Excitation Emission Spectroscopy Research Articles

Access to the Antenna System of Photosystem I via Single-Molecule Excitation-Emission Spectroscopy.

In the development of single-molecule spectroscopy, the simultaneous detection of the excitation and emission spectra has been limited. The fluorescence excitation spectrum based on background-free signals is compatible with the fluorescence-emission-based detection of single molecules and can provide insight into the variations in the input energy of the different terminal emitters. Here, we implement single-molecule excitation-emission spectroscopy (SMEES) for photosystem I (PSI) via a cryogenic optical microscope. To this end, we extended our line-focus-based excitation-spectral microscope system to the cryogenic temperature-compatible version. PSI is one of the two photosystems embedded in the thylakoid membrane in oxygen-free photosynthetic organisms. PSI plays an essential role in electron transfer in the photosynthesis reaction. PSIs of many organisms contain a few red-shifted chlorophylls (Chls) with much lower excitation energies than ordinary antenna Chls. The fluorescence emission spectrum originates primarily from the red-shifted Chls, whereas the excitation spectrum is sensitive to the antenna Chls that are upstream of red-shifted Chls. Using SMEES, we obtained the inclining two-dimensional excitation-emission matrix (2D-EEM) of PSI particles isolated from a cyanobacterium, Thermosynechococcus vestitus (equivalent to elongatus), at about 80 K. Interestingly, by decomposing the inclining 2D-EEMs within time course observation, we found prominent variations in the excitation spectra of the red-shifted Chl pools with different emission wavelengths, strongly indicating the variable excitation energy transfer (EET) pathway from the antenna to the terminal emitting pools. SMEES helps us to directly gain information about the antenna system, which is fundamental to depicting the EET within pigment-protein complexes.

Effect of electrolytic zero-valent iron activated sodium hypochlorite on sludge dewatering performance.

Using electrolytic zero-valent iron-activated sodium hypochlorite (EZVI-NaClO) to pretreat sludge, the capillary suction time (CST) was utilized to evaluate sludge dewaterability. Ammonia nitrogen (NH4-N), dissolved phosphorus, and total phosphorus in the supernatant were used to analyze sludge disintegration. This approach aimed to evaluate the effectiveness of the pretreatment process and its impact on the sludge composition. The migration and transformation of extracellular polymeric substances (EPS), including dissolved EPS (S-EPS), loosely boundEPS, and tightly bound-EPS (TB-EPS), were analyzed by detecting protein and polysaccharide concentrations and three-dimensional fluorescence excitation-emission spectroscopy (3D-EEM). The sludge particle properties, including sludge viscosity and particle size, were also analyzed. The results suggested that the optimal pH value, NaClO dosage, current, and reaction time were 2, 100 mg/gDS (dry sludge), 0.2A, and 30 min, respectively, with a CST reduction of 43%. Protein and polysaccharide contents in TB-EPS were significantly reduced in the EZVI-NaClO group. Conversely, protein and polysaccharides contents in S-EPS increased, suggesting that EZVI-NaClO treatment could disrupt the EPS. Besides, the viscosity of the treated sludge decreased from 195.4 to 54.9 mPa·S, indicating that sludge fluidity became better. ZEVI-NaClO could enhance sludge dewaterability by destructing protein and polysaccharide structure and improving sludge hydrophobicity.

An efficiently excited Eu3+ luminescent site formed in Eu,O-codoped GaN

For the development of III-nitride-semiconductor-based monolithic micro-light-emitting diode (LED) displays, Eu,O-codoped GaN (GaN:Eu,O) is a promising material candidate for the red LEDs. The luminescence efficiency of Eu-related emission strongly depends on the local atomic structure of Eu ions. Our previous research has revealed that post-growth thermal annealing is an effective method for reconfiguring luminescent sites, leading to a significant increase in light output. We observed the preferential formation of a site with a peak at ∼2.004 eV by the annealing process. In this study, we demonstrate that it is a previously unidentified independent site (OMVPE-X) using combined excitation–emission spectroscopy and time-resolved photoluminescence measurements. In addition, we perform excitation power-dependent photoluminescence measurements and show that this OMVPE-X site dominates the emission at a low excitation power region despite its small relative abundance, suggesting a high excitation efficiency. Most importantly, applying our annealing technique to an LED exhibits a reasonably increased electroluminescence intensity associated with OMVPE-X, confirming that this site has a high excitation efficiency also under current injection. These results demonstrate the importance of OMVPE-X as a notable luminescent site for brighter and more efficient GaN:Eu,O-based LEDs.

