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Ancient glass has been extensively studied from a technological and raw material provenance perspective since the middle of the 20th century. With the rising applications of analytical techniques in the field of Heritage Studies, the last two decades saw an exponential increase in publications on ancient and historical glass technology from around the globe. Given the amount of works on glass chemical composition, it is surprising to note that the long-held production model for Iron Age glasses found in Europe has only recently been challenged by the publication of uncharacteristic glass compositions. Traditionally, LBA glass industries based on plant-ash fluxes/HMG (Egypt and the Levant) and mixed-alkali fluxes/LMHK (Italy) are thought to be supplanted by natron-fluxed/LMG production operating in Egypt and the Levant since around the 9th century BCE. Recently, however, arguments have been put forth for a more diversified network of glassmaking traditions, including small-scale autonomous European workshops. This article reviews the current state of research into Iron Age (1st millennium BCE) glasses in Europe by examining the available published data on glass compositions to critically assess some practical and theoretical issues stemming from this heterogenous field of research. Key questions are addressed, and future lanes of research are proposed. [ABSTRACT FROM AUTHOR]

A mustard-gold-colored talc bead was recovered during the 2014 excavation campaign carried out in Lumbu (Mbanza Kongo, Angola) together with the nineteenth-century glass trade beads imported from Bohemia and Venice. Results from this multi-analytical and minimally invasive study suggest that this bead may have been brought to the kingdom’s capital by means of an established intra-kingdom trade network or as an offering intended for the king or a member of the nobility. However, it was undoubtedly manufactured within the Kongo kingdom using talc sources known by the local population. As such, this talc bead constitutes the first evidence of local production of personal adornment objects in the Kongo kingdom and one of the first examples of craft specialization for personal adornment purposes in central and southern Africa since pre-historic times. [ABSTRACT FROM AUTHOR]

The steep increase in nontuberculous mycobacteria (NTM) infections makes understanding their unique physiology an urgent health priority. NTM synthesize two polysaccharides proposed to modulate fatty acid metabolism: the ubiquitous 6-O-methylglucose lipopolysaccharide, and the 3-O-methylmannose polysaccharide (MMP) so far detected in rapidly growing mycobacteria. The recent identification of a unique MMP methyltransferase implicated the adjacent genes in MMP biosynthesis. We report a wide distribution of this gene cluster in NTM, including slowly growing mycobacteria such as Mycobacterium avium, which we reveal to produce MMP. Using a combination of MMP purification and chemoenzymatic syntheses of intermediates, we identified the biosynthetic mechanism of MMP, relying on two enzymes that we characterized biochemically and structurally: a previously undescribed α–endomannosidase that hydrolyses MMP into defined-sized mannoligosaccharides that prime the elongation of new daughter MMP chains by a rare α-(1→4)-mannosyltransferase. Therefore, MMP biogenesis occurs through a partially conservative replication mechanism, whose disruption affected mycobacterial growth rate at low temperature. The mechanism of methylmannose polysaccharide (MMP) biogenesis in nontuberculous mycobacteria (NTM) is characterized, which involves an MMP-specific hydrolase (MmpH) and a rare mannosyltransferase (ManT). MmpH and ManT structures are presented. [ABSTRACT FROM AUTHOR]

The steep increase in nontuberculous mycobacteria (NTM) infections makes understanding their unique physiology an urgent health priority. NTM synthesize two polysaccharides proposed to modulate fatty acid metabolism: the ubiquitous 6-O-methylglucose lipopolysaccharide, and the 3-O-methylmannose polysaccharide (MMP) so far detected in rapidly growing mycobacteria. The recent identification of a unique MMP methyltransferase implicated the adjacent genes in MMP biosynthesis. We report a wide distribution of this gene cluster in NTM, including slowly growing mycobacteria such as Mycobacterium avium, which we reveal to produce MMP. Using a combination of MMP purification and chemoenzymatic syntheses of intermediates, we identified the biosynthetic mechanism of MMP, relying on two enzymes that we characterized biochemically and structurally: a previously undescribed α–endomannosidase that hydrolyses MMP into defined-sized mannoligosaccharides that prime the elongation of new daughter MMP chains by a rare α-(1→4)-mannosyltransferase. Therefore, MMP biogenesis occurs through a partially conservative replication mechanism, whose disruption affected mycobacterial growth rate at low temperature. The mechanism of methylmannose polysaccharide (MMP) biogenesis in nontuberculous mycobacteria (NTM) is characterized, which involves an MMP-specific hydrolase (MmpH) and a rare mannosyltransferase (ManT). MmpH and ManT structures are presented. [ABSTRACT FROM AUTHOR]

