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Understanding the spatial distribution patterns of microplastics (plastics 5 mm) contributes to the assessment of sources and sinks of pollution thus providing information for the management of biota safety and overall ecosystem functionality. We chose a semi-closed study area, Lake Bracciano (Italy), to assess the environmental variability of contamination, focusing on the water compartment and the exposure of biota, specifically fish, by analysing the ingestion of microplastics. The focus of this study is to evaluate the concentration of microplastics in water (surface and column) across the lake and the ingestion of microplastics by two fish species of economic interest: Atherina boyeri and Coregonus lavaretus, inhabiting demersal and pelagic habitats respectively. Results show a surface contamination of 392,000 ± 417,000 items km

Background Molecular analysis of thyroid fine-needle aspiration biopsy (FNA) was proposed to improve indeterminate nodules management. However, sensibility and specificity as well as the cost of molecular diagnostics require to be improved to increase their cost-effectiveness for medical practice setting. Raman spectroscopy (RS) demonstrated ability in separating benign from malignant thyroid lesions in surgically removed tissues, based on specific RS profile. This study aimed to investigate the diagnostic performance of RS on cytological samples obtained by thyroid FNA. Methods In this prospective, blinded monocentric study, we enrolled 123 patients with indeterminate or worse cytological diagnosis, candidate to surgery according to international guidelines, and submitted to RS analysis of FNA samples. Cytology specimens were evaluated in agreement to Italian Reporting System for Thyroid Cytology1 as follows: TIR1 (non-diagnostic), TIR1C (non-diagnostic-cystic), TIR 2 non-malignant/benign, TIR3A (low-risk indeterminate lesion), TIR3B (high-risk indeterminate lesion), TIR 4 (suspicious of malignancy), or TIR 5 (malignant). As previously published2, the two diagnostic subcategories referred to indeterminate nodules with low (TIR3A) and high risk (TIR3B) of malignancy, may be respectively compared to the class III and Class IV of The Bethesda System for Reporting Thyroid Cytopathology. We compared RS, cytology and final histology, as reference standard, using various statistical approaches. Findings: Our study population included 37 TIR3A, 32 TIR3B, 16 TIR4 and 38 TIR5; the 30.9% of patients had benign histological diagnosis after surgery. In particular, 72.9% of patients classified TIR3A and 31.3% TIR3B had benign histological diagnosis. RS analysis of FNA samples had overall specificity of 86.8% in predicting thyroid malignancy. In indeterminate cytological categories, RS specificity was 86.5%. In patients with TI-RADS score four or five, the specificity of RS increased to 87.5% for TIR3A and reached 100% in TIR3B.; if considering RS positive test, unnecessary surgery was reduced to 7.4% in the whole sample, 33.3% in TIR3A, and 6.7% in TIR 3B. Interpretation: We demonstrated for the first time that RS represents a valuable tool for thyroid cytology and a valid alternative to molecular analyses, able to improve management and reduce unnecessary surgery in indeterminate nodules. Funding: This study was supported by Ministero della Salute, through TIRAMA project (RF-2018-12366568). 1 J Endocrinol Invest. 2014;37(6): 593-599. doi: 10.1007/s40618-014-0062-0 2Cytopathology. 2021;32(6): 714-717. Presentation: Saturday, June 11, 2022 1:00 p.m. - 3:00 p.m.

Manganese oxides are important geomaterials, used in a large number of applications. For instance, as pigments in art works or in the treatment and removal of heavy metals from drinking water. Particularly, ramsdellite [Mn4+O2] and groutellite [(Mn0.54+,Mn0.53+)O1.5(OH)0.5], because of their 2 1 frameworks that enable proton diffusion, are very important cathode materials. Manganese oxides commonly occur as crypto-crystalline and very fine mixtures of different Mn-phases, iron oxides, silicates and carbonates. Thus, proper characterization can be a difficult task using XRPD. The lack of Raman data on groutellite and the little and conflicting data on ramsdellite do not allow their proper identification by Raman spectroscopy. In this work we characterize natural mixtures of ramsdellite and groutellite by combining SEM-EDS, XRPD, FT-IR and Raman spectroscopy, to provide reference Raman spectra. Our data show that they have a typical and unmistakable spectra, allowing clear recognition. Moreover, we have investigated their laser-induced degradation. Our data show that groutellite transforms into ramsdellite, by the loss of H+ and the oxidation of Mn3+ to Mn4+, already at a very low laser power. Further increasing the laser power the formation of hausmannite [Mn2+Mn2 3+O4] occurs via the reduction of Mn cations. Our data can be used to study the discharge mechanism in cathodic battery materials, by monitoring the Mn reduction from ramsdellite to groutellite, and finally to groutite [a-Mn3+OOH]. Moreover, Raman mapping allows the study of their distribution in all the investigated samples and, indirectly, those of H+ and Mn3+, which plays a key-role in electrochemical activity of these compounds.

