Search Results (64)

The carved lacquer horse-hoof-shaped box excavated from Yulin, Shaanxi Province, represents a typical example of lacquerware preservation in the arid environment of northern China, exhibiting multiple deterioration phenomena, including substrate deformation, lacquer film peeling, and pigment fading. To systematically analyze its structural composition and craftsmanship features, this study employed multiple analytical techniques, including ultra-depth microscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), confocal laser micro-Raman spectroscopy (Raman), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Based on these analyses, a targeted conservation protocol was developed. Results revealed that the carved lacquer horse-hoof-shaped box has a wooden substrate structure, with the lacquer ash layer composed of mixed materials, including calcium carbonate (CaCO₃), quartz (SiO₂), and hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂). The lacquer film layer contains Chinese lacquer and plant oils, with cinnabar applied as surface decoration. Based on these findings, a stratified reinforcement conservation strategy was proposed: under dynamic monitoring with optical fiber sensors and three-dimensional scanning, the wooden substrate was reinforced with moisture-curable polyurethane (MCPU), the lacquer ash layer was strengthened with acrylic emulsion (Primal AC33), aged areas were restored with nano calcium hydroxide (Ca(OH)₂) aqueous dispersion, and polyethylene glycol (PEG 400) poultice application was implemented to restore the flexibility of the lacquer film. This research significantly enhanced the integrity and stability of the carved lacquer horse-hoof-shaped box, providing practical evidence and technical references for the scientific conservation of lacquerware excavated from arid regions of northern China. Full article

This study examines the pigments and materials used in Girolamo Romanino’s Musicians fresco (1537–1538), located in the Duomo Vecchio in Brescia, with the aim of identifying and analyzing the artist’s colour palette. Ten samples of the pictorial layer and mortar were collected from two frescoes and characterized using microscopic and spectroscopic techniques. Confocal laser scanning microscopy (CLSM) was used to define the best positions where single-point, spectroscopic techniques could be applied. Raman spectroscopy and micro-Fourier transform Infrared spectroscopy (micro-FTIR) were used to detect pigments and organic binders, respectively. X-ray powder diffraction (XRPD) provided additional insights into the mineral composition of the pigmenting layers, in combination with environmental scanning electron microscopy equipped with energy-dispersive spectroscopy (ESEM-EDS). The analysis revealed the use of traditional fresco pigments, including calcite, carbon black, ochres, and copper-based pigments. Smalt, manganese earths, and gold were also identified, reflecting Romanino’s approach to colour and material selection. Additionally, the detection of modern pigments such as titanium white and baryte points to restoration interventions, shedding light on the fresco’s conservation history. This research provides one of the most comprehensive analyses of pigments in Romanino’s works, contributing to a deeper understanding of his artistic practices and contemporary fresco techniques. Full article

The Chengyang City (城阳城) site in Xinyang, Henan Province, China, was a significant northern military stronghold of the Chu state during the Warring States period (475/403–221 BCE). The lacquered armor unearthed from Tomb M18 provides critical material evidence for studying ancient military technology and lacquer craftsmanship. In this study, a comprehensive analytical approach combining ultra-depth optical microscopy, Fourier-transform infrared spectroscopy (FTIR), confocal micro-Raman spectroscopy, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS) and pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS) were employed to systematically characterize the structural and compositional features of the armor samples. The results indicate that the armor was constructed with a leather substrate and lacked any lacquer ash layer, while the surface exhibited multiple layers of mixed laccol and urushiol-based lacquer coatings. Cinnabar (HgS) was identified as the primary red pigment, and no carbon black or iron-based blackening agents were detected in the dark lacquer layers. Notably, the presence of laccol suggests that such lacquer resources may have also been produced in mainland China, offering new perspectives on the prevailing view that associates laccol exclusively with “Vietnamese lacquer.” This study elucidates the technological characteristics of mid-Warring States period lacquered armor, provides scientific insights into ancient lacquering techniques, and contributes valuable data for the conservation and restoration of similar cultural heritage artifacts. Full article

Cutaneous melanoma is an aggressive form of skin cancer and a leading cause of cancer-related mortality. In this sense, Raman Spectroscopy (RS) could represent a fast and effective method for melanoma-related diagnosis. We therefore introduced a new method based on RS to distinguish Compound Naevi (CN) from Primary Cutaneous Melanoma (PCM) from ex vivo solid biopsies. To this aim, integrating Confocal Raman Micro-Spectroscopy (CRM) with four Machine Learning (ML) algorithms: Linear Discriminant Analysis (LDA), Quadratic Discriminant Analysis (QDA), Support Vector Machine (SVM), and Random Forest Classifier (RFC). We focused our attention on the comparison between traditional pre-processing operations with Continuous Wavelet Transform (CWT). In particular, CWT led to the maximum classification accuracy, which was ∼89.0%, which highlighted the method as promising in view of future implementations in devices for everyday use. Full article