Temporary tattoos and dyes constitute a great analytical challenge in relation to the regulatory control of their ingredients. Most of these commercial products are not labeled according to their content and their chemical nature is highly diverse. Therefore, it is necessary to analyze these complex samples to evaluate the potential presence of metallic impurities, to ensure the safety of cosmetic products contributing to health protection. This study proposes a multi-analytical methodology, which includes handheld X-ray fluorescence (h-XRF) and X‐ray diffraction (XRD), complemented by variable pressure scanning electron microscopy coupled with energy-dispersive X‐ray spectrometry (VP-SEM–EDS) to fully characterize 34 commercial samples of jagua and henna tattoos and dyes. The approach allowed the identification of the main constituents providing complementary compositional data and differences between sample types were established. In addition, information on the degree of natural pigments homogeneity was also obtained. The results' discussion considering the current European cosmetics regulation may be useful to support the drafting of safety requirements and specific regulation. [ABSTRACT FROM AUTHOR]

In the present study, mono‐ and multi‐material laser textured Ti6Al4V implants are manufactured and characterized in vivo to explore their applicability in orthopedic implants. Laser surface texturing is used for manufacturing grooved Ti6Al4V implants while a pressure‐assisted sintering technique is employed to impregnate beta‐tricalcium phosphate into grooves for an improved bioactivity. After implantation into Sprague Dawley rat's femur for 4 and 12 weeks, bone‐implant fixation and osseointegration are assessed, by performing push‐out tests and histological characterization. Histological characterization showed bone formation around all implants, characterized by immature bone at 4 weeks of implantation and a more mature bone after 12 weeks. The maximum push‐out forces are higher for the textured and multi‐material solution, when compared to non‐textured implants right after 4 weeks of implantation (p < 0.05). After 12 weeks, multi‐material implant displayed higher fracture energy when compared to non‐textured implants (p < 0.05). Results revealed that laser surface texturing and bioactive multi‐material solutions are highly effective to promote bone regeneration and enhance bone‐implant fixation for further application in orthopedic implants. [ABSTRACT FROM AUTHOR]

This analysis focused on one hundred and fifteen lithic arrowheads recovered from the Zambujeiro and Mitra 2 dolmens, funerary monuments in Évora, Portugal. These were analyzed by noninvasive and minimally invasive analytical techniques, including handheld X‐ray fluorescence (hXRF), variable pressure scanning electron microscope coupled with energy dispersive X‐ray spectrometry (VP‐SEM‐EDS), and laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) to establish the sources of the raw materials used to manufacture these arrowheads and to compare and cluster different artefacts. The raw materials used in the manufacture of the arrowheads were found to be from different sources suggesting that long‐distance trade routes extending south, east and possibly west were in place in Southern Iberia during the Neolithic and Chalcolithic periods. Whether this difference is related to the availability of raw materials throughout time, different procurement strategies, or simply by choice, remains unknown. The trade routes associated with the Mitra 2 Dolmen also seem to have a greater range than those connected to the Zambujeiro Dolmen. [ABSTRACT FROM AUTHOR]

This paper reports the first analytical approach carried out on two working palettes by Portuguese modernist master Almada Negreiros, found in 1991 behind old wood cabinets at the DN building in Lisbon. This is the only known occasion Almada left behind the color experiments done before starting to paint in the nearby walls and as such, it is a unique opportunity to analyze the materials and painting techniques that were originally used. The analytical setup comprised in loco technical photography in Vis, UVF and NIR; p-OM, spectrophotometry in Vis and h-EDXRF, complemented by OM-Vis, µ-FT-IR and VP-SEM-EDS of painting micro-samples and pigments in powder form. Preliminary results suggested the use of fresco painting technique and revealed some technical details, such as the use of a coarse lime sand finishing mortar mixed with natural vegetable fibers, and the extensive use of cadmium-based pigments that were not commonly used (or even recommended) in an alkaline environment. The Cd pigments were used alone or in mixtures with Fe based pigments in the warm hues and with cobalt and ultramarine blue pigments in some green paint layers. No clear evidence of organic materials that could have been used as binders was detected. [ABSTRACT FROM AUTHOR]

