Scientific investigation in the cultural heritage field is generally aimed at the characterization of the constituent materials and the conservation status of artworks. Since the 1990s, reflectance spectral imaging proved able to map pigments, reveal hidden details and evaluate the presence of restorations in paintings. Over the past two decades, hyperspectral imaging has further improved our understanding of paints and of its changes in time. In this work, we present an innovative hyperspectral camera, based on the Fourier transform approach, utilising an ultra-stable interferometer and we describe its advantages and drawbacks with respect to the commonly used line- and spectral-scanning methods. To mitigate the weaknesses of the Fourier transform hyperspectral imaging, we propose a strategy based on the virtual extension of the dynamic range of the camera and on the design of an illumination system with a balanced emission throughout the spectral range of interest. The hyperspectral camera was employed for the analysis of a painting from the “Album of Nasir al-din Shah”. By applying analysis routines based on supervised spectral unmixing, we demonstrate the effectiveness of our camera for pigment mapping. This work shows how the proposed hyperspectral imaging camera based on the Fourier transform is a promising technique for robust and compact in situ investigation of artistic objects in conditions compatible with museum and archaeological sites. Graphic abstract
A fluorescence imaging system was used to monitor the emission of disulfonated aluminum phthalocyanine (AlS2Pc) during the photodynamic therapy (PDT) of murine tumors. Cells of the MS‐2 fibrosarcoma were injected in mice in two compartments in order to cause the development of tumors in different host tissues. Two drug doses and two uptake times were considered. Moreover, the fluorescence of the AlS2Pc was excited using two wavelengths on the opposite sides of the absorption peak to detect a possible change in the absorption spectrum of the sensitizer induced by the PDT. In the tumors, the treatment induces a variation of the fluorescence intensity: in some mice a mild photobleaching takes place, in others a fluorescence enhancement occurs. Which effect predominates depends on the experimental conditions, even though a large spread of data was found amongst mice of the same group. In all mice, independently of the drug dose, uptake time or tumor compartment, a marked increase in the fluorescence signal takes place at the borders of the irradiated area. To quantify this effect we evaluated the ratio between the fluorescence intensities in the peritumoral area and in the tumor itself. This ratio increases monotonically during the PDT, showing a different behavior with the two excitation wavelengths. This indicates that the AlS2Pc absorption spectrum shifts toward shorter wavelengths as a result of the irradiation.
This paper accounts for the diagnostic campaign aimed at understanding the phenomenon of black stains appeared on the passepartout close to the margins of Folio 843 of Leonardo da Vinci’s Codex Atlanticus. Previous studies excluded microbiological deterioration processes. The study is based on a multi-analytical approach, including non-invasive imaging measurements of the folio, micro-imaging and synchrotron spectroscopy investigations of passepartout fragments at different magnifications and spectral ranges. Photoluminescence hyperspectral and lifetime imaging highlighted that black stains are not composed of fluorescent materials. μATR-FTIR imaging of fragments from the passepartout revealed the presence of a mixture of starch and PVAc glues localized only in the stained areas close to the margin of the folio. FE-SEM observations showed that the dark stains are localized inside cavities formed among cellulose fibers, where an accumulation of inorganic roundish particles (∅100–200 nm in diameter size), composed of Hg and S, was detected. Finally, by employing synchrotron μXRF, μXANES and HR-XRD analyses it was possible to identify these particles as metacinnabar (β-HgS). Further research is needed to assess the chemical process leading to the metacinnabar formation in the controlled conservation condition of Leonardo’s Codex.
Hypericin is the active ingredient of the off‐the‐shelf antidepressant St. John's Wort. It is an effective phototoxic agent and its systemic administration at therapeutic doses could induce particular damage in the eye due to continuous light exposure. Hypercin is strongly fluorescent and its fluorescence properties can be monitored to investigate noninvasively its localization and interactions. To this aim, time‐resolved microspectrofluorimetry and fluorescence life‐time imaging were used to assess the spectral and temporal properties as well as the spatial distribution of the fluorescence emitted by retinal pigment epithelium (RPE) cells treated with Hyp at concentrations in the micromolar range (0.5–10 μM). In the presence of hypericin, the emission peaks at 600‐605 nm and the fluorescence decay is best fitted with three lifetimes (5.5‐7 ns, 1.9‐2.5 ns and < 0.8 ns). Spectral and temporal differences were observed between high (≥5 μM) and low hypericin concentrations. In particular, upon increasing concentration, the emission spectrum of the slow component broadens and its lifetime shortens. The latter change is observed also when high concentrations are reached locally, due to more efficient localization within the cell.
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