Until now, achieving both a high spectral resolution on the order of a few wavenumbers and the highest sensitivity in Raman scattering spectroscopy has required reliance on high-end laboratory instruments. Here, we introduce an innovative yet design-wise simple alternative: a cost-effective and compact micro-Raman spectrometer (µRS) that combines exceptional spectral resolution and sensitivity. Leveraging industrial-grade CMOS cameras and high-quality photographic objectives, our µRS maintains a footprint at least five times smaller than traditional lab-based spectrometers. Through detailed characterization and direct experimental comparison, which includes the use of calcite as a Raman standard, we demonstrate that our µRS achieves a spectral resolution of down to 2.5 cm⁻¹. Using a single-layer MoS₂ sample, we found that the sensitivity of our system, while somewhat lower, remains within a useful range compared to commercial research-grade confocal Raman microscopy systems. This study presents a compelling solution for researchers seeking efficient and high-resolution Raman spectroscopy tools across diverse applications, particularly in resource-limited or field-based settings. Full article

Non-isothermal differential scanning calorimetry (DSC) and Raman microscopy were used to study the crystallization behavior of the 20–50 μm amorphous nifedipine (NIF) powder. In particular, the study was focused on the diffusionless glass-crystal (GC) growth mode occurring below the glass transition temperature (T_g). The exothermic signal associated with the GC growth was indeed directly and reproducibly recorded at heating rates q⁺ ≤ 0.5 °C·min⁻¹. During the GC growth, the α_p polymorphic phase was exclusively formed, as confirmed via Raman microscopy. In addition to the freshly prepared NIF samples, the crystallization of the powders annealed for 7 h at 20 °C was also monitored—approx. 50–60% crystallinity was achieved. For the annealed NIF powders, the confocal Raman microscopy verified a proportional absence of the crystalline phase on the sample surface (indicating its dominant formation along the internal micro-cracks, which is characteristic of the GC growth). All DSC data were modeled in terms of the solid-state kinetic equation paired with the autocatalytic model; the kinetic complexity was described via reaction mechanism based on the overlap of 3–4 independent processes. The kinetic trends associated with decreasing q⁺ were identified, confirming the temperature-dependent kinetic behavior, and used to calculate a theoretical kinetic prediction conformable to the experimentally performed 7 h annealing at 20 °C. The theoretical model slightly underestimated the true extent of the GC growth, predicting the crystallinity to be 35–40% after 7 h (such accuracy is still extremely good in comparison with the standard kinetic approaches nowadays). Further research in the field of kinetic analysis should thus focus on the methodological ways of increasing the accuracy of considerably extrapolated kinetic predictions. Full article

Surface-enhanced Raman scattering (SERS) technology has important applications in many fields, such as biomedicine, environmental monitoring, and food safety. Plasmonic nanocavities have the ability to superdiffract localized light and enhance light-matter interactions. As a key SERS active substrate, research on plasmonic nanocavities has made significant progress regarding the enhancement mechanism, the utilization of hotspots for the detection of specific molecular groups, and practical applications. However, challenges related to improving the enhancement factor of nanocavity SERS, enhancing the stability and reproducibility of hotspots, and enabling the detection of single-molecule layers remain. In this study, we adopt a bottom-up approach to construct a silver microplate–molecule–multi-sized silver nanosphere nanoparticle-on-mirror (NPoM) nanocavity and achieve the efficient stable enhancement of Raman scattering from 4-mercaptobenzoic acid and biphenyl-4,4′-dithiol molecules via the electromagnetic mechanism. By characterizing the fabricated nanocavity using dark-field scattering and micro-confocal Raman scattering, we observed that the Raman scattering intensity in the NPoM nanocavity was enhanced by a factor of 10³ compared to that of individual silver nanospheres. Furthermore, we achieved the efficient stabilization of SERS by precisely tuning the size of the silver nanospheres to match their resonance frequency with the Raman shift of the target molecules. This approach offers a valuable reference for the detection of various single-molecule layers and demonstrates significant potential for applications in biosensing and chemical analysis. Full article