Acinetobacter baumanni, is an opportunistic nosocomial multi-drug resistant bacterium, which represents a threat for human health. This pathogen is able to persist in intensive care units thanks to its extraordinary resistance towards dehydration, whose mechanisms are unknown and enable it to easily spread through surfaces, contaminating also medical devices. In this article we reveal, with a multimodal approach, based on μ-R Spectroscopy, Gas Chromatography coupled to Mass Spectroscopy, Atomic Force Microscopy and Fluorescence Recovery After Photobleaching, the bio-physical mechanisms that the membrane of two A. baumannii strains undergoes during dehydration. Showing a substantial decoupling of the phase transition from liquid crystalline to gel phase from evidence of cell lysis. Such decoupling may be the core of the resistance of A. baumannii against dehydration and highlights the different ability to resist to drought between strains.

Microplastics (plastics

The conservation of stone monuments is a constant concern due to their continuous weathering, in which biofouling plays a relevant role. To enhance the effectiveness of biocidal treatments and to avoid environmental issues related to their possible toxicity, this research aims at formulating and characterizing a coating charged with an eco-friendly biocide and showing hydrophobic properties. For this purpose, zosteric sodium salt—a natural biocide product—has been encapsulated into two silica nanocontainers and dispersed into a tetraethoxysilane-based (TEOS) coating also containing TiO2 nanoparticles. The coatings were applied on four different types of stone: brick, mortar, travertine, and Carrara marble. The effectiveness of the coating formulations and their compatibility concerning the properties of coated stones were assessed. The results showed that all coatings conferred a hydrophobic character to the substrate, as demonstrated by the increase of the static contact angle and the reduction in the capillary water absorption coefficient. The transmission of water vapor of the natural stones was preserved as well as their natural aspect. Furthermore, the coatings were homogeneously distributed on the surface and crack-free. Therefore, the protective capability of the coatings was successfully demonstrated.

Purpose: Recently, it has been demonstrated that Raman spectroscopy is able to differentiate between healthy parathyroid tissues and parathyroid adenoma based on the basis of a specific molecular fingerprint. However, to our knowledge, no previous studies have been performed to evaluate the metabolic profile of parathyroid adenoma. Therefore, we designed a proof of concept study aimed to investigate the glucose/fatty acid metabolisms, in addition to the mitochondrial changes, in solitary parathyroid adenoma and in healthy parathyroid glands. Methods: Nine females with primary hyperparathyroidism due to a solitary parathyroid adenoma and formal surgical indication for parathyroidectomy have been enrolled. At the time of surgery, the removed specimens were immediately submitted unfixed and a tissue slice of about 0.5 cm in diameter was obtained from the nodular lesion. The expression of selected metabolic enzymes and proteins has been evaluated by western blot analysis, using human parathyroid whole tissue lysates as control. Results: Data obtained highlighted an increase, compared with the healthy group, of: (i) the glucose uptake by the GLUT-1 receptor and its phosphorylation by hexokinase II (HXKII); (ii) the expression of 3-phosphoglycerate dehydrogenase (3-PGDH) and glucose-6-phosphate dehydrogenase (G6PD); (iii) lipids biosynthesis; and (iv) cytochrome c expression. Conclusions: Our findings highlight for the first time the parathyroid adenoma metabolic hallmarks that could represent potential molecular targets usable for the development of new pharmacological treatments, allowing to reduce surgical parathyroidectomy.

In this work, an innovative analytical approach focused on the use of advanced imaging techniques for the chemical mapping of degradation and/or restoration products is proposed. A representative cross-section showing a very complex stratigraphy from the Saint Wilgefortis Triptych (Hieronymus Bosch), exhibited in the Galleria dell'Accademia di Venezia, was investigated. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) experiments were performed using a time-of-flight detector operating in the so-called delayed extraction mode. The time delay applied during the extraction of the secondary ions permitted mass spectra to be obtained with an excellent mass resolution and chemical maps with nanometer scale spatial resolution. The painting's cross-section was also analysed at the micrometer scale by micro-Fourier transform infrared spectroscopy (micro-FTIR). The combined analytical approaches highlighted the colocalization of lead chloride, oxychloride, and hydroxychloride ions, suggesting the transformation of lead white ((PbCO3)2Pb(OH)2) into laurionite (PbClOH). Furthermore, chlorine appears evenly diffused in the cinnabar (HgS) layer, inducing the alteration of its more external part into calomel (Hg2Cl2). In fact, from the chemical maps the presence in the sample of an unaltered portion of the cinnabar layer is evident. Such degradation products were probably due to the exposure of the painting to a chloride-rich atmosphere for a long time. This led to a global blackening of the painting. To protect the painting from aggressive chemical species, siloxane compounds were probably used as a modern restorative treatment. ToF-SIMS chemical maps revealed permeation of the silicon-based consolidants within the sample's cracks and no interaction products with the other constitutive materials of the painting were found. Finally, the presence of different lead soaps was detected in correspondence with the lead white layer.