Characteristics and Influencing Factors of Dissolved Organic Matter in Cave Drip Water—A Case Study from Furong Cave, Southwest China

Understanding the hydrological processes of dissolved organic matter (DOM) in the surface karst zone is crucial for the utilization and safety of groundwater resources. However, research on DOM in drip water from karst caves is limited. In this study, continuous monitoring was conducted for four years at four drip water monitoring sites (MP1, MP2, MP3, and MP9) in Furong Cave, Southwest China. The three-dimensional fluorescence excitation–emission spectroscopy (3D-EEM) and fluorescence region integration (FRI) methods were employed, along with correlation analysis, to investigate the spectral characteristics, composition, sources, and influencing factors of the DOM in the drip water of Furong Cave. The results indicated that (1) the three-dimensional fluorescence peaks in the drip water were classified into six categories: A, B, C, T, Ti, and M. (2) The dominant source of the drip water DOM is endogenous organic matter. (3) The FRI analysis indicates a relatively high proportion of Type II substances in the drip water, predominantly composed of tryptophan-like substances. (4) The DOM in the drip water of Furong Cave was influenced by various factors, including the mixing effect of “new” and “old” water, water residence time in karst systems, and water–rock interactions (WRI), resulting in the complex responses of drip rates and DOM to surface precipitation and temperature at different drip water sites. This study provides a reference for comparative research on DOM in cave drip water in karst regions, which contributes to a better understanding of the migration mechanism of DOM in karst aquifers under different climate and karst ecological conditions.

Fast and accurate identification of pathogenic bacteria using excitation-emission spectroscopy and machine learning.

Fast and reliable identification of pathogenic bacteria is of upmost importance to human health and safety. Methods that are currently used in clinical practice are often time consuming, require expensive equipment, trained personnel, and therefore have limited applications in low resource environments. Molecular identification methods address some of these shortcomings. At the same time, they often use antibodies, their fragments, or other biomolecules as recognition units, which makes such tests specific to a particular target. In contrast, array-based methods use a combination of reporters that are not specific to a single pathogen. These methods provide a more data-rich and universal response that can be used for identification of a variety of bacteria of interest. In this report, we demonstrate the application of the excitation-emission spectroscopy of an environmentally sensitive fluorescent dye for identification of pathogenic bacterial species. 2-(4'-Dimethylamino)-3-hydroxyflavone (DMAF) interacts with the bacterial cell envelope resulting in a distinct spectral response that is unique to each bacterial species. The dynamics of dye-bacteria interaction were thoroughly investigated, and the limits of detection and identification were determined. Neural network classification algorithm was used for pattern recognition analysis and classification of spectral data. The sensor successfully discriminated between eight representative pathogenic bacteria, achieving a classification accuracy of 85.8% at the species level and 98.3% at the Gram status level. The proposed method based on excitation-emission spectroscopy of an environmentally sensitive fluorescent dye is a powerful and versatile diagnostic tool with high accuracy in identification of bacterial pathogens.

Spatio-temporal characterization of dissolved organic matter in karst rivers disturbed by acid mine drainage and its correlation with metal ions

Dissolved organic matter (DOM) is widely present in surface water environments and plays a critical role in the biogeochemical cycling of metal ions. Metal ions in acid mine drainage (AMD) have seriously polluted karst surface water environments, but few studies have explored interactions between DOM and metal ions in AMD-disturbed karst rivers. Here, the composition and sources of DOM in AMD-disturbed karst rivers were investigated by fluorescence excitation-emission spectroscopy combined with parallel factor analysis. In addition, correlations between metal ions and other factors (DOM components, total dissolved carbon (TDC) and pH) were determined using structural equation modeling (SEM). Results showed that there were evident differences in the seasonal distribution of TDC and metal ion concentrations in AMD-disturbed karst rivers. The concentrations of DOC, dissolved inorganic carbon (DIC), and metal ions were generally higher in the dry season than in the wet season, with Fe and Mn pollution being the most pronounced. The DOM in AMD contained two types of protein-like substances that were mainly from autochthonous inputs, while DOM in AMD-disturbed karst rivers contained two additional types of humic-like substances from both autochthonous and allochthonous inputs. The SEM results showed that the influence of DOM components on the distribution of metal ions was greater than that of TDC and pH. Among the DOM components, the influence of humic-like substances was greater than that of protein-like substances. Additionally, DOM and TDC had direct positive effects on metal ions, while pH had a direct negative effect on these. These results further elucidated the geochemical interactions between DOM and metal ions in AMD-disturbed karst rivers, which will assist in the pollution prevention of metal ions in AMD.

