Emission Spectra Research Articles

Circularly Polarized Luminescence from Pure and Eu-Doped Trigonal TbPO4·nH2O Nanocrystals.

In this contribution, we describe the preparation, by means of a precipitation reaction from aqueous solution at 40 °C, and the structural characterization of nanocrystalline powders of trigonal Tb1-xEuxPO4·nH2O (with x = 0, 0.005, 0.01, 0.05, and 0.1; n tentatively assigned as 0.67) which crystallize in the two possible P3121 or P3221 enantiomorphic space groups. While the volume of the crystal lattice is not significantly affected by the Tb3+/Eu3+ substitution, the average crystallite size seems to depend on the Eu3+ dopant concentration and ranges from 13 to 30 nm. The desired handedness of the crystals has been induced by using, during the synthesis, one of the two possible enantiomers of tartaric acid (l or d). The analysis of the luminescence excitation and emission spectra, together with the decay kinetics of the 5D4 Tb3+ excited state, suggests the presence of a very efficient Tb3+ → Eu3+ energy transfer process in the Eu3+-doped orthophosphates. Upon excitation of Tb3+ ions at 368 nm, the enantiomorphic powders grown with l- or d-tartaric acid (i.e., l-TbPO4·0.67H2O/d-TbPO4·0.67H2O, l-Tb0.995Eu0.005PO4·0.67H2O/d-Tb0.995Eu0.005PO4·0.67H2O, and l-Tb0.9Eu0.1PO4·0.67H2O/d-Tb0.9Eu0.1PO4·0.67H2O) exhibited mirror circularly polarized luminescence signals in the visible spectral region (in the green and/or in the red).

Optical Emission Spectra of Molecular Excitonic Polariton Computed at the First‐Principles Level QED‐TDDFT

Optical Emission Spectra of Molecular Excitonic Polariton Computed at the First‐Principles Level QED‐TDDFT

Kinetic study of the reaction of thiophene-tocopherols with peroxyl radicals enlightenings the role of O˙⋯S noncovalent interactions in H-atom transfer.

Three new α-tocopherol thiophene derivatives were efficiently synthesized, characterized and used for the first time as chain-breaking antioxidants for the inhibition of the autoxidation of reference oxidizable substrates. The rate constant of the reaction with alkylperoxyl (ROO˙) radicals and the stoichiometry of radical trapping (n) for the thiophene-tocopherol compounds were determined by measuring the oxygen consumption during the autoxidation of styrene or isopropylbenzene, using a differential pressure transducer. The measurement of the reaction with ROO˙ radicals in an apolar solvent at 30 °C showed inhibition rate constants (kinh) in the order of 104 M-1 s-1. To rationalise the kinetic results, the effect of the thiophene ring on the H-atom donation by O-H groups of the functionalized tocopherols was investigated by theoretical calculations. The importance of noncovalent interactions (including an unusual O˙⋯S bond) for the stability of the conformers has been shown, and the O-H bond dissociation enthalpy (BDE(OH)) of these derivatives was determined. Finally, the photophysical properties of these new compounds were investigated to understand if the addition of thiophene groups changes the absorption or emission spectra of the tocopherol skeleton for their possible application as luminescent molecular probes.

Formation mechanism of bright and dark concentric-ring pattern in dielectric barrier discharge

In this work, a bright and dark concentric-ring pattern is reported in a dielectric barrier discharge for the first time. The spatiotemporal dynamics of the bright and dark concentric-ring pattern are investigated with an intensified charge-coupled device and photomultiplier tubes. The results indicate that the bright and dark concentric-ring pattern is composed of three concentric-ring sublattices. These are bright concentric-ring structures, dark concentric-ring structures and wider concentric-ring structures, respectively. The bright concentric-ring structures and dark concentric-ring structures are alternately distributed. The bright concentric-ring structures are located at the centre of the wider concentric-ring structures. The wider concentric-ring structures first form from the outer edge and gradually develop to the centre. The essence of all three concentric-ring structures is the individual discharge filaments. The optical emission spectra of different sublattices are acquired and analysed. It is found that the plasma parameters of the three concentric-ring sublattices are different. Finally, the formation mechanism of the bright and dark concentric-ring pattern is discussed.

