Promising Molecular Architectures for Two-Photon Probes in the Diagnosis of α-Synuclein Aggregates.

The abnormal deposition of protein in the brain is the central factor in neurodegenerative disorders (NDs). These detrimental aggregates, stemming from the misfolding and subsequent irregular aggregation of α-synuclein protein, are primarily accountable for conditions such as Parkinson's disease, Alzheimer's disease, and dementia. Two-photon-excited (TPE) probes are a promising tool for the early-stage diagnosis of these pathologies as they provide accurate spatial resolution, minimal intrusion, and the ability for prolonged observation. To identify compounds with the potential to function as diagnostic probes using two-photon techniques, we explore three distinct categories of compounds: Hydroxyl azobenzene (AZO-OH); Dicyano-vinyl bithiophene (DCVBT); and Tetra-amino phthalocyanine (PcZnNH2). The molecules were structurally and optically characterized using a multi-technique approach via UV-vis absorption, Raman spectroscopy, three-dimensional fluorescence mapping (PLE), time-resolved photoluminescence (TRPL), and pump and probe measurements. Furthermore, quantum chemical and molecular docking calculations were performed to provide insights into the photophysical properties of the compounds as well as to assess their affinity with the α-synuclein protein. This innovative approach seeks to enhance the accuracy of in vivo probing, contributing to early Parkinson's disease (PD) detection and ultimately allowing for targeted intervention strategies.

Rapid In Situ Detection of THC and CBD in Cannabis sativa L. by 1064 nm Raman Spectroscopy.

The need to find a rapid and worthwhile technique for the in situ detection of the content of delta-9-tetrahydrocannabinol (THC) and cannabidiol (CBD) in Cannabis sativa L. is an ever-increasing problem in the forensic field. Among all the techniques for the detection of cannabinoids, Raman spectroscopy can be identified as the most cost-effective, fast, noninvasive, and nondestructive. In this study, 42 different samples were analyzed using Raman spectroscopy with 1064 nm excitation wavelength. The use of an IR wavelength laser showed the possibility to clearly identify THC and CBD in fresh samples, without any further processing, knocking out the contribution of the fluorescence generated by visible and near-IR sources. The results allow assigning all the Raman features in THC- and CBD-rich natural samples. The multivariate analysis underlines the high reproducibility of the spectra and the possibility to distinguish immediately the Raman spectra of the two cannabinoid species. Furthermore, the ratio between the Raman bands at 1295/1440 and 1623/1663 cm-1 is identified as an immediate test parameter to evaluate the THC content in the samples.

Synergistic effects of Tb doping in long-persistent luminescence in Ca3Ga4O9: xBi3+, yZn2+ phosphors: Implications for novel phosphorescent materials.

Long afterglow phosphors constitute an emerging class of compounds with wide application in several fields, from photonic to dosimetry, solar energy storage and photocatalysis. In this study, we synthesized and thoroughly characterized a new class of persistent emitting materials, Ca3Ga4O9: xBi3+, yZn2+, zTb3+. Through the utilization of X-ray and Raman spectroscopy, as well as optical measurements including static and time-resolved luminescence, thermoluminescence, and phosphorescence, the effects of the Tb concentration on the optical and structural properties of the material has been deeply studied. A suitable mechanism was proposed to account for the long afterglow emission, wherein Tb3+ and Bi3+ ions occupying the Ca2+ sites serve as recombination centers, facilitating the generation of oxygen defects. Zn2+ in the Ga3+ sites, contribute to the charge balance and generates hole traps in the matrix. The enduring phosphorescence persists for over 3 h following the cessation of UV irradiation, discernible to the naked eye in low-light conditions.

Stratigraphy of Fresco Paintings: A New Approach with Photoacoustic and SORS Imaging.

Photoacoustic (PA) imaging is a novel, powerful diagnostic technique utilized in different research fields. In particular, during recent years it has found several applications in Cultural Heritage (CH) diagnostics. PA imaging can be realized in transmittance or epi-illumination (reflectance) modes, obtaining variable levels of contrast and spatial resolution. In this work, we confirmed the applicability of the PA technique as a powerful tool for the imaging of one of the most challenging artwork objects, namely fresco wall paints, to obtain precise stratigraphic profiles in different layered fresco samples. In this regard, we studied some multi-layered fragments of the vault of San Giuseppe Church in Cagliari (1870 AD) and some mock-ups realized specifically to test the potentiality of this technique. Due to complex structures of the frescoes, we used the Spatially Off-set Raman Spectroscopy (SORS) technique to provide complementary information. The experimental results were in agreement for both techniques, even for the three-layered complex structure, and were confirmed with Scanning Electron Microscopy (SEM) analysis of cross-sections. The combined use of these two techniques proved useful to investigate detailed hidden information on the fresco samples.

