers using the conventional spectral methods (cathodoluminescence and photoluminescence), as well as the advanced time-resolved luminescent spectroscopy under excitation by the synchrotron radiation in the fundamental absorption edge of this material. The Alq3 films with a thickness of 100–300 nm were deposited by the PVD (Physical Vapor Deposition) method on silicon substrates. The structural properties of Alq3 layers were studied using scanning electronic microscopy and X ray diffraction. The structure of the luminescence spectra of the Alq3 layer in the green-yellow range at 10 K and 300 K confirms the complex structure of the emission centers of this material, associated with the internal fast radiation transitions in the Al3+ molecule surrounded by three 8-hydroxynoline ligands. It has been determined the energy of creation of excitons associated with Alq3 green emission centers, which has been equal to 6.78 eV and 6.86 eV at 10 K and 300 K, respectively.

Efficient Ultrafast Scintillation of KLuS2:Pr3+ Phosphor: A Candidate for Fast-Timing Applications

A set of ${\mathrm{Pr}}^{3+}$-doped ${\mathrm{KLuS}}_{2}$ samples with different $\mathrm{Pr}$ concentrations are synthesized in the form of transparent crystalline hexagonal platelets by chemical reaction under a flow of hydrogen sulfide. Their structural, optical, and scintillation properties are investigated thoroughly by means of x-ray powder diffraction, time-resolved luminescence spectroscopy, scintillation light yield, and decay measurements to assess the spectroscopic properties of ${\mathrm{Pr}}^{3+}$ ions in the ${\mathrm{KLuS}}_{2}$ host. Charge-trapping processes are further investigated by electron paramagnetic resonance. The fundamental absorption band edge of the ${\mathrm{KLuS}}_{2}$ host is located at 303 nm, the absorption due to the ${\mathrm{Pr}}^{3+}$ 4f \ensuremath{\rightarrow} 5d transition is found at 347 nm, the emission maximum is given by the $4{f}^{1}5d1$ \ensuremath{\rightarrow} ${}^{3}{H}_{4}$ transition of the ${\mathrm{Pr}}^{3+}$ ion at 380 nm, and the leading photoluminescence and scintillation decay time is around 1 ns at room temperature. The moderate scintillation light yield reaches 7200 ph/MeV. A phenomenological model is fitted to the measured temperature dependences of the photoluminescence emission spectra and photoluminescence decay times to better understand the dynamics of the 5d excited state of the ${\mathrm{Pr}}^{3+}$ center in the ${\mathrm{KLuS}}_{2}$ host. The number of photons emitted in the first nanosecond of the scintillation response is evaluated and found to be considerably higher (1.6--2.5 times) than that in the commercial $(\mathrm{Lu};\mathrm{Y}{)}_{2}({\mathrm{SiO}}_{4})\mathrm{O}$:$\mathrm{Ce},\mathrm{Ca}$ scintillator, which shows the potential of $\mathrm{Pr}$-doped ${\mathrm{KLuS}}_{2}$ for fast-timing scintillator applications.

Influence of gluconate on the retention of Eu(III), Am(III), Th(IV), Pu(IV), and U(VI) by C-S-H (C/S = 0.8)

