Optical Spectroscopy Techniques Research Articles

Study of the microstructure and temperature dependent luminescence of Na- and Li-beta gallia rutile compounds

We present the structural, vibrational and luminescence properties of Na- and Li- stabilized gallium-titanium oxides studied by optical spectroscopy techniques. The microstructure and characteristic vibrational modes of this homologous series, which are not well known, have been determined with the aid of Raman spectroscopy and compared to density functional theory (DFT) calculations. On the other hand, intense cathodoluminescence bands in the visible and in the near-infrared are observed depending on the term of the series and related to native defects. Besides, the study of the temperature evolution of the photoluminescence and photoluminescence excitation spectra has allowed us to determine both the band gap energy temperature dependence as well as to get some insight into the luminescence mechanisms of the defect-related emissions in these compounds. The results pave the way to exploit the physical properties of these Na- and Li- gallium titanate series in functional optoelectronic devices to operate from the ultraviolet to the infrared range.

Metal accumulation in fish species of a vast hydrographic network in the Moyen-Ogooué and Haut-Ogooué Provinces of Gabon: Implications for human health

With an obsolete livestock sector, Gabon relies on its huge hydrographic network rich in fish to supply its populations with animal proteins. This study aimed to conduct metal analyses in four fish species (Oreochromis niloticus, Clarias gariepinus, Chrysichthys nigrodigitatus, Polydactylus quadrifilis) frequently consumed by human populations in the Moyen-Ogooué and Haut-Ogooué Provinces of Gabon and infer the potential human health risks for those populations who rely on these freshwater produces as a source of proteins. Fish were sampled from Ezanga, Oguemoué, Onangué, Nguenè (Moyen-Ogooué) and Grand Poubara (Haut-Ogooué) Lakes during the high flow period (HF) and low flow period (LF) from 2021 to 2022, and analysed for seven heavy metals (HMs) using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) techniques. Throughout the flow periods, and regardless of the lake and fish species, Fe was found to have the highest concentration, followed by Al > Mn > Hg > Pb> As> Cd. The relatively high concentration of Hg was recorded in the muscle tissues of C. gariepinus (6.65mg. kg−1) sampled during the LF period at Grand Poubara. The concentrations of Hg found in the muscle of all fish species also exceeded the maximum acceptable limits set by the American Environmental Protection Agency. The concentrations of Fe in C. gariepinus (Grand Poubara, LF) and O. niloticus (Onangué, LF), and those of Al in O. niloticus (Nguenè, HF), P. quadrifilis (Onangué, HF) and C. nigrodigitatus (Oguemoué, LF) were amongst the highest concentrations ever reported on the African continent. Health risk assessments indicated a heightened risk of cancer for local populations consuming the fish species from all the lakes investigated. There is a need to implement an increased surveillance programme at national level in order to raise awareness and improve the management of fishery resources while preserving the environment and the health of local populations that rely upon these resources for their subsistence.

Pressure control of tritiated hydrogen isotopologues in hermetically sealed vessels by non-evaporable getters for sub-Doppler-resolution spectroscopy

Small molecules serve as valuable benchmarks for testing quantum chemical theories. Ultra-high-resolution spectroscopy currently offers the capability of measuring molecular hydrogen energy levels with a relative accuracy on the order of 10-10. Expanding such investigations to encompass different isotopologues of molecular hydrogen has emerged as a promising avenue for examining mass-dependent contributions to the full description of molecular structure in the framework of relativistic quantum electrodynamics. However, the delicate nature of handling radioactive tritium in a high-resolution spectroscopy environment poses significant technological challenges, thereby limiting the extension of these studies to include T2, DT and HT isotopologues. In this work, we present the experimental setup of the very sensitive, Doppler-free technique of Noise-Immune Cavity-Enhanced Optical Heterodyne Molecular Spectroscopy (NICE-OHMS), used to measure rovibrational transitions in the HT molecule. The NICE-OHMS measurements were performed in a closed cavity system without connection to an actively pumped vacuum system. For this reason, a new method for tritium storage and pressure regulation within 0.05–1Pa based on a temperature-controlled mini-getter system is employed using less activity than the tritium exemption limit (1GBq). Non-Evaporable Getters of the type SAES St171 were used for this purpose exploiting their property that hydrogen is released upon heating, while other gases remain being pumped. Prior to the NICE-OHMS experiment, the reversible sorption properties of the getter for hydrogen isotopes were investigated. We show measurements of the equilibrium (hydrogen) pressure for all three pure isotopes and for a H2:HT:T2 mixture (with H:T = 1:1) as a function of temperature for a system of defined volume and amount of gas. For the read-out of the temperature, a method using the resistance of the getter in combination with a pyrometric calibration has been implemented. We discuss the experiences from practical use of the tritium getter and show results obtained with the NICE-OHMS setup leading to frequency calibration of near-infrared transitions in HT at an accuracy, surpassing previous studies by nearly three orders of magnitude.