Phoenician-Punic glass beads recovered from the necropolis of Vinha das Caliças 4 (Beja, Portugal), dated to the Iron Age, were studied by variable pressure scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (VP-SEM–EDS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). All glass was found to be soda-lime-silica natron-based glass. Trace element and rare earth element analysis suggest that the blue, turquoise, white, and colorless glass was manufactured in the Levant region, using rather pure coastal sands, while two amber and black-colored glass beads seem to have been produced in Egypt. Although the exact manufacture location of these Phoenician-Punic glass beads remains unknown, these results are in agreement with the commercialization of raw glass produced in established primary glass workshops in the Levant and in Egypt. The procurement of cobalt ores from specific geological provinces, on the other hand, is a strong evidence of the existence of large-scale trade routes of both raw materials and finished artefacts in the Iron Age. The finished artefacts trade routes included not only the previously established Mediterranean world and sub-Saharan Africa, but also Southern Central Iberia. [ABSTRACT FROM AUTHOR]

An in situ archaeometrical campaign was organized in 2018 for the physicochemical analysis of the exceptional Mosaico de los Amores of the Cástulo archaeological site (Linares, Spain). Several mobile instruments were brought on the field to investigate the colourful tesserae of the mosaic. The main aim of the current research paper is the comparison of different mobile instruments and their applicability on measuring in open air environments. In this study, the comparison of four mobile Raman instruments, using different excitation lasers and technologies, is discussed. Three portable, the EZRaman‐I dual Raman analyser from TSI Inc. (USA), the i‐Raman® EX from BWTEK (USA), and the BWS445‐785S InnoRam™ Raman spectrometer from BWTEK (USA), and one handheld system, the Bravo Raman spectrometer from Bruker (Europe), are compared in terms of their characteristics, applicability, and performance when conducting non‐invasive and non‐destructive analysis. [ABSTRACT FROM AUTHOR]

This paper presents the first insight into how Almada Negreiros, a key artist of the first generation of modernism in Portugal, created his mural painting masterpiece in the maritime station of Rocha do Conde de Óbidos in Lisbon. This set of six monumental mural paintings dates from 1946 to 1949 and is considered Almada's artistic epitome. As part of the ALMADA project: Unveiling the mural painting art of Almada Negreiros, the murals are being analyzed from a technical and material perspective to understand his modus operandi and the material used. This is the first study of this nature carried out on site and in the laboratory using standard and more advanced imaging, non-invasive analysis, and microanalysis techniques. This article reports the results obtained with visual examination, technical photography in visible (Vis), visible raking (Vis-Rak), complemented by 2D and 3D optical microscopy (OM), scanning electron microscopy with energy-dispersive spectrometry (SEM-EDS), and Fourier transform infrared micro-spectroscopy (µ-FTIR) of the paint layers. The results show the similarities, differences, and technical difficulties that the painter may have had when working on the first, third, and presumably last mural to be painted. Vis-Rak light images were particularly useful in providing a clear idea of how the work progressed from top to bottom through large sections of plaster made with lime mortars. It also revealed an innovative pounced technique used by Almada Negreiros to transfer the drawings in full scale to the walls. Other technical characteristics highlighted by the analytical setup are the use of textured, opaque, and transparent paint layers. The structure of the paintings does not follow a rigid build-up from light to dark, showing that the artist freely adapted according to the motif represented. As far as the colour palette is concerned, Almada masterfully uses primary and complementary colours made with Fe-based pigments and with synthetic ultramarine blue, cadmium pigments, and emerald green. [ABSTRACT FROM AUTHOR]