The retention of actinides in different oxidation states (An(X), X = III, IV, VI) by a calcium-silicate-hydrate (C-S-H) phase with a Ca/Si (C/S) ratio of 0.8 was investigated in the presence of gluconate (GLU). The actinides considered were Am(III), Th(IV), Pu(IV), and U(VI). Eu(III) was investigated as chemical analogue for Am(III) and Cm(III). In addition to the ternary systems An(X)/GLU/C-S-H, also binary systems An(X)/C-S-H, GLU/C-S-H, and An(X)/GLU were studied. Complementary analytical techniques were applied to address the different specific aspects of the binary and ternary systems. Time-resolved laser-induced luminescence spectroscopy (TRLFS) was applied in combination with parallel factor analysis (PARAFAC) to identify retained species and to monitor species-selective sorption kinetics. 13C and 29Si magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were applied to determine the bulk structure and the composition of the C-S-H surface, respectively, in the absence and presence of GLU. The interaction of Th(IV) with GLU in different electrolytes was studied by capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS). The influence of GLU on An(X) retention was investigated for a large concentration range up to 10−2 M. The results showed that GLU had little to no effect on the overall An(X) retention by C-S-H with C/S of 0.8, regardless of the oxidation state of the actinides. For Eu(III), the TRLFS investigations additionally implied the formation of a Eu(III)-bearing precipitate with dissolved constituents of the C-S-H phase, which becomes structurally altered by the presence of GLU. For U(VI) sorption on the C-S-H phase, only a small influence of GLU could be established in the luminescence spectroscopic investigations, and no precipitation of U(VI)-containing secondary phases could be identified.

The complexation of lanthanides by glycolamide extractants: Evidences from electronic spectroscopy and DFT calculations

The extraction of trivalent metal ions (Nd and Eu) in N,N,N’,N’-tetraoctyldiglycolamide (TODGA) was compared with N,N-di-octyl-2-hydroxyacetamide (DOHyA), a monoglycolamide derivative of TODGA. The studies based on UV–visible spectroscopy showed the differences in Nd(III) ion complexation for the extractants in both polar and non-polar diluents. n-Dodecane modified with 5 vol% 1-octanol was employed as diluent for extraction studies with TODGA, while DOHyA was studied with no modifiers in n-Dodecane. Time resolved luminescence spectroscopy studies of the Eu(III) extracted organic phases showed strong complexation of metal ion with both the extractants. The co-extraction of water in DOHyA solvent phase during Eu(III) extraction from nitric acid medium was found to be more as compared to TODGA. The better solubilization of water in DOHyA solvent was substantiated by DFT analysis of the optimized electronic structures of Eu-DMHyA (dimethyl hydroxyacetamide) and Eu-TMDGA (tetramethyldiglycolamide) complexes.

Fluorescent boron difluoride curcuminoides as perspective materials for bio-visualization

Curcuminoids of boron difluoride, 1-aryl(hetaryl)-5-phenylpenta-2,4-dien-1-onates of boron difluoride, have been synthesized. A comparative study of the electronic structure, luminescent properties and their potential for applications in bio-imaging has been carried out. The influence of the electronic structure of α-substituents on the luminescence of compounds was studied by the methods of stationary and time-resolved luminescence spectroscopy and DFT modeling. The introduction of π-donor substituents leads to a noticeable bathochromic shift and an increase in the Stokes shift in the luminescence spectra. On going from σ-donor substituents in the phenyl ring to π-donor substituents, the luminescence quantum yield increases from 0.03 to 0.22. The maximum Stokes shift and high quantum yield of luminescence is exhibited by the complex with a stilbene substituent, which has the longest π-system and the maximum efficiency of charge transfer. Dyes are able to penetrate into the cells of the model cell line and accumulate, moreover, accumulation occurs mainly in the cytoplasm of cells. The compounds penetrate into the cells by 12 h of incubation without damaging it’s structure and without causing rapid cell death. The submicromolar range of non-toxic concentrations during long-term incubation for a model cell line was determined, which is a characteristic of fluorescent imaging. Due to uniform distribution in the cytoplasm of cells dye with naphtyl substituent is promising for visualization of the cell cytoplasm. This leader compound has the lowest cytotoxicity for cells from the synthesized series of dyes, which makes it promising for further studies as a fluorescent imaging agent.The leader compound has the lowest cytotoxicity for cells from the synthesized series of dyes, which makes it promising for further studies as a fluorescent imaging agent.