The Photoionization Processes of Deep Trap Levels in n-GaN Films Grown by MOVPE Technique on Ammono-GaN Substrates

In this paper, we present various theoretical models that accurately approximate the spectral density of the optical capture cross-section (σe0) obtained through the analysis of photo-capacitance transients using the deep-level optical spectroscopy (DLOS) technique applied to semi-transparent Ni/Au Schottky barrier diodes (SBDs) fabricated on n-GaN films. The theoretical models examined in this study involved a variety of approaches, from the Lucovsky model that assumes no lattice relaxation to more sophisticated models such as the Chantre–Bois and the Pässler models, which consider the electron–phonon coupling phenomenon. By applying theoretical models to the experimentally determined data, we were able to estimate the photoionization (E0), trap level position (ET), and Franck–Condon (dFC) energy, respectively. In addition, the results of our analysis confirm that the photoionization processes of deep traps in n-GaN grown by the metal–organic vapor-phase epitaxy technique (MOVPE) are strongly coupled to the lattice. Moreover, it was shown that the Pässler model is preferred for the accurate determination of the individual trap parameters of defects present in n-GaN films grown on an Ammono-GaN substrate. Finally, a new trap level, Ec-1.99 eV with dFC = 0.15, that has not been previously reported in n-GaN films grown by MOVPE was found.

New insights on thermal ageing of electrical insulating oils as revealed from photoluminescence and absorption spectroscopy

AbstractRecently, significant efforts have been exerted to replace mineral oil with environmentally friendly oils due to safety and environmental issues. However, there is a need to clarify the physical mechanisms behind the ageing impact of these oils. The authors use advanced optical spectroscopy techniques in correlation with dielectric measurements to understand the ageing processes in environmentally friendly oils as well as mineral oil. Firstly, different samples of environmentally friendly oils and mineral oil were utilised to investigate the ageing mechanism. The samples were subjected to different ageing periods using a thermal accelerated ageing process. Secondly, the severity of the produced byproducts due to the oil degradation is examined based on several measured properties representing macroscopic and microscopic categories. The macroscopic category was evaluated through dielectric properties, including breakdown voltage, dielectric permittivity, and dissipation factor. The microscopic category, on the other hand, was assessed using techniques such as ultraviolet–visible absorption spectroscopy and photoluminescence spectroscopy. These techniques enabled a deep understanding of the molecular‐level changes occurring in the oil under ageing conditions, thereby getting new insights into oil ageing mechanisms. It is worth mentioning that natural ester oil demonstrated the most favourable performance across various properties under ageing conditions.

Gamma radiation-induced changes in the structural and optical properties of CsPbBr3 thin films for space applications

Perovskite nanocrystals (NCs) are emerging as a next generation display technology. In this regard, exploring the structural and optical stability when subjected to radiation is crucial for expanding their application in aerospace and radiation detection technologies. In this study, we investigated the effects of gamma radiation on CsPbBr3 heterojunction thin films through a comprehensive analysis of their structural and optical characteristics. The thin films of CsPbBr3 were subjected to varying doses of gamma radiation, ranging from 100 krad to 1 Mrad, followed by thorough examination using X-ray diffraction (XRD) and optical spectroscopy techniques. Our findings unveil significant changes in the crystal structure of CsPbBr3 thin films when exposed to gamma radiation, including shifts in diffraction peak positions from cubic to monoclinic phases, broadening of peaks, and variations in peak intensities due to induced surface defects. The optical properties, such electroluminescence (EL) and photoluminescence (PL) intensity slightly drops at the moderate irradiation dose of 300 krad, while at an irradiation dose of 1 Mrad deteriorated severely. Notably, 300 krad is equivalent to the radiation dose accumulated by satellites in low-Earth orbit over 10 years. The findings in this work suggest the fabricated CsPbBr3 thin film has the potential to be used in space applications.

