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AbstractThe visible light absorption capabilities, along with its electrical characteristics, of a low-cost, plant-based, biopolymer, gum acacia, have been chemically modified by tailoring its defect concentrations via pH modification, where the acid solvent of fruit (peel) extracts of jamun was used to influence the chemical structure by reactive modification. Ultraviolet-visible and photoluminescence spectroscopy of the gum acacia biopolymer treated with the extracted anthocyanin from jamun peel showed a prominent, characteristic red shift in the visible spectrum range. Impedance spectroscopy analysis showed the occurrence of localized ionic conduction. The bulk conductivity of the modified specimens increased due to the profound release of conducting ions in the water-swollen network. The reactively modified biopolymer could be used in multiple fields of material science, specifically in energy device applications, viz., photovoltaics (PV), by utilizing its cost effectiveness and photolytic effectiveness. 2nd, as a polymer electrolyte and dye-sensitised solar cells (DSSCs) material by utilizing its capacity of gel formation. In our research described in this article, the underlying charge transfer mechanism for such responses was examined after crosslinking in the organic dyes extracted from the peel of jamun fruit with gum acacia. [ABSTRACT FROM AUTHOR]

This paper presents a novel technique for extracting the alveolar part of human breath. Gas exchange occurs between blood and inhaled air in the alveoli, which is helpful in medical diagnostics based on breath analysis. Consequently, the alveolar portion of the exhaled air contains specific concentrations of endogenous EVOC (exogenous volatile organic compound), which, among other factors, depend on the person's health condition. As this part of the breath enables the screening for diseases, accurate sample collection for testing is crucial. Inaccurate sampling can significantly alter the composition of the specimen, alter the concentration of EVOC (biomarkers) and adversely affect the diagnosis. Furthermore, the volume of alveolar air is minimal (usually <350 mL), especially in the case of people affected by respiratory system problems. For these reasons, precise sampling is a key factor in the effectiveness of medical diagnostic systems. A new technique ensuring high accuracy and repeatability is presented in the article. It is based on analyzing the changes in carbon dioxide concentration in human breath using a fast and compensated non-dispersive infrared (NDIR) sensor and the simple moving adjacent average (SMAA) algorithm. Research has shown that this method accurately identifies exhalation phases with an uncertainty as low as 20 ms. This provides around 350 ms of breath duration for carrying out additional stages of the diagnostic process using various types of analyzers. [ABSTRACT FROM AUTHOR]

Absorption spectra and cross-sections of Diisopropyl Methylphosphonate (DIMP) are measured in argon at temperatures of 600–1250 K in a shock tube using rapid scanning, broadband absorption spectroscopy. Measurements are obtained at approximately 2.3 kHz with each complete scan of the 925–1350 wavenumber band taking 90 microseconds. This technique enables spectra behind incident and reflected shocks to be obtained in a single test. In addition, multiple spectra are obtained behind the reflected shock during the test time. A significant reduction in absorption cross section with temperature is observed, and the spectra taken during the test time show no decomposition or significant changes, suggesting that vibrational equilibrium is achieved. [ABSTRACT FROM AUTHOR]

The interaction of Thorium(IV) with a group of non‐symmetric CF3‐diketones has been studied by means of electronic absorption spectroscopy in HCl aqueous solutions at I=0.5 M (NaCl) and T=298 K. Six heterocyclic dicarbonyl ligands (2‐thenoyl‐trifluoroacetone, 2‐furoyl‐trifluoroacetone, 2‐selenophen‐trifluoroacetone, 2‐tellurophen‐trifluoroacetone, phenyl‐trifluoroacetone, and 2‐naphthyl‐trifluoroacetone) demonstrate the chelation activity toward ThIV in the acidic pH range. Obtained values of the "true" stability constants lie in the range 6.2–6.8 logarithmic units, respectively. A significant (10–15 nm) bathochromic shift between the maximum absorption wavelength of lanthanide and actinide monocomplexes has been detected. Observed spectral shift increases with the atomic number of substituted chalcogen atoms in the heterocyclic ring of the corresponding ligand: 10 nm for furan, 11 nm for thiophen, 14 nm for selenophen, and 15 nm for tellurophene rings. The complexation with Thorium occurs in an acidic media, where studied ligands do not interact with transition and rare earth metals. Spectral and pH shifts make studied ligands useful reagents for the detection and analytical determination of Thorium in the mixture with other metals without prior separation. Quantum‐chemical simulations (DFT and TD‐DFT) demonstrate that the nine‐ and deco‐coordinated structures of ThoriumIV complexes reproduce experimental values within reasonable errors. [ABSTRACT FROM AUTHOR]

Photodynamic diagnosis and therapy (PDD and PDT) are emerging techniques for diagnosing and treating tumors and malignant diseases. Photoproducts of protoporphyrin IX (PpIX) used in PDD and PDT may be used in the diagnosis and treatment, making a detailed analysis of the photoproduct formation under various treatment and diagnosis conditions important. Spectroscopic and mass spectrometric analysis of photoproduct formation from PpIX dissolved in dimethyl sulfoxide were performed under commonly used irradiation conditions for PDD and PDT, i.e., wavelengths of 405 and 635 nm and fluence rates of 10 and 100 mW/cm2. Irradiation resulted in the formation of hydroxyaldehyde photoproduct (photoprotoporphyrin; Ppp) and formyl photoproduct (product II; Pp II) existing in different quantities with the irradiation wavelength and fluence rate. Ppp was dominant under 635 nm irradiation of PpIX, with a fluorescence peak at 673 nm and a protonated monoisotopic peak at m/z 595.3. PpIX irradiation with 405 nm yielded more Pp II, with a fluorescence peak at 654 nm. A higher photoproduct formation was observed at a low fluence rate for irradiation with 635 nm, while irradiation with 405 nm indicated a higher photoproduct formation at a higher fluence rate. The photoproduct formation with the irradiation conditions can be exploited for dosimetry estimation and may be used as an additional photosensitizer to improve the diagnostics and treatment efficacies of PDD and PDT. Differences in environmental conditions of the present study from that of a biological environment may result in a variation in the photoproduct formation rate and may limit their clinical utilization in PDD and PDT. Thus, further investigation of photoproduct formation rates in more complex biological environments, including in vivo, is necessary. However, the results obtained in this study will serve as a basis for understanding reaction processes in such biological environments. [ABSTRACT FROM AUTHOR]

The differentially pumped rare‐gas filter at the end of the VUV beamline of the Swiss Light Source has been adapted to house a windowless absorption cell for gases. Absorption spectra can be recorded from 7 eV to up to 21 eV photon energies routinely, as shown by a new water and nitrous oxide absorption spectrum. By and large, the spectra agree with previously published ones both in terms of resonance energies and absorption cross sections, but that of N2O exhibits a small shift in the band and tentative fine structures that have not yet been fully described. This setup will facilitate the measurement of absorption spectra in the VUV above the absorption edge of LiF and MgF2 windows. It will also allow us to carry out condensed‐phase measurements on thin liquid sheets and solid films. Further development options are discussed, including the recording of temperature‐dependent absorption spectra, a stationary gas cell for calibration measurements, and the improvement of the photon energy resolution. [ABSTRACT FROM AUTHOR]