A Simplified Approach for the Aqueous Synthesis of Luminescent CdSe/ZnS Core/Shell Quantum Dots and Their Applications in Ultrasensitive Determination of the Biomarker 3-Nitro-l-tyrosine

In contrast to the hot-injection organometallic routes, synthesizing stable and highly luminescent core/shell nanocrystals with encapsulation of biocompatible groups through an aqueous route is a long-standing challenge. In recent years, relatively high quantum efficiency and unique properties of core/shell nanostructured materials (quantum dots) have contributed toward enhancement in sensing capability. The present work reports a facile aqueous synthesis process of core/shell CdSe/ZnS quantum dots (QDs) with encapsulation of glutathione (GSH). The optimal conditions for the synthesis of the most stable particles were ascertained, and the different experimental analyses suggest that the stable core/shell QDs in question have good crystallinity with a size around 4.7 nm with a shell thickness of 0.7 nm and a photoluminescence quantum yield of about 35%. Further, it is demonstrated that the as-synthesized material has great potential in detecting as low as 0.28 nM 3-nitro-l-tyrosine (3-NT), an important marker for oxidative stress, the level of which in our body signals several chronically diseased conditions. The enthalpy-driven interactions of CdSe/ZnS-GSH QDs with 3-NT were characterized through steady-state and time-resolved luminescence spectroscopy and isothermal microcalorimetry. The devised method of probing 3-NT was further validated with human serum samples. Thus, the proposed strategy may provide a protocol for selective determination of 3-NT under different pathological conditions.

Recent advances in time-resolved luminescence spectroscopy at MAX IV and PETRA III storage rings

Short-wavelength synchrotron radiation excitation has been an indispensable tool in the studies of the properties of wide gap materials using time-resolved low-temperature luminescence spectroscopy. In recent years, several setups for such investigations have been launched at MAX IV Laboratory and Photon Science at DESY. Two permanently stationed time-resolved luminescence setups at FinEstBeAMS and P66 beamlines are in operation at MAX IV 1.5 GeV and Petra III storage rings, respectively. Mobile luminescence setups have been developed for studies at FemtoMAX and P23 beamlines. FinEstBeAMS, P66 and P23 provide time resolution from ∼160 to 100 ps. The FemtoMAX photon source based on an in-vacuum undulator getting an electron beam from the 3 GeV linear accelerator provides an exceptional time resolution of ∼30 ps, limited by time response of the photodetector. The performance of the setups, achieved milestones and research challenges are discussed for four new luminescence stations available for the research community with the main focus on time-resolved techniques.

Emission characteristics of gadolinium ions in a water Cherenkov detector

Abstract To observe supernova relic neutrino events, 13 tons of gadolinium sulfate octahydrate (Gd2(SO4)3·8H2O), corresponding to 0.01% Gd solution, was dissolved in the Super-Kamiokande water Cherenkov detector in 2020. The aim is to improve the detection efficiency of neutrons from inverse β decay involving electron antineutrinos. However, Gd3+ ions can be excited by the Cherenkov light from cosmic muons, and the subsequent emission at 312 nm is a possible background (BG) source for Cherenkov signal detection. In this work, we constructed an experimental setup based on time-resolved laser-induced luminescence spectroscopy to investigate the emission characteristics of Gd3+ ions in water. The excitation laser wavelength was tuned in the range of 245–255 nm, and large resonant peaks were observed at 246.2 nm and 252.3 nm with measured emission lifetimes of around 3 ms. Good linearity was observed between Gd concentration and emission intensity for these two wavelengths, indicating that our setup is useful for remote monitoring of Gd concentration. According to the simulation results using our spectroscopic data and reference values, the Gd3+ emission BG rate from cosmic muons is expected to be 10−1 counts/μs or less, which seems small but not negligible.

Synthesis and Fluorescence Studies of Diborene Coinage Metal Complexes.