Sensing Biomolecules Associated with Cells' Radiosusceptibility by Advanced Micro- and Nanospectroscopy Techniques.

Radiotherapy is one of the most common approaches for cancer treatment, especially in the case of peripheral nervous system tumors. As it requires exposure to high doses of ionizing radiation, it is important to look for substances that support efficient reduction of the tumor volume with simultaneous prevention of the surrounding noncancerous cells. Cannabidiol (CBD), which exhibits both anticancer and neuroprotective properties, was applied as a potential modulator of radiological response; however, its influence on cells undergoing irradiation remains elusive. Here, we have applied high-resolution optical spectroscopy techniques to capture biomolecules associated with CBD shielding of normal and damaging cancerous cells upon X-ray exposure. Conventional Raman (RS) and Fourier transformed infrared (FT-IR) spectroscopies provided semiquantitative information mainly about changes in the concentration of total lipids, DNA, cholesteryl esters, and phospholipids in cells. A through assessment of the single cells by atomic force microscopy coupled with infrared spectroscopy (AFM-IR) allowed us to determine not only the alterations in DNA content but also in its conformation due to cell treatment. Pronounced nanoscale changes in cholesteryl ester metabolites, associated with CBD treatment and radiation, were also observed. AFM-IR chemoselective maps of the single cells indicate the modified distribution of cholesteryl esters with 40 nm spatial resolution. Based on the obtained results, we propose a label-free and fast analytical method engaging optical spectroscopy to assess the mechanism of normal and cancerous cell susceptibility to ionizing radiation when pretreated with CBD.

Effects of Dislocation Filtering Layers on Optical Properties of Third Telecom Window Emitting InAs/InGaAlAs Quantum Dots Grown on Silicon Substrates.

Integrating light emitters based on III-V materials with silicon-based electronics is crucial for further increase in data transfer rates in communication systems since the indirect bandgap of silicon prevents its direct use as a light source. We investigate here InAs/InGaAlAs quantum dot (QD) structures grown directly on 5° off-cut Si substrate and emitting light at 1.5 μm, compatible with established telecom platform. Using different dislocation defect filtering layers, exploiting strained superlattices, and supplementary QD layers, we mitigate the effects of lattice constant and thermal expansion mismatches between III-V materials and Si during growth. Complementary optical spectroscopy techniques, i.e. photoreflectance and temperature-, time- and polarization-resolved photoluminescence, allow us to determine the optical quality and application potential of the obtained structures by comparing them to a reference sample-state-of-the-art QDs grown on InP. Experimental findings are supported by calculations of excitonic states and optical transitions by combining multiband k•p and configuration-interaction methods. We show that our design of structures prevents the generation of a considerable density of defects, as intended. The emission of Si-based structures appears to be much broader than for the reference dots, due to the creation of different QD populations which might be a disadvantage in particular laser applications, however, could be favorable for others, e.g., in broadly tunable devices, sensors, or optical amplifiers. Eventually, we identify the overall most promising combination of defect filtering layers and discuss its advantages and limitations and prospects for further improvements.

Effect of doping with carbon dots on the alignment and dielectric properties of nematic liquid crystal 4-cyano-4′-pentylbiphenyl in ITO sample cells without conventional alignment layers for low-cost display applications