Unpolarized FTIR and Raman spectra were collected in the regions 4000–4600 cm–1 (NIR) and 100–4000 cm–1 from previously synthesized and characterized amphiboles in the systems richterite–fluoro-richterite, potassic-richterite–potassic-fluoro-richterite, rubidium-richterite–rubidium-fluoro-richterite, and potassic-richterite–deuterated potassic-richterite. The NIR spectra of Na-, K-, and Rb-richterites have peaks at 4325, 4210 cm–1, and 3735–3730 cm–1. All three peaks decrease in intensity with increasing F content, indicating that the higher-energy peaks are combination bands involving the principal OH-stretch at 3735–3730 cm–1 and two OH-libration modes, the frequencies of which can be calculated from the relation ωcombination ≈ ωOH + ωlibration; these are 590 and 475 cm–1, respectively. The FTIR spectra of the richterite–fluoro-richterite and potassic-richterite–potassic-fluoro-richterite series show decreasing intensity and eventual disappearance of the band at ∼600 cm–1 with increasing F in accord with the assignment of this band as due to OH-libration. Raman spectra of the potassic-richterite–deuterated potassic-richterite amphiboles in the low-energy region show the disappearance of two peaks at 585 and 473 cm–1 that we have assigned to OH-libration modes. Collectively, these spectroscopic results indicate that there are two OH-libration modes at ∼590 and ∼475 cm–1 in these synthetic richterites and, by implication, in all monoclinic OH-bearing amphiboles with filled A sites. Similarly to FTIR, the relative intensities of the stretching modes associated with OH-A-OH and OH-A-F local configurations in the Raman spectra provide a reliable estimation of the F content in these A site-filled amphiboles.

The interaction of microorganisms with stone materials leads to biodeterioration processes, which may cause aesthetic damages and the loss of durability and strength of the substrates. Innovative solutions against this process are represented by nanotechnologies. In our previous works, 2-mercaptobenzothiazole was successfully encapsulated within two silica-based nanodevices: nanocapsules and mesoporous nanoparticles. Such loaded nanodevices have been dispersed in TEOS based coatings, characterized as far as their chemical–physical properties and in vitro biocide efficacy. Here, we adopt a multi-technic approach, to assess the coatings efficacy and compatibility with four types of stones of cultural heritage interest, namely, mortar, brick, travertine, and Carrara marble. In particular, we determine the protective function of the coatings, based on water transport properties (reduction up to a factor 10 of the water absorption for brick and mortar, without significantly influencing water vapor transmission rate), morphology of the surface (absence of coating cracks and color changes), and TiO2 photocatalytic activity. Consequently, these coatings can be considered suitable for application on stone artifacts, without interfering with their artistic appearance.

Illicit trade in archaeology is a widespread phenomenon connected to the market of archaeological objects from clandestine excavations or faking manufacture, which includes bronze objects. As a consequence, authentication and provenance studies are required on objects of unknown provenance when they are recovered thanks to the investigation activity of the police, before returning them to the museums. Various strategies and approaches can be used to identify fake bronzes, as for instance patinas studies, since the corrosion can spontaneously occur over time, due to the interaction of the surface with the environment, or induced by artificial treatments, performed to mimic the archaeological aging effects in short time. The artificial patina has outward appearance and colours very similar to the natural patinas, but with different mineralogical composition. In this work, Raman spectroscopy is used to discriminate between artificial and natural patinas by a non-destructive approach, supported by the microanalysis SEM-EDS and optical microscope observations in the case of two ‘Etruscan-Roman’ bronze statuettes of illicit and unknown provenance, and demonstrates their recent and fake manufacture. Indeed, the patinas of both statuettes contain covellite, antlerite, langite, chalcanthite and rouaite, minerals or metastable chemical species traced back to corrosion induced by chemical attack and thermal treatment, as distinct from their stable polymorphs usually formed in burial condition. Moreover, we have not found evidence of the presence of malachite and azurite, typical of natural aged patinas. Finally, the abundance of Zn in the alloy suggest a modern manufacture.