Red Electroluminescence from Light Emitting Diodes Based on Eu-Doped ZnO Embedded in p-GaN/Al2O3/n-ZnO Heterostructures

Heterojunction p-GaN/n-ZnO light emitting diode (LED) structure using Eu-doped ZnO (ZnO:Eu) as an active component is demonstrated in order to realize low-cost and environmentally-friendly red LEDs with sharp linewidth and temperature stability against surrounding environment including operating temperature and injection current. Chemically stable Al2O3 is inserted as an electron blocking layer between p-GaN and ZnO:Eu/n-ZnO in order to facilitate the injection of carriers into the ZnO:Eu active layer. Al2O3 insertion with a moderate thickness (∼10 nm) facilitates the carrier recombination at the ZnO layer with comparatively low resistivity. Device characteristics of the p-GaN/Al2O3/ZnO:Eu/n-ZnO LED structures show red luminescence under current injection with reversed bias voltage originated from Eu3+ ions in the ZnO host. Detailed optical characteristics of the ZnO:Eu layer in the LED structures utilizing the combined excitation emission spectroscopy measurement enable the identification of the luminescence centers contributing to Eu luminescence under both indirect excitation and collisional excitation. The luminescence center contributing to Eu luminescence under indirect excitation via the ZnO host is different from that under collisional excitation, which would pave the way to understand the Eu luminescence mechanism in ZnO:Eu, and hence realize high-brightness LED structures based on rare-Earth doped ZnO as an active component.

Dual-emitting from Bi[formula omitted], Ln[formula omitted] (Ln [formula omitted] Eu, Sm) co-activated Ca[formula omitted]Sb[formula omitted]O[formula omitted] phosphor for optical temperature measurement

In this paper, a series of Ca(2−x−y) Sb2O7: xBi3+, yLn3+ (Ln = Eu, Sm) fluorescent powder samples were successfully obtained, which used the traditional high-temperature solid-phase synthesis method in the preparation process. Samples of Ca2Sb2O7: Bi3+, Ln3+ (Ln = Eu, Sm) fluorescent powder samples were structurally and optically characterized​ using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), photoluminescence excitation spectroscopy and emission spectroscopy, and fluorescence decay measurements. The results show that the prepared Ca(2−x−y) Sb2O7: xBi3+, yLn3+ (Ln = Eu, Sm) samples have an orthogonal spider web structure, which remains unchanged whether Bi3+ is single doped or Bi3+ is co-doped with Ln3+ (Ln = Eu, Sm). Under ultraviolet lamp (λex=340nm) irradiation, Bi3+ doped Ca2Sb2O7 powder shows a wide emission band centered at 435 nm, which is owing to the 3P1→1S0 transition of Bi3+ ion. Therefore, the effect of Bi3+ and Ln3+ (Ln = Eu, Sm) co-doped Ca2Sb2O7 samples on the luminescence intensity of the samples at different concentrations was studied. When the temperature was varied from 293 K to 483 K, the absolute temperature sensitivity (Sa) of doped Bi3+/Eu3+ and Bi3+/Sm3+ phosphors is 0.001K−1 (at 483 K) and 0.02K−1 (at 293 K), respectively, and the relative temperature sensitivity (Sr) is 1.03% K−1 (at 343 K) and 1.19% K−1 (at 293 K), respectively. These results demonstrate that Ca(2−x−y) Sb2O7: xBi3+, yLn3+(Ln = Eu, Sm) phosphors are prospective double emission thermal thermometers.