Nine different coinage metal (Cu, Ag) π complexes of diborenes with various anionic diborene (aryl, heteroaryl) and metal substituents (Cl, Br, C6F5, C2SiMe3), stabilizing neutral donors (N-heterocyclic carbene = NHC, phosphine), configurations (cis/trans, acyclic/cyclic diborene), and charges (neutral, cationic) were synthesized and characterized by multinuclear NMR spectroscopy and X-ray crystallographic analyses. Their optical properties were investigated by UV-vis absorption and steady-state as well as time-resolved luminescence spectroscopy in solution and the solid state to gain insights into the excited-state behavior of this unusual class of photoactive compounds and to provide structure-property relationships. The structural and electronic modification of the (B═B)···M motif greatly influences not only the visible light absorption but also the photostability and quantum yields, which can reach high values of up to f = 0.42. The lifetimes are found in the nanosecond regime, providing estimated radiative rate constants over a wide range of kr = 1.3-14 × 107 s-1, indicative of fluorescence. Intersystem crossing (ISC) is sufficiently slow for prompt emission from the S1 state to be observed, while the spin-orbit coupling in the T1 state is too weak for phosphorescence to occur at room temperature. ISC can be accelerated, however, by modifying diborene ligand substitution and the coinage metal center, hinting at the potential for exploiting the properties of long-lived triplet excited states of metal diborene complexes in the future.

Time-Resolved Photoluminescence Spectroscopy of Semiconductor Nanocrystals and Other Fluorophores.

Time-resolved photoluminescence (TRPL) is a key technique for understanding the photophysics of semiconductor nanocrystals and light-emitting materials in general. This work is a primer for setting up and conducting TRPL on nanocrystals and related materials using single-photon-counting (SPC) systems. Basic sources of error in the measurement can be avoided by consideration of the experimental setup and calibration. The detector properties, count rate, the spectral response, reflections in optical setups, and the specific instrumentation settings for single photon counting will be discussed. Attention to these details helps ensure reproducibility and is necessary for obtaining the best possible data from an SPC system. The main aim of the protocol is to help a student of TRPL understand the experimental setup and the key hardware parameters one must generally comprehend in order to gain useful TRPL data in many common single-photon-counting setups. The secondary purpose is to serve as a condensed primer for the student of experimental time-resolved luminescence spectroscopy.

Excited state dynamics in Bi3+-doped lutetium gallium garnet

Microcrystalline powders of Bi3+-doped Lu3Ga5O12 garnet are investigated by the X-ray diffraction, time-resolved luminescence spectroscopy, and thermally stimulated luminescence methods. The mechanisms of the processes are clarified, which take place in the excited states of the Bi3+-related luminescence centers and result in the appearance of two (ultraviolet and visible) emission bands with strongly different characteristics in the photo- and thermoluminescence spectra as well as in the creation of stable electron and hole centers of different types. The conclusion is made that besides the electron transitions between the Bi3+ levels, the photoexcitation of Lu3Ga5O12:Bi results in the ionization of Bi3+ and in the Bi3+ → Ga3+oct, Bi3+ → Ga3+tetr, and Bi3+ → Lu3+ electron transfer transitions. These processes can lead to the release of free electrons into the conduction band, their trap at different electron traps, and formation of hole centers of the type of Bi4+ and {O- - Bi3+}. The recombination of electrons with these hole centers results in the ultraviolet emission of a Bi3+ ion and visible emission of an exciton localized around the Bi3+ ion, respectively.

Effect of Ca(II) on U(VI) and Np(VI) retention on Ca-bentonite and clay minerals at hyperalkaline conditions - New insights from batch sorption experiments and luminescence spectroscopy