In the present paper, for the first time, non-invasive techniques have been employed to improve the knowledge of a Coronation of the Virgin dating back to 1560–70. This is an old master drawing by Giorgio Vasari, considered one of the major painters and art theoric of Italian late 16th Century. The adopted multi-technique approach, involving preliminary macroscopic and microscopic observations, and followed by X- ray fluorescence mapping (MA-XRF), μ-Raman, and Fourier Transform infrared spectroscopy (FTIR) analyses, along with the historical information, has allowed to identify the original materials and to understand the drawing's realization process. The results show that paper preparation has been realized by using a yellow mineral, namely goethite, in order to obtain a particular shade. Moreover, a proteinaceous component, likely animal gelatin, has been used as a binder for goethite or during the paper preparation process. Small white flakes, composed of lead white and massicot, have been randomly found on the surface of the drawing: the specific function and/or origin of these flakes is unknown. Finally, the use of black chalk for a preliminary sketch and iron gall ink for the final drawing has been observed.

We report in this paper a new crystal-chemical study of synthetic basic ferric sulfate FeOHSO4. The structure solution performed by the Endeavour program, from new X-ray powder diffraction (XRPD) data, indicated that the correct space group of the monoclinic polytype of FeOHSO4 is C2/c. Selected Area Electron Diffraction (SAED) patterns are also consistent with this structure solution. The arrangement of Fe and S atoms, based on linear chains of Fe3+ octahedra cross-linked by SO4 tetrahedra, corresponds to that of the order/disorder (OD) family. The positions of the hydrogen atoms were located based on DFT calculations. IR and Raman spectra are presented and discussed according to this new structure model. The decomposition of FeOHSO4 during heating was further investigated by means of variable temperature XRPD, thermogravimetry, and differential thermal analysis as well as IR and Raman spectroscopies.

Over the last 50 years, the incidence of human thyroid cancer disease has seen a significative increment. This comes along with an even higher increment of surgery, since, according to the international guidelines, patients are sometimes addressed to surgery also when the fine needle aspiration gives undetermined cytological diagnosis. As a matter of fact, only 30% of the thyroid glands removed for diagnostic purpose have a post surgical histological report of malignancy: this implies that about 70% of the patients have suffered an unnecessary thyroid removal. Here we show that Raman spectroscopy investigation of thyroid tissues provides reliable cancer diagnosis. Healthy tissues are consistently distinguished from cancerous ones with an accuracy of $$\sim $$ ∼ 90%, and the three cancer typology with highest incidence are clearly identified. More importantly, Raman investigation has evidenced alterations suggesting an early stage of transition of adenoma tissues into cancerous ones. These results suggest that Raman spectroscopy may overcome the limits of current diagnostic tools.

In cultural heritage field, significant research efforts have been recently made to improve the efficacy of anti-vegetative treatments and to reduce the environmental impact caused by biocides high concentration. According to the pro-ecological approach, this work reports a novel approach based on the encapsulation/incorporation of environmentally-friendly biocides in different silica nanosystems in order to control the development of biological patinas on outdoor cultural heritage. Two different green biocides have been selected and tested in silica nanosystems: the zosteric acid sodium salt (ZS), a natural antifoulant compound produced by Zostera marina (eelgrass), and the usnic acid (UA), a secondary metabolite produced by some saxicolous lichens. ZS was previously successfully encapsulated but never entrapped in mesoporous silica; instead, UA is, for the first time, encapsulated and in situ entrapped into the silica nanosystems in order to control the release over time. Both silica nanosystems have been characterized as far as their dimensions and superficial properties and loading capability. The antifouling activity was assessed against microorganisms from biopatinas colonising the Aurelian Walls in Rome. Our results have shown that the two nanosystems have complementary properties, thus it is possible to tune the antifouling efficiency by combining the two in different proportions.

Manganese oxides are important geomaterials, widespread in terrestrial and Martian environments. Characterisation of the oxidation state of Mn is a central issue in science; this task has been addressed up to the present by X-ray spectroscopy or diffraction techniques. The former, however, requires access to synchrotron facilities, while the latter does not provide crystal-chemical information at the local scale. In this work, we compare a large set of Raman data from wellcharacterised samples, already published by the same authors of this paper or as found in the literature. We show a clear correlation between the oxidation state of Mn and the wavenumber of peculiar bands; octahedrally co-ordinated Mn2+ is recognised by a band around 530 cm-1, Mn3+ by a band around 580 cm-1 and Mn4+ by a band around 630 cm-1, while tetrahedrally co-ordinated Mn2+ is recognisable by a band around 650 cm-1. Strongly distorted Mn3+ octahedra are indicated by the appearance of Jahn–Teller modes. Our method allows a reliable, easily accessible tool to characterise the oxidation states of Mn in oxides, also suitable for microscale mapping. It provides a robust analytical basis for the use of these minerals as redox indicators in geology/geochemistry, in exoplanetary research or for monitoring technological processes.