Chromophores and chemical composition of brown carbon characterized at an urban kerbside by excitation–emission spectroscopy and mass spectrometry

Abstract. The optical properties, chemical composition, and potential chromophores of brown carbon (BrC) aerosol particles were studied during typical summertime and wintertime at a kerbside in downtown Karlsruhe, a city in central Europe. The average absorption coefficient and mass absorption efficiency at 365 nm (Abs365 and MAE365) of methanol-soluble BrC (MS-BrC) were lower in the summer period (1.6 ± 0.5 Mm−1, 0.5 ± 0.2 m2 g−1) than in the winter period (2.8 ± 1.9 Mm−1, 1.1 ± 0.3 m2 g−1). Using a parallel factor (PARAFAC) analysis to identify chromophores, two different groups of highly oxygenated humic-like substances (HO-HULIS) dominated in summer and contributed 96 ± 6 % of the total fluorescence intensity. In contrast, less-oxygenated HULIS (LO-HULIS) dominated the total fluorescence intensity in winter with 57 ± 12 %, followed by HO-HULIS with 31 ± 18 %. Positive matrix factorization (PMF) analysis of organic compounds detected in real time by an online aerosol mass spectrometer (AMS) led to five characteristic organic compound classes. The statistical analysis of PARAFAC components and PMF factors showed that LO-HULIS chromophores were most likely emitted from biomass burning in winter. HO-HULIS chromophores could be low-volatility oxygenated organic aerosol from regional transport and oxidation of biogenic volatile organic compounds (VOCs) in summer. Five nitro-aromatic compounds (NACs) were identified by a chemical ionization mass spectrometer (C7H7O3N, C7H7O4N, C6H5O5N, C6H5O4N, and C6H5O3N), which contributed 0.03 ± 0.01 % to the total organic mass but can explain 0.3 ± 0.1 % of the total absorption of MS-BrC at 365 nm in winter. Furthermore, we identified 316 potential brown carbon molecules which accounted for 2.5 ± 0.6 % of the organic aerosol mass. Using an average mass absorption efficiency (MAE365) of 9.5 m2g−1 for these compounds, we can estimate their mean light absorption to be 1.2 ± 0.2 Mm−1, accounting for 32 ± 15 % of the total absorption of MS-BrC at 365 nm. This indicates that a small fraction of brown carbon molecules dominates the overall absorption. The potential BrC molecules assigned to the LO-HULIS component had a higher average molecular weight (265 ± 2 Da) and more nitrogen-containing molecules (62 ± 1 %) than the molecules assigned to the HO-HULIS components. Our analysis shows that the LO-HULIS, with a high contribution of nitrogen-containing molecules originating from biomass burning, dominates aerosol fluorescence in winter, and HO-HULIS, with fewer nitrogen-containing molecules as low-volatility oxygenated organic aerosol from regional transport and oxidation of biogenic volatile organic compounds (VOC), dominates in summer.

Two-Photon Fluorescence in Red and Violet Conjugated Polymer Microspheres

We investigate the two-photon fluorescence (TPF) of conjugated polymer (CP) microspheres with diameters up to tens of micrometers. Two polymers, emitting in either the violet or red, were first synthesized and characterized in terms of their one-photon fluorescence and three-dimensional internal microstructure. Under femtosecond infrared excitation, both types of microspheres showed a strong TPF, which was investigated by the excitation intensity dependence, emission spectroscopy, time-resolved luminescence, and photobleaching dynamics. While the violet-fluorescent microspheres performed similarly compared to dye-doped polystyrene counterparts emitting at a similar wavelength, the red-fluorescent microspheres showed a two-orders-of-magnitude stronger TPF. This excellent performance is attributed to enhanced hyperpolarizability associated with intermolecular interactions in the polymer solid, indicating a route toward designed CP microspheres that could outperform currently-available microparticles for sensing or imaging applications involving two-photon fluorescence.

Pretreatment of rice straw by newly isolated fungal consortium enhanced lignocellulose degradation and humification during composting

The slow decomposition rate of the reluctant structure of lignocellulose in agricultural waste is the great limitation of composting processes, which can be averted by pretreatment-strategies. This study focused on the impacts of pretreating rice straw using a consortium of newly isolated fungal species on lignocellulose degradation and humic substances during composting. Fungal pretreatment had a significant impact on lignocellulose degradation (84%) of rice straw by producing higher lignocellulytic enzymes than chemical pretreatments (79%) or the control (61%). The compost with fungal pretreated rice straw (FPT) showed significantly high composting temperature in the late mesophilic stage, which enhanced the degradation of lignocellulose. The fluorescence excitation emission spectroscopy revealed that significantly more humic acid-like compounds were formed in FPT. These findings suggest that fungal pretreatment is a feasible method to accelerate straw degradation and humification.