The present manuscript reports the synthesis of undoped CeO2 and Ce1−xAgxO2 (x = 0.03, 0.05, and 0.07) nanoparticles using a microwave-assisted co-precipitation route to understand the Ag doping effect in CeO2 nanoparticles. The structural and optical properties of these nanoparticles were investigated using x-ray diffraction, UV–Vis–NIR, and PL spectroscopy. The XRD result confirmed the formation of cubic fluorite structures with undoped and Ag-doped CeO2 nanoparticles. The crystallite size of Ag-doped CeO2 nanoparticles was observed within the range of 26–47 nm. The absorption peak was observed using UV–Vis–NIR spectroscopy and obtained at below 400 nm, indicating a blue shift with the incorporation of Ag+ ions in the CeO2 nanolattice, and the causes are explained in terms of the BM effect and electronic transitions. The PL measurements were taken to determine the defects and excitation wavelength. The prepared samples depicted good luminescence properties with a high value color rendering index (CRI). The results demonstrated that Ag-doped CeO2 nanoparticles can be used for white light emission, since the structural and optical properties of semiconductors were enhanced upon doping with elements such as Ag. Therefore, these nanoparticles may act as promising candidates for various applications such as UV-absorption, photocatalysis, light-emitting diodes, luminescence, and optoelectronics. [ABSTRACT FROM AUTHOR]

Linear tomographic absorption spectroscopy (LTAS) is a non-destructive diagnostic technique widely employed for gas sensing. The inverse problem of LTAS represents a classic example of an ill-posed problem. Linear iterative algorithms are commonly employed to address such problems, yielding generally poor reconstruction results due to the incapability to incorporate suitable prior conditions within the reconstruction process. Data-driven deep neural networks (DNN) have shown the potential to yield superior reconstruction results; however, they demand a substantial amount of measurement data that is challenging to acquire. To surmount this limitation, we proposed an untrained neural network (UNN) to tackle the inverse problem of LTAS. In conjunction with an early-stopping method based on running variance, UNN achieves improved reconstruction accuracy without supplementary training data. Numerical studies are conducted to explore the optimal network architecture of UNN and to assess the reliability of the early-stopping method. A comparison between UNN and superiorized ART (SUP-ART) substantiates the exceptional performance of UNN. [ABSTRACT FROM AUTHOR]

The differentially pumped rare-gas filter at the end of the VUV beamline of the Swiss Light Source has been adapted to house a windowless absorption cell for gases. Absorption spectra can be recorded from 7 eV to up to 21 eV photon energies routinely, as shown by a new water and nitrous oxide absorption spectrum. By and large, the spectra agree with previously published ones both in terms of resonance energies and absorption cross sections, but that of N2O exhibits a small shift in the {\tilde{\bf D}} band and tentative fine structures that have not yet been fully described. This setup will facilitate the measurement of absorption spectra in the VUV above the absorption edge of LiF and MgF2 windows. It will also allow us to carry out condensed-phase measurements on thin liquid sheets and solid films. Further development options are discussed, including the recording of temperature-dependent absorption spectra, a stationary gas cell for calibration measurements, and the improvement of the photon energy resolution.

Abstract Background Medicinal plant-mediated combinational therapies have gained importance globally due to minimal side effects and enhanced treatment outcomes compared to single-drug modalities. We aimed to analyze the cytotoxic potential of each conventional treatment i.e., photodynamic therapy (PDT), chemotherapy (doxorubicin hydrochloride; Dox-HCl) with or without various concentrations of medicinal plant extracts (PE) on soft tissue cancer Rhabdomyosarcoma (RD) cell line. Methods The Rhabdomyosarcoma (RD) cell line was cultured and treated with Photosensitizer (Photosense (AlPc4)), Chemo (Dox-HCl), and their combinations with different concentrations of each plant extract i.e., Thuja occidentalis, Moringa oleifera, Solanum surattense. For the source of illumination, a Diode laser (λ = 630 nm ± 1 nm, Pmax = 1.5 mW) was used. Photosensitizer uptake time (∼ 45 min) was optimized through spectrophotometric measurements (absorption spectroscopy). Drug response of each treatment arm was assessed post 24 h of administration using 3-(4, 5-dimethyl-2-thiazolyl)-2, 5- 5-diphenyl-2 H- tetrazolium bromide (MTT) assay. Results PE-mediated Chemo-Photodynamic therapy (PDT) exhibited synergistic effects (CI

The photodecomposition behavior of cationic porphyrin ZnTMAP4+ (zinc tetrakis-(N,N,N-trimethylanilinium-4-yl) porphyrin) in water and complexed with clay nanosheets was investigated by light irradiation to the Soret band of ZnTMAP4+. The decomposition of ZnTMAP4+ was observed by UV–visible absorption spectroscopy. While the decomposition quantum yield (ϕdec) was 3.4 × 10−4 in water, that was 9.4 × 10−7 on the exfoliated clay nanosheets. It was revealed that the photostability of ZnTMAP4+ was stabilized by the complex formation with clay. When ZnTMAP4+ was intercalated between the stacked clay nanosheets, ϕdec was further decreased to 4.9 × 10−7. The photostability increased by 361 times and 693 times for the exfoliated and stacked state, respectively. These results indicate that the flat clay surface has the potential to control intra- and intermolecular photochemical reactions. [ABSTRACT FROM AUTHOR]

Here, the optical properties of the Nafion polymer membrane containing colloidal CdSe/CdS/ZnS nanocrystals embedded by diffusion have been studied. The CdSe/CdS/ZnS nanocrystals have a core/shell/shell appearance. All experiments were carried out at room temperature (22 ± 2) °C. A toluene solution was used to provide mobility to the active sulfone groups of the Nafion membrane and to embed the nanocrystals inside the membrane. The diffusion process of colloidal CdSe/CdS/ZnS nanocrystals into Nafion proton exchange membrane has resulted in a new molecular complex "Nafion–colloidal CdSe/CdS/ZnS nanocrystals". The kinetics of the nanocrystals embedding into the membrane matrix was investigated using luminescence analysis and absorption spectroscopy techniques. The embedding rate of CdSe/CdS/ZnS nanocrystals into the Nafion polymer membrane was approximately 4·10−3 min−1. The presence of new luminescence centers in the membrane was proved independently by laser emission spectroscopy. The luminescence spectrum of the resulting molecular complex contains intensity maxima at wavelengths of 538, 588, 643 and 700 nm. The additional luminescence maximum observed at the 643 nm wavelength was not recorded in the original membrane, solvent or in the spectrum of the semiconductor nanoparticles. The luminescence maximum of the colloidal CdSe/CdS/ZnS nanocrystals was registered at a wavelength of 634 nm. The intensity of the luminescence spectrum of the membrane with embedded nanocrystals was found to be higher than the intensity of the secondary emission peak of the initial nanocrystals, which is important for the practical use of the "Nafion–colloidal nanocrystals" complex in optical systems. The lines contained in the luminescence spectrum of the membrane, which has been in solution with colloidal nanocrystals for a long time, registered upon its drying, show the kinetics of the formation of the molecular complex "Nafion membrane–nanocrystals". Colloidal nanocrystals located in the Nafion matrix represent an analog of a luminescent transducer. [ABSTRACT FROM AUTHOR]