The artwork “St. Joseph with the Child”, preserved in Palazzo Chigi of Ariccia (Rome), is today the only painting signed by Gian Lorenzo Bernini. In this work, for the first time, an integrated spectroscopic imaging and analysis approach was performed to study and characterize Bernini's wall painting. Complementary in situ analyses, imaging in the UV–VIS–NIR–SWIR range, FT-IR spectroscopy, Raman spectroscopy, laser-induced fluorescence and XRF were performed to obtain information on the state of conservation, the execution technique and the composition of the materials of the painting investigated. The results achieved were discussed and delivered to the conservator of Palazzo Chigi, to plan further restoration treatments and conservation programs. In conclusion, preliminary considerations are presented to define if the painting studied represents a definitive painting or a preparatory drawing.

In the last years, significant research efforts have been devoted to the reduction of the environmental impact of biocides and to the improvement of their effectiveness over time against degradation of stone artifacts. This work reports the spectroscopic characterization of two silica nanosystems, with different geometry and structure, loaded with a biologically-active compound, the 2-mercaptobenzothiazole (MBT), for controlled antifouling release on the surface of outdoor stone artefacts. We have combined FT-IR spectroscopy in ATR mode and Raman spectroscopy to investigate the biocide loading mechanism in both nanosystems from the physical and chemical point of view. These techniques demonstrate that the geometry of confinement influences the loading of the nanoparticles and their interaction with the confining medium, with possible consequences in the biocide release rate. Moreover, we have seen that the biocide interacts with the surfactant (cetrimonium bromide, CTAB) and tends to dimerize.

Raman spectroscopy and time of flight secondary ion mass spectrometry (ToF‐SIMS) were used to answer conservation questions left open after the preliminary analysis performed by the restoration team on the Bosch painting Saint Wilgefortis Triptych, within the project “Bosch in Venice.” In this work, we present the results obtained by combining these two techniques on five cross sections, concerning a detailed study of pigments and bindings degradation processes, the identification of organic components (binders/lakes), and the characterization of restoration products. Raman measurements show the presence of degradation products, such as calomel on the red pigment cinnabar, calcium‐oxalate, in particular weddellite, localized in a not original external layer, and finally lead soaps in several layers of the investigated samples. Although the detection of lead soaps suggests the use of oils as binders, Raman spectroscopy has given no conclusive information about such binders, neither on the possible presence of red lakes, suggested by independent UV observations. Complementary ToF‐SIMS investigations have instead revealed the presence of lead palmitate and stearate in the painting layers along with miristic, palmitic, oleic, and stearic acids, thus confirming the use of an oil medium, likely linseed oil. Additionally, ToF‐SIMS shows the presence of polydimethylsiloxane, likely from a previous restoration treatment in the 1990s, in the external layer of the investigated cross sections. Due to experimental difficulties during the analysis of the red lake, we can only hypothesize the presence of alizarin.

The crystal structure of ferrinatrite, Na3[Fe(SO4)3]·3H2O, was refined based on a new single-crystal X-ray diffraction experiment on a sample from the type locality Sierra Gorda, Chile. The data allowed H to be successfully located and the H-bonding system to be defined. Infrared and Raman spectra are presented and discussed for this compound on the basis of the crystal structure. The Oacceptor···H–Odonor bond distances determined from the structure refinement agree well with the geometric correlation obtained from spectroscopic data. The thermal stability and dehydration process of ferrinatrite was investigated by in situ high temperature (HT) synchrotron X-ray powder diffraction, Raman and Fourier transform infrared spectroscopies.

We report a Raman spectroscopy study of glucose, fructose, and mannose. The spectra have been recorded for the dry powders and for solutions in H2O and D2O and commented in the so-called “fingerprint region” of the spectra (200–1,400 cm−1), in order to study the influence of the interaction with water on the solute vibrational modes. We have evidenced splitting of some bands, due to the presence of different anomers in solution. The isotopic substitution of the solvent has allowed in some instances to confirm the band assignment and, in other cases, to propose new assignments. Importantly, the isotopic substitution of the solvent has evidenced differences in the interaction of the investigated monosaccharides with water, which are rationalized as due to a balance between the inertia of the oscillator due to H-bonding and bond strength. In particular, glucose and fructose interact strongly with water, whereas in the case of mannose, we have observed a weaker interaction with water and a different behaviour of its anomers.

