Search

The dark matter interpretation of the DAMA/LIBRA annual modulation signal represents a long-standing open question in astroparticle physics. The SABRE experiment aims to test such claim, bringing the same detection technique to an unprecedented sensitivity. Based on ultra-low background NaI(Tl) scintillating crystals like DAMA, SABRE features a liquid scintillator Veto system, surrounding the main target, and it will deploy twin detectors: one in the Northern hemisphere at Laboratori Nazionali del Gran Sasso (LNGS), Italy and the other in the Stawell Underground Physics Laboratory (SUPL), Australia, first laboratory of this kind in the Southern hemisphere. The first very-high-purity crystal produced by the collaboration was shipped to LNGS in 2019 for characterization. It features a potassium contamination, measured by mass spectroscopy, of the order of 4 ppb, about three times lower than DAMA/LIBRA crystals. The first phase of the SABRE experiment is a Proof-of-Principle (PoP) detector featuring one crystal and a liquid scintillator Veto, at LNGS. This contribution will present the results of the stand-alone characterization of the first SABRE high-purity crystal, as well as the status of the PoP detector, commissioned early in the summer of 2020.

Archaeological high-tin copper-based artefacts, dated back to VIII and IV centuries BC and recently discovered in the Italic necropolises of ancient Abruzzo (Central Italy), were investigated in order to determine the micro-chemical and micro-structural nature of the corrosion products and the chemical composition and metallurgical features of the alloys. The Cu-based artefacts were defensive weapons mainly as bronze belts and pectoral disc armours with engraved decorations. A rather detailed picture of the chemical composition, structural and morphological characteristics of such Cu-based artefacts was provided by combining different techniques as scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), optical microscopy (OM) and X-ray diffraction (XRD) analysis. The results, as a whole, evidence that some artefacts were manufactured by casting and shaping uncommon high-tin bronze alloys thus conferring an attractive silver-like appearance. The manufacturing process was based on tailored multiple hot hammering, carefully carried out at about 700 °C to shape the high-tin alloys in the form of sheets avoiding breaking. The mechanical work was followed by an annealing treatment, polishing and final decorative finishing. Furthermore, our investigation on the corrosion process, suggest that it is a mixture of rather complex phenomena leading to the degradation of the main alloying elements which give rise to mineral alteration products in the form of complex structures. These latter contain SnO2 (cassiterite), cuprous oxide, copper carbonates (azurite and malachite) and, in particular, chlorine-based compounds like nantokite and atacamite and its polymorphs, which have heavy detrimental effects, their presence being considered a symptom of the destructive “bronze disease” degradation phenomenon. Moreover, it was found an unusual presence of re-deposited Cu inclusions to be likely related to long-term corrosion processes and to a low oxygen availability in the burial environment. All these findings show, as a whole, that there is a strict relationship between alloy elements, metallurgical features, burial soil conditions and chemical and structural features of the corrosion products. This paper highlights also as the combined use of different techniques as SEM-EDS, ATR-FTIR, XPS, XRD and OM can be one of the possible successfully way to study the corrosion products of archaeological copper-based artefacts, thus helping to choose the more appropriate strategies for the long-lasting conservation of archaeological bronze artworks, in most cases so valuable for the cultural heritage.

SABRE (Sodium-iodide with Active Background REjection) is a direct dark matter search experiment based on an array of radio-pure NaI(Tl) crystals surrounded by a liquid scintillator veto. Twin SABRE experiments in the Northern and Southern Hemispheres will differentiate a dark matter signal from seasonal and local effects. The experiment is currently in a Proof-of-Principle (PoP) phase, whose goal is to demonstrate that the background rate is low enough to carry out an independent search for a dark matter signal, with sufficient sensitivity to confirm or refute the DAMA result during the following full-scale experimental phase. The impact of background radiation from the detector materials and the experimental site needs to be carefully investigated, including both intrinsic and cosmogenically activated radioactivity. Based on the best knowledge of the most relevant sources of background, we have performed a detailed Monte Carlo study evaluating the expected background in the dark matter search spectral region. The simulation model described in this paper guides the design of the full-scale experiment and will be fundamental for the interpretation of the measured background and hence for the extraction of a possible dark matter signal., Comment: 13 pages, 5 figures

We present new results on the radiopurity of a 3.4-kg NaI(Tl) crystal scintillator operated in the SABRE proof-of-principle detector setup. The amount of potassium contamination, determined by the direct counting of radioactive $^{40}$K, is found to be $2.2\pm1.5$ ppb, lowest ever achieved for NaI(Tl) crystals. With the active veto, the average background rate in the crystal in the 1-6 keV energy region-of-interest (ROI) is $1.20\pm0.05$ counts/day/kg/keV, which is a breakthrough since the DAMA/LIBRA experiment. Our background model indicates that the rate is dominated by $^{210}$Pb and that about half of this contamination is located in the PTFE reflector. We discuss ongoing developments of the crystal manufacture aimed at the further reduction of the background, including data from purification by zone refining. A projected background rate lower than $\sim$0.2 counts/day/kg/keV in the ROI is within reach. These results represent a benchmark for the development of next-generation NaI(Tl) detector arrays for the direct detection of dark matter particles.

