Search Results (69)

Introduction: Aquatic chemical pollution is among the most worrying threats to ecosystem health. There is an ever-increasing variety of pollutant substances detected across the source-to-sea continuum, causing loss of biodiversity and ecological disequilibrium. Achieving cleaner and healthier systems relies on carrying out sustained, cost-effective, diagnosis and aquatic effects monitoring, within the adaptive management cycle. The available methods are, however, cumbersome, which creates a clear need for innovative expeditious approaches for low-cost surveillance monitoring. In the last decade, Raman Spectroscopy (RS) has gained wide recognition for application to biological questions, for its ability to uncover the complexity of molecules and their interactions. Various fields, from pharmacology to disease diagnosis and prognosis, have suffered an innovation revolution through the application of RS. In this technique inelastic light scattering of a small part of photons of an incident electromagnetic monochromatic light beam (ranging from near-infrared to visible or ultraviolet) is caused by the molecular vibration of chemical bonds. This results in shifts in energy, which indicate discrete vibrational modes of polarisable molecules, providing qualitative and quantitative assessments of the chemical composition and molecular structure of the sample. The technique shows high sensitivity, no need for sample preparation and the possibility of use in non-invasive and label-free analysis. Objective: The aim of this work is to present and discuss evidence about the application of Raman Spectroscopy (RS) to environmental diagnosis and aquatic effect monitoring of pollution. Methodology: The technique was applied to different biological models, i.e., diatoms, zebrafish embryos and larvae and freshwater snails. Quality assessments with diatoms were tested in environmental monitoring, while assessments with other models were done upon exposure to metals and organic contaminants. Results and conclusions: The Raman spectra obtained from the samples analysed comprised bands detected within the 800 to 2000 cm⁻¹ wavenumber range. These were related to bond vibrations of carbohydrates, DNA phosphate groups, proteins or CH, NH and OH stretching in lipids and proteins. Data analysis using chemometric methods clearly distinguished pollutant exposure from control sites or treatments, pointing out the potential for surveyance monitoring. The next steps include the comparison with other sensitive methods (e.g., locomotion and avoidance behaviours, omics methods) to assess efficiency and bring further mechanistic understanding. Full article

In high-power laser systems, extrinsic impurities—particularly Ce introduced during conventional ring polishing—have been identified as critical contributors to the degradation of laser-induced damage resistance in fused silica optical components. This study systematically investigates the effects of cerium substitutional doping on the electronic structure and optical properties of fused silica, integrating first-principles density functional theory calculations with experimental characterizations. The results demonstrate that substitutional incorporation of cerium atoms into the fused silica framework introduces deep-level defect states within the band gap, resulting in band gap narrowing and absorption edge redshift of the material. The energy position of the defect states depends on the Ce doping configuration. Among them, the Ce-4f orbital constitutes the dominant component of the defect state’s electronic structure, while the neighboring atomic orbitals such as O-2p and Si-3s/3p participate in bonding through hybridization, thereby determining the depth and distribution characteristics of the defect levels. The optical absorption edge of cerium-doped fused silica undergoes a significant redshift from the intrinsic value of 222 nm to 468 nm in the dual-Ce adjacent-site doping configuration, thereby endowing the material with substantial optical absorption capability at a wavelength of 355 nm. μ-UVPL spectroscopy combined with μ-XRD and other characterization analyses confirmed that the characteristic emission peak at 450 nm on the surface region of fused silica originated from Ce-related defect centers; this spectral feature was consistent with the defect state electronic structure predicted by the diatomic nearest-neighbor doping model. LIDT tests further indicated that the Ce-contaminated area significantly weakened the material’s laser damage resistance under 355 nm laser irradiation. This study further explained the mechanism by which traditional polishing-induced Ce element doping causes the low laser damage threshold of fused silica optical components, providing a theoretical basis for improving their performance. Full article