Effect of TOC Concentration of Humic Substances as an Electron Shuttle on Redox Functional Groups Stimulating Microbial Cr(VI) Reduction.

Humic substances as an electron shuttle play an essential role in the biogeochemistry processes. However, the influence of total organic carbon (TOC) concentrations of humic substances on microbial Cr(VI) reduction remains unclear. In this study, the rates and extents of Cr(VI) reduction by Shewanella oneidensis MR-1 in the presence of Leonardite humic acids (LHA) and Pahokee peat humic acids (PPHA) with different TOC concentrations were evaluated. We found that the enhanced reduction in Cr(VI) was associated with TOC concentrations of 2.5–50 mg C/L of HA samples. The result shows that HA as an electron shuttle impacted both rates and extents of microbial Cr (VI) reduction, which delivered differently in terms of low TOC concentration range of 2.5 to 15 mg C/L and high concentration range of 15–50 mg C/L. The rates of Cr(VI) reduction significantly enhanced in the low TOC concentration range of HA compared to a high concentration range. The highest acceleration rate of Cr(VI) reduction was achieved at 15 mg C/L of HA. The quinone-like fluorophore was responsible for the main redox-active functional groups of HA by the three-dimensional excitation-emission spectroscopy. The fluorescence intensity of quinone-like fluorophore of HA in the low TOC concentration range was positively correlated with its acceleration coefficient, corresponding to the highest microbial Cr(VI) reduction rate obtained in 15 mg C/L of HA. These findings highlighted the effect of the TOC concentration of HA on microbial Cr(VI) reduction processes. It emphasized that the low TOC concentration of HA contributed to the high rates of Cr(VI) reduction, which is critical for better understanding the fate of Cr(VI) and evaluating the effectiveness of Cr(VI) restoration strategies in the future.

Long-term grass mulching waste recycling and evaluation activation of dissolved organic carbon

This study aimed to clarify that long-term leguminous grass mulching (crown vetch (CV) and white clover (WC)) and gramineous grass (orchardgrass (OG)) drive the distribution of soil aggregates and are associated with dissolved organic matter (DOM) components. Excitation emission spectroscopy and parallel factor analysis (EEM-PARAFAC) were used to evaluate the influence of different grass mulches among aggregates. The results indicated that legumes had a more significant impact on the distribution of aggregates and DOM content than gramineae grass mulching. Leguminous grass mulching significantly increased the proportion of macroaggregates >250 μm (74.65%–83.50%) and aggregates associated with dissolved organic carbon (DOC), especially in microaggregates <250 μm (172.27 mg kg−1 to 391.55 mg kg−1). In addition, leguminous grass mulching (CV and WC) contributed more to the increase in soil total nitrogen (TN) and three identified fluorescent components (UVC humic-like, UVA humic-like and protein-like). The component of UVC humic-like relative abundance decreased (48.66%–36.57%), and the protein-like component increased (21.88%–36.50%) as the aggregate size decreased, but the DOM three compositions did not change. The DOM of macroaggregates had higher aromaticity and lower molecular weight than microaggregates, and the highest abundance of UVC humic-like component (54.52%) was found in the gramineous (OG) large macroaggregates, while the higher abundance of protein-like components (31.07%–36.50%) occurs in leguminous mulching (CV and WC) microaggregates. The results contribute to a further understanding of the dynamic process by which grass mulching mediates aggregate formation and DOM component transformation in semiarid apple orchards under grass waste management.