Background and importance The introduction of the unit dose (DU) as a drug dispensing system produces a multiplicity of advantages, ranging from prescribing to administering therapies. Aim and objectives The purpose of this study was to evaluate, through the computerised prescription, the prescriptive appropriateness of antibiotic therapy and the economic impact of a targeted therapy after an antibiogram compared with empirical therapy. Material and methods The analysis was carried out by extrapolating, from the prescription software and administration in use, the antibiotic prescriptions subjected to a single request motivated (SRM) from 1 January 2019 to 31 December 2019. With the Modulab software, a clinical information management system, prescriptions with antibiograms were verified and divided into appropriate and inappropriate. Prescriptions initiated as empirical therapies were defined as appropriate if the results of the antibiogram confirmed the therapy already started or if the prescriptions changed following the antibiogram. Therapies were considered inappropriate if the antibiogram results were different from the antibiotics used as empirical therapy (resistant/intermediate) or were not tested. Prescriptions were grouped for empirically prescribed antibiotics and for sensitive antibiotics (as a result of the antibiogram), considering a median duration of therapy. The maximum daily dosage from the technical data sheet was considered for the calculation of the cost of the therapy. Only inappropriate prescriptions were considered in the pharmacoeconomic evaluation. Results During the study period, total prescriptions of antibiotics with SRM were 2067 of which 1322 (64%) had no antibiogram and 745 (36%) had an antibiogram. The latter were divided into appropriate (63%) and inappropriate (37%). The pharmacoeconomic analysis showed a cost of non-appropriate therapy of 53 950€, with a possible saving of around 49 274€ if the same had been transferred to the sensitive antibiotic resulting from the antibiogram. Conclusion and relevance We hope, in the future, to directly consult the antibiogram from the computerised prescription to highlight extemporaneously the limitations of long term empirical therapies both for prescriptive appropriateness and for cost savings. References and/or acknowledgements Conflict of interest No conflict of interest

Background and importance In the context of the single dose, the pharmacist is involved in the validation of patients‘ personalised therapies, attempting to minimise errors in therapy. Aim and objectives The aim of this study was to evaluate, through the computerised prescription, the increase in prescribing appropriateness of antibiotic therapy, following notification by the pharmacist, with relative money saving costs. Material and methods The analysis was carried out by extrapolating, from the unit dose (UD) software, prescriptions of antibiotics subjected to a single request motivated (SRM) in the period from 1 January 2019 to 31 December 2019. We analysed inappropriate prescriptions where the hospital pharmacist affixed the ‘note’, sent immediately to the prescriber. These prescriptions were divided into inappropriate for: posology, duration of therapy and interaction/incompatibility. Subsequently, the variation in prescriptions due to the pharmacist’s intervention was evaluated (ie, the number of inappropriate prescriptions which were changed by the physician was extrapolated). In the pharmacoeconomic field, we evaluated the expenditure of inappropriate prescriptions without notification of the hospital pharmacist and the savings obtained following the change in therapy. Results During the study period, total prescriptions of antibiotics with SRM were 2067; 216 (10.45%) were not appropriate. The number of prescriptions modified following the pharmacist’s intervention was 104 (48%). Pharmacoeconomic analysis showed that the expenditure incurred for the dispensation of antibiotics related to inappropriate prescriptions changed by notification from the pharmacist was 77 537€ for 12 months. If the physician had not modified the therapies, the expenses would have been 162 762€ and therefore the amount of money saved was 85 225€ in 12 months. Conclusion and relevance The control and validation of medical prescriptions by the pharmacist produced an important added value to the risk management process, in that in almost 50% of cases the pharmacist’s notes led to an actual change in the medical prescription. The use of computerised prescriptions and single dose management contributed strongly to the objectives of verifying prescriptive appropriateness as a tool to govern effectiveness, efficiency and costs in healthcare. References and/or acknowledgements Conflict of interest No conflict of interest

Background: Despite the current therapeutic options for the treatment of inflammatory bowel disease, surgery is still frequently required in the emergency setting, although the number of cases performed seems to have decreased in recent years. The World Society of Emergency Surgery decided to debate in a consensus conference of experts, the main pertinent issues around the management of inflammatory bowel disease in the emergent situation, with the need to provide focused guidelines for acute care and emergency surgeons. Method: A group of experienced surgeons and gastroenterologists were nominated to develop the topics assigned and answer the questions addressed by the Steering Committee of the project. Each expert followed a precise analysis and grading of the studies selected for review. Statements and recommendations were discussed and voted at the Consensus Conference of the 6th World Society of Emergency Surgery held in Nijmegen (The Netherlands) in June 2019. Conclusions: Complicated inflammatory bowel disease requires a multidisciplinary approach because of the complexity of this patient group and disease spectrum in the emergency setting, with the aim of obtaining safe surgery with good functional outcomes and a decreasing stoma rate where appropriate. © 2021, The Author(s).

BackgroundSeveral data have demonstrated the occurrence of erosive arthritis in Systemic Lupus Erythematosus (SLE) patients. However, few studies have focused on the pathogenic mechanisms involved in this feature. The implication of oral pathogens has been proved in Rheumatoid Arthritis: in particular, Porphyromonas gingivalis (Pg), by inducing citrullination, could trigger autoimmune response.ObjectivesWe evaluated amount of Pg of the tongue in a cohort of SLE patients with arthritis, focusing on the association with the erosive phenotype.MethodsSLE patients with arthritis were enrolled. We evaluated the presence of ACPA and RF by using commercially enzyme-linked immunosorbent assay kits. SLEDAI-2k was applied to assess disease activity and DAS28 to assess joint inflammatory status. Erosive damage was evaluated by ultrasound at level of metacarpophalangeal and proximal interphalangeals joints. All subjects underwent a tongue cytologic swab in order to quantify the amount of Pg (real-time PCR). The bacterium expression was obtained from the ratio between the patient’s DNA amount and that obtained from healthy subjects.ResultsThe present analysis included 33 SLE patients (M/F 3/30; median age 47 years, IQR 17; median disease duration 216 months, IQR 180). Concerning activity at the time of the enrollment, we found a median DAS28 value of 3.8 (IQR 2.8) and a median SLEDAI-2k of 4 (IQR 5). Twelve patients (36.4%) showed US-detected erosive damage in at least one joint, significantly associated with ACPA positivity (pConclusionThe possible contribution of oral microbiota in SLE erosive arthritis was here evaluated for the first time, finding a significant association between erosive damage and higher expression of Pg at tongue level.Disclosure of InterestsNone declared

