Ancient wood of the Acqualadrone rostrum: Materials history through gas chromatography/mass spectrometry and sulfur X-ray absorption spectroscopy

In 2008 the rostrum from an ancient warship was recovered from the Mediterranean near Acqualadrone, Sicily. To establish its provenance and condition, samples of black and brown rostrum wood were examined using sulfur K-edge X-ray absorption spectroscopy (XAS) and gas chromatography/mass spectrometry (GC/MS). GC/MS of pyrolytic volatiles yielded only guaiacyl derivatives, indicating construction from pinewood. A derivatized extract of black wood yielded forms of abietic acid and sandaracopimaric acid consistent with pine pitch waterproofing. Numerical fits to the sulfur K-edge XAS spectra showed that about 65% of the endogenous sulfur consisted of thiols and disulfides. Elemental sulfur was about 2% and 7% in black and brown wood, respectively, while pyritic sulfur was about 12% and 6%. About 2% of the sulfur in both wood types was modeled as trimethylsulfonium, possibly reflecting biogenic (dimethylsulfonio)propionate. High-valent sulfur was exclusively represented by sulfate esters, consistent with bacterial sulfotransferase activity. Traces of chloride were detected, but no free sulfate ion. In summary, the rostrum was manufactured of pine wood and subsequently waterproofed with pine pitch. The subsequent 2300 years included battle, foundering, and marine burial followed by anoxia, bacterial colonization, sulfate reduction, and mobilization of transition metals, which produced pyrite and copious appended sulfur functionality

Scienza e Arti Perdute: i Segreti degli Antichi Maestri Liutai

Lo scopo di questo lavoro è illustrare agli insegnanti la connessione tra due settori di attività apparentemente lontani: la scelta dei materiali utilizzati nella liuteria artigianale e la chimica. Il ruolo, la composizione e la classificazione delle principali vernici per liuteria sono qui descritte assieme ad una breve sintesi dello stato dell’arte. Nel lavoro, vengono presentati i principali concetti di una tecnica analitica non distruttiva abbastanza semplice (la spettroscopia di fluorescenza da raggi X) ma, probabilmente, non abbastanza nota ai non addetti ai lavori. Un caso di studio a essa correlato è inoltre presentato per evidenziare uno dei possibili contributi del chimico nello studio dei beni culturali.The aim of this paper is showing teachers the connection between two apparently distant working fields: the choice of materials used in artisanal lute making and chemistry. The role, the composition and the classification of the main varnishes for classical lute making are here described with a brief review of the state of the art. Furthermore, the main theoretical basis of a relatively simple non-destructive analytical technique (X-Ray Fluorescence Spectroscopy), probably not very well known by non-specialists, is here illustrated. A case study is also presented to highlight one of the possible roles of the chemist in the study of cultural heritage

A new methodological approach to correlate protective and microscopic properties by soft x-ray microscopy and solid state nmr spectroscopy: The case of cusa’s stone

Hydrophobic treatment is one of the most important interventions usually carried out for the conservation of stone artefacts and monuments. The study here reported aims to answer a general question about how two polymers confer different protective performance. Two fluorinated-based polymer formulates applied on samples of Cusa’s stone confer a different level of water repellence and water vapour permeability. The observed protection action is here explained on the basis of chemico-physical interactions. The distribution of the polymer in the pore network was investigated using scanning electron microscopy and X-ray microscopy. The interactions between the stone substrate and the protective agents were investigated by means of solid state NMR spectroscopy. The ss-NMR findings reveal no significant changes in the chemical neighbourhood of the observed nuclei of each protective agent when applied onto the stone surface and provide information on the changes in the organization and dynamics of the studied systems, as well as on the mobility of polymer chains. This allowed us to explain the different macroscopic behaviours provided by each protective agent to the stone substrate

Conservation state of two paintings in the Santa Margherita cliff cave: role of the environment and of the microbial community

The conservation of ancient paintings sited in humid environments is an actual challenge for restorers, because it needs the knowledge of the materials the paintings are made up and of their interaction with a peculiar surrounding environment; thus, tailored procedures and strategies aimed at restoring and preserving paintings are necessary. Santa Margherita’s cave in Castellammare del Golfo (Trapani, Italy) is a natural cave, containing the remains of paintings, in a poor state of conservation, belonging to an ancient church dated back to the Middle Age. The present manuscript reports the monitoring of environmental conditions (i.e., temperature and humidity) in a full year, as well as a study on the materials constituting the stone support and the paintings together with a survey of the microbial community. The findings allow us to define the causes that mainly involve the degradation of the paintings. In detail, the degradation of the east and the west walls occurred differently because of the exposure to the sea aerosol, which influenced the salt composition, also contributing to diversifying the bacterial community. Some specific actions to plan the conservation and restoration of paintings and to preserve the site are suggested

Sicilian byzantine icons through the use of non-invasive imaging techniques and optical spectroscopy: The case of the madonna dell’elemosina