Characterisation of Organic Matter and Its Transformation Processes in On-Site Wastewater Effluent Percolating through Soil Using Fluorescence Spectroscopic Methods and Parallel Factor Analysis (PARAFAC)

This research has used fluorescence spectroscopy and parallel factor analysis (PARAFAC) in order to characterize dissolved organic matter in septic tank effluent, as it passes through the biomat/biozone, infiltrating into the unsaturated zone beneath domestic wastewater treatment systems (DWWTSs). Septic tank effluent and soil moisture samples from the percolation areas of two DWWTSs have been analyzed using fluorescence excitation–emission spectroscopy. Using PARAFAC analysis, a six-component model was obtained whereby individual model components could be assigned to humified organic matter, fluorescent whitening compounds (FWCs), and protein-like compounds. This has shown that fluorescent dissolved organic matter (FDOM) in domestic wastewater was dominated by protein-like compounds and FWCs and that, with treatment in the percolation area, protein-like compounds and FWCs are removed and contributions from terrestrially derived (soil) organic decomposition compounds increase, leading to a higher degree of humification and aromaticity. The results also suggest that the biomat is the most important element determining FDOM removal and consequently affecting DOM composition. Furthermore, no significant difference was found in the FDOM composition of samples from the percolation area irrespective of whether they received primary or secondary effluent. Overall, the tested fluorometric methods were shown to provide information about structural and functional properties of organic matter which can be useful for further studies concerning bacterial and/or virus transport from DWWTSs.

Distinguishing between coherent and incoherent signals in excitation-emission spectroscopy.

The separation of incoherent emission signals from coherent light scattering often poses a challenge in (time-resolved) microscopy or excitation-emission spectroscopy. While in spectro-microscopy with narrowband excitation this is commonly overcome using spectral filtering, it is less straightforward when using broadband Fourier-transform techniques that are now becoming commonplace in, e.g., single molecule or ultrafast nonlinear spectroscopy. Here we show that such a separation is readily achieved using highly stable common-path interferometers for both excitation and detection. The approach is demonstrated for suppression of scattering from flavin adenine dinucleotide (FAD) and weakly emissive cryptochrome 4 (Cry4) protein samples. We expect that the approach will be beneficial, e.g., for fluorescence lifetime or Raman-based imaging and spectroscopy of various samples, including single quantum emitters.

Site-selective characterisation of electron trapping centres in relation to chemistry, structural state and mineral phases present in single crystal alkali feldspars

Feldspars are ubiquitous natural dosimeters widely used in luminescence dating. Despite decades of research, the lattice defects as well as the mechanisms involved in luminescence production in feldspars remain poorly understood. The recently developed method of infrared photoluminescence (IRPL) excitation-emission spectroscopy has revealed the presence of two electron trapping centres emitting IRPL at 1.3 eV and 1.41 eV (IRPL1.3 and IRPL1.41 centres), and it enables detailed investigations into the ground and excited state energies of these centres. Here we make measurements of a range of single crystal alkali feldspars to understand the effects of feldspar chemical composition, crystal structure and framework disorder on the physical characteristics of IRPL1.3 and IRPL1.41 electron trapping centres. Measurements of our sample suite reveals IRPL and IR-radioluminescence (RL) emissions at 1.41 eV, 1.3 eV and, for the first time, at 1.2 eV. Our results show that whilst the IRPL1.3 trapping centre is unaffected by the M site cation occupancy, the presence of IRPL1.41 trapping centres seems to be linked to the presence of K+ ions on M sites. However, no clear trends in IRPL and IR-RL emission energies and signal intensities with chemical composition of the samples were found. Exploring the effect of framework disorder on IRPL1.3 and IRPL1.41 emissions revealed no significant changes to IRPL and IR-RL emission energies or ground state energies of the trapping centres, suggesting that the corresponding defects are not located on bridging O ions. Variations in ground state energies across the whole sample suite range from 2.04 eV to 2.20 eV for the IRPL1.3 centre and from 2.16 eV to 2.46 eV for the IRPL1.41 centre. Variations in trap depth seem to be driven by other factors than sample chemistry, degree of Al3+ disorder and number of phases present in a single crystal feldspar. Interestingly, the IR resonance peak is invariant between samples. Regarding the use of IRPL in luminescence dating, we show that optical resetting differs for the three different emissions, with the emission at ∼1.41 eV not being reset in some samples even after 18 h of solar bleaching.

Optical characteristics and luminescence of amorphous BaTiO3 thin films doped with Eu3+

Sol-gel spin coated BaTiO3:Eu3+ thin films on fused silica substrate were thermally annealed between 400°C and 800°C. The multilayer films were doped with Eu3+ which was limited to 10 mol % doping concentration. Standard physical and optical characterizations were performed in addition to excitation-emission and UVPL spectroscopy. The films were amorphous at temperatures below 600°C and exhibited stronger luminescence at 613.0 nm (5D0 → 7F2) than crystalline films. Optical energy band-gap ranged from 3.825 eV (crystalline) to 4.325 eV (amorphous) and the amorphous films’ CIE showed excellent red coordinates whilst red/orange (R/O) asymmetry ratio shows tailored emission color is possible.