This study proposes a new nondestructive methodology that combines micro‐Raman spectroscopy and micro‐X‐ray diffraction (μ‐XRD), complemented by variable pressure scanning electron microscopy coupled with energy dispersive X‐ray spectrometry, to determine the composition of glass artifacts and the manufacturing techniques employed in their production. The use of micro‐Raman spectroscopy revealed that most samples belong to the alkaline glass family. Chemical analysis also allowed the identification of the main colorants used in the manufacture of the glass beads in this study. Dark blue and turquoise glass were colored using cobalt ions and copper ions, respectively. Amber or light brown hues were produced using the iron–sulfur amber chromophore. Iron ions were also used to produce green, yellow, cream‐colored gray, and black hues. White glass was produced using calcium antimonate phases. These compounds, identified by micro‐Raman spectroscopy and μ‐XRD, were also used as opacifying agents. This study highlights the importance of using micro‐Raman spectroscopy in the study of ancient glass artifacts. In fact, micro‐Raman spectroscopy not only allows the determination of the glass family of heavily degraded samples but was also found to be the only technique capable of identifying evidences of the rearrangement of the silicate network following selective leaching. The combined use of micro‐Raman spectroscopy and μ‐XRD permitted the identification of the opacifying agents and heat treatment used in the manufacture of the opaque glass beads in this study. This study proposes a new nondestructive methodology that combines micro‐Raman spectroscopy and μ‐XRD to determine the composition and manufacturing techniques employed in the production of glass artifacts. Results show that micro‐Raman spectroscopy allows the determination of the glass family of heavily degraded samples and reveals evidences of the rearrangement of the silicate network following selective leaching. This methodology allowed the identification of the opacifiers and heat treatment used in the manufacture of the opaque glass beads in this study. [ABSTRACT FROM AUTHOR]

Mycobacteria are a wide group of organisms that includes strict pathogens, such as Mycobacterium tuberculosis, as well as environmental species known as nontuberculous mycobacteria (NTM), some of which--namely Mycobacterium avium--are important opportunistic pathogens. In addition to a distinctive cell envelope mediating critical interactions with the host immune system and largely responsible for their formidable resistance to antimicrobials, mycobacteria synthesize rare intracellular polymethylated polysaccharides implicated in the modulation of fatty acidmetabolism, thus critical players in cell envelope assembly. These are the 6-O-methylglucose lipopolysaccharides (MGLP) ubiquitously detected across the Mycobacterium genus, and the 3-O-methylmannose polysaccharides (MMP) identified only in NTM. The polymethylated nature of these polysaccharides renders the intervening methyltransferases essential for their optimal function. Although the knowledge of MGLP biogenesis is greater than that of MMP biosynthesis, the methyltransferases of both pathways remain uncharacterized. Here, we report the identification and characterization of a unique S-adenosyl-L-methionine-dependent sugar 1-O-methyltransferase (MeT1) from Mycobacterium hassiacum that specifically blocks the 1-OH position of 3,3'-di-O-methyl-4α-mannobiose, a probable early precursor ofMMP, whichwe chemically synthesized. The highresolution 3D structure of MeT1 in complex with its exhausted cofactor, S-adenosyl-L-homocysteine, together with mutagenesis studies and molecular docking simulations, unveiled the enzyme's reaction mechanism. The functional and structural properties of this unique sugar methyltransferase further our knowledge of MMP biosynthesis and provide important tools to dissect the role of MMP in NTM physiology and resilience. [ABSTRACT FROM AUTHOR]