Background: Medicinal plant-mediated combinational therapies have gained importance globally due to minimal side effects and enhanced treatment outcomes compared to single-drug modalities. We aimed to analyze the cytotoxic potential of each conventional treatment i.e., photodynamic therapy (PDT), chemotherapy (doxorubicin hydrochloride; Dox-HCl) with or without various concentrations of medicinal plant extracts (PE) on soft tissue cancer Rhabdomyosarcoma (RD) cell line. Methods: The Rhabdomyosarcoma (RD) cell line was cultured and treated with Photosensitizer (Photosense (AlPc4)), Chemo (Dox-HCl), and their combinations with different concentrations of each plant extract i.e., Thuja occidentalis, Moringa oleifera, Solanum surattense. For the source of illumination, a Diode laser (λ = 630 nm ± 1 nm, Pmax = 1.5 mW) was used. Photosensitizer uptake time (∼ 45 min) was optimized through spectrophotometric measurements (absorption spectroscopy). Drug response of each treatment arm was assessed post 24 h of administration using 3-(4, 5-dimethyl-2-thiazolyl)-2, 5- 5-diphenyl-2 H- tetrazolium bromide (MTT) assay. Results: PE-mediated Chemo-Photodynamic therapy (PDT) exhibited synergistic effects (CI < 1). Moreover, Rhabdomyosarcoma culture pretreated with various plant extracts for 24 h exhibited significant inhibition of cell viability however most effective outcomes were shown by low and high doses of Moringa oleifera compared to other plant extracts. Post low doses treated culture with all plant extracts followed by PDT came up with more effectiveness when compared to all di-therapy treatments. Conclusion: The general outcome of this work shows that the ethanolic plant extracts (higher doses) promote the death of cancerous cells in a dose-dependent way and combining Dox-HCl and photo-mediated photodynamic therapy can yield better therapeutic outcomes. [ABSTRACT FROM AUTHOR]

Anthraquinones constitute an important class of compounds with wide applications. The solubility of derivatives at 298.15 K was discussed in ethanol–water solution and at atmospheric pressure, the solubility of 1-amino-4-hydroxy-9,10-anthraquinone (AHAQ) in binary solvents (ethanol–water combinations) was determined. Colour strength and fastening properties depend upon the kind and position of a hydrophobic group connected to the phenoxy ring of Anthraquinone moiety. There is a continuing interest in the creation of novel anthraquinone derivatives with biological activities since they have demonstrated potential for treating multiple sclerosis. For this purpose, by utilizing voltammetric and absorption studies, interactions of various derivatives with calf thymus DNA (ct-DNA) and the cationic surfactant cetyltrimethylammoniumbromide (CTAB) were examined. Here prominent Hydrophobic interaction and electron transfer resulting in binding to CTAB micelles were observed. The polarity index of the media was assessed and associated with the electrochemical parameters. The medicinal behaviour of Anthraquinone derivatives was a result of electron transfer reactions with DNA. UV–Visible and fluorescence properties were due to the transitions between n* and π* orbitals. Large absorption band with low dichroic ratio was characteristic of various derivatives of Anthraquinone. Presence of –NH group proves various derivatives remarkable calorimetric and anionic sensors. [ABSTRACT FROM AUTHOR]

The epidermal growth factor receptor (EGFR) is a pivotal target in cancer therapy due to its significance within the tyrosine kinase family. EGFR inhibitors like AG-1478 and PD153035, featuring a 4-anilinoquinazoline moiety, have garnered global attention for their potent therapeutic activities. While pre-clinical studies have highlighted the significant impact of halogen substitution at the C3'-anilino position on drug potency, the underlying mechanism remains unclear. This study investigates the influence of halogen substitution (X = H, F, Cl, Br, I) on the structure, properties, and spectroscopy of halogen-substituted 4-anilinoquinazoline tyrosine kinase inhibitors (TKIs) using time-dependent density functional methods (TD-DFT) with the B3LYP functional. Our calculations revealed that halogen substitution did not induce significant changes in the three-dimensional conformation of the TKIs but led to noticeable alterations in electronic properties, such as dipole moment and spatial extent, impacting interactions at the EGFR binding site. The UV–visible spectra show that more potent TKI-X compounds typically have shorter wavelengths, with bromine's peak wavelength at 326.71 nm and hydrogen, with the lowest IC50 nM, shifting its lambda max to 333.17 nm, indicating a correlation between potency and spectral characteristics. Further analysis of the four lowest-lying conformers of each TKI-X, along with their crystal structures from the EGFR database, confirms that the most potent conformer is often not the global minimum structure but one of the low-lying conformers. The more potent TKI-Cl and TKI-Br exhibit larger deviations (RMSD > 0.65 Å) from their global minimum structures compared to other TKI-X (RMSD < 0.15 Å), indicating that potency is associated with greater flexibility. Dipole moments of TKI-X correlate with drug potency (ln(IC50 nM)), with TKI-Cl and TKI-Br showing significantly higher dipole moments (>8.0 Debye) in both their global minimum and crystal structures. Additionally, optical spectral shifts correlate with potency, as TKI-Cl and TKI-Br exhibit blue shifts from their global minimum structures, in contrast to other TKI-X. This suggests that optical reporting can effectively probe drug potency and conformation changes. [ABSTRACT FROM AUTHOR]

Fabry–Perot interferometers (FPIs), comprising foundry-compatible dielectric thin films on sapphire wafer substrates, were investigated for possible use in chemical sensing. Specifically, structures comprising two vertically stacked distributed Bragg reflectors (DBRs), with the lower DBR between a sapphire substrate and a silicon-oxide (SiO2) resonator layer and the other DBR on top of this resonator layer, were investigated for operation in the near-ultraviolet (near-UV) range. The DBRs are composed of a stack of nitride-rich silicon-nitride (SiNx) layers for the higher index and SiO2 layers for the lower index. An exemplary application would be formaldehyde detection at sub-ppm concentrations in air, using UV absorption spectroscopy in the 300–360 nm band, while providing spectral selectivity against the main interfering gases, notably NO2 and O3. Although SiNx thin films are conventionally used only for visible and near-infrared optical wavelengths (above 450 nm) because of high absorbance at lower wavelengths, this work shows that nitride-rich SiNx is suitable for near-UV wavelengths. The interplay between spectral absorbance, transmittance and reflectance in a FPI is presented in a comparative study between one FPI design using stoichiometric material (Si3N4) and two designs based on N-rich compositions, SiN1.39 and SiN1.49. Spectral measurements confirm that if the design accounts for phase penetration depth, sufficient performance can be achieved with the SiN1.49-based FPI design for gas absorption spectroscopy in near-UV, with peak transmission at 330 nm of 64%, a free spectral range (FSR) of 20 nm and a full-width half-magnitude spectral resolution (FWHM) of 2 nm. [ABSTRACT FROM AUTHOR]