Ultra-pure NaI(Tl) crystals are the key element for a model-independent verification of the long standing DAMA result and a powerful means to search for the annual modulation signature of dark matter interactions. The SABRE collaboration has been developing cutting-edge techniques for the reduction of intrinsic backgrounds over several years. In this paper we report the first characterization of a 3.4 kg crystal, named NaI-33, performed in an underground passive shielding setup at LNGS. NaI-33 has a record low $$^{39}$$ 39 K contamination of 4.3 ± 0.2 ppb as determined by mass spectrometry. We measured a light yield of 11.1 ± 0.2 photoelectrons/keV and an energy resolution of 13.2% (FWHM/E) at 59.5 keV. We evaluated the activities of $$^{226}$$ 226 Ra and $$^{228}$$ 228 Th inside the crystal to be $$5.9\pm 0.6~\upmu $$ 5.9 ± 0.6 μ Bq/kg and $$1.6\pm 0.3~\upmu $$ 1.6 ± 0.3 μ Bq/kg, respectively, which would indicate a contamination from $$^{238}$$ 238 U and $$^{232}$$ 232 Th at part-per-trillion level. We measured an activity of 0.51 ± 0.02 mBq/kg due to $$^{210}$$ 210 Pb out of equilibrium and a $$\alpha $$ α quenching factor of 0.63 ± 0.01 at 5304 keV. We illustrate the analyses techniques developed to reject electronic noise in the lower part of the energy spectrum. A cut-based strategy and a multivariate approach indicated a rate, attributed to the intrinsic radioactivity of the crystal, of $$\sim $$ ∼ 1 count/day/kg/keV in the [5–20] keV region.

Ancient silver-based alloys objects are of a great interest because they were world-wide used to produce high value works of art and precious items as jewels and ornaments with a relevant artistic, religious or historical value. Silver-based alloys were also largely used everyday as monetary currency and form of saving playing a relevant role for the development and growth of the economy. By means of the combined use of complementary surface analytical techniques such as scanning electron microscopy coupled with energy dispersive spectrometry (SEM + EDS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and optical microscopy (OM) we have investigated the micro- and nano-chemical nature of the products of corrosion naturally formed on archaeological silver-based Roman objects characterised by different burial conditions. The results allow the identification of different corrosion products formed during the long interaction between the elements constituting the alloy, i.e. Ag and Cu, and degradation agents present in the surrounding environment. The results of the integrated analytical methodologies highlight the role of chlorine, that is always present in the patina as chloroargyrite (AgCl, also known as cerargyrite or horn silver) and also in some cases of bromine which forms bromargyrite (AgBr) or bromian-chloroargyrite [Ag(Br,Cl)] as dominant corrosion products. The unusual presence of Br in the silver patina reflects the peculiar environmental chemistry suffered by the buried object likely due to the presence of degrading organic matter under aerobic conditions. Furthermore, the results reveal that chlorine often preferentially corrodes the numerous local copper enrichments randomly dispersed in the silver host matrix inducing the formation of harmful copper-chlorine compounds including Cu2Cl(OH)(3) (atacamite and its polymorphs) and likely CuCl (nantokite) generally related to the copper cyclic corrosion called by conservators "bronze disease". Finally, different corrosion patterns have been observed with the outermost layers often enriched by soil elements as S, Ca, Al, Si and Fe thus confirming the strong interaction of the alloys elements with the burial soil components. (C) 2017 Elsevier B.V. All rights reserved.

Naturally grown patinas are typically detected onto the surface of modern copper-based artefacts and strictly affect their surface reactivity and appearance. The production of representative patinas is a key issues in order to obtain model systems which can be used for the development and validation of appropriate conservation materials and methods. In this study, we have prepared different artificial representative patinas by using a quaternary Cu-Sn-Zn-Pb alloy with chemical composition and metallurgical features similar to those of valuable modern works of art. In order to produce degradation products usually observed onto their surface, chloride and sulphate species were used to induce corrosion processes. Different patinas were produced by changing the nature of corrosive species and the set-up for the accelerated degradation. The composition and structural properties of the patinas were investigated by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray diffraction, optical microscopy and scanning electron microscopy combined with energy dispersive X-ray spectroscopy. The results allow to identify degradation products and to distinguish copper hydroxychloride polymorphs and copper hydroxysulphates with similar structure. Our findings show that patina composition can be tailored by modifying the degradation procedure and patinas representative of modern artefacts made of quaternary Cu-Sn-Zn-Pb alloy can be obtained.

