A recently developed variant of spatially offset Raman spectroscopy (SORS) for the non‐invasive analysis of thin painted layers, micro‐SORS, has been applied, for the first time, to real objects of Cultural Heritage – namely painted sculptures and plasters. Thin layers of paint originating from multiple restoration processes often applied over many centuries have been analysed non‐destructively using micro‐SORS to depths inaccessible to, or unresolvable into separate layers, by conventional confocal Raman microscopy. The concept has been demonstrated on several artistic artefacts of historical significance originating from Italy and dating from the medieval to the 18th century. The technique extends the depth applicability of Raman spectroscopy and with its inherently high chemical specificity that expands the portfolio of existing non‐destructive analytical tools in Cultural Heritage permitting to avoid cross‐sectional analysis often necessitated with this type of samples with conventional Raman microscopy. Currently, the method is non‐invasive only for artworks that can be placed under Raman microscope although there is a prospect for its use in a mobile system with largely removed restrictions on sample dimensions. © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd.

A system for advanced fluorescence investigation of works of art has been assembled and integrated in a characterization procedure that allows one to localize and identify organic compounds that are present in artworks. At the beginning of the investigation, fluorescence lifetime imaging and spectroscopy address a selective microsampling of the artwork. Then analytical measurements of microsamples identify the chemical composition of the materials under investigation. Finally, on the basis of fluorescence lifetime and amplitude maps, analytical data are extended to the whole artwork. In such a way, information on the spatial distribution of organic materials can be inferred. These concepts have been successfully applied in an extensive campaign for analysis of Renaissance fresco paintings in Castiglione Olona, Italy. Residue of various types of glue and stucco left from a restoration carried out in the early 1970s was localized and classified. Insight into the technique used by the painter to make gilded reliefs was also obtained.

Here we present, for the first time, an extension of spatially offset Raman spectroscopy to thin (tens of micrometers thick), highly turbid stratified media such as those encountered in paintings. The method permits the non-destructive interrogation of painted layers in situations where conventional Raman microscopy is not applicable due to high turbidity of the top layer(s). The concept is demonstrated by recovering the pure Raman spectra of paint sub-layers that are completely obscured by paint over-layers. Potential application areas include the analysis of paintings in art preservation and restoration avoiding the cross-sectional analysis used currently with this type of samples. The technique also holds promise for the development as a non-destructive subsurface tool for in situ analysis using portable instruments.

The influence of permanent atrial fibrillation on exercise tolerance and cardio-respiratory function during exercise in heart failure (HF) is unknown. We retrospectively compared the results of 942 cardiopulmonary exercise tests, performed consecutively at seven Italian laboratories, in HF patients with atrial fibrillation ( n = 180) and sinus rhythm ( n = 762). By multivariable logistic regression analysis, peak VO ₂ (OR 0.376, 95% CI 0.240–0.588, P < 0.0001), O ₂ pulse (VO ₂ /heart rate, HR) (OR 0.236, 95% CI 0.152–0.366, P < 0.0001), VCO ₂ (OR 3.97, 95% CI 2.163–7.287, P < 0.0001), and ventilation (OR 1.38, 95% CI 1.045–1.821, P = 0.0231) were independently associated with atrial fibrillation. Anaerobic threshold (AT) was identified in 132 of 180 (73%) atrial fibrillation and in 649 of 762 (85%) sinus rhythm patients ( P = 0.0002). By multivariable logistic regression analysis, only peak VO ₂ (OR 0.214, 95% CI 0.155–0.296, P < 0.0001) was independently associated with unidentified AT. At AT, atrial fibrillation HF patients had higher HR ( P < 0.0001) and higher VO ₂ ( P < 0.001) compared with sinus rhythm HF patients. Among AT variables, by multivariable logistic regression analysis, only HR was an independent predictor of atrial fibrillation. In HF patients with permanent atrial fibrillation, exercise performance is reduced as reflected by reduced peak VO ₂ . The finding of unidentified AT is associated with a poor performance. In atrial fibrillation patients, VO ₂ is higher at AT whereas lower at peak. This last observation raises uncertainties about the use of AT data to define performance and prognosis of HF patients with atrial fibrillation.

We present the first validation and application of portable Sequentially Shifted Excitation (SSE) Raman spectroscopy for the survey of painted layers in art. The method enables the acquisition of shifted Raman spectra and the recovery of the spectral data through the application of a suitable reconstruction algorithm. The technique has a great potentiality in art where commonly a strong fluorescence obscures the Raman signal of the target, especially when conventional portable Raman spectrometers are used for in situ analyses. Firstly, the analytical capability of portable SSE Raman spectroscopy is critically discussed using reference materials and laboratory specimens, comparing its results with other conventional high performance laboratory instruments (benchtop FT-Raman and dispersive Raman spectrometers with an external fiber optic probe); secondly, it is applied directly in situ to study the complex polychromy of Italian prestigious terracotta sculptures of the 16^th century. Portable SSE Raman spectroscopy represents a new investigation modality in art, expanding the portfolio of non-invasive, chemically specific analytical tools.