Plastic and microplastic (MP) pollution, along with alien species invasion, are of great concern for natural habitat preservation and human health, and are two important and concomitant likely causes for global biodiversity loss. In the present study, a Seabin, a device for buoyant waste collection in calm waters, was used to also characterize the waste collected in northernmost side of Lake Garda (Italy) in a period of very low anthropogenic pressure, the Winter season of 2024–2025. During the survey, 92.6 g of plastic was collected, i.e., a total of 540 pieces. About 6.9 mg of plastic per m³ of water was found, corresponding to about 0.04 plastic items per m³ and approximately 13 pieces of microplastics per day. Fourier-transform Infrared (FTIR) spectroscopy identification showed that the plastic was composed mainly of polyethylene (PE), polypropylene (PP), and polystyrene (PS). Microorganisms (Diatoms, Bacillariophyta) and microcrack formation with deposits of inorganic matter (mainly Si, Al, O, Ca) were also evidenced by SEM/EDX in all the observed aged MP. Qualitative evaluation of the captured biota highlighted the presence of at least five alien species, including invasive Dikerogammarus villosus. This study describes an easy and cost-effective novel methodology for simultaneously monitoring plastic waste and alien species presence in calm waters, which acts also as a mitigation tool for plastic pollution. The results could be of interest not only to policymakers and scientists, but also for public health and for environmental monitoring. Full article

A precise characterization of molecular vibrations and thermodynamic properties is essential for applications in spectroscopy, computational modeling, and chemical process design. In this study, the q-deformed Tietz (qDT) oscillator is applied to examine vibrational energy spectra of diatomic molecules and thermodynamic properties of nonlinear symmetric triatomic molecules. Vibrational energy eigenvalues were obtained analytically using the improved Nikiforov-Uvarov method. The symmetric vibrational mode was described with the qDT oscillator, while asymmetric and bending modes were modeled using the rigid rotor harmonic oscillator (RRHO); translational and rotational contributions were incorporated from standard models. For diatomic molecules (BrF, CO⁺, CrO, ICl, KRb, NaBr), mean absolute percentage errors (MAPE) ranged from 0.53% to 1.73% for vibrational energy eigenvalues and 0.34% to 1.08% for potential fits. Extending the analysis to triatomic molecules, thermodynamic properties of AlCl₂, BF₂, Cl₂O, OF₂, O₃, and SO₂ were calculated with the qDT model, yielding low MAPE benchmarked against NIST-JANAF reference data: entropy 0.203% to 0.614%, enthalpy 1.792% to 5.861%, Gibbs free energy 0.419% to 1.270%, and constant-pressure heat capacity 1.475% to 4.978%. These results demonstrate the versatility and accuracy of the qDT oscillator as an analytical framework connecting molecular potentials, vibrational energies, and thermodynamic functions, providing a practical and tractable approach for modeling both diatomic and symmetric triatomic systems. Full article

Bioaccumulation by diatoms, as the first stage of biomineralisation, has been widely studied for various metals, such as cadmium, copper, zinc, aluminium, gold, silver, etc. However, despite the fact that the mining and utilization of rare earth elements (REEs) are currently increasing, there is almost no data on their bioaccumulation by diatoms. Therefore, the aim of this study was to determine the ability of diatoms to bioaccumulate REEs by the example of lanthanum (La), and to compare this ability for two marine diatoms Nanofrustulum shiloi and Halamphora kolbei. As a result of experiments on the cultivation of diatoms in nutrient media supplemented with La at concentrations of 10 mg·L⁻¹ and 50 mg·L⁻¹, energy-dispersive X-ray spectroscopy revealed the ability of diatoms to bioadsorb La on their frustule surface, as a first stage of its bioaccumulation. The high concentration of La (50 mg·L⁻¹) has a noticeable visual effect on the morphofunctional state of diatoms and causes a decrease in the rate of accumulation. The low concentration (10 mg·L⁻¹) promotes the hyperaccumulation of La by the diatom biomass as a whole, including both bioadsorption and bioabsorption within the cells. This resulted in an increase in La concentration in the biomass by nearly 2000-fold in H. kolbei (6.06 mg·g⁻¹) and by 1000-fold in N. shiloi (6.90 mg·g⁻¹). The results on La bioaccumulation by diatoms are significant for advancing methods to remediate aquatic environments contaminated with rare earth elements and for the bioindication purposes. Full article