Titania-based cotton textiles have been prepared by covering the surface of the fabrics with crystalline titania anatase, which is known for its nontoxicity, low cost and for its photocatalytic activity in the degradation of many organic compounds. The coatings were prepared by using the widely used commercial P25 titania (35-65 m2/g), as reference, and an ordered mesoporous titania with high surface area (165 m2/g) prepared by soft template assisted route. In order to promote the interaction between titania and cotton textile, titania-silica nanocomposite coatings have been prepared by dispersing the titania powder into a silica sol used as binder. FE-SEM investigations revealed that the fabrics are uniformly covered by silica-titania coatings and titania particles are partially embedded into silica matrix. The presence of crystalline anatase onto cotton fabrics was confirmed by Raman and XRD measurements and it was observed that the anatase peaks were more pronounced by using mesoporous titania. The self-cleaning performances of the functionalized textiles were investigated by monitoring the discoloration of anthocyanin stains after irradiation with a solar simulator. Our findings reveal that the use of mesostructured titania leads to a more efficient discoloration with respect to the commercial P25 titania, suggesting the importance of the titania textural properties on the photocatalytic activity. The high surface area and the smaller crystallites of ordered mesoporous titania allow to gain a high number of exposed sites that can improve the self-cleaning performances of the functionalized textiles with respect to commercial P25 titania. These results appear promising to further improve the efficiency of self-cleaning cotton fabrics.

A new system to assign accurate timestamps to events recorded by experiments running underground has been designed, installed and tested at INFN Gran Sasso National Laboratory, Italy. This facility is based on a Master unit installed on surface and receiving time information from a GPS receiver, and Slave units placed underground which get data packet from the Master via optical fiber and assign the timestamps. The system is able to provide a time accuracy of 15 ns (1 $\sigma$) and precise reference frequencies to the experiments. It is now part of the infrastructure of the Laboratory for all the experimental activities which need accurate timestamps.

Gold and silver coated copper-based artefacts subjected to long-term natural corrosion phenomena were studied by means of the combined use of X-ray photoelectron spectroscopy (XPS), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM + EDS), and optical microscopy (OM). The results allowed the identification of the chemistry and structure of the Au or Ag layers deposited by fire-gilding or mercury-silvering and the determination of the corrosion products formed due to interaction with the surrounding environment. Different degradation phenomena of the noble metal layer and copper substrate are induced by the presence of chlorine, sulphur and phosphorous and they are boosted by the metal galvanic coupling which makes gilded-metal art works unstable from a chemico-physical point of view. The SEM + EDS and OM results also suggest that particular care must be used during the removal of the encrustations and of the external corrosion products to avoid the loss of the remains of the noble layer often floating or embedded in the corrosion products. Furthermore, in order to avoid the reaction between nantokite (CuCl) and moisture the use no or low toxic inhibitors is suggested to avoid further severe degradation phenomena enhancing the long-lasting chemico-physical stability of these precious artefacts and giving them a greater chance of survival. (C) 2016 Elsevier B.V. All rights reserved.

On the north coast of present-day Peru, between the Andes and the Pacific Ocean, approximately between 100 and 600 ad, the Moche civilization prospered. The Moche were very sophisticated artisans and metal smiths, so that they are considered the finest producers of jewels and artifacts of the region. Their metalworking ability was impressively demonstrated by the excavations of the tomb of the ‘Lady of Cao’ (dated around third–fourth century ad) discovered by Regulo Franco in 2005. Impressive is the beauty of the artifacts, and also the variety of metallurgical solutions, demonstrated by not only the presence of objects composed of gold and silver alloys but also of gilded copper, gilded silver, and tumbaga, a poor gold Cu-Au alloy subject to depletion gilding. About 100 metal artifacts from the tomb of the Lady of Cao, never before analyzed, were studied by using various portable equipments based on following non-destructive and non-invasive methods: energy-dispersive X-ray fluorescence with completely portable equipments; transmission of monenergetic X-rays; radiographic techniques; and optical microscopy. Gold objects and gold areas of nose decorations are characterized by approximately the same composition, that is, Au = (79.5 ± 2.5) %, Ag = (16 ± 3) %, and Cu = (4.5 ± 1.5) %, while silver objects and silver areas of the same nose decorations show completely erratic results, and a systematic high gold concentration. Many gilded copper and tumbaga artifacts were identified and analyzed. Further, soldering gold–silver was specifically studied by radiographs. Additional measurements are needed, particularly because of the suspect that depletion gilding was systematically employed also in the case of some nose decorations. Copyright © 2016 John Wiley & Sons, Ltd.

SABRE is a dark matter direct detection experiment aiming to measure the annual modulation of the dark matter interaction rate in NaI(Tl) crystals. SABRE focuses on the achievement of an ultra-low background rate operating high-purity NaI(Tl) crystals in a liquid scintillator veto for active background rejection. Moreover, twin experiments will be located in both Northern and Southern hemispheres (Italy and Australia) to disentangle any possible contribution from seasonal or site-related effects. In this article the results of the first measurements with a NaI(Tl) crystal for the SABRE experiment performed at LNGS are presented.

SABRE is a dark matter direct detection experiment based on NaI(Tl) scintillating crystals. The primary goal of the experiment is to test the dark matter interpretation of the DAMA/LIBRA annual modulation signal. To reach its purpose, SABRE will operate an array of ultra-low background NaI(Tl) crystals within an active veto, based on liquid scintillator. Finally two twin detectors will be used, one in the northern hemisphere at Laboratori Nazionali del Gran Sasso, Italy (LNGS) and the other, first of its kind, in the southern hemisphere, in the Stawell Underground Physic Laboratory (SUPL). The collaboration has successfully developed a NaI(Tl) crystal with the impressive potassium content of about 4 ppb, according to the mass spectroscopy measurements. A value that, if confirmed, would be about 3 times lower than the DAMA/LIBRA crystals one. The first phase of the SABRE experiment, called SABRE Proof of Principle (PoP), aims to prove the achieved radiopurity by direct measurement of crystals at LNGS. This work reports the status of the PoP setup and the recent progresses on the development of low radioactivity NaI(Tl) crystals.