Whispering gallery mode resonator sensors are nondisruptive optical sensors that can detect and monitor perturbations in a gaseous environment. Through its resonant properties of peak wavelength, amplitude, and quality factor (Q factor), changes in concentration can be quantified within seconds and monitored over days with great stability. In addition, the small footprint, low cost, and high sensitivity are ideal properties for a disposable sensor that can be utilized in extreme environments. The large Q factor of the resonant cavity enables long interaction lengths and amplifies the effect of small changes in the background refractive index, which is detectable in picometer shifts of the resonance wavelength. However, this measurement is susceptible to changes in other environmental factors such as temperature, pressure, and humidity, which manifest on the picometer wavelength scale, reinforcing the need to decouple the variables. In this work, we compare the spectral response of different diameter resonators to carbon dioxide, nitrogen, and its mixtures, observing the spectral shifting and broadening of the cavity resonance near 1550 nm. In addition, the effect of environmental temperature on spectral shifting due to the thermo-optic effect is characterized and quantified. Lastly, the gas concentrations are changed in real time to showcase the tracking and recovery capabilities of the resonator sensor. [ABSTRACT FROM AUTHOR]

Synchrotron x-ray diffraction (SR-XRD) and X-ray absorption fine structure spectroscopy (XAFS) were used to investigate the crystal and electronic properties of boron-substituted CuFeO2 material at room temperature. Without boron substitution, the polycrystalline structures of the trigonal (rhombohedral) ' $R\bar{3}m$ R 3 ¯ m ' CuFeO2 (87.7%) and hexagonal 'P63/mmc' (12.3%), which were also present in each sample but in different proportions, were utilised to identify the base material. XRD patterns revealed that, beyond 10% boron substitution, the metal–oxygen bonds (Fe-O and Cu-O) weakened, resulting in the formation of new tetragonal 'I41/amd' CuFe2O4 crystals. Although the CuFeO2 structure was preserved, it is conceivable that the presence of other crystal structures could lead to the formation of new features. This state arose as a result of CuFe2O4 crystallization and the impact of boron activity on the surrounding oxygen structures. By measuring magnetisation at both swept temperatures (10–300 K) and applied magnetic fields (±30 kOe), the magnetic properties of the samples were investigated. In the 10–300 K temperature range, the polycrystalline samples exhibit a ferromagnetic property without a magnetic phase transition. This suggests that replacing B with Fe in CuFe1−xBxO2 does not influence the primary magnetic property of CuFeO2. The samples' saturation magnetisation (Ms) values gradually fall as the B substitution content increases with Fe. This is because there's a chance that the non-transition metal B in CuFe1−xBxO2 will boost antiferromagnetic superexchange Cu-O interactions while lowering the p-d exchange interaction. [ABSTRACT FROM AUTHOR]

In absorption spectroscopy, it is challenging to detect absorption peaks with significant differences in their intensity in a single measurement. We enable high-dynamic-range measurements by dispersing scatterers within a sample to create a broad distribution of path lengths (PLs). The sample is placed within an integrating sphere (IS) to capture all scattered light of various PLs. To address the complexities of PLs inside the IS and the sample, we performed a ray-tracing simulation using the Monte Carlo (MC) method, which estimates the measured absorbance A and PL distribution from the sample's absorption coefficient µa and scattering properties at each wavelength λ. This method was validated using dye solutions with two absorption peaks whose intensity ratio is 95:1, employing polystyrene microspheres (PSs) as scatterers. The results confirmed that both peak shapes were delineated in a single measurement without flattening the high absorption peak. Although the measured peak shapes A(λ) did not align with the actual peak shapes µa(λ), MC enabled the reproduction of µa(λ) from A(λ). Furthermore, the analysis of the PL distribution by MC shows that adding scatterers broadens the distribution and shifts it toward shorter PLs as absorption increases, effectively adjusting it to µa. [ABSTRACT FROM AUTHOR]

Oxidative coupling of methane (OCM) is a promising process of direct transformation of CH4 to ethylene instead of a complicated two-step process in terms of first forming syngas through reforming or partial oxidation and then producing ethylene with Fischer–Tropsch synthesis (FTS). Na2WO4 has been one of the most studied catalysts of OCM. Here we investigated how the introduced transition metal elements Co, Mn, or Mo to Na2WO4 could influence the catalytic performance of OCM on the supported Na2WO4. It is found that Co, Mn and Mo can obviously promote catalytic activity of transforming CH4 and selectivity for producing ethylene and ethane in OCM performed on Na2WO4 supported on microporous silicate-1 (S-1). A similar promotion of Co, Mn and Mo to the catalytic activity and selectivity in OCM performed on Na2WO4 was found when the Na2WO4 was supported on Matériaux de l′Institut Lavoisier-53(Al) [MIL-53(Al)]. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy studies of these catalysts with added transition metal Co, Mn or Mo show that these metals diffused into the lattice of Na2WO4, further suggesting that the promotional effect likely arises from modification of the active phase of the supported Na2WO4 during OCM. [ABSTRACT FROM AUTHOR]

The homoleptic cationic complex formed by reacting suitable manganese(II) salts with 2,2′-bipyridine-1,1′-dioxide (bipyO2) has been subjected to several studies in the past because of its peculiar absorption and electrochemical features. Here, the first single-crystal X-ray structure determination of a [Mn(bipyO2)3]2+ salt is reported, where the charge of the cation is balanced by perchlorate anions. The hydrated salt [Mn(bipyO2)3](ClO4)2 crystallizes in the monoclinic system (P21/n space group) and the asymmetric unit contains three cationic complexes and six perchlorate anions. The environment of the manganese(II) ions is best described as octahedral, with scarce variations among the three cations in the asymmetric unit. The bipyO2 ligands exhibit κ2 coordination mode, forming seven-membered metallacycles. The X-ray outcomes have been used as the starting point for DFT and TDDFT calculations, aimed to elucidate the charge transfer origin of the noticeable absorption in the visible range. The MLCT nature is confirmed by the hole and electron distributions associated with the spin-allowed transitions. DFT calculations on the related manganese(III) complex indicate that the geometry of [Mn(bipyO2)3]2+ changes only slightly upon oxidation, in agreement with the reversible electrochemical behaviour experimentally observed. [ABSTRACT FROM AUTHOR]

The intrinsic and extrinsic defects in LiNbO3 (LN) bulk crystals have been investigated with experimental and theoretical methods for many years. However, nowadays, scientific attention has turned to nanocrystals (e.g., for quantum nanophotonic applications). Herein, the results of spectroscopic measurements and theoretical calculations on Yb3+‐ or Er3+‐doped LN nanocrystals are presented. A series of congruent LN nanocrystals doped with Er3+ or Yb3+ have been produced by grinding process under wet conditions in a high‐energy ball mill. The effect of size reduction on the rare‐earth (RE) ions has been followed by absorption measurement of the characteristic electronic transitions using a Fourier‐transform infrared spectrometer. Out‐diffusion of the RE ions from the nano‐LN particle and the appearance of an unordered phase have been concluded from the experimental results. GULP software has been used to make force‐field calculations on a Li245Nb245O735 unit to model the nano‐LN structure containing Er3+ or Yb3+ dopants. From the calculations taking into account, one Er3+ or Yb3+ ion, their out‐diffusion, and the appearance of the ions in the unordered phase have been demonstrated, while in the double‐doped case, independent RE incorporation has been found. [ABSTRACT FROM AUTHOR]