The melding of nanomaterials with liquid crystalline materials is at the frontier of scientific research due to the transformative impact of nanoparticles on the functionalities of host liquid crystal materials. Here, we report the effect of doping of carbon dots (CDs) in the nematic liquid crystal (NLC), 5CB (4-cyano-4′-pentylbiphenyl) in indium tin oxide (ITO) sample cells without alignment layers (i.e., unaligned ITO (U-ITO) sample cells) using polarizing optical microscopy and dielectric spectroscopic techniques. Polarizing optical microscopy reveals largely dark optical textures under crossed polarizers confirming vertical alignment of Pure 5CB in U-ITO sample cells. However, defects present in the texture pose severe constraints on the use of induced vertical alignment in U-ITO sample cells for device applications. To improve the quality of vertical alignment, CDs of size 2.8 nm at concentrations of 0.03, 0.05 and 0.1 wt% are doped into 5CB. Optical texture studies show the quality of induced vertical alignment of the 0.03 wt% composite is better than pure 5CB and other composites. Frequency-temperature dependent dielectric studies verify the induced vertical alignment by observation of the short-axis molecular relaxation. The stability of the vertical alignment throughout the nematic phase of 5CB is confirmed through temperature dependent dielectric and optical texture studies. The induced vertical alignment of 5CB in U-ITO sample cells could be attributed to the stronger LC-LC interaction than the ITO-LC interaction. The improvement in the quality of vertical alignment of CDs-5CB composites could be due to the CDs influencing LC-LC and ITO-LC interactions. Finally, the effect of CDs on the increasing dc electrical conductivity of 5CB in U-ITO sample cells is investigated. Our results clearly indicate that CD-5CB composites would be useful in cost-effective display and other photonic devices devoid of alignment layers.

Detection of ultra-low concentration NH3, SO2, and NO using UV-DOAS combined with multidimensional spectral fusion

Since nitric oxide (NO), sulfur dioxide (SO2), and ammonia (NH3) in flue gas cause severe air pollution, accurate measurements of their concentrations are crucial for optimizing the efficiency of flue gas denitrification in coal-fired power plants and protecting the atmosphere. Due to their large absorption cross sections in the ultraviolet (UV) band, NH3, SO2, and NO in flue gas can be detected by UV Differential Optical Absorption Spectroscopy (UV-DOAS) techniques. However, spectral overlap and noise caused by short optical path limitations in the measurement are the main obstacles to achieve concentration inversion. Here, we propose a multidimensional spectral fusion method one-dimensional convolutional neural network combined with two-dimensional convolutional neural network (1D-2D-CNN) with the ability to invert concentration of NH3, SO2 and NO at ppb level with 0.5 m optical-length. To separate the absorption features, one-dimensional spectra are converted into two-dimensional time-frequency plots by continuous wavelet transform (CWT). After denoising the spectra by wavelet thresholding, one-dimensional and two-dimensional spectral features are extracted by 1D-2D-CNN model and fused for inversion. The experimental results show that the proposed system can effectively eliminate interferences from NH3, SO2, and NO, significantly improving the concentration inversion accuracy. The detection limits for NH3, SO2 and NO in the mixture are 0.95 ppb∙m, 6.31 ppb∙m, and 2.53 ppb∙m, respectively, demonstrating that our approach outperforms other reported methods for flue gas analysis. The proposed system is expected to be applied to ammonia slip monitoring of Selective Catalytic Reduction (SCR) in power plants.

Influence of Applied Discharge Voltage and Gas Flow Rate on Nickel Plasma Jet Parameters Diagnosed by Optical Emission Spectroscopic Technique

Abstract: In this work, we measure the plasma parameters by using an AC high-voltage power supply that generates a non-thermal plasma jet system at atmospheric pressure. A nickel (Ni) metal strip, with dimensions of 1.5 × 10 cm2, was connected to the anode electrode of the AC power supply. This nickel strip was immersed in a flask with a small amount of distilled water positioned below the plasma plume nozzle. Optical emission spectroscopy (OES) was used to diagnose the plasma system at different argon gas flow rates (1-5 L/min) and varying applied voltage values (11-15 kV). It is significant to know the processes accompanying plasma generation to measure their parameters which include the electron temperature (Te), electron number density (ne) of the plasma, Debye length (λD), and plasma frequency (fp). Our results showed an increase in the intensity of spectral lines with the increase in applied discharge voltage (11-15 kV). The maximum peak for ArI was observed at a wavelength of 811.531 nm, and the maximum peaks for nickel (Ni) were observed at wavelengths of 285.21 and 519.70 nm. Also, the results indicated a gradual increase in electron temperature (Te) and electron density (ne) values at the applied voltage of 0.403-0.468 eV. Likewise, the electron density (ne) was in the range of (11.486-13.851) × 1017 cm-3. Keywords: Atmospheric plasma jet, Nickel (Ni) plasma parameters, Electron temperature, Spectroscopic optical emission (OES).

