Search Results (391)

Spruce wood is a natural polymeric material, consisting of cellulose, lignin, hemicelluloses and other secondary components, which gives it a unique chemical footprint and architecture. Varnishes are used in musical instruments to protect the wood against humidity variations, wood being a hygroscopic material, but also to protect the wood from dirt. The varnishes used both to protect the wood from resonance and to ensure a special aesthetic appearance are either polymeric varnishes (nitrocellulose, oil-based) or volatile solvents (spirit). In this study, the color changes, the surface morphology and the chemical spectrum produced by three types of varnishes, applied in 5, 10 and 15 layers, on resonance spruce plates were analyzed. The results revealed significant changes in the color parameters: the lightness decreased by approximately 17% after the first layer, by 50% after 5 layers, by 65% after 10 layers and by 70% after 15 layers. The color parameters are most influenced by the anatomical quality of spruce wood (annual ring width and earlywood/latewood ratio) in the case of oil-based varnishes and least influenced in the case of nitrocellulose varnishes. The chemical fingerprint was determined by FTIR spectrum analysis, which revealed that the most pronounced absorptions were the double band 2926–2858 cm⁻¹, corresponding to aliphatic methylene and methyl groups (asymmetric and symmetrical C-H stretch), and the bands at 1724 cm⁻¹ (oil-based varnish), 1722 cm⁻¹ (nitrocellulose varnish) and 1708 cm⁻¹ (spirit varnish), all assigned to non-conjugated carbonyl groups in either carboxylic acids, esters aldehydes or ketones. The novelty of the study lies in the comparative analysis of three types of varnishes used in the musical instrument industry, applied to samples of spruce resonance wood with different macroscopic characteristics in three different layer thicknesses. Full article

Background: Population persistence for organisms to survive in a world with a rapidly changing climate will require either dispersal to suitable areas, evolutionary adaptation to altered conditions and/or sufficient phenotypic plasticity to withstand it. Given the slow growth and geographically isolated populations of many tree species, there is a high likelihood of local adaption or the acclimation of functional traits in these populations across the UK. Objectives: Given the slow growth and often isolated populations of Tilia cordata (lime tree), we hypothesised that there is a high likelihood of local adaptation or the acclimation of metabolic traits in these populations across the UK. Our aim was to test if the functional metabolomic traits of Tilia cordata (lime tree), collected in situ from natural populations, varied within and between populations and to compare this to neutral allele variation in the population. Methods: We used a metabolic fingerprinting approach to obtain a snapshot of the metabolic status of leaves collected from T. cordata from six populations across the UK. Environmental metadata, longer-term functional traits (specific leaf area) and neutral allelic variation in the population were also measured to assess the plastic capacity and local adaptation of the species. Results: The metabolic fingerprints derived from leaf material collected and fixed in situ from individuals in six populations of T. cordata across its UK range were similar, despite contrasting environmental conditions during sampling. Neutral allele frequencies showed almost no significant group structure, indicating low differentiation between populations. The specific leaf area did vary between sites. Conclusions: The low metabolic variation between UK populations of T. cordata despite contrasting environmental conditions during sampling indicates high levels of phenotypic plasticity. Full article

In this study, we perform density functional theory (DFT) simulations to investigate the Raman spectra of the bulk and surface phases of β-Li₃PS₄ (LPS) and Li₂S, as well as their interfaces at varying compositional ratios. This analysis is relevant given the widespread application of these materials in Li–S solid-state batteries, where Li₂S functions not only as a cathode material but also as a protective layer for the lithium anode. Understanding the interfacial structure and how compositional variations influence its chemical and mechanical stability is therefore crucial. Our results demonstrate that the LPS/Li₂S interface remains stable regardless of the compositional ratio. However, when the content of both materials is low, the Raman-active vibrational mode associated with the [PS₄]³⁻ tetrahedral cluster dominates the interface spectrum, effectively obscuring the characteristic peaks of Li₂S and other interfacial features. Only when sufficient amounts of both LPS and Li₂S are present does the coupling between their vibrational modes become sufficiently pronounced to alter the Raman profile and reveal distinct interfacial fingerprints. Full article