The ammonia spectrum is revisited in the important 1.6 µm atmospheric transparency window between 5650 and 6350 cm $ ^{-1} $ − 1 on the basis of recently recorded high-resolution Fourier transform spectra. These spectra offer an improved frequency sampling and better traceability of the measurement conditions compared to previously studied Kitt Peak spectra (Cacciani et al. J. Quant Spectrosc Radiat Transf 2021; 258:107334. https://doi.org/10.1016/j.jqsrt.2020.107334). Overall, 4812 $ ^{14} $ 14 NH $ _3 $ 3 lines were measured in the 5650–6350 cm $ ^{-1} $ − 1 region corresponding to 4866 transitions including 2066 new ones compared with our previous study, included in the HITRAN2020 database. The energy of 1023 upper state levels (including 107 new ones) was derived from 2608 assigned transitions. Independently, ammonia spectra recorded in a supersonic jet expansion using a tunable extended cavity diode laser allow us to check the absolute transition energies in the 5980–6080 cm $ ^{-1} $ − 1 range. Accurate jet spectra calibration was achieved using CH $ _4 $ 4 reference line positions known with kHz accuracy. The position agreement with the FTS data is within the $ 4\times 10^{-4} $ 4 × 10 − 4 cm $ ^{-1} $ − 1 uncertainty of the positions measured in the jet expansion. A recommended line list of 5620 transitions is provided for $ ^{14} $ 14 NH $ _3 $ 3 in the considered 5650–6350 cm $ ^{-1} $ − 1 region. [ABSTRACT FROM AUTHOR]

The ammonia spectrum is revisited in the important 1.6 µm atmospheric transparency window between 5650 and 6350 cm $ ^{-1} $ − 1 on the basis of recently recorded high-resolution Fourier transform spectra. These spectra offer an improved frequency sampling and better traceability of the measurement conditions compared to previously studied Kitt Peak spectra (Cacciani et al. J. Quant Spectrosc Radiat Transf 2021; 258:107334. https://doi.org/10.1016/j.jqsrt.2020.107334). Overall, 4812 $ ^{14} $ 14 NH $ _3 $ 3 lines were measured in the 5650–6350 cm $ ^{-1} $ − 1 region corresponding to 4866 transitions including 2066 new ones compared with our previous study, included in the HITRAN2020 database. The energy of 1023 upper state levels (including 107 new ones) was derived from 2608 assigned transitions. Independently, ammonia spectra recorded in a supersonic jet expansion using a tunable extended cavity diode laser allow us to check the absolute transition energies in the 5980–6080 cm $ ^{-1} $ − 1 range. Accurate jet spectra calibration was achieved using CH $ _4 $ 4 reference line positions known with kHz accuracy. The position agreement with the FTS data is within the $ 4\times 10^{-4} $ 4 × 10 − 4 cm $ ^{-1} $ − 1 uncertainty of the positions measured in the jet expansion. A recommended line list of 5620 transitions is provided for $ ^{14} $ 14 NH $ _3 $ 3 in the considered 5650–6350 cm $ ^{-1} $ − 1 region. [ABSTRACT FROM AUTHOR]

Optical spectroscopy is a powerful tool for characterizing the properties of two-dimensional (2D) heterostructures. However, extracting the permittivity information of each 2D layer in optically thick heterostructures is challenging because of interference. To accurately measure the optical permittivity of each 2D layer in a heterostructure or on a substrate with a thick insulating spacer, such as oxides, we propose deterministic reflection contrast ellipsometry (DRCE). Our DRCE method has two advantages over conventional techniques. It deterministically measures the optical permittivity of 2D materials using only the measured reflection spectra of the heterostructure, rather than dispersion fitting as in spectroscopic ellipsometry. Additionally, the DRCE is free of excitonic energy errors in reflection-contrast spectroscopy. We believe that DRCE will enable accurate and rapid characterization of 2D materials. [ABSTRACT FROM AUTHOR]

The 1,4‐dithiin motif is known for its reversible redox properties to generate radical cations and diradical dications and thus is interesting for organic electronic applications. However, examples where this motif is embedded into chiral larger fused aromatic compounds are very rare. Here we describe the syntheses of several structurally related pyrene fused dithiins and their spectroscopic investigations with a focus on tuning circular dichroism, with respect to the g values, depending on their connectivity. [ABSTRACT FROM AUTHOR]

Nanosphere lithography, a low‐cost fabrication technique, depends on the self‐assembly of nanoscale features to create nanostructures in a hexagonally close‐packed structure. In this article, the fabrication of 3D nanostructures over a large surface‐area with anisotropy along the growth direction through the combination of chemical and physical plasma etching is reported. The anisotropy stems from etching the nanosphere mask and the substrate at different rates. Due to the dynamic masking effect, a systematic variation of etching time gives rise to intriguing nanostructures with sharp edges that have strong potential for plasmonic applications, with the possibility of manipulating electromagnetic radiation. The structures obtained include nanocylinders, truncated hexagon‐based pyramids, circular pads on a conical base, and nanocones from a single‐layer nanosphere mask. Simulations of the fabrication process offer further insight into the understanding of nanostructure formation. A good agreement between predicted results and experiments confirms the potential of our numerical design. In addition, the optical properties of the nanostructures are investigated by UV–vis and the experimental findings are consistent with simulations based on a finite‐difference time‐domain method. The nanostructures described in this study contribute to the emerging 3D plasmonics and 3D magnonics, with strong potential for a significant impact on biosensor applications. [ABSTRACT FROM AUTHOR]

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Copper nanoparticles (CuNPs) have drawn considerable interest because of recent evidences on greater Surface Enhanced Raman Spectroscopic (SERS) signal enhancing capability, high antibacterial activity and strong catalytic property with regard to the long existing popular silver and gold particles. The existing chemical synthesis methods usually require extensive purification to remove unreacted inorganic reducing agents, like sodium borohydride used to convert Cu2+ ions to Cu0 and it limits direct use of as-prepared materials in biologic systems. Here, we have endeavored to synthesize starch encapsulated CuNPs through radiation chemical approach which is considered to be one of the cleanest routes and involve in-situ generated hydrated electrons to reduce metal ions directly. Presence of large number of hydroxyl groups within starch molecules facilitates complexation of Cu(II) and thereby stabilizes CuNPs. Transmission electron microscopy (TEM) coupled with selected area electron diffraction (SAED) illustrate that particles synthesized at a typical dose of 83.6 kGy are spherical with size of ca. 8 nm having polycrystalline face-centered cubic phase. The observed blue shift of the absorption maximum suggests formation of smaller sized particles with increase in applied radiation dose keeping other parameters same and this is supported by dynamic light scattering (DLS) data. Further, catalytic efficiency of as-synthesized CuNPs was tested by monitoring sodium borohydride mediated catalytic reduction of para-nitrophenol to para-aminophenol and the apparent rate constant (kapp) was estimated as 3 × 10–3 s−1. Thus, as-synthesized CuNPs appears to be better catalyst than the copper nanoparticles synthesized through conventional method for having kapp of about 1.6 × 10–3 s−1. [ABSTRACT FROM AUTHOR]