With the rise in global temperatures, it is of great significance to achieve rapid and accurate detection of greenhouse gases, such as carbon dioxide and methane. Raman spectroscopy not only overcomes the weakness of absorption spectroscopy in simultaneously measuring homonuclear diatomic molecules but also enables the simultaneous detection of multiple gases using a single-wavelength laser. However, due to the small Raman scattering cross-section and weak intensity of molecules, its application in gas detection is limited. To enhance the intensity of Raman scattering, this paper designs and constructs a multi-pass enhanced Raman spectroscopy setup. This study focuses on the effects of Raman scattering collection geometry, laser multi-pass patterns, and laser polarization relative to the Raman collection direction on signal intensity. Investigations into Raman scattering collection angles of 30°, 60°, and 90° reveal that the Raman scattering signal intensity increases as the collection angle decreases. Different laser multi-pass patterns also impact the signal, with the near-concentric linear multi-pass pattern found to collect more signals. To minimize the influence of excitation light on the signal, a side collection system is employed. Experiments show that the Raman scattering signal is stronger when the laser polarization is perpendicular to the collection direction. This study achieves overall system performance enhancement through coordinated optimization of multiple physical mechanisms, including Raman scattering collection geometry, laser multi-pass patterns, and laser polarization characteristics. The optimized setup was employed to characterize the laser power dependence for nitrogen, oxygen, and carbon dioxide detection. The results showed that the Raman scattering intensity varied linearly with the laser power of the gases, with linear fitting goodness R² values of 0.9902, 0.9848, and 0.9969, respectively. Finally, by configuring different concentrations of carbon dioxide gas using nitrogen, it was found that the Raman scattering intensity varied linearly with the concentration of carbon dioxide, with a linear fitting goodness R² of 0.9812. The system achieves a CO₂ detection limit of 500 ppm at 200 s integration time, meeting the requirements for greenhouse gas emission monitoring applications. Full article

Achnanthidium minutissimum is a widely distributed benthic freshwater diatom. The alga can produce stalks that stick the cell to the surface and subsequently extracellular capsules developing into biofilms. Extracts of the diatom-associated bacterium Dyadobacter sp. 32 have been shown previously to induce stalk and capsule formation by the diatom. Here, we studied the impact of macronutrients on the generation of stalks induced by bacterial extracts with respect to the frequency of stalk generation and stalk lengths, using axenic cultures to avoid any additional impact of bacteria on the nutrient availability. We found that nitrate deprivation inhibited cell division of A. minutissimum within four days, but it did not initially affect stalk production or elongation. Silica limitation instead inhibited both stalk production and elongation. Similarly, sulfate was required for stalk formation, which was supported by the energy-dispersive X-ray spectroscopy of A. minutissimum cells showing that sulfur was abundant in the stalks. Full article

Marennine is the specific bluish pigment produced by the marine diatom Haslea ostrearia Gaillon (Simonsen), responsible for the greening of oysters in France’s Atlantic coast. For decades, H. ostrearia was considered the only blue diatom and described as such. However, new blue Haslea species have been described recently, among which Haslea karadagensis Davidovich, Gastineau, and Mouget (Black Sea, Crimea, Ukraine); Haslea provincialis Gastineau, Hansen, and Mouget (Mediterranean Sea, southern France); Haslea silbo Gastineau, Hansen, and Mouget (West Atlantic Ocean, USA); and one not characterized yet, Haslea sp. nov., isolated in Tenerife (Spain). These species produce marennine-like pigments, for which little information is available yet. The present work aims at studying spectral characteristics of these pigments by UV–visible spectrometry, Raman spectrometry, infrared spectrometry, nuclear magnetic resonance, energy-dispersive X-ray spectroscopy, and cyclic voltammetry, and comparing them to those of marennine produced by H. ostrearia strains originating from the north Atlantic Ocean (western France and Macaronesia), and north Pacific Ocean (southwestern USA). Results show that marennine produced by H. ostrearia strains and marennine-like pigments produced by H. provincialis, H. silbo, and Haslea sp. nov. are quite similar regarding their polysaccharide skeleton, and absorption in the UV–visible, infrared, and Raman regions. The most different marennine-like pigment is produced by H. karadagensis, but all Haslea blue pigments studied so far belong to the same family of organic molecules. Full article

Recent progress in studies of Rydberg double-well electronic energy states of MeNg (Me = 12-group atom, Ng = noble gas atom) van der Waals (vdW) molecules is presented and analysed. The presentation covers approaches in experimental studies as well as ab initio-calculations of potential energy curves (PECs). The analysis is shown in a broader context of Rydberg states of hetero- and homo-diatomic molecules with PECs possessing complex ‘exotic’ structure. Laser induced fluorescence (LIF) excitation spectra and dispersed emission spectra employed in the spectroscopical characterization of Rydberg states are presented on the background of the diverse spectroscopic methods for their investigations such as laser vaporization–optical resonance (LV-OR), pump-and-probe methods, and polarization labelling spectroscopy. Important and current state-of-the-art applications of Rydberg states with irregular potentials in photoassociation (PA), vibrational and rotational cooling, molecular clocks, frequency standards, and molecular wave-packet interferometry are highlighted. Full article