We analyze the vacuum structure of a generalized lattice Nambu--Jona-Lasinio model with two flavors of Wilson fermions, such that its continuum action is the most general four-fermion action with 'trivial' color interactions, and having a $SU(2)_V x SU(2)_A$ symmetry in the chiral limit. The phase structure of this model in the space of the two four-fermion couplings shows, in addition to the standard Aoki phases, new phases with $ != 0$, in close analogy to similar results recently suggested by some of us for lattice QCD with two degenerate Wilson fermions. This result shows how the phase structure of an effective model for low energy QCD cannot be entirely understood from Wilson Chiral Perturbation Theory, based on the standard QCD chiral effective Lagrangian approach., Comment: 24 pages, 3 figures, sent to Nuclear Physics B

The mineral species forming the patinas naturally grown on copper-based artefacts retrieved from sea-water have been studied by means of the combined use of scanning electron microscopy coupled with energy dispersive spectrometry (SEM+EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and optical microscopy (OM). The selected artefacts include fragments of bronze statues and commonly used objects that were recently found in the Sicilian channel and along the Italian coasts. Our findings show that the composition and structure of the corrosion products is different depending on several parameters and the local environment. Furthermore, the study of the metallurgical features of the artefacts revealed also some interesting manufacturing details. From a conservation point of view, the SEM-EDS, XPS, FTIR, XRD and OM results show, as a whole, that the alloy matrix is often heavily corroded also in the bulk where the ubiquitous and dangerous presence of chlorine was always detected as the main dangerous corroding agent. Chlorine forms nantokite (CuCl) which is the species inducing the cyclic and inexorable copper corrosion commonly called "bronze disease". Other elements from the marine environment that contribute to form the patina are sulphur, phosphorous and seawater cations like Ca and Mg. On the basis of our results, an attempt is made to find a correlation between the nature of the patina, the chemical composition of the objects and the marine retrieving environment where the objects lived for many hundreds, or thousands, years. From a conservation point of view, our findings may be useful to suggest, or select, tailored conservation methods and materials with the purpose to turn the dangerous copper chlorides, or oxy-chlorides (atacamite and its polymorphs), into less reactive and more stable phases. This should hamper the copper cyclic reaction thus ensuring a long-term chemical-physical stability to the bronze artefacts.

Gilded brooches dating back to 16th-17th centuries CE were investigated by means of integrated and complementary analytical techniques such as high spatial resolution field emission scanning electron microscopy coupled with energy dispersive X-ray spectrometry (FE-SEM+EDS), time of flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and optical microscopy (OM). The results reveal in detail the surface and subsurface morphology and the chemical features of the micrometric decorative Au layer that has been deposited by means of the so-called fire-gilding technique based on the use of an amalgam. Moreover, the results allow to recognise chlorine, sulphur and phosphorous species as the main degradation agents and to identify the corrosion products naturally formed during the long-term interaction with the burial soil constituents. The findings show also that the galvanic coupling between the two dissimilar metals, i.e. Cu and Au, lead to enhancement of corrosion phenomena causing the spalling of the gold thin film and the disfigurement of the object. From a conservation point of view, the results suggest a targeted use of low-toxic inhibitors to hinder the detrimental role of chlorine as possible responsible of future further severe degradation phenomena. In conclusions, the micro and nano-chemical, structural and morphological investigations in a depth range from a few nanometers to micrometers have revealed the complex nature of corroded surface of ancient gold coated artefacts, highlighting some specific aspects related to their peculiar degradation mechanisms thus extending the scientific relevance of the tailored use of complementary and integrated surface and subsurface analytical techniques for the investigation of ancient coated artefacts. (C) 2018 Elsevier B.V. All rights reserved.

Time modulations at per mil level have been reported to take place in the decay constant of several nuclei with period of one year (most cases) but also of about one month or one day. On the other hand, experiments with similar or better sensitivity have been unable to detect any modulation. In this letter we give the results of the activity study of two different sources: 40K and 226Ra. The two gamma spectrometry experiments have been performed underground at the Gran Sasso Laboratory, this way suppressing the time dependent cosmic ray background. Briefly, our measurements reached the sensitivity of 3.4 and 3.5 parts over 10^6 for 40K and 226Ra, respectively (1 sigma) and they do not show any statistically significant evidence of time dependence in the decay constant. We also give the results of the activity measurement at the time of the two strong X-class solar flares which took place in September 2017. Our data do not show any unexpected time dependence in the decay rate of 40K in correspondence with the two flares. To the best of our knowledge, these are the most precise and accurate results on the stability of the decay constant as function of time., Comment: Accepted for publication in Physics Letters B, 6 pages, 8 figures. arXiv admin note: text overlap with arXiv:1311.7043

High-tin copper-based artefacts, recently discovered during archaeological excavations of the Italic necropolises of ancient Abruzzo (Central Italy), were investigated in order to determine the chemical composition and metallurgical features of the alloys and the micro-chemical and micro-structural nature of the corrosion products grown during the long-term burial. The investigated Cu-based artefacts, dated back to 6th and 5th centuries BC, were defensive weapons, in particular bronze belts and disc armors with embossed decoration and ornamental objects such as rivets, buckles and small rings that were applied to large belts to form complex patterns with the addition of small and large shaped pieces of amber. The analytical characterisation was performed by means of the combined use of scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS), optical microscopy (OM) and X-ray diffraction (XRD) analysis. The results put in evidence that the bronze artefacts were manufactured by casting an unusual high-tin bronze alloy in a ceramic bivalve mould thus producing artefacts with a silver-like appearance. In some cases the manufacturing process included also tailored cycles of thermal treatments and hot mechanical working under reducing conditions and well defined thermal parameters in order to shape the high-tin alloys in the form of sheets. The ancient metallurgists have also used low tin bronze alloys coated with a thin layer of tin for producing a highly reflective silver-like appearance. From a corrosion point of view, the main alloying elements have formed degradation products in the form of stratified structures containing tin oxides (romarkite and cassiterite), cuprous oxide, copper carbonates (azurite and malachite) and dangerous chlorine-based compounds (nantokite and atacamite polymorphs). These findings show that there is a strict interaction with the soil components and the pH variation of the different areas of the necropolis, suggesting that post-burial degradation phenomena occur. It can be concluded that SEM-EDS, XRD and OM can be successfully combined for studying the corrosion products of archaeological copper-based artefacts, thus helping to choose the best strategies for the long-lasting conservation of these ancient artworks.