Hybrid organic–inorganic metal halide perovskites are emerging materials in photovoltaics, whose bandgap is one of the most crucial parameters governing their light‐harvesting performance. This work presents the temperature and photocarrier density dependence of the bandgap in two phase‐stabilized perovskite thin films (MA0.3FA0.7PbI3 and MA0.3FA0.7Pb0.5Sn0.5I3) using photoluminescence and absorption spectroscopy. Contrasting bandgap shifts with temperature are observed between the two perovskites. Using X‐ray diffraction and in situ high‐pressure photoluminescence spectroscopy, it is shown that thermal expansion plays only a minor role in the large bandgap blueshift, which is attributed to the enhanced structural stability of the samples. The first‐principles calculations further demonstrate the significant impact of thermally induced lattice distortions on the bandgap widening. It is proposed that the anomalous trends are caused by the competition between static and dynamic distortions. Additionally, both the bandgap renormalization and band‐filling effects are directly observed for the first time in fluence‐dependent photoluminescence measurements and are employed to estimate the exciton effective mass. The results provide new insights into the basic understanding of thermal and charge‐accumulation effects on the band structure of hybrid perovskite thin films. [ABSTRACT FROM AUTHOR]

Copyright of Romanian Journal of Materials / Revista Romana de Materiale is the property of Foundation for Materials Science & Engineering Serban Solacolu and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Exsolution is one of the most successful functionalization techniques to improve the catalytic activity of electrodes in solid oxide fuel and electrolyzer cells (SOFC/SOEC). The objective of this technique is to produce the highest possible number of metallic nanoparticles on the surface of a host-oxide, without significantly altering its structure. In this work, we compare three similar SOFC electrodes: STF (SrTi 0.3 Fe 0.7 O 3), STFN (Sr 0.93 Ti 0.3 Fe 0.63 Ni 0.07 O 3), and STFNC (Sr 0.93 Ti 0.3 Fe 0.56 Ni 0.07 Co 0.07 O 3), revealing that there is a significant difference between Ni–Fe/Ni–Co–Fe nanoparticle formation in STFN/STFNC and pure Fe0 particle formation in STF, which is evidenced by the size and amount of produced nanoparticles, but also by their anchoring to the host-oxide. The terms exsolution and particle segregation will be used, respectively, to distinguish these phenomena. Next, we explore two different reduction methods and observe that the characteristics of exsolution do not only depend on temperature, atmosphere and reduction times, but also on the reduction path taken to reach such conditions. [Display omitted] • Exsolution differs from particle segregation in the NP distribution, density, size and anchorage. • The characteristics of exsolved NPs are influenced by the hydrogen reduction path. • In-situ absorption spectroscopy is used to determine the exsolution temperature threshold. [ABSTRACT FROM AUTHOR]

Background: Radiochromic material such as lithium pentacosa‐10,12‐diynoate (LiPCDA) has been suggested as the radiation‐sensitive material for real‐time in vivo fiber‐optic dosimetry. In this configuration, micron‐thick radiochromic coating would measure the absorbed dose, where a major challenge is the uncertainty in the active material thickness, necessitating calibration. A homogeneously incorporated inert infrared (IR) dye, which must also be stable in ambient conditions and against radiolysis, can be added to the radiochromic film to enable optical calibration. Purpose: This study investigates four commercial cyanine‐based dyes (IR‐783, IR‐806, IR‐868, and IR‐880) for use as an optical calibrant in fiber‐optic radiochromic dosimeters. Methods: All dyes were dissolved in water to confirm solubility. IR‐783 and IR‐806 were dissolved in 10% w/w gelatin solution and coated onto a polyester substrate, which were then sandwiched between two layers of adhesives forming IR‐783 and IR‐806 films. A second batch of IR dyes in gelatin incorporated the LiPCDA, and was coated onto substrate and sandwiched between adhesive to form IR dye + LiPCDA films. The absorbance spectra of the films were measured periodically (176 and 102 days for IR‐dye films, and IR dye + LiPCDA, respectively). The average percentage absorbance, normalized to day 1, was fit to either a single or a double exponential decay model to calculate the spectral stability lifetime (τ1, τ2). Films were irradiated using a 6 MV LINAC beam with a standard setup of 100 source to axis distance (SAD), 10 cm × 10 cm field size and 1.5 cm depth. The change in absorbance of the IR‐dye + LiPCDA films were measured after they were irradiated to 1, 2, 5, 10, and 20 Gy at 3 Gy/min. Results: Only IR‐783 and IR‐806 were sufficiently water soluble. In gelatin matrix, these dyes demonstrated a decrease in absorbance with time for IR‐783 and IR‐806 dyes, with IR‐783 films having an average τ1 = 73 ± 7 days and IR‐806 films τ1 = 7 ± 3 days. When combined with LiPCDA, IR‐806 degraded, losing its original peak at ∼820 nm. Similarly, IR‐783, combined with LiPCDA, showed signs of degradation; however, its original absorbance peak was still observed at ∼800 nm. In the IR‐783 + LiPCDA films, the IR‐783 dye had a τ = 4 ± 1 days, an order of magnitude faster than the IR‐783 with no LiPCDA films. When exposed to x‐ray irradiation, the IR‐783 dye in the IR‐783 + LiPCDA films showed no change in absorbance with increasing absorbed dose. In contrast, the LiPCDA in the films responded as expected, increasing in optical density with increased absorbed dose. Conclusions: IR‐783 and IR‐806 dyes were observed to degrade over time following exponential decay curves. IR‐806 could not be combined with the LiPCDA without degrading. The combination of IR‐783 with LiPCDA demonstrated single exponential decay behavior at a comparatively faster rate than films that did not have LiPCDA. IR‐783 was insensitive to ionizing radiation and thus may be suitable for thickness correction, but an alternative manufacturing procedure may need to be developed. [ABSTRACT FROM AUTHOR]

The Bouguer–Lambert–Beer (BLB) law serves as the fundamental basis for the spectrophotometric determination of pigment content in microalgae. Although it has been observed that the applicability of the BLB law is compromised by the light scattering effect in microalgae suspensions, in-depth research concerning the relationship between the light scattering effect and the accuracy of spectrophotometric pigment determination remains scarce. We hypothesized that (1) the precision of spectrophotometric pigment content determination using the BLB law would diminish with increasing nonlinearity of absorbance, and (2) employing the modified version of the BLB (mBLB) law would yield superior performance. To assess our hypotheses, we cultivated Phaeodactylum tricornutum under varying illumination conditions and nitrogen supplies in controlled indoor experiments, resulting in suspensions with diverse pigment contents. Subsequently, P. tricornutum samples were diluted into subsamples, and spectral measurements were conducted using different combinations of biomass concentrations and path lengths. This was carried out to assess the applicability of the BLB law and the nonlinearity of absorbance. The chlorophyll a and fucoxanthin contents in the samples were analyzed via high-performance liquid chromatography (HPLC) and subsequently used in our modeling. Our findings confirm our hypotheses, showing that the modified BLB law outperforms the original BLB law in terms of the normalized root mean square error (NRMSE): 6.3% for chlorophyll a and 5.8% for fucoxanthin, compared to 8.5% and 7.9%, respectively. [ABSTRACT FROM AUTHOR]