In the framework of the inter-disciplinary KongoKing project, a set of beads from archaeological excavations in the Democratic Republic of the Congo was analysed by means of a minimally invasive, multi-analytical approach based on micro-Raman spectroscopy. The full characterization of the materials, including glassy network, opacifiers and colorizers, was achieved thanks to the combination of data from handheld X-ray fluorescence, variable pressure scanning electron microscopy coupled with energy-dispersive X-ray spectrometry, micro-Fourier transform infrared spectroscopy and pyrolysis coupled to gas chromatography and mass spectrometry. The obtained chemical information was used to fill the existing gap in the chemical study of beads from Western Central Africa. The cobalt-rich blue beads were found to be of Central European origin, while the copper-rich turquoise beads were manufactured using distinct copper sources. Cadmium yellow and cadmium red are the colourants responsible for the bright colours of bead types 10 and 12, respectively. The type 12 beads were found to be composed of glass covered with a waxy layer tentatively identified as Japan wax. Prosser-moulded bead type 9 was coloured by means of a chrome-tin pigment, while a combination of Mn and Fe is responsible for the black colour of the type 47 beads. Cuprite is most likely responsible for the red hue of glass layers from type 14. The dark palm green exterior of the type 17 bead was produced by using a combination of Cu and Fe compounds; iron was the only chromophore detected in the Indian red decoration. Copyright © 2017 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The preservation of natural stone heritage is still a major challenge for the scientific community. This topic assumes a greater importance since it impacts economic and socio-cultural values. Recent research has indicated that water action and microorganism activity are among the major contributors to the deterioration of this material. Despite the emergence of new protective solutions in the market, some constraints still need to be overcome. This study aims to contribute to unveiling the effectiveness of innovative commercial coatings on the preservation of natural stone frequently used in built heritage. Four different commercial coatings are assessed regarding their compatibility with the substrata and effectiveness against UV radiation, water action, and microbial development under accelerated ageing. The protective solutions are tested on five different Portuguese lithotypes, including carbonate and silicate-based stones. Colour change is measured to assess compatibility, while profilometric change of the stones' surface and antimicrobial potential are evaluated to determine their effectiveness. Our research demonstrates that the solution that exhibits the greatest compatibility and effectiveness potential is composed of modified silanes and siloxanes derivatives. [ABSTRACT FROM AUTHOR]

Some microorganisms accumulate glucosylglycerate (GG) during growth under nitrogen deprivation. However, the molecular mechanisms underlying the role of GG and the regulation of its levels in the nitrogen stress response are elusive. Since GG is required for biosynthesis of mycobacterial methylglucose lipopolysaccharides (MGLP) we examined the molecular mechanisms linking replenishment of assimilable nitrogen to nitrogen-starved M. hassiacum with depletion of GG accumulated during nitrogen deficiency. To probe the involvement of a newly identified glycoside hydrolase in GG depletion, we produced the mycobacterial enzyme recombinantly and confirmed the specific hydrolysis of GG (GG hydrolase, GgH) in vitro.We have also observed a pronounced up-regulation of GgH mRNA in response to the nitrogen shock, which positively correlates with GG depletion in vivo and growth stimulation, implicating GgH in the recovery process. Since GgH orthologs seem to be absent from most slowly-growing mycobacteria including M. tuberculosis, the disclosure of the GgH function allows reconfiguration of the MGLP pathway in rapidly-growing species and accommodation of this possible regulatory step. This new link between GG metabolism, MGLP biosynthesis and recovery from nitrogen stress furthers our knowledge on the mycobacterial strategies to endure a frequent stress faced in some environments and during long-term infection. [ABSTRACT FROM AUTHOR]

• Use of LA-ICP-MS to determine the trace element content in order to identify the main production regions of each glass bead type. • Determination of the fluxing agents, (de)coloring and opacifying agents used in the manufacture of each glass bead type. • Application of combined multi-analytical minimally invasive methodology, which includes hXRF, VP-SEM-EDS, micro-Raman spectroscopy and LA-ICP-MS to the study of several glass beads. A collection of glass beads found in Lumbu (Mbanza Kongo, Angola) were analyzed by means of a multi-analytical minimally invasive methodology, which included handheld X-ray fluorescence (hXRF), variable pressure scanning electron microscope coupled with energy dispersive X-ray spectrometry (VP-SEM-EDS), micro-Raman spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Trace element analysis, and rare earth element pattern analysis in particular, was found to be essential to establish the provenance of the European trade beads in this study. The glass beads from types 30, 31, 32, 36, 38, 39, 40, 41, 42, 43 and 45 were found to have been produced in Venice, and the glass beads from types 26 and 28 have been assigned to the Bohemian glass industry. While determining the provenance of each glass artefact was a major goal of this study, the process of glass coloring and opacification was also studied in an attempt to establish the technology employed in the production of these artefacts. Chemical data indicate that cobalt and copper were used to produce blue hues, while a combination of copper and iron ions was used to produce green glass. Black colored glass was obtained by the combined use of iron and manganese ions, whereas the iron-sulfur chromophore was used to impart a distinct amber hue to the glass. Red was produced using trace amounts of metallic gold particles (ruby red glass) and metallic copper nano-particles or cuprous oxide (brownish-red glass). Lead arsenates, calcium phosphate, and cassiterite were used as opacifying agents. The use of both morphological and chemical analysis enabled the identification of distinct European production centers, allowing a glimpse into the consumption patterns and economic interactions in place between Europe and West-Central Africa throughout the 17th-19th centuries. Image, graphical abstract [ABSTRACT FROM AUTHOR]