The development of active materials for the protection of metallic substrates from corrosion is a task of primary importance for many applications. Several organic compounds were studied to investigate their corrosion inhibition potential in order to replace hazardous compounds [1-2]. The purpose of this research has been the investigation of the efficiency of a new environmental-friendly anticorrosive coating that takes advantage from the synergist effect of a biopolymer matrix combined with amino acids. The inhibition of the corrosion of the copper-based alloys has been studied using Chitosan (CH) as a biopolymer and L-Cysteine (Cy) as amino acid. The latter was selected since, in addition to the amino group, Cy also contains the -SH groups which have a strong affinity with copper. The CH/Cy coatings were optimized paying particular attention to the requirements necessary for their application in the field of cultural heritage. To evaluate the protective efficacy of the coatings, accelerated corrosion tests, purposely tailored, were carried out on bare and coated metal disks. Our tests reveal that the efficiency in the corrosion inhibition increases with a minimum amount of Cy (0.5 mg/ml). The nature of the protective film formed on the copper-based alloy surface was analysed by FTIR spectroscopy 42 whereas the surface modifications due to the corrosion treatments were characterized by Optical Microscopy. The experimental data show that the CH/Cy coatings have a protective action onto the copper-based alloy surface with a consequent inhibition of the corrosion process. [1] G. Giuliani, M. Pascucci, C. Riccucci, E. Messina, M. Salzano de Luna, M. Lavorgna, G.M. Ingo, and G. Di Carlo, Progress in Organic Coatings, 122, 138-146 (2018). [2] M.A. Amin, K.F. Klaled, Q. Mohsen and H.A. Arida, Corrosion Science 52, 1684-1699 (2010).

We give the results of a study on the 222Rn decay we performed in the Gran Sasso Laboratory (LNGS) by detecting the gamma rays from the radon progeny. The motivation was to monitor the stability of radioactivity measuring several times per year the half-life of a short lifetime (days) source instead of measuring over a long period the activity of a long lifetime (tens or hundreds of years) source. In particular, we give a possible reason of the large periodical fluctuations in the count rate of the gamma rays due to radon inside a closed canister which has been described in literature and which has been attributed to a possible influence of a component in the solar irradiation affecting the nuclear decay rates. We then provide the result of four half-life measurements we performed underground at LNGS in the period from May 2014 to January 2015 with radon diffused into olive oil. Briefly, we did not measure any change of the 222Rn half-life with a 8*10^-5 precision. Finally, we provide the most precise value for the 222Rn half-life: 3.82146(16){stat}(4){syst} days., Accepted for publication in Physics Letters B, 6 pages, 6 figures

Investigation of the chemical composition, surface structure, metallurgical features, corrosion mechanism, and surface modification techniques of archeological metallic artifacts from Romans and pre-Roman times aimed to simulate the most commonly used Cu-based and Ag-based alloys. These simulated reference alloys will be used as sacrificial materials to study the most appropriate conservation materials and procedures. In the present work, laser-induced breakdown spectroscopy (LIBS) is introduced as a new validated surface mapping technique to study the micro-chemical distribution of elements in binary reference copper–silver alloy samples. Using different techniques for surface and bulk analysis, such as SEM coupled with energy-dispersive X-ray spectroscopy and X-ray diffraction, it has been proven that LIBS is a simple, sensitive, and direct technique in the determination of heterogeneity of the sample's surface. By changing the laser wavelength (λ/nm) and focal length of the used focusing lens (f/cm), different spot sizes can be obtained. It was possible to control the spatial resolution in mapping the investigated samples' surface and to achieve local chemical information. In the present work, Q-switched neodymium-doped yttrium aluminum garnet laser has been used at its fundamental wavelength 1064 nm and its second harmonic 532 nm. The studied samples were specially manufactured heterogeneous copper–silver alloys with known grain size as studied via SEM investigation. The obtained LIBS results are in good agreement with those by other analytical techniques and extend the applicability of the surface techniques to study metallic ancient objects. Copyright © 2015 John Wiley & Sons, Ltd.

Gold coated commonly used copper-based objects such as studs, brooches, clasps and a small pendants, dating back to 16th-17th centuries CE, were studied by means of the combined use of FE-SEM/EDS, TOF-SIMS, ?- FTIR, XRD and optical microscopy (OM). In particular, the surface and subsurface chemical features of the gilded objects were investigated, revealing some aspects of the manufacturing methods as well as disclosing the mechanism of degradation occurring during the long-term burial in the soil and the agents involved in this process. Our investigation has made possible to identify the chemistry of the decorative Au layer deposited by using an amalgam, i.e. the fire-gilding, its structure and the corrosion products naturally formed from the interaction with the surrounding environment. The main degradation agents are chlorine, sulphur and phosphorous species that gave rise to the formation of different corrosion products. Indeed the corrosion phenomena are boosted by the metal galvanic coupling which makes gilded-metal art works unstable from a chemical-physical point of view. In perspective of preservation, our results suggest that it is important to prevent the interaction between moisture and nantokite (CuCl), located at the interface between the gilding layer and the substrate, in order to avoid further severe degradation phenomena such as "bronze disease" which transforms the copper substrate into a greenish powder.