Investigating crater formation in nanosecond laser ablation of aluminum foils

A nanosecond Nd:YAG laser was used to study the laser ablation of aluminum foil in the phase explosion regime at a laser intensity range of 0.63–3.61 ×1012W/cm2. Laser ablation and plasma characteristics were studied using microscopic ablation crater images, plasma emission spectra, and plasma plume images. Measured plasma density using a Stark width of Al I (396.2 nm) showed a strong linear correlation with crater size, with a Pearson correlation coefficient (r) of 0.97. To understand the origin of this linear correlation, plasma temperature was estimated using Bremsstrahlung emission from 512 to 700 nm. The estimated plasma temperature and aspect ratio of the plasma plume were negatively correlated, having r=−0.76. This negative correlation resulted from a laser-plasma interaction, which heated the plasma and increased its hydrodynamic length. The percentages of laser energy used for plasma heating (Ep/EL) and Al foil ablation (EAl/EL) were estimated from plasma temperature. Increased EAl/EL, such as crater size, with increasing laser intensity, confirms that greater mass ablation is the fundamental reason for the strong linear correlation between crater size and plasma density.

Structural and Spectroscopic analysis of Reddish-Orange Emitting (Y1-x)2WO6:xEu3+ (0≤x≤0.11) Nanophosphors for Anti-Counterfeiting Application

Abstract Exploring luminescent materials that meet the necessary specifications for anti-counterfeiting applications has been the focus of extensive research. In this study, we delve into a double perovskite-structured material, (Y1-x)2WO6:xEu3+ (0≤x≤0.11), synthesized via a chemical combustion method. The crystallographic studies using the X-ray diffraction pattern confirm the crystallization of the nanophosphors into the monoclinic phase with a P2/c space group. The Raman and Fourier transform infrared spectroscopy studies provide insights into the nature of chemical bonding within the material. UV visible spectra are analysed to determine the optical energy gap. Notably, the photoluminescence emission spectra of the Eu3+ incorporated phosphors exhibit a distinct emission peak at 609nm, corresponding to the 5D0→7F2 electric dipole transition of the Eu3+ ions. The optimal photoluminescence intensity is observed for the x=0.07 nanophosphor, with estimated chroma coordinates of (0.500, 0.316), placing it in the reddish-orange region of the chromaticity diagram. The incorporation of Eu3+ enhances magnetization, attributed to the presence of Eu3+ ions in the 7F2 state. The luminance stability is a critical factor for long-term performance, the x=0.07 phosphor was analysed under rigorous physical and chemical testing and is found to be stable, making it a favourable candidate as a luminescence pigment for anti-counterfeiting applications.

Hot Carrier Temperature Dynamics in Semiconductor Nanostructures: Full Lineshape Modeling of Ultrafast Time-Resolved Emission Spectra

Hot Carrier Temperature Dynamics in Semiconductor Nanostructures: Full Lineshape Modeling of Ultrafast Time-Resolved Emission Spectra

Effects of specular reflectance in laser-induced breakdown of metals

We investigate the effects of specular reflection on the laser-induced breakdown (LIB) of copper, iron, and tungsten using fast photography and optical emission spectroscopy. The laser parameters include spot diameter ranging from 30.89 to 1589.33 μm, irradiance from 467.10 to 0.17 GW/cm2, with a single pulse of 6 ns duration and 21 mJ energy. As the laser spot defocuses, the plasma morphology changes from a single plasma near the target surface to a separated, independently evolving two-component plasma, and then to a single plasma suspended above. The defocusing distance for this transition is significantly influenced by specular reflectance. The separate plasma, comprising of a metallic component and an air component, occurs only under high specular reflectance conditions: ≥66.7% for copper, ≥51.4% for iron, and ≥44.9% for tungsten. The spectral emission of the metallic component initially increases and then decreases with reducing specular reflectance, due to a trade-off between enhanced surface absorption and reduced irradiance caused by surface roughening. LIB threshold irradiance increases with specular reflectance, rising from 0.31 to 1.22 GW/cm2 for copper, 0.24 to 0.70 GW/cm2 for iron, and 0.38 to 0.87 GW/cm2 for tungsten. These findings show the impact of sample pretreatment on LIB ignition and subsequent plasma evolution, offering insights into potential sources of inaccuracy in LIB applications.