Polymeric Intraocular lenses (IOLs) are vital for restoring vision following cataract surgery and for correcting refractive errors. Despite technological and medical advancements, challenges persist in achieving optimal vision and preventing complications. Surface modifications aim to mitigate the risk of posterior capsule opacification (PCO), while pre-operative measurements aid in selecting suitable IOLs. However, individualized solutions are lacking and there is a clear demand for the development of fully customized IOL surfaces. We employ laser micromachining technology for precise modifications via ablation on PMMA and acrylic IOLs, using femtosecond (fs), nanosecond (ns), and diode continuous wave (CW) lasers, at wavelengths ranging from near-ultraviolet to infrared. Characterization reveals controlled ablation patterning, achieving feature sizes from as small as 400 nm to several micrometers. Regular and confocal micro-Raman spectroscopy revealed alterations of the IOL materials’ structural integrity for some patterning cases, thus affecting the optical properties, while these can be minimized by the proper selection of micromachining conditions. The results suggest the feasibility of accurate IOL patterning, which could offer personalized vision correction solutions, based on relevant corneal wavefront data, thus surpassing standard lenses, marking a significant advancement in cataract surgery outcomes. Full article

Cangjie Temple was built to commemorate Cangjie, the legendary inventor of Chinese characters. It stands as one of the few remaining temples in China dedicated to the invention and creation of writing. In this study, the material properties of wooden paintings from the Cangjie temple were characterized using Polarized Light Microscopy (PLM), Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (SEM-EDS), Micro-confocal Raman Spectroscopy, X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Pyrolysis-Gas Chromatography-Mass Spectrometry (Py-GC/MS). It was confirmed that the pigments of the paintings included cinnabar, lapis lazuli, lead white, Paris green, and carbon black. The proteinaceous glue was used as an adhesive in the pigment samples, with tung oil likely being utilized as a primer for the wooden structures before painting. This study not only provides valuable data support for the conservation and restoration of the architectural features of Cangjie Temple but also provides useful reference for the maintenance and inheritance of similar ancient buildings. Full article

Microfluidic technology provides a solution to the challenge of continuous CaCO₃ particle synthesis. In this study, we utilized a 3D-printed microfluidic chip to synthesize CaCO₃ micro- and nanoparticles in vaterite form. Our primary focus was on investigating a continuous one-phase synthesis method tailored for the crystallization of these particles. By employing a combination of confocal and scanning electron microscopy, along with Raman spectroscopy, we were able to thoroughly evaluate the synthesis efficiency. This evaluation included aspects such as particle size distribution, morphology, and polymorph composition. The results unveiled the existence of two distinct synthesis regimes within the 3D-printed microfluidic chips, which featured a channel cross-section of 2 mm². In the first regime, which was characterized by chaotic advection, particles with an average diameter of around 2 $\mathsf{\mu }$m were produced, thereby displaying a broad size distribution. Conversely, the second regime, marked by diffusion mixing, led to the synthesis of submicron particles (approximately 800–900 nm in diameter) and even nanosized particles (70–80 nm). This research significantly contributes valuable insights to both the understanding and optimization of microfluidic synthesis processes, particularly in achieving the controlled production of submicron and nanoscale particles. Full article

A simple and efficient method for the synthesis of biodegradable, highly branched polycaprolactone (PCL) is presented. The solvent-free (bulk) reaction was carried out via ring opening polymerization (ROP), catalyzed by tin octanoate Sn(Oct)₂, and it employed hyperbranched polyamide (HPPA) as a macro-initiator. The core–shell structure of the obtained products (PCL-HPPA), with the hyperbranched HPPA core and linear PCL chains as shell, was in the focus of the product characterization. ¹H nuclear magnetic resonance (¹H NMR) and elemental analysis confirmed the covalent incorporation of the HPPA in the products, as well as a high degree of grafting conversion of its amino functional groups. Confocal Raman Micro spectroscopy, and especially Time-of-Flight Secondary Ion Mass Spectrometry, further supported the existence of a core–shell structure in the products. Direct observation of macromolecules by means of cryogenic transmission electron microscopy, as well as gel permeation chromatography (GPC), suggested the existence of a minor ‘aggregated’ product fraction with multiple HPPA cores, which was attributed to transesterification reactions. Differential scanning calorimetry, as well as X-ray diffraction, demonstrated that the PCL-HPPA polymers displayed a similar degree of crystallinity to linear neat PCL, but that the branched products possessed smaller and less regular crystallites. Full article