Pursuing improved electrode materials is essential for addressing the challenges associated with large-scale Li-ion battery applications. Specifically, silicon oxide (SiO_x) has emerged as a promising alternative to graphite anodes, despite issues related to volume expansion and rapid capacity degradation. In this study, we synthesized carbon-coated SiO_x using diatom biomass derived from artificially cultured diatoms. However, the inherent carbon content from diatoms poses a significant challenge for the electrochemical performance of diatom-based anodes in large-scale applications. Subsequently, we conducted further research and demonstrated excellent performance with a carbon content of 33 wt.% as anodes. Additionally, real-time characterization of the carbonization process was achieved using thermogravimetry coupled with infrared spectroscopy and gas chromatography mass spectrometry (TG-FTIR-GCMS), revealing the emission of CO and C₃O₂ during carbonization. Furthermore, electrochemical tests of the processed diatom and carbon (PD@C) anode exhibited outstanding rate capability (~500 mAh g⁻¹ at 2 A g⁻¹), high initial Coulomb efficiency (76.95%), and a D_Li⁺ diffusion rate of 1.03 × 10⁻¹² cm² s⁻¹. Moreover, structural characterization techniques such as HRTEM-SAED were employed, along with DFT calculations, to demonstrate that the lithium storage process involves not only reversible transport in Li₂Si₂O₅ and Li₂₂Si₅, but also physical adsorption between the PD and C layers. Exploring the integration of diatom frustules with the intrinsic carbon content in the fabrication of battery anodes may contribute to a deeper understanding of the mechanisms behind their successful application. Full article

Magnesium monofluoride is a polar molecule amenable to laser cooling which has caused renewed interest in its spectroscopy. In this work, we consider the case of three low-lying electronic excitations, namely $X^2{\mathrm{\Sigma }}^{+}$→$A^2\mathrm{\Pi }$, $X^2{\mathrm{\Sigma }}^{+}$→$B^2{\mathrm{\Sigma }}^{+}$, $X^2{\mathrm{\Sigma }}^{+}$→$C^2{\mathrm{\Sigma }}^{+}$, using well-developed quantum chemistry approaches, i.e., without reference to the spin-orbit splitting of the $A^2\mathrm{\Pi }$ states. Accurate experimental data for these transitions have been available for over 50 years. Here, we explore the linear response method at the level of CC2 theory, as well as equation of motion methods at the level of CCSD and CC3, using two families of basis sets. Excellent agreement is obtained for the first three transitions when using the correlation-consistent basis sets and extrapolation to the complete basis limit within EOM-CC3 (at a relative precision of ${10}^{-4}$), and qualitative agreement for the other two methods. The purpose of this paper is to serve as a guide on how to approach the accurate calculation of excitations in polar diatomic molecules. Full article

Microbial degradation represents an eco-friendly alternative to traditional physicochemical treatments in removing persistent and toxic environmental pollutants, including synthetic dyes (i.e., methylene blue, MB) employed in different industries. The exploitation of thermophilic bacilli, such as those isolated from the shallow hydrothermal vents of the Eolian Islands (Italy), could provide valuable resources for the treatment of warm, dye-containing wastewater. In this study, we evaluated the ability of preformed biofilms on polypropylene perforated balls (BBs) of fifteen thermophilic bacilli, to decolor, degrade, and detoxify MB in aqueous solutions. Among them, BBs of Bacillus licheniformis B3-15 and Bacillus sp. s7s-1 were able to decolorize MB more than 50% in saline solution (NaCl 2%), incubated in static conditions at 45 °C for 48 h. At optimized initial conditions (10 mg L⁻¹ MB, pH 5.2 for B3-15 or pH 4 for s7s-1), the two strains enhanced their decolorization potential, reaching 96% and 67%, respectively. As indicated by ATR-FTIR spectroscopy, the treatment with BB B3-15 was the most efficient in degrading the Cl–C and –NH groups of MB. This degraded solution was 40% less toxic than undegraded MB, and it has no impact on the bioluminescence of Vibrio harveyi, nor the growth of the marine diatom Phaeodactylum tricornutum. Biofilm formed by strain B3-15 on polypropylene perforated balls could be proposed as a component of bioreactors in the treatment of warm, dye-containing wastewater to concomitantly remediate MB pollution and simultaneously counteract harmful effects in aquatic environments. Full article