Optical emission characterization of an atmospheric pressure dielectric barrier discharge in nitrogen: Evolution of CN emissions during PTFE etching

AbstractThe present work investigates the etching of coated polytetrafluoroethylene (PTFE) films using an atmospheric pressure dielectric barrier discharge operating in nitrogen in a filamentary regime. For different treatment durations, the optical emission spectra were recorded over time. Most of the emissions are attributed to the N2 second positive system. The presence of CN is also observed, and its emissions rise with the exposure time of PTFE. This rise is attributed to the density of CN produced. The X‐ray photoelectron spectroscopy surface characterization suggests two etching regimes. This is linked with a change in slope in the intensity evolution of the optical emissions of the CN. At longer times, a fluorinated deposit on the electrode is observed, confirming a different nature of the etched material.

Harnessing liquid crystal attributes of near-unit photoluminescent benzothioxanthene photosensitizers: Photophysical profiling in solution, solid state, and polymer matrix embedding

Liquid crystals (LCs) have garnered significant attention for their unique optical and electrical properties, making them promising candidates in various technological applications such as smart displays, sensors, telecommunications, biomedicals or wearable electronics. In this study, we explore the potential of several highly emissive benzothioxanthene imide (BTI) derivatives as LC materials with a focus on their robustness and temperature-stable emission behavior. By tailoring the molecular structure of BTIs, we have accomplished exceptional emissive properties while maintaining the inherent advantages of LCs, such as their self-organizing ability and responsive nature. We describe the formation of enantiotropic liquid crystals whose mesomorphic properties dependent on the nature, length, and position of the side chain. Moreover, we have investigated the thermal stability of their emission spectra over a wide range of temperature, highlighting their potential use in demanding conditions where precise optical performances are critical. Our findings underscore the importance of molecular design in achieving highly emissive LC materials with enhanced robustness and temperature stability, opening new avenues for the use of BTI derivatives.

Improving the Two-Color Temperature Sensing Using Machine Learning Approach: GdVO4:Sm3+ Prepared by Solution Combustion Synthesis (SCS)

The gadolinium vanadate doped with samarium (GdVO4:Sm3+) nanopowder was prepared by the solution combustion synthesis (SCS) method. After synthesis, in order to achieve full crystallinity, the material was annealed in air atmosphere at 900 °C. Phase identification in the post-annealed powder samples was performed by X-ray diffraction, and morphology was investigated by high-resolution scanning electron microscope (SEM) and transmission electron microscope (TEM). Photoluminescence characterization of emission spectrum and time resolved analysis was performed using tunable laser optical parametric oscillator excitation and streak camera. In addition to samarium emission bands, a weak broad luminescence emission band of host VO43− was also observed by the detection system. In our earlier work, we analyzed the possibility of using the host luminescence for two-color temperature sensing, improving the method by introducing the temporal dependence in line intensity ratio measurements. Here, we showed that further improvements are possible by using the machine learning approach. To facilitate the initial data assessment, we incorporated Principal Component Analysis (PCA), t-Distributed Stochastic Neighbor Embedding (t-SNE) and Uniform Manifold Approximation and Projection (UMAP) clustering of GdVO4:Sm3+ spectra at various temperatures. Good predictions of temperature were obtained using deep neural networks. Performance of the deep learning network was enhanced by data augmentation technique.

Joint regional uptake quantification of thorium-227 and radium-223 using a multiple-energy-window projection-domain quantitative SPECT method.