Transferable Optical Enhancement Nanostructures by Gapless Stencil Lithography.

Optical spectroscopy techniques are central for the characterization of two-dimensional (2D) quantum materials. However, the reduced volume of atomically thin samples often results in a cross section that is far too low for conventional optical methods to produce measurable signals. In this work, we developed a scheme based on the stencil lithography technique to fabricate transferable optical enhancement nanostructures for Raman and photoluminescence spectroscopy. Equipped with this new nanofabrication technique, we designed and fabricated plasmonic nanostructures to tailor the interaction of few-layer materials with light. We demonstrate orders-of-magnitude increase in the Raman intensity of ultrathin flakes of 2D semiconductors and magnets as well as selective Purcell enhancement of quenched excitons in WSe2/MoS2 heterostructures. We provide evidence that the method is particularly effective for air-sensitive materials, as the transfer can be performed in situ. The fabrication technique can be generalized to enable a high degree of flexibility for functional photonic devices.

Hybrid NiCo2O4-BiOCOOH heterostructure nanocomposite impregnated porous polymer monolith as high-performance visible light photocatalyst for the decontamination of antimicrobial pollutants

We report a first-of-its-kind preparation of a NiCo2O4-BiOCOOH heterostructure as visible light-responsive nanocomposites (NCs) for the fast decontamination of moxifloxacin drug molecules, with longer persistence and non-biodegradability nature that could promote gene-resistance bacteria in aqueous medium. Further, a reusable/recoverable photocatalyst is fabricated through the uniform decoration of NiCo2O4(15 %)-BiOCOOH(85 %), i.e., NB-15 NCs across a tailor-made poly(EGDMA) monolith (PEM) that serves as the host template for the photoactive NCs. The electron microscopy, optical spectroscopy, diffraction, and surface analysis techniques confirm the photocatalyst's superior structural morphology, surface topography, and porosity features that assist in high-performance photocatalysis. The inorganic-organic hybrid photocatalyst exhibits a narrow energy bandgap that promotes ample generation of reactive oxygen species upon visible light irradiation, as confirmed by the electrochemical and spectroscopic analysis. The BET/BJH plot for the photocatalyst reveals a large surface area of 345 m2/g, with voluminous pore distributions (2–80 nm), indicating the coexistence of mesopores-infused macroporous framework that offers better contact/equilibration of the pollutant molecules with the abundantly dispersed photoactive sites. The optimized parameters reveal ≥99.2 % drug dissipation in ≤0.33 h and drug mineralization in ≤2.0 h, using a mere 50 mg of photocatalyst irradiated with a 150 W/cm2 tungsten lamp. The synthesized photocatalyst has a simple/cost-saving procedure that can transform into scalable, cheaper, and eco-friendly products for the real-time monitoring of toxic pollutants. Besides, the photocatalyst exhibits excellent stability and reusability characteristics for efficiently decontaminating organic pollutants, thus highlighting an innovative approach for fabricating high-performance photocatalysts.

Confinement of excited states in two-dimensional, in-plane, quantum heterostructures

Two-dimensional (2D) semiconductors are promising candidates for optoelectronic application and quantum information processes due to their inherent out-of-plane 2D confinement. In addition, they offer the possibility of achieving low-dimensional in-plane exciton confinement, similar to zero-dimensional quantum dots, with intriguing optical and electronic properties via strain or composition engineering. However, realizing such laterally confined 2D monolayers and systematically controlling size-dependent optical properties remain significant challenges. Here, we report the observation of lateral confinement of excitons in epitaxially grown in-plane MoSe2 quantum dots (~15-60 nm wide) inside a continuous matrix of WSe2 monolayer film via a sequential epitaxial growth process. Various optical spectroscopy techniques reveal the size-dependent exciton confinement in the MoSe2 monolayer quantum dots with exciton blue shift (12-40 meV) at a low temperature as compared to continuous monolayer MoSe2. Finally, single-photon emission (g2(0) ~ 0.4) was also observed from the smallest dots at 1.6 K. Our study opens the door to compositionally engineered, tunable, in-plane quantum light sources in 2D semiconductors.