The perpetually fluctuating economic and environmental climate significantly increases the demand for alternative fuel sources. The utilization of hydrogen gas is a viable option for such a fuel source. Hydrogen is one of the most energy-dense known substances; however, it is unfortunately also highly volatile, especially in the diatomic gaseous state most commonly used to store it. The utilization of a hydrogen feedstock material such as sodium borohydride (NaBH₄) may prove to mitigate this danger. When NaBH₄ reacts with water, hydrogen stored within its chemical structure is released. However, the rate of hydrogen release is slow and thus necessitates a catalyst. Platinum nanoparticles were chosen to act as a catalyst for the reaction, and to prevent them from conglomerating, they were embedded in a backbone of mesoporous carbon material (MCM) derived from a sustainable corn starch source. The nanocomposite (Pt-MCM) was characterized via transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD). Pt-MCM underwent catalytic testing, revealing that the catalytic activity of the Pt-MCM composite catalysts increased with increasing quantities of sodium borohydride, lower pH levels, and higher temperatures. The activation energy of the catalyzed reaction was found to be 37.7 kJ mol⁻¹. Reusability experiments showed an initial drop off in hydrogen production after the first trial but subsequent stability. This Pt-MCM catalyst’s competitive activation energy and sustainable MCM backbone derived from readily available corn starch make it a promising option for optimizing the hydrogen generation reaction of NaBH₄. Full article

The geometric structure and bonding features of dinuclear vanadium-group transition metal carbonyl cation complexes in the form of VM(CO)_n⁺ (n = 9–11, M = V, Nb, and Ta) are studied by infrared photodissociation spectroscopy in conjunction with density functional calculations. The homodinuclear V₂(CO)₉⁺ is characterized as a quartet structure with C_S symmetry, featuring two side-on bridging carbonyls and an end-on semi-bridging carbonyl. In contrast, for the heterodinuclear VNb(CO)₉⁺ and VTa(CO)₉⁺, a C_2V sextet isomer with a linear bridging carbonyl is determined to coexist with the lower-lying C_S structure analogous to V₂(CO)₉⁺. Bonding analyses manifest that the detected VM(CO)₉⁺ complexes featuring an (OC)₆M–V(CO)₃ pattern can be regarded as the reaction products of two stable metal carbonyl fragments, and indicate the presence of the M–V d-d covalent interaction in the C_S structure of VM(CO)₉⁺. In addition, it is demonstrated that the significant activation of the bridging carbonyls in the VM(CO)₉⁺ complexes is due in large part to the diatomic cooperation of M–V, where the strong oxophilicity of vanadium is crucial to facilitate its binding to the oxygen end of the carbonyl groups. The results offer important insight into the structure and bonding of dinuclear vanadium-containing transition metal carbonyl cluster cations and provide inspiration for the design of active vanadium-based diatomic catalysts. Full article

New 3D micro-nanostructured composite materials have been synthesised. These materials comprise SiO₂/CaCO₃/C_org/NdVO₄NPs and SiO₂/CaO/C_org/NdVO₄NPs, exhibiting strong upconversion luminescence. The synthesis was accomplished by metabolically doping diatom cells with neodymium and vanadium. Subsequently, the biomass of these doped diatoms was subjected to pyrolysis at 800 °C. The morphology, structure, and physicochemical properties of the doped diatom biomass as well as dried (SiO₂/CaCO₃/C_org/NdVO₄NPs) and pyrolysed (SiO₂/CaO/C_org/NdVO₄NPs) samples were characterised using scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), energy dispersive X-ray spectroscopy (EDX), X-ray powder diffraction (XRD), thermal analysis (TG), and fluorescence spectroscopy (FS). Studies have shown that the surface of diatom shells is covered with trigonal prismatic nanocrystallites (nanoparticles) of NdVO₄ with dimensions of 30–40 nm, forming the crystallite clusters in the form of single-layer irregular flakes. The synthesised composites produced intense anti-Stokes fluorescent emission in the visible region under xenon lamp excitation in the near-infrared (λ_ex = 800 nm) at room temperature in an ambient atmosphere. Such materials could be attractive for applications in solar spectrum conversion, optical sensing, biosensors, or photocatalysts. Full article