Thorium-227 (227Th)-based α-particle radiopharmaceutical therapies (α-RPTs) are currently being investigated in several clinical and pre-clinical studies. After administration, 227Th decays to 223Ra, another α-particle-emitting isotope, which redistributes within the patient. Reliable dose quantification of both 227Th and 223Ra is clinically important, and SPECT may perform this quantification as these isotopes also emit X- and γ-ray photons. However, reliable quantification is challenging for several reasons: the orders-of-magnitude lower activity compared to conventional SPECT, resulting in a very low number of detected counts, the presence of multiple photopeaks, substantial overlap in the emission spectra of these isotopes, and the image-degrading effects in SPECT. To address these issues, we propose a multiple-energy-window projection-domain quantification (MEW-PDQ) method that jointly estimates the regional activity uptake of both 227Th and 223Ra directly using the SPECT projection data from multiple energy windows. We evaluated the method with realistic simulation studies conducted with anthropomorphic digital phantoms, including a virtual imaging trial, in the context of imaging patients with bone metastases of prostate cancer who were treated with 227Th-based α-RPTs. The proposed method yielded reliable (accurate and precise) regional uptake estimates of both isotopes and outperformed state-of-the-art methods across different lesion sizes and contrasts, as well as in the virtual imaging trial. This reliable performance was also observed with moderate levels of intra-regional heterogeneous uptake as well as when there were moderate inaccuracies in the definitions of the support of various regions. Additionally, we demonstrated the effectiveness of using multiple energy windows and the variance of the estimated uptake using the proposed method approached the Cramér-Rao-lower-bound-defined theoretical limit. These results provide strong evidence in support of this method for reliable uptake quantification in 227Th-based α-RPTs.

The effect of bending angle on a flexible electrode DBD plasma under sinusoidal excitation

There is a critical demand for sophisticated surface disinfection and sterilization devices accessible to the public by using cold atmospheric pressure air plasmas. A flexible printed circuit design of a dielectric barrier discharge reactor under non-bending and two bending configurations with an angle of 120° and 180° was studied. The characteristics of power consumption, the optical emission spectrum, dynamic process, electrode temperature and ozone concentration are evaluated. The non-bending configuration produces more O3, as compared to the bending configuration at the same applied voltage. The 180° configuration has a maximum concentration of excited species at the expense of higher electrode temperature. Both bending configurations demonstrated the propagation of filaments to bending axis where the continues luminescence is observed due to the high electrical field. The energy efficiency for plasma-generated reactive species reaches to 40% for non-bending configuration and decreases with the increase of bending angle. This research provides a new strategy for perspective into the plasma generated reactive species in biomedical and environmental applications.

Towards machine learning-based quantitative hyperspectral image guidance for brain tumor resection

BackgroundComplete resection of malignant gliomas is hampered by the difficulty in distinguishing tumor cells at the infiltration zone. Fluorescence guidance with 5-ALA assists in reaching this goal. Using hyperspectral imaging, previous work characterized five fluorophores’ emission spectra in most human brain tumors.MethodsIn this paper, the effectiveness of these five spectra was explored for different tumor and tissue classification tasks in 184 patients (891 hyperspectral measurements) harboring low- (n = 30) and high-grade gliomas (n = 115), non-glial primary brain tumors (n = 19), radiation necrosis (n = 2), miscellaneous (n = 10) and metastases (n = 8). Four machine-learning models were trained to classify tumor type, grade, glioma margins, and IDH mutation.ResultsUsing random forests and multilayer perceptrons, the classifiers achieve average test accuracies of 84–87%, 96.1%, 86%, and 91% respectively. All five fluorophore abundances vary between tumor margin types and tumor grades (p < 0.01). For tissue type, at least four of the five fluorophore abundances are significantly different (p < 0.01) between all classes.ConclusionsThese results demonstrate the fluorophores’ differing abundances in different tissue classes and the value of the five fluorophores as potential optical biomarkers, opening new opportunities for intraoperative classification systems in fluorescence-guided neurosurgery.

Switching of photoinduced proton transfer from one six-membered hydrogen-bonded ring to other: a molecule of hydrazine and pH sensor.