The iconographic heritage is one of the treasures of Byzantine art that have enriched the south of Italy, and Sicily in particular, since the early 16th century. In this work, the investigations of a Sicilian Icon of Greek-Byzantine origin, the Madonna dell’Elemosina, is reported for the first time. The study was carried out using mainly non-invasive imaging techniques (photography in reflectance and grazing visible light, UV fluorescence, infrared reflectography, radiography, and computed tomography) and spectroscopic techniques (X-ray fluorescence and infrared spectroscopy). The identification of the constituent materials provides a decisive contribution to the correct historical and artistic placement of the Icon, a treasure of the Eastern European historical community in Sicily. Some hidden details have also been highlighted. Most importantly, the information obtained enables us to define its conservation state, the presence of foreign materials, and to direct its protection and restoration

Effect of the cerium loading on the HMS structure. Preparation, characterization and catalytic properties

Ce–HMS mesoporous materials were prepared by incipient wetness method starting from HMS synthesized in acid condition. The effect of ceriumquantity, in the range of Ce/Si atomic ratio 0.02–0.3, on its structure and properties was investigated. Results showed that the HMS hexagonal structure was maintained after the cerium adding. Furthermore, the surface area and the pore volume were reduced. The presence of the cerianite nanoparticles located within the HMS channels up to 0.05, thus covering the HMS surface at higher Ce/Si atomic ratio,was observed. The catalytic performances of the materials were tested in ethanol partial oxidation reactio

Clinical presentations leading to arrhythmogenic left ventricular cardiomyopathy

Objectives To describe a cohort of patients with arrhythmogenic left ventricular cardiomyopathy (ALVC), focusing on the spectrum of the clinical presentations. Methods Patients were retrospectively evaluated between January 2012 and June 2020. Diagnosis was based on (1) ≥3 contiguous segments with subepicardial/midwall late gadolinium enhancement in the left ventricle (LV) at cardiac magnetic resonance plus a likely pathogenic/pathogenic arrhythmogenic cardiomyopathy (AC) associated genetic mutation and/or familial history of AC and/or red flags for ALVC (ie, negative T waves in V4-6/aVL, low voltages in limb leads, right bundle branch block like ventricular tachycardia) or (2) pathology examination of explanted hearts or autoptic cases suffering sudden cardiac death (SCD). Significant right ventricular involvement was an exclusion criterion. Results Fifty-two patients (63% males, age 45 years (31-53)) composed the study cohort. Twenty-one (41%) had normal echocardiogram, 13 (25%) a hypokinetic non-dilated cardiomyopathy (HNDC) and 17 (33%) a dilated cardiomyopathy (DCM). Of 47 tested patients, 29 (62%) were carriers of a pathogenic/likely pathogenic DNA variant. Clinical contexts leading to diagnosis were SCD in 3 (6%), ventricular arrhythmias in 15 (29%), chest pain in 8 (15%), heart failure in 6 (12%) and familial screening in 20 (38%). Thirty patients (57%) had previously received a diagnosis other than ALVC with a diagnostic delay of 6 years (IQR 1-7). Conclusions ALVC is hidden in different clinical scenarios with a phenotypic spectrum ranging from normal LV to HNDC and DCM. Ventricular arrhythmias, chest pain, heart failure and SCD are the main clinical presentations, being familial screening essential for the affected relatives' identification

Electrocardiogram analysis in Anderson-Fabry disease: a valuable tool for progressive phenotypic expression tracking

BackgroundElectrocardiogram (ECG) has proven to be useful for early detection of cardiac involvement in Anderson-Fabry disease (AFD); however, little evidence is available on the association between ECG alterations and the progression of the disease.Aim and MethodsTo perform a cross sectional comparison of ECG abnormalities throughout different left ventricular hypertrophy (LVH) severity subgroups, providing ECG patterns specific of the progressive AFD stages. 189 AFD patients from a multicenter cohort underwent comprehensive ECG analysis, echocardiography, and clinical evaluation.ResultsThe study cohort (39% males, median age 47 years, 68% classical AFD) was divided into 4 groups according to different degree of left ventricular (LV) thickness: group A & LE; 9 mm (n = 52, 28%); group B 10-14 mm (n = 76, 40%); group C 15-19 mm (n = 46, 24%); group D & GE; 20 mm (n = 15, 8%). The most frequent conduction delay was right bundle branch block (RBBB), incomplete in groups B and C (20%,22%) and complete RBBB in group D (54%, p < 0.001); none of the patients had left bundle branch block (LBBB). Left anterior fascicular block, LVH criteria, negative T waves, ST depression were more common in the advanced stages of the disease (p < 0.001). Summarizing our results, we suggested ECG patterns representative of the different AFD stages as assessed by the increases in LV thickness over time (Central Figure). Patients from group A showed mostly a normal ECG (77%) or minor anomalies like LVH criteria (8%) and delta wave/slurred QR onset + borderline PR (8%). Differently, patients from groups B and C exhibited more heterogeneous ECG patterns: LVH (17%; 7% respectively); LVH + LV strain (9%; 17%); incomplete RBBB + repolarization abnormalities (8%; 9%), more frequently associated with LVH criteria in group C than B (8%; 15%). Finally, patients from group D showed very peculiar ECG patterns, represented by complete RBBB + LVH and repolarization abnormalities (40%), sometimes associated with QRS fragmentation (13%).ConclusionsECG is a sensitive tool for early identification and long-term monitoring of cardiac involvement in patients with AFD, providing "instantaneous pictures" along the natural history of AFD. Whether ECG changes may be associated with clinical events remains to be determined