Impaction of deciduous teeth is an uncommon event. The purpose of this report is to describe two unusual eruption failures of a second primary molar and their treatment management.The diagnostic and therapeutic protocol of two cases selected at the Unit of Paediatric Dentistry, Department of Oral and Maxillofacial Science, "Sapienza" University of Rome, Italy, are presented. In both cases, the second deciduous molar was impacted, while no mechanical obstacle like odontomas or supernumerary teeth were present.The two case reports presented in this work are of scientific relevance, due to the rarity of this type of pathology.

By means of the combined use of X-ray photoelectron spectroscopy (XPS), optical microscopy (OM) and scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS) the surface and subsurface chemical and metallurgical features of silver counterfeited Roman Republican coins are investigated to decipher some aspects of the manufacturing methods and to evaluate the technological ability of the Roman metallurgists to produce thin silver coatings. The results demonstrate that over 2000 ago important advances in the technology of thin layer deposition on metal substrates were attained by Romans. The ancient metallurgists produced counterfeited coins by combining sophisticated micro-plating methods and tailored surface chemical modification based on the mercury-silvering process. The results reveal that Romans were able systematically to chemically and metallurgically manipulate alloys at a micro scale to produce adherent precious metal layers with a uniform thickness up to few micrometers. The results converge to reveal that the production of forgeries was aimed firstly to save expensive metals as much as possible allowing profitable large-scale production at a lower cost. The driving forces could have been a lack of precious metals, an unexpected need to circulate coins for trade and/or a combinations of social, political and economic factors that requested a change in money supply. Finally, some information on corrosion products have been achieved useful to select materials and methods for the conservation of these important witnesses of technology and economy.

"Bronze disease" is a very dangerous cyclic copper corrosion phenomenon which commonly develops after the discovery of the artefact. Therefore, in the cultural heritage field every object is inimitable and whatever loss is irreplaceable, causing a protective coating to be indispensable. Herein we studied the efficiency of a transparent, protective and reversible diamond-like carbon (DLC) coating, deposited by plasma enhanced chemical vapour deposition on copper based alloys, to enhance the corrosion resistance of archaeological artefacts. The nano structured DLC film resulted in the formation of a structure that exhibits water repellent properties and can act as a barrier layer to corrosion. Exposure of copper based alloys, with and without the DLC coating, to an aggressive chemical environment led to a remarkable inhibition of corrosion only for the coated samples. Moreover the DLC film on the Cu-based substrate was shown to have no effect on the morphology of the surfaces indicating that surface appearance is not affected. Consequently DLC coatings open a pathway into the development of safe and tailored solutions in the ancient metals conservation field. Furthermore the use of DLC coatings can be extended for the protection of objects that do not belong to cultural heritage but may still be subject to corrosion. (C) 2016 Elsevier B.V. All rights reserved.

The role played by environmental species affecting the long-term stability of archaeological Ag-based artefacts during museum exhibition or storage has been studied by means of the combined use of selected area X-ray photoelectron spectroscopy, X-ray diffraction, optical microscopy and scanning electron microscopy + energy dispersive spectrometry. The presence of fine particulate and of aggressive compounds in the museum atmospheres has been investigated by means of an innovative testing methodology based on Ag-based reference alloys. The procedure has been applied to different areas of some museums in the Mediterranean Basin in order to consider representative environmental conditions of storage and exhibition of Ag-based artefacts. The case studies of the National Roman Museum in Rome, Italy and of the Egyptian Museum of Cairo, Egypt will be illustrated. Furthermore, the study has been performed as a function of the alloy chemical composition and of the position of the reference specimens. The results of the superficial, micro-chemical and morphological characterisations of the reference alloys are related to degradation parameters of ancient silver artefacts, as the presence of sulfur dioxide and chloride ions. The chosen methodology can be recommended to investigate the environmental key factors to consider for a safe storage or exhibition of archaeological silver artefacts, ensuring them a long stable life from a chemical–physical point of view. Copyright © 2014 John Wiley & Sons, Ltd.

It has been recently reported that prolactin (PRL) plays an important role in immune system regulation. In this study we investigated the activity of three natural drugs with immunomodulatory activity: Echinacea purpurea (EP), Hypericum perforatum (HP) and Eleutherococcus senticosus (ES) on PRL production. Male rats were orally treated with two different doses (30 and 100 mg/kg) of extract of these drugs for 3 or 15 days. A 3-day treatment was not able to modify PRL serum levels, whereas a 15-day treatment with EP and HP at the higher dose significantly inhibits PRL production. A treatment with ES was always ineffective. A possible mechanism for this effect could be that both HP and EP extracts display a direct dopaminergic activity, although an involvement of the GABA-ergic system cannot be excluded.

The activity of a 137Cs source was measured using a germanium detector installed deep underground in the Gran Sasso Laboratory. In total about 5100 energy spectra, one hour measuring time each, were collected and used to search for time variations of the decay constant with periods from a few hours to 1 year. No signal with amplitude larger than 9.6 × 10−5 at 95% C.L. was detected. These limits are more than one order of magnitude lower than the values on the oscillation amplitude reported in the literature. The same data give a value of 29.96±0.08 years for the 137Cs half life, which is in good agreement with the world mean value of 30.05 ± 0.08 years.