Inelastic electron tunneling spectroscopy (IETS) has emerged as a powerful vibrational spectroscopy technique for molecular electronic junctions, providing unique insights into molecular vibrations and electron–phonon coupling at the nanoscale. In this review, we present a comprehensive overview of IETS in molecular junctions, tracing its development from foundational principles to the latest advances. We begin with the theoretical background, detailing the mechanisms by which inelastic tunneling processes generate vibrational fingerprints of molecules, and highlighting how IETS complements optical spectroscopies by accessing electrically driven vibrational excitations. We then discuss recent progress in experimental techniques and device architectures that have broadened the applicability of IETS. Central focus is given to emerging applications of IETS over the last decade: molecular sensing (identification of chemical bonds and conformational changes in junctions), thermoelectric energy conversion (probing vibrational contributions to molecular thermopower), molecular switches and functional devices (monitoring bias-driven molecular state changes via vibrational signatures), spintronic molecular junctions (detecting spin excitations and spin–vibration interplay), and advanced data analysis approaches such as machine learning for interpreting complex tunneling spectra. Finally, we discuss current challenges, including sensitivity at room temperature, spectral interpretation, and integration into practical devices. This review aims to serve as a thorough reference for researchers in physics, chemistry, and materials science, consolidating state-of-the-art understanding of IETS in molecular junctions and its growing role in molecular-scale device characterization. Full article

This study reported covalent organic frameworks (COFs) and their hybrid composites with two-dimensional materials, graphene oxide (GO), graphitic carbon nitride (g-C₃N₄), and boron nitride (BN), to examine their structural, textural, and gas adsorption properties. Material characterization confirmed the crystallinity of COF-1 and the preservation of framework integrity after integrating the 2D nanomaterials. FT-IR spectra exhibited pronounced vibrational fingerprints of imine linkages and validated the functional groups from the COF and the integrated nanomaterials. TEM images revealed the integration of the two components, porous, layered structures with indications of interfacial interactions between COF and 2D nanosheets. Nitrogen adsorption–desorption isotherms revealed the microporous characteristics of the COFs, with hysteresis loops evident, indicating the development of supplementary mesopores at the interface between COF-1 and the 2D materials. The BET surface area of pristine COF-1 was maximal at 437 m²/g, accompanied by significant micropore and Langmuir surface areas of 348 and 1290 m²/g, respectively, offering enhanced average pore widths and hierarchical porous strcuture. CO₂ adsorption tests were investigated showing maximum adsorption capacitiy of 1.47 mmol/g, for COF-1, closely followed by COF@BN at 1.40 mmol/g, underscoring the preserved sorption capabilities of these materials. These findings demonstrate the promise of designed COF-based hybrids for gas capture, separation, and environmental remediation applications. Full article

Natural colorants, with their sustainable origins, offer a promising alternative for various applications. Advanced studies have unveiled the remarkable properties, resilience, and durability of these ancient dyes, which our ancestors developed through sustainable material processing. This serves as a testament to the potential of sustainable solutions in our field. As part of our research, we prepared three medieval temperas using gum arabic, parchment glue, and casein glue. These tempera were explicitly designed to protect the purples obtained from Chrozophora tinctoria extracts. A comprehensive multi-analytical approach guides our research on natural colorants. Central to this approach is the use of molecular fluorescence by microspectrofluorimetry, a key tool in our study. By analyzing the emission and excitation spectra in the visible range, we can identify specific formulations. This method is further supported by fingerprinting techniques, including Fourier Transform Infrared Spectroscopy (FTIR) and High-Performance Liquid Chromatography with Diode Array Detection (HPLC-DAD). These are further complemented by Fiber Optics Reflectance Spectroscopy (FORS) and colorimetry. Building on our understanding of orcein purples, we have extended our research to purples derived from Chrozophora tinctoria extracts. Our findings reveal the unique properties of Chrozophora tinctoria, which can be accurately distinguished from orcein purples, highlighting the distinctiveness of each. Full article

Papilloscopy, the science of human identification through fingerprints, has seen notable advancements in developing less toxic latent fingerprint developers (LFDs), especially from natural feedstock. Tannins, the second most abundant natural polyphenol, present a potential eco-friendly and cost-effective alternative, with no record of their use as LFDs in the existing literature. This study characterized four types of tannins from black wattle, using Fourier Transform Infrared Spectroscopy, revealing key functional groups like C=O, C=C, and O–H. Ultraviolet–visible absorption spectra showed similar behaviors for all tannins, indicating phenolic and benzenoid structures. Energy-dispersive X-ray Spectroscopy identified high concentrations of chlorine, sodium, potassium, and sulfur, naturally found in biomass and soil. Finally, elements in significant concentrations, such as sodium, potassium, iron, zinc, and copper, were found through the incineration of the spent bark. On the basis of these findings, the tannin with the highest potential for LFD was selected. Combining this tannin with spent bark ash resulted in a composite whose performance was evaluated using different methods, including depletion studies, tests with various donors, and assessments on different surfaces. The results demonstrated that this combination significantly enhanced the material’s efficiency by integrating organic and inorganic properties, which improved visual contrast and powder adhesion. Full article