The ubiquitous occurrence of mycotoxins in the environment results in unavoidable and repeated human exposure to mixtures of mycotoxins, the main exposure being through the consumption of contaminated foods, such as cereals and milk. Considering the frequency of contamination of these foods with mycotoxins, this study aimed to evaluate the risk of exposure to aflatoxins, ochratoxin A, deoxynivalenol and zearalenone in a Portuguese population under 17 years old through the consumption of these foods. To assess mycotoxin exposure, food contamination data was provided by the Official National Plan to Control Food and the food consumption information from the National Food, Nutrition, and Physical Activity Survey of the Portuguese General Population (2015–2016); risk assessment calculations were performed through the Monte Carlo probabilistic method. In view of the results obtained for aflatoxins, ochratoxin A, deoxynivalenol and zearalenone, and considering the legislation in force, the levels observed were below the maximum levels. However, there was a risk in deoxynivalenol exposure for children from 0 to 9 years old (average and high consumers), and for high consumers from 10 to 17 years old. Given the potential adverse effects of these mycotoxins, their co-existence in the same foods and being a priority issue defined by the European Food Safety Authority, tight control should be carried out, in addition to re-evaluation of the maximum levels of these mycotoxins. [ABSTRACT FROM AUTHOR]

In 1949, Almada Negreiros painted at the maritime station of Rocha do Conde de Óbidos, in Lisbon, six monumental mural paintings, which are considered as his highest artistic achievement. On these paintings, he resorted to a bright colourful palette, which needs to be studied to support conservation and preservation of these artworks for future generations. Among the pigments under study within project ALMADA, the identification of the green samples is the most challenging, as Almada Negreiros seems to have explored different hues by using simultaneously inorganic (e.g., emerald green, Scheele's green and viridian) as well as organo‐synthetic pigments that were rather unusual when employing a traditional mural painting technique (e.g., PG7 and PG8). Moreover, he seems to have admixed white (e.g., titanium white) or blue pigments (e.g., ultramarine) to modify the hues. The different colourants found, as well as the use of mixtures of pigments, hints that Almada Negreiros was keen on experimenting and applying relatively novel painting materials. Raman spectroscopy, given its ability to identify inorganic as well as organic components, is a key analytical tool to discriminate between all these compounds. The findings were also supported by complimentary analytical techniques, including colourimetry, handheld X‐ray fluorescence spectroscopy (h‐XRF) and micro‐Fourier‐transform infrared spectroscopy (μ‐FT‐IR). Identification of the green pigments by Raman spectroscopy is, however, not always straightforward, and it is demonstrated how changes in relative band intensities and band broadening can point to mixtures, where the Raman spectral features of some compounds can easily be overseen in the spectrum. [ABSTRACT FROM AUTHOR]

Natural stone has been used worldwide in the construction of archaeological and historical heritage. However, its preservation continues to be threatened by weathering and degradation phenomena. Water is widely recognized as the most threatening external component that contributes to stone deterioration, increasing the need for the development of protective hydrophobic coatings to eliminate water penetration. This study intends to contribute to the better understanding of natural stone treatment strategies to prevent water penetration and subsequent stone alteration by studying the effect of coating and stone substrate temperatures, and the number of coating applications, on the effectiveness, compatibility, and durability of commercial hydrophobic coatings. The results obtained revealed that while more than one application increases coating hydrophobic effectiveness, it frequently leads to changes in the aesthetic appearance of natural stone, including whitening and darkening of the substrate's original hues. Improved hydrophobic effectiveness (maximum gain of ≈ 9%) is also achieved when applying the commercial coatings at 4 °C to natural stone substrates maintained at room temperature, conditions that are feasible to be used in real life. Additionally, the commercial coating composed of silane/siloxane with modified fluorinated additives was found to be the most effective and durable hydrophobic solution. [ABSTRACT FROM AUTHOR]