In deep geological repositories for radioactive waste, interactions of radionuclides with mineral surfaces occur under complex geochemical conditions involving complex solution compositions and high pH resulting from degradation of cementitious geo-engineered barriers. Ca2+ cations have been hypothesized to play an important role as mediators for the retention of U(VI) on Ca-bentonite at (hyper)alkaline conditions, despite the anionic character of both the mineral surface and the aqueous uranyl species. To gain deeper insight into this sorption process, the effect of Ca2+ on U(VI) and Np(VI) retention on alumosilicate minerals has been comprehensively evaluated, using batch sorption experiments and time-resolved laser-induced luminescence spectroscopy (TRLFS). Sorption experiments with Ca2+ or Sr2+ and zeta potential measurements showed that the alkaline earth metals sorb strongly onto Ca-bentonite at pH 8–13, leading to a partial compensation of the negative surface charge, thereby generating potential sorption sites for anionic actinyl species. U(VI) and Np(VI) sorption experiments in the absence and presence of Ca2+ or Sr2+ confirmed that these cations strongly enhance radionuclide retention on kaolinite and muscovite at pH ≥ 10. Concerning the underlying retention mechanisms, site-selective TRLFS provided spectroscopic proof for two dominating U(VI) species at the alumosilicate surfaces: (i) A ternary U(VI) complex, where U(VI) is bound to the surface via bridging Ca cations with the configuration surface ≡ Ca – OH – U(VI) and, (ii) U(VI) sorption into the interlayer space of calcium (aluminum) silicate hydrates (C-(A-)S-H), which form as secondary phases in the presence of Ca due to partial dissolution of alumosilicates under hyperalkaline conditions. Consequently, the present study confirms that alkaline earth elements, which are ubiquitous in geologic systems, enable strong retention of hexavalent actinides on clay minerals under hyperalkaline repository conditions.

Probing Prolamin-Anthocyanin Interactions for the Rational Design of Plant-Based Encapsulation Systems

Plant proteins are increasingly focused upon as alternatives to animal-derived macromolecules for the encapsulation of bioactives. The rational design of encapsulation carriers should be based on a solid understanding of the interactions between the proteins and bioactives. Encapsulation technology for food applications has focused predominantly on the protection and controlled release of hydrophobic bioactives. For hydrophilic molecules, although not less important from a nutritional and health perspective, significantly fewer encapsulation systems have been explored, designed and described. As hydrophilic molecules tend to partition into the aqueous food matrix, it is even more crucial to understand and to be able to modulate the interactions between the hydrophilic bioactive and the encapsulating matrix material in food relevant conditions. Therefore, examining the nature of the interactions between anthocyanins (ACNs), a hydrophilic bioactive, and prolamin plant proteins (gliadin, hordein, secalin, and avenin) is timely. These interactions were examined using steady-state and time-resolved luminescence spectroscopy techniques. The ACN-induced quenching of the prolamins intrinsic fluorescence emission did not follow a linear Stern-Volmer relationship, but rather displayed an upward curvature for all the prolamins tested. Hence, both static and dynamic quenching likely occurred in the prolamin-ACN systems. The quenching mechanism was further explored based on the changes in fluorescence lifetime as ACN concentration increased. As the independent lifetimes of the prolamin-ACN combinations did not decrease discernibly as a function of ACN concentration, static quenching is presumably the predominant quenching mechanism. The thermodynamic parameters revealed that the interactions between secalin- and avenin-ACN are mainly driven by the hydrophobic effect, while those between gliadin- and hordein-ACN are dominated by ionic interactions. Zeta-potential measurements support the dominant ionic interactions found for gliadin and hordein. The insights gained in this research will serve as a sound basis for further studies focusing on matrix selection with regard to creating performant encapsulation systems for ACNs.