The concept of ions being either water "structure makers" or water "breakers" seems to be inconsistent with the existence of a critical number of water molecules per ion dictating the properties of an aqueous solution, independent of the ion identity. To investigate this issue, Raman spectra of hydroxide aqueous solutions in the region of the OH stretching mode have been obtained under ambient conditions and at concentrations ranging from extreme dilution to the solubility limit. Spectra have been analyzed with a relatively model-free approach, in terms of a superposition of contributions due to the vibrations of the OH-ions, with two contributions due to the solvent. One of these latter contributions falls at wavenumbers very close to that of the OH-stretching band, sharing with it its concentration dependence of the full width at half maximum (FWHM). The other contribution due to the solvent is very broad, with increasing FWHM with increasing ion concentration. In the light of these observations, an interpretation of the Raman spectra, based on the possibility of distinguishing the self and distinct contributions, is proposed. The present analysis is supported by structural data on the same solutions and puts into evidence relevant structural and dynamical changes occurring when the number of water molecules available per solute is below ∼20, irrespective of the ion identity.

In the last decade, worldwide research has focused on innovative natural biocides and the development of organic and inorganic nanomaterials for long-lasting reliability. In this work, the biocide effects of two different biocides encapsulated in two different silica nanosystems for a multifunctional coating have been performed through in vitro tests, by using Chlorococcum sp. as a common stone biodeteriogen. Zosteric sodium salt (ZS), a green biocide, was compared with the commercial biocide, 2-mercaptobenzothiazole (MBT), widely used in the treatment of cultural heritage. The analyzed systems are the following: silica nanocapsules (NC) and silica nanoparticles (MNP) not loaded with biocides, two nanosystems loaded with ZS and MBT, and free biocides. The qualitative and quantitative evaluations of biocide efficiency were performed periodically, analyzing pigment autofluorescence to discriminate between active and inactive/dead cells. The analyses showed multiple differences. All the nanocontainers presented an initial reduction in chlorophyll’s autofluorescence. For the free biocide, the results highlighted higher efficiency for MBT than ZS. Finally, the nanosystems loaded with the different biocides highlighted a higher activity for nanocontainers loaded with the commercial biocide than the green product, and better efficiency for MNP in comparison with NC.

The aim of this work is the historical and archaeometric investigation of a unique six-colour single-sheet relief print on paper belonging to a private collector. It is undescribed, undated and unsigned, and it depicts Charlemagne enthroned in Aachen Cathedral. The print was tentatively dated to the 16th century based on the style and iconography. This study offers a revised dating based on stylistic analysis of the design and archaeometric investigation of the six printing inks. The methodology consists of the complementary use of imaging and spectroscopic techniques, which are entirely non-invasive and non-destructive due to the rarity and fragility of the object. In particular, preliminary unaided visual analysis, UV fluorescence and IR reflectography were used to investigate the surface condition of the impression and to select the most promising areas for further analysis. Raman spectroscopy and XRF were used to identify pigments and treatments. Our results show that the paper support is in good condition. The pigments of all six inks have been identified. Results suggest that this impression was printed after 1850 and before 1900. In its conception and production, this artwork used then-modern methods and materials to pay homage to the styles and production techniques of the earliest German colour woodcuts.

In the attempt of satisfying the quest for new antifouling products tailored for applications on Cultural Heritage, we have synthesized and characterized two different silica nanosystems. The first consists of core-shell nanocapsules and the second one of mesostructured nanoparticles. Both systems have been successfully loaded in situ with the commercial biocide 2-mercaptobenzothizole (MBT). The synthesis procedure and particles characterization measurements, as far as their dimensions and superficial properties, loading capability, and release rate in aqueous solution, are reported. We stress that both particles have the dimensions required to avoid undesired light scattering once dispersed on the artefact surface. Interestingly, the two nanoparticles have complementary properties, suggesting that combining them in a coating may have a higher potential for production of new generation active products.

Sodalite-group minerals are silicates belonging to the zeolite group hosting in their cages a variety of cations and anions. Four mineral species of the sodalite-group are known in nature, the main difference being connected to the identity of the chemical species in the cages, particularly the sulfur molecular arrangements. Notably, the sodalite-group minerals show different colours; lazurite, in particular, is the main constituent of the well-known lapis lazuli, a material used throughout the human history as a precious stone or as a blue pigment for artworks. In this paper, we exploit Raman and Fourier-transform infrared (FTIR) spectroscopy to highlight an existing connection between the chalcogen species entrapped within the samples originated from the volcanic region of Latium (Italy) and their final colour. We show that Raman spectroscopy is a very valuable tool in characterizing the extraframework content in these minerals. Further, our analysis demonstrates how the blue hue of the sodalite species is related to the S-3(-)/SO42- relative content. We finally show how most specimen are also rich in CO2, a feature addressed by combination with FTIR spectroscopy. These findings have a particular interest not only in geology, but also in Cultural Heritage studies.

Neutron diffraction with isotopic H/D substitution on water, augmented by Empirical Potential Structure Refinement has been applied to extract the hydration properties of the osmolyte zwitterionic ectoine at 1.5 M concentration. This has evidenced differences between the hydration of COO− and NH groups, both in terms of number of water molecules involved in the hydration shell and of three-dimensional symmetry. Signatures of ectoine–ectoine contacts, due to hydrogen bonds, have been found, as possible precursors of ectoine aggregation at higher concentrations. The influence of ectoine on the water structure is ascribed to the dipolar electric field generated by the exposed charges of ectoine.