The present study describes photophysical properties of 3-(benzo[d]oxazol-2-yl)-5-bromo-2-hydroxybenzaldehyde (HBOB) and (E)-2-(benzo[d]oxazol-2-yl)-4-bromo-6-(hydrazonomethyl)phenol (HBON) molecules with asymmetric two-way proton transfer sites. The purpose of this study is to know the direction of ESIPT out of the two-way proton transfer pathways in these molecules in both the solid and solution state. The steady state and time-resolved spectral behaviour of HBOB and HBON and a comparison of the spectral features with the two distinct control compounds 2-(benzo[d]oxazol-2-yl)-4-bromophenol (HBO) and (E)-4-bromo-2-(hydrazonomethyl)phenol (HBN) having single 6-membered hydrogen bonded network reveal that HBOB undergoes imine-amine photoisomerisation by proton transfer towards the oxazole side and HBON undergoes towards the hydrazone side with characteristic Stokes' shifted emission. Proton transfer forms with the red shifted emission of these molecules shows fast decay than the locally excited state. In the solid state, extremely high fluorescence intensity was observed, following a similar type of ESIPT pattern. Calculated ground (S0) and excited state (S1) energy barriers for the PT process obtained using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) corroborate the unidirectional excited state intramolecular proton transfer (ESIPT) process for HBOB and HBON, and the theoretical spectral features validate our experimental absorption and emission spectra well. Interestingly, the unique unidirectional ESIPT behaviour of HBOB was utilised to detect hydrazine both in solution and solid phases. On the other hand, HBON was found to be a good fluorescence pH sensor with a ratiometric color change from yellow to green in acidic and basic media.

Characterization of a Novel Pathogenic PLCG2 Variant Leading to APLAID Syndrome Responsive to a TNF inhibitor.

Autoinflammation and PLCγ2-associated antibody deficiency and immune dysregulation (APLAID) syndrome is an autoinflammatory disease caused by gain-of-function variants in PLCG2. This study investigates the pathogenic mechanism of a novel variant of PLCG2 in a patient with APLAID syndrome. Whole exome sequencing and Sanger sequencing were used to identify the pathogenic variant in the patient. Single-cell RNA sequencing, immunoblotting, luciferase assay, IP-one ELISA, calcium flux assay, quantitative PCR, and immunoprecipitation were used to define inflammatory signatures and evaluate the effects of the PLCG2 variant on protein functionality and immune signaling. We identified a novel de novo variant, PLCG2 p.D993Y, in a patient with colitis, pansinusitis, skin rash, edema, recurrent respiratory infections, B cell deficiencies, and hypogammaglobulinemia. The single-cell transcriptome revealed exacerbated inflammatory responses in the patient's PBMCs. Expression of the D993Y variant in HEK293T, COS-7, and PLCG2 knock-out THP-1 cell lines showed heightened PLCγ2 phosphorylation, elevated IP3 production and intracellular Ca2+ release, and activation of the MAPK, NFκB, and NFAT signaling pathways compared to control-transfected cells. In vitro experiments indicated that the D993Y variant altered amino acid properties, disrupting the interaction between the catalytic and auto-inhibitory domains of PLCγ2, resulting in PLCγ2 auto-activation. Our findings demonstrated that the PLCG2 D993Y variant is a gain-of-function mutation via impairing its auto-inhibition, activating multiple inflammatory signaling pathways, thus leading to APLAID syndrome. This study further broadens the molecular underpinnings and phenotypic spectrum of PLCγ2-related disorders.

Double perovskite quantum dots Cs2AgInCl6: Tb3+/Sm3+/Bi3+ for dual-mode fluorescence temperature sensing

In this research, double perovskite quantum dots Cs2AgInCl6: Tb3+/Sm3+/Bi3+ are synthesized employing a high-temperature thermal injection method. The temperature-dependent emission spectra and the fluorescence decay curves of samples show the quantum dots can be applied to dual-mode temperature sensing employing fluorescence intensity ratio technique (between 656 nm (Sm3+) and 549 nm (Tb3+)) and fluorescence lifetime thermometry (549 nm (Tb3+)), achieving maximal relative sensitivities of 3.24%/K (351 K) and 0.68%/K (373 K), respectively. This study offers valuable insights into the temperature sensing capabilities of these quantum dots, which shows that these quantum dots are promising high-sensitivity dual-mode temperature sensing materials.

Computational studies on a selection of phosphite esters as antioxidants for polymeric materials.