Understanding the metastable states in K-Na aluminosilicates using novel site-selective excitation-emission spectroscopy

Optically stimulated luminescence (OSL) and thermoluminescence (TL) from the metastable states in solids are widely used in luminescent phosphors, dosimetry, geochronology, and thermo- and photo-chronometry. OSL and TL result from a combination of three different processes (charge detrapping, transport, and recombination) and are, therefore, not ideal for characterizing the charge trapping states. Therefore, despite many decades of research, the OSL and TL kinetics and the associated defect systems remain poorly understood in natural minerals. Recently, a radio-photoluminescence (RPL) signal has been discovered in feldspar (K-Na-Ca aluminosilicates occupying > 50% of Earth’s crust) which helps overcome this limitation. This site-selective signal termed infrared photoluminescence (IRPL) arises from radiative relaxation of the excited state of the main electron trapping center (principal trap).In this study, IRPL excitation and emission spectroscopy at cryogenic temperatures reveals two distinct electron-trapping centers (i.e. two principal traps) in feldspar, and helps to determine their trap depths and the excited-state energies. The two trapping centers show the same electron capture cross-sections and the excited-state relaxation lifetimes, but different ground- and excited-state energies. Based on this peculiar combination of trap characteristics, we conclude that that the principal traps consist of the same defect residing at two different crystal sites. The differences in the energy levels of the two principal traps explain their distinct optical and thermal bleaching behavior.

Seawater Fluorescence Near Oil Occurrence

Petroleum and its related products pose a serious pollution risk to the world’s seas and require a simple, rapid detection method. This is a difficult task if the pollution is under the water surface. One common approach to oil detection is excitation-emission spectroscopy (EEMs) of seawater exposed to oil for analyzing the fluorometric index (FIo/w) as a potential indicator of oil presence in the marine environment. In this paper, FIo/w was determined for both natural seawater and samples of the same water, but exposed to a relatively small portion of oil. The water samples were collected from the coastal and port waters of the Gdynia region (Southern Baltic Sea) from five stations, four times at two-week intervals. FIo/w indicates the changes between seawater sampled from the marine environment and the same seawater polluted with oil substances. Moreover, the obtained FIo/w values do not depend on the point and time of sampling. In all cases of seawater exposed to oil, significantly higher FIo/w values were observed than for unpolluted seawater. Moreover, the detection of oil by analyzing the value of FIo/w is efficient if the oil-to-water weight ratio is close to or above 5 × 10−6.

A Highly Stable Metal-Organic Framework-Engineered FeS2/C Nanocatalyst for Heterogeneous Electro-Fenton Treatment: Validation in Wastewater at Mild pH.

Herein, the novel application of FeS2/C nanocomposite as a highly active, stable, and recyclable catalyst for heterogeneous electro-Fenton (EF) treatment of organic water pollutants is discussed. The simultaneous carbonization and sulfidation of an iron-based metal-organic framework (MOF) yielded well-dispersed pyrite FeS2 nanoparticles of ∼100 nm diameter linked to porous carbon. XPS analysis revealed the presence of doping N atoms. EF treatment with an IrO2/air-diffusion cell ensured the complete removal of the antidepressant fluoxetine spiked into urban wastewater at near-neutral pH after 60 min at 50 mA with 0.4 g L-1 catalyst as optimum dose. The clear enhancement of catalytic activity and stability of the material as compared to natural pyrite was evidenced, as deduced from its characterization before and after use. The final solutions contained <1.5 mg L-1 dissolved iron and became progressively acidified. Fluorescence excitation-emission spectroscopy with parallel factor analysis demonstrated the large mineralization of all wastewater components at 6 h, which was accompanied by a substantial decrease of toxicity. A mechanism with •OH as the dominant oxidant was proposed: FeS2 core-shell nanoparticles served as Fe2+ shuttles for homogeneous Fenton's reaction and provided active sites for the heterogeneous Fenton process, whereas nanoporous carbon allowed minimizing the mass transport limitations.