Tc-99m labelled bone scintigraphy in suspected cardiac amyloidosis

Aims: To perform evaluation of widely embraced bone scintigraphy-based non-biopsy diagnostic criteria (NBDC) for ATTR amyloid cardiomyopathy (ATTR-CM) in clinical practice, and to refine serum free light chain (sFLC) ratio cut-offs that reliably exclude monoclonal gammopathy (MG) in chronic kidney disease. Methods and results: A multi-national retrospective study of 3354 patients with suspected or histologically proven cardiac amyloidosis (CA) referred to specialist centres from 2015 to 2021; evaluations included radionuclide bone scintigraphy, serum and urine immunofixation, sFLC assay, eGFR measurement and echocardiography. Seventy-nine percent (1636/2080) of patients with Perugini grade 2 or 3 radionuclide scans fulfilled NBDC for ATTR-CM through absence of a serum or urine monoclonal protein on immunofixation together with a sFLC ratio falling within revised cut-offs incorporating eGFR; 403 of these patients had amyloid on biopsy, all of which were ATTR type, and their survival was comparable to non-biopsied ATTR-CM patients (p = 0.10). Grade 0 radionuclide scans were present in 1091 patients, of whom 284 (26%) had CA, confirmed as AL type (AL-CA) in 276 (97%) and as ATTR-CM in only one case with an extremely rare TTR variant. Among 183 patients with grade 1 radionuclide scans, 122 had MG of whom 106 (87%) had AL-CA; 60/61 (98%) without MG had ATTR-CM. Conclusion: The NBDC for ATTR-CM are highly specific [97% (95% CI 0.91-0.99)] in clinical setting, and diagnostic performance was further refined here using new cut-offs for sFLC ratio in patients with CKD. A grade 0 radionuclide scan all but excludes ATTR-CM but occurs in most patients with AL-CA. Grade 1 scans in patients with CA and no MG are strongly suggestive of early ATTR-type, but require urgent histologic corroboration

Clinical and Prognostic Implications of Right Ventricular Uptake on Bone Scintigraphy in Transthyretin Amyloid Cardiomyopathy

Background: The extent of myocardial bone tracer uptake with technetium pyrophosphate, hydroxymethylene diphosphonate, and 3,3-diphosphono-1,2-propanodicarboxylate in transthyretin amyloid cardiomyopathy (ATTR-CM) might reflect cardiac amyloid burden and be associated with outcome. Methods: Consecutive patients with ATTR-CM who underwent diagnostic bone tracer scintigraphy with acquisition of whole-body planar and cardiac single-photon emission computed tomography (SPECT) images from the National Amyloidosis Centre and 4 Italian centers were included. Cardiac uptake was defined according to the Perugini classification: 0=absent cardiac uptake; 1=mild uptake less than bone; 2=moderate uptake equal to bone; and 3=high uptake greater than bone. Extent of right ventricular (RV) uptake was defined as focal (basal segment of the RV free wall only) or diffuse (extending beyond basal segment) on the basis of SPECT imaging. The primary outcome was all-cause mortality. Results: Among 1422 patients with ATTR-CM, RV uptake accompanying left ventricular uptake was identified by SPECT imaging in 100% of cases at diagnosis. Median follow-up in the whole cohort was 34 months (interquartile range, 21 to 50 months), and 494 patients died. By Kaplan-Meier analysis, diffuse RV uptake on SPECT imaging (n=936) was associated with higher all-cause mortality compared with focal (n=486) RV uptake (77.9% versus 22.1%; P<0.001), whereas Perugini grade was not associated with survival (P=0.27 in grade 2 versus grade 3). On multivariable analysis, after adjustment for age at diagnosis (hazard ratio [HR], 1.03 [95% CI, 1.02-1.04]; P<0.001), presence of the p.(V142I) TTR variant (HR, 1.42 [95% CI, 1.20-1.81]; P=0.004), National Amyloidosis Centre stage (each category, P<0.001), stroke volume index (HR, 0.99 [95% CI, 0.97-0.99]; P=0.043), E/e' (HR, 1.02 [95% CI, 1.007-1.03]; P=0.004), right atrial area index (HR, 1.05 [95% CI, 1.02-1.08]; P=0.001), and left ventricular global longitudinal strain (HR, 1.06 [95% CI, 1.03-1.09]; P<0.001), diffuse RV uptake on SPECT imaging (HR, 1.60 [95% CI, 1.26-2.04]; P<0.001) remained an independent predictor of all-cause mortality. The prognostic value of diffuse RV uptake was maintained across each National Amyloidosis Centre stage and in both wild-type and hereditary ATTR-CM (P<0.001 and P=0.02, respectively). Conclusions: Diffuse RV uptake of bone tracer on SPECT imaging is associated with poor outcomes in patients with ATTR-CM and is an independent prognostic marker at diagnosis