Rare earth elements doped (beta-tricalcium phosphates Ca9RE(PO4)(7) (RE = La, Pr, Nd, Eu, Gd, Dy, Tm, Yb) were synthesized by solid-state reaction at T = 1200 degrees C. The obtained RE-doped beta-TCP phases were studied by a combination of Scanning Electron Microscopy (SEM) equipped with energy dispersive X-Ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier Transform Infra Red (FTIR) and Raman spectroscopies. SEM morphological analyses revealed the presence of sub spherical micro crystalline aggregates, while EDS semi quantitative analyses confirmed the nominal RE/Ca composition for all the phases. The unit cell and the space group were determined by X-ray powder diffraction data showing that all phases in the series crystallize in the rhombohedral R3c whitlockite-type structure; the unit cell constants are a linear function of the dimension of the substituting rare-earth element, and range from a = b = 10.4695(3) angstrom, c = 37.500(3) angstrom and V= 3559.7(2) angstrom(3) (La) up to a = b = 10.4073(2) angstrom, c = 37.2725(2) angstrom, V = 3496.2(2) angstrom(3) (Yb). The analysis of each compound was completed with the structure model refinement by the Rietveld method and the distribution of RE within the available structural sites is discussed according to the results of the Rietveld refinement. The FTIR and Raman spectra show slight band shifts of the phosphate modes correlated to the evolving size of the RE element.

Even though gamma radiation application, also at the minimum dosage required for disinfection, causes depolymerization and degradation of the paper substrate, recently published papers seemed, instead, to suggest that γ-rays application could be envisaged in some conditions for Cultural Heritage original documents and books. In some of the published papers, the possible application of γ-rays was evaluated mainly by using mechanical tests that scarcely reflect the chemical modifications induced in the cellulosic support. In the present article the effect of low dosage γ-irradiation on cellulosic substrates was studied and monitored applying different techniques: colorimetry, spectroscopic measurements, carbonyl content and average viscometric degree of polymerization. Two different papers were investigated, a non-sized, non-filled cotton paper, and a commercial permanent paper. To simulate a real deteriorated document, which could need γ-rays irradiation, some samples were submitted to a hydrolysis treatment. We developed a treatment based on the exposition of paper to hydrochloric acid vapors, avoiding any contact of the samples with water. This method induces a degradation similar to that observed on original documents. The samples were then irradiated with 3 kGy γ-rays at a 5258 Gy/h rate. The aforementioned analyses were performed on the samples just irradiated and after artificial ageing. All tests showed negative effects of gamma irradiation on paper. Non-irradiated paper preserves better its appearance and chemical properties both in the short term and after ageing, while the irradiated samples show appreciable color change and higher oxidation extent. Since the Istituto centrale restauro e conservazione patrimonio archivistico e librario is responsible for the choice of all restoration treatments that could be applied on library and archival materials under the protection of the Italian State ( http://www.icpal.beniculturali.it/allegati/DM-7-10-2008-Istituto.pdf ), it has been evaluated that the modifications induced by γ-rays irradiation are not acceptable as safe conservation treatment ( http://www.icpal.beniculturali.it/allegati/Nota_uso_raggi_gamma.pdf ).

Opals are naturally occurring hydrous silica materials (SiO2*nH2O), characterized by different degrees of crystallinity and crystal structure. Because of their optical properties, opals have been largely used in jewelry and as decorative elements in artworks. For this reason, a complete characterization and a provenance study of this kind of materials is mandatory in order both to avoid frauds and to reconstruct ancient and modern trade routes of gems. In this work, we present a combined spectroscopic (Raman, FTIR) and X-ray powder diffraction (XRD) investigation of nine opals from the main deposits around the world (Australia, Madagascar, Slovakia, Mexico, Honduras and Ethiopia). Four of these samples are the rare and precious fire opals, characterized by an intense red–orange color. Ethiopia, Honduras and Mexico opals showed spectra and diffraction patterns typical of Opal-CT, generally associated to volcanic genesis, while Australia, Madagascar and Slovakia opals are Opal-A type, associated to sedimentary origin. Unexpectedly the fire opal from Brazil behaves as a CT one. The presence of CO2 was detected only in the latter group, and exceptionally in the Honduras sample; FTIR-FPA imaging showed carbon dioxide to be homogeneously distributed inside the gems. Opals-CT are CO2-free and give much more complex FT-IR spectra in the NIR region where H2O combination modes occur. The obtained results are discussed in terms of relevance of the above experimental techniques for geosourcing opals, and contribute to increase the database of the chemical–physical properties of opals. Copyright © 2016 John Wiley & Sons, Ltd.