Nanosphere lithography, a low‐cost fabrication technique, depends on the self‐assembly of nanoscale features to create nanostructures in a hexagonally close‐packed structure. In this article, the fabrication of 3D nanostructures over a large surface‐area with anisotropy along the growth direction through the combination of chemical and physical plasma etching is reported. The anisotropy stems from etching the nanosphere mask and the substrate at different rates. Due to the dynamic masking effect, a systematic variation of etching time gives rise to intriguing nanostructures with sharp edges that have strong potential for plasmonic applications, with the possibility of manipulating electromagnetic radiation. The structures obtained include nanocylinders, truncated hexagon‐based pyramids, circular pads on a conical base, and nanocones from a single‐layer nanosphere mask. Simulations of the fabrication process offer further insight into the understanding of nanostructure formation. A good agreement between predicted results and experiments confirms the potential of our numerical design. In addition, the optical properties of the nanostructures are investigated by UV–vis and the experimental findings are consistent with simulations based on a finite‐difference time‐domain method. The nanostructures described in this study contribute to the emerging 3D plasmonics and 3D magnonics, with strong potential for a significant impact on biosensor applications.

The photodecomposition behavior of cationic porphyrin ZnTMAP4+ (zinc tetrakis-(N,N,N-trimethylanilinium-4-yl) porphyrin) in water and complexed with clay nanosheets was investigated by light irradiation to the Soret band of ZnTMAP4+. The decomposition of ZnTMAP4+ was observed by UV–visible absorption spectroscopy. While the decomposition quantum yield (ϕdec) was 3.4 × 10−4 in water, that was 9.4 × 10−7 on the exfoliated clay nanosheets. It was revealed that the photostability of ZnTMAP4+ was stabilized by the complex formation with clay. When ZnTMAP4+ was intercalated between the stacked clay nanosheets, ϕdec was further decreased to 4.9 × 10−7. The photostability increased by 361 times and 693 times for the exfoliated and stacked state, respectively. These results indicate that the flat clay surface has the potential to control intra- and intermolecular photochemical reactions.

Here, the optical properties of the Nafion polymer membrane containing colloidal CdSe/CdS/ZnS nanocrystals embedded by diffusion have been studied. The CdSe/CdS/ZnS nanocrystals have a core/shell/shell appearance. All experiments were carried out at room temperature (22 ± 2) °C. A toluene solution was used to provide mobility to the active sulfone groups of the Nafion membrane and to embed the nanocrystals inside the membrane. The diffusion process of colloidal CdSe/CdS/ZnS nanocrystals into Nafion proton exchange membrane has resulted in a new molecular complex “Nafion–colloidal CdSe/CdS/ZnS nanocrystals”. The kinetics of the nanocrystals embedding into the membrane matrix was investigated using luminescence analysis and absorption spectroscopy techniques. The embedding rate of CdSe/CdS/ZnS nanocrystals into the Nafion polymer membrane was approximately 4·10−3 min−1. The presence of new luminescence centers in the membrane was proved independently by laser emission spectroscopy. The luminescence spectrum of the resulting molecular complex contains intensity maxima at wavelengths of 538, 588, 643 and 700 nm. The additional luminescence maximum observed at the 643 nm wavelength was not recorded in the original membrane, solvent or in the spectrum of the semiconductor nanoparticles. The luminescence maximum of the colloidal CdSe/CdS/ZnS nanocrystals was registered at a wavelength of 634 nm. The intensity of the luminescence spectrum of the membrane with embedded nanocrystals was found to be higher than the intensity of the secondary emission peak of the initial nanocrystals, which is important for the practical use of the “Nafion–colloidal nanocrystals” complex in optical systems. The lines contained in the luminescence spectrum of the membrane, which has been in solution with colloidal nanocrystals for a long time, registered upon its drying, show the kinetics of the formation of the molecular complex “Nafion membrane–nanocrystals”. Colloidal nanocrystals located in the Nafion matrix represent an analog of a luminescent transducer.

The epidermal growth factor receptor (EGFR) is a pivotal target in cancer therapy due to its significance within the tyrosine kinase family. EGFR inhibitors like AG-1478 and PD153035, featuring a 4-anilinoquinazoline moiety, have garnered global attention for their potent therapeutic activities. While pre-clinical studies have highlighted the significant impact of halogen substitution at the C3’-anilino position on drug potency, the underlying mechanism remains unclear. This study investigates the influence of halogen substitution (X = H, F, Cl, Br, I) on the structure, properties, and spectroscopy of halogen-substituted 4-anilinoquinazoline tyrosine kinase inhibitors (TKIs) using time-dependent density functional methods (TD-DFT) with the B3LYP functional. Our calculations revealed that halogen substitution did not induce significant changes in the three-dimensional conformation of the TKIs but led to noticeable alterations in electronic properties, such as dipole moment and spatial extent, impacting interactions at the EGFR binding site. The UV–visible spectra show that more potent TKI-X compounds typically have shorter wavelengths, with bromine’s peak wavelength at 326.71 nm and hydrogen, with the lowest IC50 nM, shifting its lambda max to 333.17 nm, indicating a correlation between potency and spectral characteristics. Further analysis of the four lowest-lying conformers of each TKI-X, along with their crystal structures from the EGFR database, confirms that the most potent conformer is often not the global minimum structure but one of the low-lying conformers. The more potent TKI-Cl and TKI-Br exhibit larger deviations (RMSD > 0.65 Å) from their global minimum structures compared to other TKI-X (RMSD < 0.15 Å), indicating that potency is associated with greater flexibility. Dipole moments of TKI-X correlate with drug potency (ln(IC50 nM)), with TKI-Cl and TKI-Br showing significantly higher dipole moments (>8.0 Debye) in both their global minimum and crystal structures. Additionally, optical spectral shifts correlate with potency, as TKI-Cl and TKI-Br exhibit blue shifts from their global minimum structures, in contrast to other TKI-X. This suggests that optical reporting can effectively probe drug potency and conformation changes.

In absorption spectroscopy, it is challenging to detect absorption peaks with significant differences in their intensity in a single measurement. We enable high-dynamic-range measurements by dispersing scatterers within a sample to create a broad distribution of path lengths (PLs). The sample is placed within an integrating sphere (IS) to capture all scattered light of various PLs. To address the complexities of PLs inside the IS and the sample, we performed a ray-tracing simulation using the Monte Carlo (MC) method, which estimates the measured absorbance A and PL distribution from the sample’s absorption coefficient µa and scattering properties at each wavelength λ. This method was validated using dye solutions with two absorption peaks whose intensity ratio is 95:1, employing polystyrene microspheres (PSs) as scatterers. The results confirmed that both peak shapes were delineated in a single measurement without flattening the high absorption peak. Although the measured peak shapes A(λ) did not align with the actual peak shapes µa(λ), MC enabled the reproduction of µa(λ) from A(λ). Furthermore, the analysis of the PL distribution by MC shows that adding scatterers broadens the distribution and shifts it toward shorter PLs as absorption increases, effectively adjusting it to µa.