Phosphite esters, a class of organo-phosphorus compounds, are widely used as non-discolouring antioxidants in many polymeric products. Apart from normal radical scavenging, they prevent the splitting of hydroperoxides (ROOH), one of the initial products of autoxidation, from forming extremely reactive free radicals such as alkoxy (RO.) and hydroxy (.OH) radicals. The inherent molecular properties of antioxidants and the chemistry of their action are essential for researchers working in this field of science. Four organo-phosphorous compounds well-known for their antioxidant activity are selected here for theoretical analysis: Tri(m-methylphenyl) phosphite (m-TMPP), Tri(4-methyl-2,6-di-tert-butylphenyl) phosphite (TMdtBPP), Tri(allylphenyl) phosphite (TAPP) and Tri(mercaptobenzothiazoyl) thiophosphate (TMBTTP). The antioxidant activity exhibited by these compounds is theoretically verified, and the results are consistent with the available experimental data. Such theoretical predictions offer advantages in scientific research, particularly when researchers need to select certain molecules as antioxidants for experiments from a pool of molecular systems. The chemical computations presented in this report are done in Gaussian 16 program package. The procedure of density functional theory (DFT) with the model chemistry B3LYP/6-31G(d,p) is used to generate computational data. Global reactivity indices, thermochemical data, Fukui functions, molecular electrostatic potential and NMR spectra are computed for the chosen molecular systems from their optimized geometries.

Deciphering the Nd3+ environment and energy-transfer mechanisms in thermally stable novel calcium aluminate glasses: elucidation of broadband high-gain performance for laser applications

Rare-earth-doped barium calcium aluminate (BCA) glasses, having extended infrared (IR) transmission (6 μm), are attractive materials for near IR (NIR) photonic applications. Nd2O3-doped BCA glasses display broadband emission at 1.07 µm, but they are limited, with poor glass-forming ability (GFA) and low emission cross sections. In the present study, four different barium zinc calcium aluminate (BZCA) glasses are synthesized with varied ZnO concentrations (from 9.5 to 24.5 mol%) and doped with 0.5 mol% Nd2O3 to decipher the effect on GFA and spectroscopic properties. The addition of ZnO enhances the GFA, and the NdBZCA20 glass shows the maximum GFA. Ultraviolet (UV)–visible (Vis)–NIR absorption spectra reveal a decreasing trend in the nephelauxetic effect, while J–O parameters, emission, and gain properties lead to no significant alteration with increasing ZnO, and the structure–properties correlation is established accordingly. However, the emission cross sections for all ZnO concentrations are found ∼4.5 × 10−20 cm2 accompanied by broadband emission (Δλ eff ∼ 40 nm), which ensures the potentiality of these glasses for low-threshold high-gain laser applications as well as ultrashort pulse laser applications. Furthermore, a thorough analysis of 1.06 µm emission as a function of Nd concentration in the BZCA20 glass is reported here. The emission spectra and decay time indicate that 0.5 mol% is the optimized doping concentration. Inokuti–Hirayama and Burshtein equations are adopted to study the decay kinetics and energy-transfer mechanisms, which confirm that the energy-transfer process due to cross-relaxation is dominant up to 0.5 mol% concentration, whereas, beyond that concentration, excitation energy migration via the hopping mechanism supersedes.

Design of a three-frequency Rayleigh lidar for simultaneous temperature and wind measurements

This study proposes what we believe to be a novel high-spectral-resolution three-frequency Rayleigh lidar for simultaneously measuring middle atmosphere temperature and wind. The temperature and wind could be retrieved without assuming an external reference temperature, as typical for a traditional Rayleigh Doppler lidar. Adopting a similar idea used in sodium temperature/wind lidar, this system alternatively emits laser pulses at three frequencies. It receives the corresponding Rayleigh backscattered signals filtered by an iodine cell as a frequency discriminator. The three frequencies are optimized based on the spectral characteristics resulting from the convolution of the pulse laser lineshape convolved Rayleigh scattering signal with iodine molecular absorption spectrum. A two-dimensional calibration curve for temperature and wind ratio is then generated from the theoretical calculation of the final convoluted spectra and used to retrieve temperature and wind simultaneously. Simulated with the return signals collected by a current broadband Rayleigh lidar (30-inch telescope and 15 W output laser power), the temperature and wind uncertainties with resolutions of 1 km and 1 hr are estimated to be 0.4 K and 0.35 m/s, respectively, at 30 km and increase to 16.3 K and 8.1 m/s at 70 km.