Two novel green β-substituted Zn

A film of [Pd(R(2)pipdt)(dmit)] (1), where R2pipdt = 1,4-didodecyl-piperazine-2,3-dithione (acceptor) and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate (donor) incorporated into a polymethylmethacrylate (PMMA) matrix, showing a good second-harmonic generation, has been prepared for the first time in the class of dithione-dithiolate 2nd order NLO-chromophores. Moreover full characterization of 1, including molecular second-order NLO properties in solution, is reported.

The introduction of alkoxy chains in the molecular architecture of meso push-pull porphyrins is of paramount importance aiming at high performing dye-sensitized solar cells (DSSCs) based on these specific sensitizers. Recently, we have demonstrated that the same approach is fruitful even if it is applied to tetraarylporphyrins with an acceptor/anchoring substituent in the [small beta]-pyrrolic position. In particular, among the ortho-ortho, the ortho-para and the ortho-functionalization of the aryl rings with an octyloxy chain, we identified the latter as the most performing in the series, showing a good balance between the dye loading and the reduction of [small pi]-[small pi] aggregation. Herein, focusing our attention on the mono-ortho-functionalized molecular structure, we have investigated the effect of the alkoxy chain length and nature on the reduction of dye-to-dye aggregation as well as on the enhancement of light harvesting capabilities, finding an almost linear relationship between the device photon conversion efficiency (PCE) and the alkoxy chain length both in the presence and in the absence of a co-disaggregating agent.

In the present work a detailed study of the surface morphology of purposely-prepared Cu-Ni reference alloys has been performed. These alloys have been prepared via tailored casting methods in order to have samples with same chemical composition and different local chemical enrichments of both metals. A micro-LIBS system for surface spatial scanning was set up based on a second harmonic Nd:YAG laser at 532 nm and using a focusing lens of focal length 7 cm to disclose the local chemical composition variation. Surface morphological scanning was performed for some of the binary Cu-Ni reference alloys to differentiate between chemically homogeneous and heterogeneous alloys. LIBS results were compared with the information of the Scanning Electron Microscope coupled with Energy Dispersive X-ray (SEMEDS) investigation carried out to provide surface local large-area chemical analysis via EDS technique. It has been proved that LIBS is a simple, sensitive and direct technique in the determination of homogeneity or heterogeneity of the sample's surface. The LIBS results have been shown to be more sensitive and accurate in the heterogeneity determination than other used conventional analytical techniques. (C) 2016 Elsevier B.V. All rights reserved.

By means of scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS), counterfeited Roman Republican coins are investigated to decipher some aspects of the manufacturing methods and to evaluate the technological ability of the Roman metallurgists to produce thin silver films. The results demonstrate that over 2000 ago important advances in the technology of thin film deposition on metal substrates were attained by Romans that produced counterfeited coins by combining sophisticated micro- and nano-plating methods and tailored surface chemical modification based on the mercury-silvering process. The ancient metallurgists were able systematically to manipulate metals at a micro and nano scale to produce adherent precious metal layers with a uniform thickness ranging from one to a few micrometers. Romans were able to create the appearance of solid silver coins without knowledge about the chemical-physical processes but using only their experienced skill [1]. Furthermore, the results suggest that, contrary to the more recent times, counterfeited coins were likely produced by the issuing official authorities too. The production was aimed firstly to save expensive metals as much as possible allowing profitable large-scale production at a lower cost. The driving forces could have been a lack of precious metals, an unexpected need to circulate coins for trade and/or a combinations of social, political and economic factors that requested a change in money supply. Finally, useful information on degradation agents have been achieved to tailor the selection of conservation methods able to save these important witnesses of art, technology and economy. [1] G.M. Ingo, G. Guida, E. Angelini, G. Di Carlo, A. Mezzi, G. Padeletti, Acc. Chem. Res. 46, 2365 (2013).

Copper-based alloys are affect by degradation processes leading to the formation of surface patinas, whose composition depends on several parameters such as the alloy composition, metallurgical features and environmental conditions. Naturally grown patinas are typically detected onto the surface of modern bronze works of art [1] and strictly affect the surface reactivity. The production of representative patinas onto bronze substrates is a key issues in order to obtain model systems which can be used for the development and validation of appropriate conservation strategies. In this study, we have prepared different artificial representative patinas by using a quaternary copper-based alloy (Cu-Sn-Zn-Pb) with chemical composition and metallurgical features similar to those of valuable modern works of art [1]. In order to produce degradation products commonly observed onto their surface, chloride and sulphate species were used to induce corrosion processes. Different patinas were produced by changing some experimental parameters, as concentration of corrosive species, temperature and ageing time. The composition and structural properties of the patinas were investigated by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray diffraction, optical microscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy. The results allow to identify degradation products and to distinguish polymorph species. In the case of chloride induced patina formation, red Cu2O (cuprite) and green Cu2(OH)3Cl polymorphs were mainly detected. When the patina formation is induced by sulphate species, it mainly consists of blue Cu4SO4(OH)6 polymorphs. [1] D.E. Couture-Rigert, P.J. Sirois, E.A. Moffatt, Studies in Conservation, 57, 142 (2012).

Two novel green beta-substituted Zn-II-porphyrins, G1 and G2, based on a 4D-pi-1A type substitution pattern have been synthesized. Their enhanced push-pull character, by reduction of H-L energy gaps, promotes broadening and red-shifting of absorption bands. The effective synthetic pathway and the remarkable spectroscopic properties make G2 ideal for BIPV application.