Cellulose oxidative and hydrolytical degradation is one of the greatest problems for the conservation of paper supports. To contrast these degradation processes, both deacidification and reduction of the oxidized functions are needed. Dealing with original documents, it is often impossible to perform the two mentioned treatments in aqueous solutions and in a distinct subsequent way, because of the fragility of the artifacts. After studying, in a separate way, an effective deacidifier (calcium propionate) soluble in ethyl alcohol and many reducers (boron complexes), able to act in different non-aqueous solvents, it was decided to test a simultaneous method of deacidification and reduction in ethanol. This paper presents the chemical-physical results obtained by applying simple deacidification and simultaneous deacidification-reduction on laboratory paper samples that were artificially aged and then re-measured after 10 and 15 years of natural aging. Results show that all alcoholic treatments are very effective: papers are stable also after a long period of both artificial and natural aging.

Follicular patterned nodules are sometimes complex to be classified due to ambiguous nuclear features and/or questionable capsular or vascular invasion. In this setting, there is a poor inter-observer concordance even among expert pathologists. Raman spectroscopy was recently used to separate benign and malignant thyroid nodules based on their molecular fingerprint, anyway, some histologically proved follicular adenomas were clustered as having a characteristic profile of malignant lesions. In this study, we analyzed five follicular thyroid adenomas with a malignant spectroscopic profile compared to five follicular adenomas with a benign Raman spectrum in order to assess possible molecular differences between the two groups. Morphological, immunohistochemical, and molecular analyses evidenced expression of malignancy-associated proteins in four out of five malignant clustered adenomas. The remaining malignant clustered adenoma showed a TSHR mutation previously associated with autonomously functioning follicular carcinomas. In conclusion, thyroid follicular adenomas are a group of morphologically benign neoplasms that may have altered the mutational or expression profile, cases of adenomas with altered immunophenotype are recognized as showing a profile associated with malignancy by Raman spectroscopy. This correlation warrants a more extensive evaluation and suggests a potential predictive value of spectroscopic assessment in recognizing characteristics associated with tumor progression in follicular thyroid neoplasms.

Magnetic mesoporous silica (MS) nanocomposites provide the possibility of generating multi-functional objects for application in different technological areas. This paper focuses on the magnetic properties of nanocomposites constituted by spinel iron oxide nanoparticles (magnetic nanoparticles (MNPs), < D > ≈ 8-9 nm) embedded in an MS matrix. The mesoporous structure of the silica matrix and the presence of the nanoparticles inside clearly emerge from transmission electron microscopy (TEM) measurements. Low temperature (5 K) field-dependent magnetization measurements reveal saturation magnetization (MS ) close to bulk value (M S bulk ∼ 90 emu g-1) for both MNPs and MNP/MS nanocomposites, indicating that the presence of silica does not affect the magnetic features of the single MNPs. Moreover, the dependence of the remanent magnetization on field (i.e. δM plots) at low temperature has shown a small but evident decrease of interaction in an MNP/MS sample with respect to MNP samples A m2 Kg-1. Finally, a partial orientation of the easy axis is observed when the MNPs are embedded in the silica matrix.

The identification of dyes from ancient textiles represents a challenging issue requiring high proficiency and versatility, that must be guided by the principles of non-destructiveness. The complexity of the dye/textile system influences both the choice of sampling and extraction procedures and the analytical methodology. For instance, in order to preserve both the fibre and the original chromophores on it, the extraction procedures commonly used for natural dyes have evolved in last few decades towards increasingly mild conditions. Along with this approach, the use of solid substrates for sampling has become prominent in several fields of Cultural Heritage diagnostics.With reference to these two aspects, the aim of this work is to combine gel substrates and a mild basic solution for the extraction of anthraquinone dyes (madder and cochineal) from wool textiles, in order to evaluate the versatility of the extraction procedure for different analytical techniques. Because of their wide use in the field of Conservation, agar and nanorestore gel substrates soaked in an ammonia-EDTA solution were tested. The dye-extracting substrates were then analysed with Raman and SERS spectroscopy, whilst the fraction re-extracted from them was examined with HPLC-HRMS. Finally, scanning electron microscopy was used to monitor the integrity of the wool after the extraction treatment with the ammonia-EDTA solution.HPLC-HRMS results show that the basic solution in both gels is effective for the dye extraction, and no alteration of wool fibres was evidenced by SEM-EDS. The Raman spectra give no information about the dyes, but only substrate signals are obtained. Conversely, SERS spectroscopy makes it possible to distinguish the two dyes, especially using the 633 nm laser on the agar substrate.

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