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The study explores the application of natural biocides (oregano essential oil and eugenol, directly applied in solutions or encapsulated within silica nanocapsules) for safeguarding stone cultural heritage from biodeterioration, using green algae (Chlorococcum sp.) and cyanobacteria (Leptolyngbya sp.) as common pioneer biodeteriogens. Core-shell nanocontainers were built for a controlled release of microbicidal agents, a safe application of chemicals and a prolonged efficacy. The qualitative and quantitative evaluations of biocide efficiency at different doses were periodically performed in vitro, after six scheduled intervals of time (until 100 days). The release kinetics of composite biocide-embedding silica nanocapsules were characterized by the UV-Vis spectroscopy technique. Data showed both promising potential and some limitations. The comparative tests of different biocidal systems shed light on their variable efficacy against microorganisms, highlighting how encapsulation influences the release dynamics and the overall effectiveness. Both the essential oils showed a potential efficacy in protective antifouling coatings for stone artifacts. Ensuring compatibility with materials, understanding their differences in biocidal activity and their release rates becomes essential in tailoring gel, microemulsion or coating products for direct on-site application.

Among the thyroid cancers, papillary thyroid cancer (PTC) accounts for 90% of the cases. In addition to the necessity to identify new targets for PTC treatment, early diagnosis and management are highly demanded. Previous data indicated that the multivariate statistical analysis of the Raman spectra allows the discrimination of healthy tissues from PTC ones; this is characterized by bands typical of carotenoids. Here, we dissected the molecular effects of carotenoid accumulation in PTC patients by analyzing whether they were required to provide increased retinoic acid (RA) synthesis and signaling and/or to sustain antioxidant functions. HPLC analysis revealed the lack of a significant difference in the overall content of carotenoids. For this reason, we wondered whether the carotenoid accumulation in PTC patients could be related to vitamin A derivative retinoic acid (RA) biosynthesis and, consequently, the RA-related pathway activation. The transcriptomic analysis performed using a dedicated PCR array revealed a significant downregulation of RA-related pathways in PTCs, suggesting that the carotenoid accumulation in PTC could be related to a lower metabolic conversion into RA compared to that of healthy tissues. In addition, the gene expression profile of 474 PTC cases previously published in the framework of the Cancer Genome Atlas (TGCA) project was examined by hierarchical clustering and heatmap analyses. This metanalysis study indicated that the RA-related pathways resulted in being significantly downregulated in PTCs and being associated with the follicular variant of PTC (FV-PTC). To assess whether the possible fate of the carotenoids accumulated in PTCs is associated with the oxidative stress response, the expression of enzymes involved in ROS scavenging was checked. An increased oxidative stress status and a reduced antioxidant defense response were observed in PTCs compared to matched healthy thyroids; this was possibly associated with the prooxidant effects of high levels of carotenoids. Finally, the DepMap datasets were used to profile the levels of 225 metabolites in 12 thyroid cancer cell lines. The results obtained suggested that the high carotenoid content in PTCs correlates with tryptophan metabolism. This pilot provided novel possible markers and possible therapeutic targets for PTC diagnosis and therapy. For the future, a larger study including a higher number of PTC patients will be necessary to further validate the molecular data reported here.

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.

A modular X-ray scanning system was developed, to fill in the gap between portable instruments (with a limited analytical area) and mobile instruments (with large analytical areas, and sometimes bulky and difficult to transport). The scanner has been compared to a commercial tabletop instrument, by analysing a Portuguese tile (azulejo) from the 17th century. Complementary techniques were used to achieve a throughout characterisation of the sample in a complete non-destructive approach. The complexity of the acquired X-ray fluorescence (XRF) spectra, due to inherent sample stratigraphy, has been resolved using Monte Carlo simulations, and Raman spectroscopy, as the most suitable technique to complement the analysis of azulejos colours, yielding satisfactory results. The colouring agents were identified as cobalt blue and a Zn-modified Naples-yellow. The stratigraphy of the area under study was partially modelled with Monte Carlo simulations. The scanners performance has been compared by evaluating the images outputs and the global spectrum.

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.