Characterisation of andersonite by Raman, luminescence and laser-induced breakdown spectroscopy

Andersonite (Na2Ca[UO2(CO3)3]·(5+x)(H2O) where x ≤ 1) has been reported from oxidised, hydrothermal uranium ores, typically as efflorescent coatings on the underground walls of mine workings. It may also occur in underground repositories for spent nuclear fuels owing to the preponderance of cementitious materials used as grouts, backfill and for structural stability. Should this be the case, its high solubility would be expected to lead to enhanced uranium mobility. This study reports on the use of Raman, time-resolved luminescence and laser-induced breakdown spectroscopy to characterise andersonite; the first attempt to use all three laser-based techniques in tandem for this mineral. Well defined Raman features were observed with the resolved peaks corresponding well with previous studies, although differences were found in the number of resolvable peaks due to the low Raman signal emitted in some of the wavenumber regions selected. Seven emission and eight excitation luminescence peaks were resolved for the phase and a lifetime value of 96.8 ± 6.7 μs was extracted from luminescence decay measurements. Compositional LIBS analysis was successful in identifying minor K-bearing inclusions in the specimen, confirmed by optical and scanning electron microscopy, that were not detectable by the other methods employed. The findings indicate that multiple laser-based techniques offer the potential for real-time characterisation of uranyl phases formed in environments where intrusive sampling and ‘off-site’ laboratory analysis is impracticable.

Surface Coverage- and Excitation Laser Wavelength-Dependent Luminescence Properties of U(VI) Species Adsorbed on Amorphous SiO2

Time-resolved luminescence spectroscopy is usefully used to identify U(VI) surface species adsorbed on SiO2. However, the cause of the inconsistent luminescence lifetimes and spectral shapes reported previously remains undetermined. In this study, the U(VI) surface coverage (Γ) and excitation laser wavelength (λex) were examined as the predominant factors governing the luminescence properties of U(VI) surface species. At neutral pH, the luminescence lifetimes of U(VI) surface species increased with decreasing Γ. In the low-Γ region, where a relatively large number of adjacent surface sites are involved in the formation of multidentate surface complexes, the displacement of more number of coordinated water molecules in the equatorial plane of U(VI) results in a longer lifetime. The pH-dependent luminescence lifetimes of U(VI) surface species at the same U(VI) to SiO2 concentration ratio in the pH range of 4.5–7.5 also explain the effect of the surface binding sites on the luminescence lifetime. The time-resolved luminescence properties of the U(VI) surface species were also investigated at different excitation wavelengths. Continued irradiation of the SiO2 surface with a UV laser beam at λex = 266 nm considerably reduced the luminescence intensities of the U(VI) surface species. The higher the laser pulse energy, the greater the decrease in luminescence intensity. Laser-induced thermal desorption (LITD) of U(VI) surface species is suggested to be the origin of the decrease in luminescence intensity. LITD effects were not observed at λex = 355 and 422 nm, even at high laser pulse energies.

Microscopic and spectroscopic bioassociation study of uranium(VI) with an archaeal Halobacterium isolate.

The safe disposal of high-level radioactive waste in a deep geological repository is a huge social and technical challenge. So far, one of the less considered factors needed for a long-term risk assessment, is the impact of microorganisms occurring in the different host rocks. Even under the harsh conditions of salt formations different bacterial and archaeal species were found, e. g. Halobacterium sp. GP5 1–1, which has been isolated from a German rock salt sample. The interactions of this archaeon with uranium(VI), one of the radionuclides of major concern for the long-term storage of high-level radioactive waste, were investigated. Different spectroscopic techniques, as well as microscopy, were used to examine the occurring mechanisms on a molecular level leading to a more profound process understanding. Batch experiments with different uranium(VI) concentrations showed that the interaction is not only a simple, but a more complex combination of different processes. With the help of in situ attenuated total reflection Fourier-transform infrared spectroscopy the association of uranium(VI) onto carboxylate groups was verified. In addition, time-resolved laser-induced luminescence spectroscopy revealed the formation of phosphate and carboxylate species within the cell pellets as a function of the uranium(VI) concentration and incubation time. The association behavior differs from another very closely related halophilic archaeon, especially with regard to uranium(VI) concentrations. This clearly demonstrates the importance of studying the interactions of different, at first sight very similar, microorganisms with uranium(VI). This work provides new insights into the microbe-uranium(VI) interactions at highly saline conditions relevant to the long-term storage of radioactive waste in rock salt.