Selecting molecular or surface centers in carbon dots-silica hybrids to tune the optical emission: A photo-physics study down to the atomistic level.

In this work, we unveil the fluorescence features of citric acid and urea-based Carbon Dots (CDs) through a photo-physical characterization of nanoparticles synthesized, under solvent-free and open-air conditions, within silica-ordered mesoporous silica, as a potential host for solid-state emitting hybrids. Compared to CDs synthesized without silica matrices and dispersed in water, silica-CD hybrids display a broader emission in the green range whose contribution can be increased by UV and blue laser irradiation. The analysis of hybrids synthesized within different silica (MCM-48 and SBA-15) calls for an active role of the matrix in directing the synthesis toward the formation of CDs with a larger content of graphitic N and imidic groups at the expense of N-pyridinic molecules. As a result, CDs tuned in size and with a larger green emission are obtained in the hybrids and are retained once extracted from the silica matrix and dispersed in water. The kinetics of the photo-physics under UV and blue irradiation of hybrid samples show a photo-assisted formation process leading to a further increase of the relative contribution of the green emission, not observed in the water-dispersed reference samples, suggesting that the porous matrix is involved also in the photo-activated process. Finally, we carried out DFT and TD-DFT calculations on the interaction of silica with selected models of CD emitting centers, like surface functional groups (OH and COOH), dopants (graphitic N), and citric acid-based molecules. The combined experimental and theoretical results clearly indicate the presence of molecular species and surface centers both emitting in the blue and green spectral range, whose relative contribution is tuned by the interaction with the surrounding media.

Optimizing the Mechanoluminescent Properties of CaZnOS:Tb via Microwave-Assisted Synthesis: A Comparative Study with Conventional Thermal Methods.

Recent developments in lighting and display technologies have led to an increased focus on materials and phosphors with high efficiency, chemical stability, and eco-friendliness. Mechanoluminescence (ML) is a promising technology for new lighting devices, specifically in pressure sensors and displays. CaZnOS has been identified as an efficient ML material, with potential applications as a stress sensor. This study focuses on optimizing the mechanoluminescent properties of CaZnOS:Tb through microwave-assisted synthesis. We successfully synthesized CaZnOS doped with Tb3+ using this method and compared it with samples obtained through conventional solid-state methods. We analyzed the material's characteristics using various techniques to investigate their structural, morphological, and optical properties. We then studied the material's mechanoluminescent properties through single impacts with varying energies. Our results show that materials synthesized through microwave methods exhibit similar optical and, primarily, mechanoluminescent properties, making them suitable for use in photonics applications. The comparison of the microwave and conventional solid-state synthesis methods highlights the potential of microwave-assisted methods to optimize the properties of mechanoluminescent materials for practical applications.

Unveiling Hidden Prints: Optically stimulated luminescence for latent fingerprint detection.

Fluorescent lighting and optical techniques have been widely utilized to enhance the detection of latent fingerprints. However, the development of new techniques is imperative to expand the range of surfaces from which latent fingerprints can be detected. When relying on traditional methods, fingerprint evidence can remain undetected or even disregarded due to insufficient detection and limited detail, especially when dealing with a luminescent background. In this study, we propose the utilization of optically stimulated luminescence (OSL) applied to a Ba2SiO4 matrix, co-doped with Eu2+ and Dy3+, as a powerful method for visualizing latent fingerprints on various surfaces, including thin plastic bags, rigid duct tape, thin aluminum foil, and glass slices. This technique effectively eliminates any luminescent background and significantly enhances optical imaging. This represents the first successful application of OSL in the development of latent fingerprints, thus paving the way for more efficient and effective forensic techniques in the future.

Visible Light-Mediated Inactivation of H1N1 Virus UsingPolymer-Based Heterojunction Photocatalyst.

It is well known that viruses cannot replicate on their own but only inside the cells of target tissues in the organism, resulting in the destruction of the cells or, in some cases, their transformation into cancer cells. While viruses have relatively low resistance in the environment, their ability to survive longer is based on environmental conditions and the type of substrate on which they are deposited. Recently, the potential for safe and efficient viral inactivation by photocatalysis has garnered increasing attention. In this study, the Phenyl carbon nitride/TiO2 heterojunction system, a hybrid organic-inorganic photocatalyst, was utilized to investigate its effectiveness in degrading the flu virus (H1N1). The system was activated by a white-LED lamp, and the process was tested on MDCK cells infected with the flu virus. The results of the study demonstrate the hybrid photocatalyst's ability to cause the virus to degrade, highlighting its effectiveness for safe and efficient viral inactivation in the visible light range. Additionally, the study underscores the advantages of using this hybrid photocatalyst over traditional inorganic photocatalysts, which typically only work in the ultraviolet range.