Fabry–Perot interferometers (FPIs), comprising foundry-compatible dielectric thin films on sapphire wafer substrates, were investigated for possible use in chemical sensing. Specifically, structures comprising two vertically stacked distributed Bragg reflectors (DBRs), with the lower DBR between a sapphire substrate and a silicon-oxide (SiO2) resonator layer and the other DBR on top of this resonator layer, were investigated for operation in the near-ultraviolet (near-UV) range. The DBRs are composed of a stack of nitride-rich silicon-nitride (SiNx) layers for the higher index and SiO2 layers for the lower index. An exemplary application would be formaldehyde detection at sub-ppm concentrations in air, using UV absorption spectroscopy in the 300–360 nm band, while providing spectral selectivity against the main interfering gases, notably NO2 and O3. Although SiNx thin films are conventionally used only for visible and near-infrared optical wavelengths (above 450 nm) because of high absorbance at lower wavelengths, this work shows that nitride-rich SiNx is suitable for near-UV wavelengths. The interplay between spectral absorbance, transmittance and reflectance in a FPI is presented in a comparative study between one FPI design using stoichiometric material (Si3N4) and two designs based on N-rich compositions, SiN1.39 and SiN1.49. Spectral measurements confirm that if the design accounts for phase penetration depth, sufficient performance can be achieved with the SiN1.49-based FPI design for gas absorption spectroscopy in near-UV, with peak transmission at 330 nm of 64%, a free spectral range (FSR) of 20 nm and a full-width half-magnitude spectral resolution (FWHM) of 2 nm.

Mixed cyclization of 5,7‐diphenyl‐6H‐1,4‐diazepine 2,3‐dicarbonitrile and tetrafluorophthalonitrile in the presence of boron trichloride affords along with symmetrical perfluorinated subphthakocyanine, [F12sPc], two novel subporphyrazine‐type products which were isolated by column chromatography and characterized by mass‐sprectometry, NMR, IR, UV‐VIS and fluorescent spectroscopy. It was established that co‐cyclomerization of dinitriles is accompanied by electrophilic chlorination of 1,4‐diazepine ring by evolved Cl2 resulting in formation of dibenzosubporphyrazine [F8sPc1] with fused 6‐chloro‐5,7‐diphenyl‐6H‐1,4‐diazepine fragment. According to DFT modelling and 1H NMR data, a more stable diastereomer with an axial Cl atom is formed and no inversion of the 1,4‐diazepine ring is observed. Hydrolytic cleavage of the 1,4‐diazepine fragment in [F8sPc1] is observed upon chromatography or in the presence of a strong acid (CF3COOH) and leads to 2‐amino‐3‐benzamide substituted dibenzo subporphyrazine [F8sPc2]. Fluorescence of [F8sPc1] (ΦF=0.03) is ca 10 times lower than for [F12sPc] (ΦF=0.28) due to the combined effect of intramolecular charge transfer (ICT) from the donor diazepine ring to the acceptor sPc macrocycle and heavy atom effect of chlorine. Fluorescence of [F8sPc2] is almost completely quenched by ICT from −NH2 group to the electron‐deficient subporphyrazine core (ΦF<0.001), but addition of acid leads to protonation of the amino group and switch‐ON the fluorescence. Therefore, aminobenzamide substituted subporphyrazines can be considered as perspective pH‐sensitive fluorophores. [ABSTRACT FROM AUTHOR]

We demonstrate the successful implementation of an artificial neural network (ANN) to eliminate detrimental spectral shifts imposed in the measurement of laser absorption spectrometers (LASs). Since LASs rely on the analysis of the spectral characteristics of biological and chemical molecules, their accuracy and precision is especially prone to the presence of unwanted spectral shift in the measured molecular absorption spectrum over the reference spectrum. In this paper, an ANN was applied to a scanning grating-based mid-infrared trace gas sensing system, which suffers from temperature-induced spectral shifts. Using the HITRAN database, we generated synthetic gas absorbance spectra with random spectral shifts for training and validation. The ANN was trained with these synthetic spectra to identify the occurrence of spectral shifts. Our experimental verification unambiguously proves that such an ANN can be an excellent tool to accurately retrieve the gas concentration from imprecise or distorted spectra of gas absorption. Due to the global shift of the measured gas absorption spectrum, the accuracy of the retrieved gas concentration using a typical least-mean-squares fitting algorithm was considerably degraded by 40.3%. However, when the gas concentration of the same measurement dataset was predicted by the proposed multilayer perceptron network, the sensing accuracy significantly improved by reducing the error to less than ±1% while preserving the sensing sensitivity. [ABSTRACT FROM AUTHOR]

Continuous-wave diode lasers (DLs) with tunable emission wavelengths have become extensively used in various fields of analytical spectroscopy and diagnostics. Working in the near and mid-IR spectral region, tunable diode lasers are particularly effective in detecting simple molecules, making them invaluable for environmental monitoring, industrial process control, and diagnostics of subsonic and supersonic gas flows. However, the lack of commercial diode lasers operating in the spectral region shorter than 400 nm has restricted their applicability to elemental analysis, as many resonance lines of free atoms of elements lie in the region 250–400 nm. This review aims to highlight various applications of continuous diode lasers, which are lesser-known to analytical chemists. We briefly overview their main characteristics and discuss their advantages, enabling their successful implementation in traditional analytical spectroscopy tasks, as well as for diagnosing parameters of remote gas objects, including combustion processes in mixing gas flows. [ABSTRACT FROM AUTHOR]

In this study, the development and characterization of a plant-derived biopolymer, gum acacia, chemically modified by an herbal dye, red beetroot (Latin Beta vulgaris) has been presented. Red beetroot, a flowering plant with abundant phytochemicals, prevents diseases and produces colorful chromophores. Chromophores interact with incident intense electromagnetic field and thereby absorb radiation in ultraviolet and/or visible region of the spectrum, promoting low to high-level electron excitation between different energy states. Such transition influences variation in optical and electrical properties of the system. Optical properties of both biopolymer unmodified gum acacia specimen and after modification with red beet induced chromophore are investigated by UV–visible absorption spectroscopy. Pronounced light absorption is observed in the visible range of the spectrum compared to the unmodified specimen in which absorption is found to be observed in the deep ultraviolet range. Electrical characterization of the modified biopolymer with red beetroot extract suggests eviation from ideal dielectric relaxation obeying Debye mechanism. Electrical conductivity is found to be enhanced over pure specimen. These properties are eligible for application in energy storage devices, especially as a sensitizer in photovoltaic material which are ongoing extensive research area. [ABSTRACT FROM AUTHOR]

A contactless laser hygrometer based on light absorption by H2O molecules at 1392.5 nm is described. However, measurement results can be affected by optical noise when applied to an atmospheric tunnel or glass cuvette. The noises (occurring in the form of periodic fringes in the recorded spectrum) come from unexpected interference of the light beams reflected from surfaces of the windows or other optical elements. The method of their suppression is described in this article. It is based on wavelength modulation and signal averaging over the fringes period. Also, an experiment confirming the usefulness of this method is described here.