Multidimensional fluorescence spectroscopy of wine using synchronous excitation/emission matrices and time-resolved fluorescence interferometric detection

Wines are complex mixtures of chemical compounds with broad and overlapping absorption and emission spectral features in the UV and visible spectral regions, making them challenging to study with conventional optical spectroscopic techniques. Multidimensional fluorescence spectroscopies correlate fluorescence spectra with other degrees of freedom, and have proven useful for studying complex molecular systems, offering a pathway for the analysis of wines utilising their inherent fluorescence. Here we employ steady-state excitation-emission matrix (EEM) and time-resolved fluorescence spectral measurements to investigate representative commercial white and red wine samples and a fluorescent ‘model’ wine base. Combining these multidimensional measurement methods provides information on the emission characteristics of the components that wines contain. This investigation illustrates the potential for multidimensional fluorescence techniques as diagnostic tools for the wine industry.

Elemental Profiling of Common Anti-diabetic Medicinal Plants of Swat and Peshawar Districts of Khyber Pakhtunkhwa (KPK) Province of Pakistan: An Investigation Using PIXE and ICP-OES.

The use of medicinal plants is integral to addressing liver, heart, lung, and other metabolic issues. These plants are rich in vitamins, minerals, flavonoids, and alkaloids, which collectively help in lowering intestinal glucose absorption and increasing insulin secretion by pancreatic tissues. Elemental analysis, encompassing major, minor, and trace elements, was performed on various parts (leaves, roots, and seeds) of 16 anti-diabetic medicinal plants collected from different regions of Swat and Peshawar in Khyber Pakhtunkhwa (KPK), Pakistan. This analysis utilized proton-induced X-ray emission (PIXE) and inductively coupled plasma optical emission spectroscopy (ICP-OES) techniques. Our PIXE and ICP-OES analysis revealed the presence of major (Ca, K, S, P), minor (Si, Cl), and trace (Al, Mn, Fe, Ni, Cu, Zn, Se, Cr, and Sc) elements in various parts (leaves, roots, and seeds) of the 16 anti-diabetic medicinal plants studied. Specifically, elements such as Ca, K, Cr, Cu, Mn, Zn, and Se were detected, all of which are known to contribute in maintaining normal glucose metabolism. Notably, Zn and Se are crucial trace elements for the synthesis, secretion, and action of insulin. Significant Zn concentrations were observed in ten anti-diabetic medicinal plants: Albizia lebbeck (AL), Atropa acuminata (AA), Avena fatua (AF), Citrus medica (CM), Commiphora wightii (CW), Cymbopogon citratus (CC), Daucus carota (DC), Ziziphus mauritiana (FM), Hyoscyamus niger (HN), and Martynia annua (MA), and significant Se concentrations were observed in twelve medicinal plants, i.e., Albizia lebbeck (AL), Allium sativum (AS), Atropa acuminata (AA), Avena fatua (AF), Cannabis sativa (CS), Capparis spinosa (CaS), Commiphora wightii (CW), Cymbopogon citratus (CC), Datura alba (DA), Daucus carota (DC), Ziziphus mauritiana (FM), and Hyoscyamus niger (HN). Our study's elemental analysis using PIXE and ICP-OES on various parts of 16 medicinal plants identified a significant number of useful elements. Elements such as Ca, K, S, P, Al, Si, Cl, Mn, Fe, Ni, Cu, Zn, Se, and Cr were identified and quantified. These findings support the potential use of these plants in managing diabetes and highlight the importance of elemental profiling in understanding their therapeutic properties.

Spectroscopic properties and luminescence of the lithium tetraborate glasses co-doped with manganese and europium

High quality Li2B4O7:Mn,Eu glasses containing 1.0 mol.% MnO2 and Eu2O3 were prepared and investigated by XRD, EPR and optical spectroscopy techniques. Obtained data analysis shows that Mn is incorporated into the glass network as Mn2+ and Mn3+. Parameters of observed Mn2+ EPR signals in the Li2B4O7:Mn,Eu glasses were determined. Optical absorption spectrum of the studied glasses consists of broad band at 464 nm corresponding to the 5Eg(D) → 5T2g(D) transition of Mn3+ (3d4) ions and few narrow weak bands of the Eu3+ (4f6) ions. Emission spectra of the Li2B4O7:Mn,Eu glasses in orange-red region exhibit several sharp bands corresponding to the 5D0 → 7FJ (J = 0–4) transitions of Eu3+ ions and broad band belonging to the 4T1g(G) → 6A1g(S) transition of Mn2+ (3d5) ions. Comparative discussions were made on the luminescence spectra and decay curves of Mn2+ and Eu3+ ions in the Li2B4O7:Mn,Eu glasses and those in Mn-doped and Eu-doped glasses with the Li2B4O7 basic composition.