Red lead is commonly employed as a red pigment in numerous valuable cultural artifacts. Raman spectrometry has been widely employed as the primary tool in many nondestructive studies on red lead. Therefore, it is necessary to evaluate and study the impact of lasers on the pigment. The degradation of red lead induced by a 532 nm laser is investigated using micro-Raman spectroscopy. At room temperature, red lead begins to degrade into β-PbO when the power density of the 532 nm laser reaches approximately 5.1 × 10⁴ W/cm² (laser: 532 nm, objective: 50×). At this point, the temperature at the focus of the sample is estimated to be at least 500 °C, aided by the Raman peak shift of β-PbO. Furthermore, the power density of the laser-induced degradation decreases as the temperature of the red lead increases. Hence, the degradation of red lead can be attributed to the photothermal effect. The temperature rise can be explained by two factors. First, red lead exhibits a high absorbance of approximately 0.5942 at 532 nm. Second, red lead has significantly low thermal diffusivity and conductivity, measuring 0.039 mm²·s⁻¹ and 0.078 W·m⁻¹·K⁻¹, respectively, which leads to heat accumulation at the focal point of the laser beam. To better preserve cultural heritage, the appropriate laser power should be prioritized when the degradation process is caused by the thermal effect of laser irradiation. Full article

Lithium fluoride (LiF) film detectors for extreme ultraviolet radiation, soft and hard X-rays, based on the photoluminescence of radiation-induced electronic defects, have been proposed and are currently under further development and investigation. LiF film detectors are versatile and can be integrated in different experimental apparatus and imaging configurations. LiF can be grown in the form of polycrystalline thin films and it is compatible with several substrates. The radiation-induced color center (CCs) photoluminescence (PL) response can be enhanced through the appropriate choice of substrates and multilayer designs, and by tailoring the micro-structural properties of polycrystalline LiF films through the control of the growth conditions. In this work, we present the characterization, through fluorescence and Raman micro-spectroscopy, of LiF films, thermally evaporated on different substrates with thicknesses of up to 1 μm, irradiated with soft X-rays produced by a laser plasma source. The combination of these micro-spectroscopy techniques could represent an advanced method to investigate the role of the polycrystalline film structures in CC formation efficiency at the microscopic level, a fundamental aspect of the development of LiF film radiation-imaging detectors. Full article

The structural biopolymer spongin in the form of a 3D scaffold resembles in shape and size numerous species of industrially useful marine keratosan demosponges. Due to the large-scale aquaculture of these sponges worldwide, it represents a unique renewable source of biological material, which has already been successfully applied in biomedicine and bioinspired materials science. In the present study, spongin from the demosponge Hippospongia communis was used as a microporous template for the development of a new 3D composite containing goethite [α-FeO(OH)]. For this purpose, an extreme biomimetic technique using iron powder, crystalline iodine, and fibrous spongin was applied under laboratory conditions for the first time. The product was characterized using SEM and digital light microscopy, infrared and Raman spectroscopy, XRD, thermogravimetry (TG/DTG), and confocal micro X-ray fluorescence spectroscopy (CMXRF). A potential application of the obtained goethite–spongin composite in the electrochemical sensing of dopamine (DA) in human urine samples was investigated, with satisfactory recoveries (96% to 116%) being obtained. Full article

Information on the penetration depth, pathways, metabolization, storage of vehicles, active pharmaceutical ingredients (APIs), and functional cosmetic ingredients (FCIs) of topically applied formulations or contaminants (substances) in skin is of great importance for understanding their interaction with skin targets, treatment efficacy, and risk assessment—a challenging task in dermatology, cosmetology, and pharmacy. Non-invasive methods for the qualitative and quantitative visualization of substances in skin in vivo are favored and limited to optical imaging and spectroscopic methods such as fluorescence/reflectance confocal laser scanning microscopy (CLSM); two-photon tomography (2PT) combined with autofluorescence (2PT-AF), fluorescence lifetime imaging (2PT-FLIM), second-harmonic generation (SHG), coherent anti-Stokes Raman scattering (CARS), and reflectance confocal microscopy (2PT-RCM); three-photon tomography (3PT); confocal Raman micro-spectroscopy (CRM); surface-enhanced Raman scattering (SERS) micro-spectroscopy; stimulated Raman scattering (SRS) microscopy; and optical coherence tomography (OCT). This review summarizes the state of the art in the use of the CLSM, 2PT, 3PT, CRM, SERS, SRS, and OCT optical methods to study skin penetration in vivo non-invasively (302 references). The advantages, limitations, possibilities, and prospects of the reviewed optical methods are comprehensively discussed. The ex vivo studies discussed are potentially translatable into in vivo measurements. The requirements for the optical properties of substances to determine their penetration into skin by certain methods are highlighted. Full article