Exploring the Impact of Nitrogen Doping on the Optical Properties of Carbon Dots Synthesized from Citric Acid.

The differences between bare carbon dots (CDs) and nitrogen-doped CDs synthesized from citric acid as a precursor are investigated, aiming at understanding the mechanisms of emission and the role of the doping atoms in shaping the optical properties. Despite their appealing emissive features, the origin of the peculiar excitation-dependent luminescence in doped CDs is still debated and intensively being examined. This study focuses on the identification of intrinsic and extrinsic emissive centers by using a multi-technique experimental approach and computational chemistry simulations. As compared to bare CDs, nitrogen doping causes the decrease in the relative content of O-containing functional groups and the formation of both N-related molecular and surface centers that enhance the quantum yield of the material. The optical analysis suggests that the main emission in undoped nanoparticles comes from low-efficient blue centers bonded to the carbogenic core, eventually with surface-attached carbonyl groups, the contribution in the green range being possibly related to larger aromatic domains. On the other hand, the emission features of N-doped CDs are mainly due to the presence of N-related molecules, with the computed absorption transitions calling for imidic rings fused to the carbogenic core as the potential structures for the emission in the green range.

Degradation of CdS Yellow and Orange Pigments: A Preventive Characterization of the Process through Pump-Probe, Reflectance, X-ray Diffraction, and Raman Spectroscopy.

Cadmium yellow degradation afflicts numerous paintings realized between the XIXth and XXth centuries. The degradation process and its kinetics is not completely understood. It consists of chalking, lightening, flaking, spalling, and, in its most deteriorated cases, the formation of a crust over the original yellow paint. In order to improve the comprehension of the process, mock-up samples of CdS in yellow and orange tonalities were studied by means of structural analysis and optical characterization, with the principal techniques used in the field of cultural heritage. Mock ups were artificially degraded with heat treatment and UV exposure. Relevant colorimetric variation appears in CIE Lab coordinates from reflectance spectra. XRD, SEM-EDS, and Raman spectroscopy revealed the formation of cadmium sulfate, whilst time-resolved photoluminescence and pump-probe transient absorption spectroscopy suggest the formation of a defective phase, compatible with Cd vacancies and the formation of both CdO and CdSO4 superficial clusters.

Formation Mechanisms and Phase Stability of Solid-State Grown CsPbI3 Perovskites.

CsPbI3 inorganic perovskite is synthesized by a solvent-free, solid-state reaction, and its structural and optical properties can be deeply investigated using a multi-technique approach. X-ray Diffraction (XRD) and Raman measurements, optical absorption, steady-time and time-resolved luminescence, as well as High-Resolution Transmission Electron Microscopy (HRTEM) imaging, were exploited to understand phase evolution as a function of synthesis time length. Nanoparticles with multiple, well-defined crystalline domains of different crystalline phases were observed, usually surrounded by a thin, amorphous/out-of-axis shell. By increasing the synthesis time length, in addition to the pure α phase, which was rapidly converted into the δ phase at room temperature, a secondary phase, Cs4PbI6, was observed, together with the 715 nm-emitting γ phase.

Formation of Citrazinic Acid Ions and Their Contribution to Optical and Magnetic Features of Carbon Nanodots: A Combined Experimental and Computational Approach.

The molecular model is one of the most appealing to explain the peculiar optical properties of Carbon nanodots (CNDs) and was proven to be successful for the bottom up synthesis, where a few molecules were recognized. Among the others, citrazinic acid is relevant for the synthesis of citric acid-based CNDs. Here we report a combined experimental and computational approach to discuss the formation of different protonated and deprotonated species of citrazinic acid and their contribution to vibrational and magnetic spectra. By computing the free energy formation in water solution, we selected the most favoured species and we retrieved their presence in the experimental surface enhanced Raman spectra. As well, the chemical shifts are discussed in terms of tautomers and rotamers of most favoured species. The expected formation of protonated and de-protonated citrazinic acid ions under extreme pH conditions was proven by evaluating specific interactions with H2SO4 and NaOH molecules. The reported results confirm that the presence of citrazinic acid and its ionic forms should be considered in the interpretation of the spectroscopic features of CNDs.

Application of Raman Spectroscopy to Ancient Materials: Models and Results from Archaeometric Analyses.

Numerous experimental techniques of analysis find applications in many branches of the archaeometry. Among them, Raman spectroscopy carved out a niche in the field of diagnostic and conservation of cultural heritage. The exceptional ability to predict and discover the structural properties of materials set for Raman spectroscopy, an exclusive role among the analytic techniques, is further boosted when it is coupled with mathematical or statistical models able to deepen the studied phenomena. In this work, we present a review of recent studies where pairing Raman spectroscopy and mathematical models allowed achieving important results in the case of potteries, porcelains, ancient and modern paper, ancient jewelry, and pigment degradation. The potentialities of this approach are evidenced and analyzed in detail.