Binding and Stabilization of a Semiquinone Radical by an Artificial Metalloenzyme Containing a Binuclear Copper (II) Cofactor.

A binuclear Cu(II) cofactor was covalently bound to a lauric acid anchor. The resulting conjugate was characterized then combined with beta-lactoglobulin (βLG) to generate a new biohybrid following the so-called "Trojan horse" strategy. This biohybrid was examined for its effectiveness in the oxidation of a catechol derivative to the corresponding quinone. The resulting biohybrid did not exhibit the sought after catecholase activity, likely due to its ability to bind and stabilize the semiquinone radical intermediate DTB-SQ. This semi-quinone radical was stabilized only in the presence of the protein and was characterized using optical and magnetic spectroscopic techniques, demonstrating stability for over 16 hours. Molecular docking studies revealed that this stabilization could occur owing to interactions of the semi-quinone with hydrophobic amino acid residues of βLG.

Effect of carbon dots on tuning molecular alignment, dielectric and electrical properties of a smectogenic cyanobiphenyl-based liquid crystal material

Here, we demonstrate the effect of dispersing organosoluble carbon dots (CDs, ∼7–8 nm) on tuning the molecular alignment, dielectric and electrical properties of smectic A (SmA) and nematic (N) mesophases of a thermotropic smectogenic LC material, 4-octyl-4′-cyanobiphenyl (8CB) in a planar anchored indium tin oxide (ITO) sample cell using polarized optical microscopy and dielectric spectroscopic techniques. The cross-polarized optical textures clearly show that the doping of CDs (concentration ⩾0.25 wt%) in planar anchored 8CB liquid crtstal (LC) led to the changing of its alignment from planar to vertical. Interestingly, such an induced vertical alignment remains stable throughout the SmA and N phases of the 8CB LC material. Moreover, the magnitude of the real dielectric permittivity is found to increase with increasing concentration of CDs and exhibits vertical alignment values for composites (⩾0.25 wt%). The observance of short axis molecular relaxation for composites (⩾0.25 wt%) without the application of bias field confirms again the induced vertical alignment. The accumulation of CDs at the substrate surface and their interaction with the alignment and ITO layers can be attributed as an important factor for such induced vertical alignment. The electrical conductivity of 8CB is observed to increase significantly with the addition of CDs (i.e. an increment of up to two orders of magnitude in composites compared to pure 8CB) and attributed to the lowering of viscosity and change in molecular alignment. We certainly believe that such tunable molecular alignment throughout the SmA and N phases of thermotropic smectogenic LC material (8CB) by dopant CDs could pave the way for their applications in flexible displays, biosensors, electro-optical memory and other tunable photonic devices.

Direct observation of photoinduced sequential spin transition in a halogen-bonded hybrid system by complementary ultrafast optical and electron probes

A detailed understanding of the ultrafast dynamics of halogen-bonded materials is desired for designing supramolecular materials and tuning various electronic properties by external stimuli. Here, a prototypical halogen-bonded multifunctional material containing spin crossover (SCO) cations and paramagnetic radical anions is studied as a model system of photo-switchable SCO hybrid systems using ultrafast electron diffraction and two complementary optical spectroscopic techniques. Our results reveal a sequential dynamics from SCO to radical dimer softening, uncovering a key transient intermediate state. In combination with quantum chemistry calculations, we demonstrate the presence of halogen bonds in the low- and high-temperature phases and propose their role during the photoinduced sequential dynamics, underscoring the significance of exploring ultrafast dynamics. Our research highlights the promising utility of halogen bonds in finely tuning functional properties across diverse photoactive multifunctional materials.