Compounds containing the pentazolate anion (cyclo-N₅⁻) represent a distinctive group of energetic materials that have received extensive attention in recent years. Cyclo-N₅⁻ was used as a polynitrogen anion for the syntheses of energetic salts through metathesis reactions. Propamidinium (1), 5-amino-4-carbamoyl-1H-imidazol-3-ium (2), (1H-1,2,3-triazol-4-yl)methanaminium (3), 5-amino-4H-1,2,4-triazol-1-ium (4), 5-amino-3-methyl-4H-1,2,4-triazol-1-ium (5), and amino(pyrimidin-2-yl)methaniminium (6) pentazolates were obtained with high yields (>80%), and their crystal structures were confirmed through single-crystal X-ray diffraction analyses. Hirshfeld surface analyses and 2D fingerprint plots generated by CrystalExplorer17 demonstrated that these compounds exhibited extensive hydrogen-bonding networks in their crystal packing. Mechanical sensitivity tests showed that all the prepared salts were highly insensitive (IS > 35 J, FS > 360 N), providing valuable insights for the further exploration of broader energetic materials containing cyclo-N₅⁻. Full article

We present a comprehensive structural and thermomechanical investigation of N-salicylideneaniline, a Schiff base derivative that exhibits remarkable thermosalient phase transition behavior. By combining variable-temperature X-ray powder diffraction (VT-XRPD), differential scanning calorimetry (DSC), hot-stage microscopy, and Hirshfeld surface analysis, we reveal two distinct thermosalient mechanisms operating in different polymorphic forms. Form I displays pronounced anisotropic thermal expansion with negative strain along a principal axis, culminating in a sudden and explosive phase transition into Form IV. In contrast, Form III transforms more gradually through a microstrain accumulation mechanism. Fingerprint plots and contact evolution from Hirshfeld surface analysis further support this dual-mechanism model. These insights highlight the importance of integrating macro- and microscale structural descriptors to fully capture the mechanical behavior of responsive molecular solids. The findings not only enhance the fundamental understanding of thermosalience but also inform the rational design of functional materials for actuating and sensing applications. Full article

Sub-wavelength metallic nanostructures allow the squeezing of light within nanoscale regions, called plasmonic hotspots. Squeezed near-field light has been demonstrated to detect, modulate, and generate light in more effective ways. The enhanced electric field in the plasmonic hotspots are also utilized for identifying molecular fingerprints in a more sensitive manner, i.e., surface-enhanced Raman spectroscopy (SERS). SERS is a versatile tool used to characterize chemicals and biomolecules with the advantages of label-free detection, specificity, and high sensitivity compared to fluorescence and colorimetric sensing methods. With its practical and diverse applications such as biomedical sensing, the evaluation of SERS on diverse nano-structure platforms and materials is highly in demand. Nanogap structures are promising SERS platforms which can be fabricated over a large area with uniform nanoscale gap size. Here, we demonstrate the fabrication of large-area metal–insulator–metal nanogap structures with different metals (i.e., Au and Ag) and analyze material dependence on SERS. While both nanometer-sized gap structures exhibit a large enhancement factor for Raman spectroscopy, Ag-based structures exhibit 58- and 15-times-larger enhancement factors for bottom and top plasmonic hotspots, respectively. The enhanced detection on a silver nanogap platform is attributed to enhanced electric field in the gap, as confirmed by simulation. Our findings provide not only a way to better understand SERS in different metallic nano platforms but also insights for designing highly sensitive nanoscale chemical and biomedical sensors. Full article

This investigation of hydroxyl and polysiloxane absorption peaks in elastic polymer composites reveals significant spectral shifts within the fingerprint region of FTIR spectra. Using poly(vinyl butyral) (PVB) as the base polymer and poly(vinyl acetate) (PVAc) and poly(vinyl alcohol) (PVA) as reference materials, solvent effects on polymer–solvent interactions were systematically analyzed. Among the tested alcohol solvents, PEG 400 induced the most pronounced spectral changes, with the C=O stretching band shifting from 1740 to 1732 cm⁻¹ and the O–H band significantly broadening and downshifting to around 3300 cm⁻¹, reflecting strong hydrogen-bonding interactions. Wavelet-based noise reduction effectively enhanced the signal-to-noise ratio, reducing the baseline standard deviation by over 90%. This study introduces a novel noise-enhanced FTIR recognition model that integrates baseline noise metrics to improve detection sensitivity. The model successfully uncovers subtle structural variations in polymer–solvent systems that are typically masked by conventional FTIR techniques, advancing materials analysis and providing a robust framework for future FTIR-based diagnostics and material characterization. Full article