Exploiting combined absorption and front face fluorescence spectroscopy to chase classification: A proof of concept in the case of Sardinian red wines.

We present the analysis of optical spectroscopy fingerprints of three different varieties of Sardinian red wine, Carignano, Cannonau and Monica, belonging to Italian DOC (Controlled Origin Designation) red wines family. We selected 15 commercial wines (five for each variety), produced in the middle and south regions of Sardinia form monovarietal grapes. Despite different grapes, farming and tasting, all the samples share common absorption and fluorescence features. A two steps analysis is applied to achieve good classification of the wines. We recorded typical absorbance spectra with a large absorption below 300 nm and a visible absorption band at about 520 nm. Colour attributes according to chromaticity coordinates were evaluated by means of transmittance data and coupled to wine aging data to achieve classification. Despite similar values of lightness (L*), chroma (C*ab), and hue angle (h°ab) for the three varieties, good clustering was gathered for Carignano and Cannonau wines, whilst Monica variety has wide spread chromatic coordinates. UV excited fluorescence spectra display large and composite emission bands from the near UV down to the whole visible range. We performed multivariate analysis in the framework of the principal component analysis of fluorescence spectra coupled with absorption ones being able to achieve good clustering between the three varieties. One anomaly among Cannonau wines is discussed.

Raman identification of cuneiform tablet pigments: emphasis and colour technology in ancient Mesopotamian mid-third millennium.

Cuneiform tablets tell the life and culture of Sumerian people in a sort of black and white tale because of the binary engraving technique. A leading question arises: did Mesopotamian people apply some kind of colour to decorate their tablets or to put emphasis on selected words? Some administrative and literary Sumerian cuneiform tablets of mid-third Millennium B.C. from the site of Kish (central Mesopotamia, modern Iraq) were dug up in twentieth-century and stored at the Ashmolean Museum of the Oxford University. Non-destructive micro-Raman spectroscopy is a powerful technique to detect the presence of residual pigments eventually applied to the engraving signs. Yellow, orange, red and white pigments have been detected and a possible identification has been proposed in this work. In particular yellow pigments are identified as Crocoite (PbCrO4), Lead stannate (Pb2SnO4); red pigments - hematite (Fe2O3) and cuprite (Cu2O); White pigments - Lead carbonate (PbCO3), calcium phosphate (Ca3(PO4)2), titanium dioxide (TiO2), gypsum (CaSO4.2H2O); orange pigment a composition of red and yellow compounds. These results suggest that Sumerian people invented a new editorial style, to overcome the binary logic of engraving process and catch the reader's eye by decorating cuneiform tablets. Finally, the coloured rendering of the tablet in their original view is proposed.

Vibrational and optical characterization of s-triazine derivatives.

The optical and electron properties of three different s-triazine derivatives are investigated to ascertain the role of the donor acceptor character in amine-triazine systems depending on the bridging radical of the ammine group. The three derivatives were obtained starting from three different ammine compounds allowing to achieve a structure with a triazine core, surrounded by three ammine group and terminated with cyano or methyl or oxy-methyl functional group. Experimental optical data were interpreted in view of the electronic insights gathered by means of density functional theory simulations on base compounds. As compared to the reference electron donating triazine core, the resulting compounds show different donor acceptor character, from electron accepting to electron donating feature. Among the analyzed derivatives, the cyano terminated ammino-triazine compound shows the most promising optical features for photonics and lighting applications.

Doping porous silicon with erbium: pores filling as a method to limit the Er-clustering effects and increasing its light emission.

Er clustering plays a major role in hindering sufficient optical gain in Er-doped Si materials. For porous Si, the long-standing failure to govern the clustering has been attributed to insufficient knowledge of the several, concomitant and complex processes occurring during the electrochemical Er-doping. We propose here an alternative road to solve the issue: instead of looking for an equilibrium between Er content and light emission using 1-2% Er, we propose to significantly increase the electrochemical doping level to reach the filling the porous silicon pores with luminescent Er-rich material. To better understand the intricate and superposing phenomena of this process, we exploit an original approach based on needle electron tomography, EXAFS and photoluminescence. Needle electron tomography surprisingly shows a heterogeneous distribution of Er content in the silicon thin pores that until now couldn't be revealed by the sole use of scanning electron microscopy compositional mapping. Besides, while showing that pore filling leads to enhanced photoluminescence emission, we demonstrate that the latter is originated from both erbium oxide and silicate. These results give a much deeper understanding of the photoluminescence origin down to nanoscale and could lead to novel approaches focused on noteworthy enhancement of Er-related photoluminescence in porous silicon.