For authentication and interpretation of palm-leaf manuscripts, material analyses are required that enable identification of specific characteristics of written artefacts. In this study, we apply infrared spectroscopy (DRIFTS) in combination with principal component analysis (PCA) as a fingerprinting technique for the analysis of eleven palm-leaf manuscripts. We demonstrate that manuscript-specific information is obtained and that a differentiation regarding the taxonomic species of palm leaves used for production and of their geographical origin in South and Southeast Asia is possible. The results show the potential of infrared spectroscopy for fingerprinting and authentication of written artefacts. Full article

Serpentinite is a common lithology in Greece with significant geotectonic and petrogenetic implications, yet its archaeometric study remains limited. This also applies to the Ras serpentinite outcrop on Tinos Island—an enigmatic ancient quarry with no prior documentation of its exploitation. This study aims to provide a holistic provenance analysis and full material characterization to establish a unique fingerprint for future comparative research. A multidisciplinary methodology was applied, including petrography, XRD, FTIR, BET, LA-ICP-MS, electron microprobe analyses, and lichenometry—the latter used to estimate the quarry’s period of activity. The Ras serpentinite consists of a dark-green, brecciated lizardite matrix cut by a pale-green chrysotile network, and notably hosts the first recorded occurrence of minnesotaite in Greece. Relict antigorite within the matrix indicates high-pressure, high-temperature metamorphism preceding a greenschist facies overprint. Geochemical data classify the Ras occurrence as a subduction-related serpentinite derived from a depleted ultrabasic protolith. The aforementioned traits distinguish it from other Greek examples. Lichenometric analysis suggests the quarry was active in the 13th century A.D., with evidence of deliberate extraction techniques. These findings offer valuable insights into archaeometric studies and the provenance of serpentinites in the Aegean. Full article

This study introduces a novel contrastive learning-based X-ray diffraction (XRD) analysis framework, an SE(3)-equivariant graph neural network (E3NN) based Atomic Cluster Expansion Neural Network (EACNN), which reduces the strong dependency on databases and initial models in traditional methods. By integrating E3NN with atomic cluster expansion (ACE) techniques, a dual-tower contrastive learning model has been developed, mapping crystal structures and XRD patterns to a continuous embedding space. The EACNN model retains hierarchical features of crystal systems through symmetry-sensitive encoding mechanisms and utilizes relationship mining via contrastive learning to replace rigid classification boundaries. This approach reveals gradual symmetry-breaking patterns between monoclinic and orthorhombic crystal systems in the latent space, effectively addressing the recognition challenges associated with low-symmetry systems and small sample space groups. Our investigation further explores the potential for model transfer to experimental data and multimodal extensions, laying the theoretical foundation for establishing a universal structure–property mapping relationship. Full article

Background: In response to the growing demand for the real-time, in-field characterization of odorous anthropogenic emissions, this study develops and uses a MEMS-based micropacked thermal desorption Gas Chromatography system coupled with a PhotoIonization Detector (GC/PID) for Hot Mix Asphalt (HMA) plant emissions. Methods: The innovative portable device, Pyxis GC, enables the high-sensitivity profiling of Volatile Organic Compounds (VOCs), particularly aldehydes and ketones, with sub-ppb detection limits using ambient air as the carrier gas. A comprehensive experimental design optimized the preconcentration parameters, resulting in an efficient, green analytical method evaluated via the Green Analytical Procedure Index (GAPI). Sorbent comparison showed quinoxaline-bridged cavitands outperform the conventional materials. Results and conclusions: The method was successfully deployed on site for source-specific sampling at an HMA plant, generating robust emission fingerprints. To assess environmental impact, a Generalized Additive Model (GAM) was developed, incorporating the process temperature and Sum of Odour Activity Values (SOAV) to predict odour concentrations. The model revealed a significant non-linear influence of temperature on emissions and validated its predictive capability despite the limited sample size. This integrated analytical–statistical approach demonstrates the utility of MEMS technology for real-time air quality assessment and odour dispersion modelling, offering a powerful tool for environmental monitoring and regulatory compliance. Full article