The glass bead assemblages recovered during the 2014 excavations of the ruins of Kulumbimbi located in Mbanza Kongo (Angola) were analyzed by means of a multi-analytical minimally invasive methodology, which includes handheld X-ray fluorescence (hXRF), variable pressure scanning electron microscope coupled with energy dispersive X-ray spectrometry (VP-SEM-EDS), micro-Raman spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Chemical data indicate that cobalt, copper, iron and manganese ions were used to produce the blue, green, reddish-brown and black hues, respectively. Lead arsenates, calcium phosphate, calcium antimonate, lead stannate, cassiterite and Pb-Sb-Sn oxide were used as opacifying agents. Chondrite-normalized trace element distribution and chondrite-normalized rare earth element patterns were used to determine the sand source used in the production of the different glass bead types. These distributions were also used to identify the manufacture location of the glass beads with previously unknown origin and production date. Based on the data collected, the glass beads from types 16, 20, 22, 24, 25, 46 and 47 have been assigned as Venetian. • Application of multi-analytical minimally invasive methodology: hXRF, VP-SEM-EDS, micro-Raman spectroscopy and LA-ICP-MS. • Determination of the coloring and opacifying agents used in the manufacture of each glass bead type. • Use of trace element analysis to identify the main production regions of each glass bead type. [ABSTRACT FROM AUTHOR]

Phoenician colonisation of the Iberian Peninsula in the 1st millennium BCE introduced many novel and luxurious goods to the local populations of the Western Mediterranean. Among them, black-appearing glass beads are characteristic of indigenous female burials in Southern Portugal during the 6th century BCE. This study presents the results of the first comprehensive archaeometric investigation of black-appearing glass from Vinha das Caliças 4 (Portugal), and of black-appearing glass from the Iberian Peninsula in general. A multi-analytical approach employing Stereomicroscopic observation of manufacture and use traces, VP-SEM-EDS, μ-XRD, and LA-ICP-MS was used to cover a wide range of questions regarding technology and provenance. All analysed samples are natron glass. All samples of black and white beads are characterized by high Zr and low Sr values typically ascribed to the use of Egyptian sands. A comparison of the results of previous studies from the same site clearly demonstrates at least two geochemical provenances for Phoenician-traded glass beads, located in the Levantine region and Egypt, respectively. Furthermore, different colours of glass in individual polychrome beads exhibit similar trace element patterns, which might suggest these beads could have been produced close to glassmaking sites/regions. [ABSTRACT FROM AUTHOR]

The objective of this study was to estimate the public health and economic benefits (from a Medicare perspective) of Fluzone High-Dose® in the US elderly population, since its introduction in 2010. A budget impact model was developed using a decision tree framework and applied over 9 influenza seasons (2010/11 to 2018/19). The decision tree model was designed to capture influenza cases, hospitalizations possibly related to influenza or laboratory confirmed influenza, and influenza-related deaths. The analysis included influenza vaccines recommended by ACIP since 2010: SD TIV (trivalent), SD QIV (quadrivalent), HD TIV, aTIV (adjuvanted), ccQIV (cell-cultured). Two strategies were compared to evaluate the impact of HD TIV: a 'with HD TIV' strategy representative of the US vaccine landscape, and a 'without HD TIV' where the absence of HD TIV was modelled. Clinical and economic inputs were based on public US data from the CDC and national databases, while data on vaccine effectiveness were extracted from published literature and clinical trials. The impact of HD TIV was further explored in five scenario analyses and deterministic sensitivity analyses (DSA). Over 10 years, it is estimated that HD TIV resulted in an averted 1,333,479 influenza cases, 769,476 medical visits, 40,004 ED presentations, 520,342 cardiorespiratory hospitalizations and 73,689 deaths and generated an absolute $4.6 billion in savings, translating into a return on investment of 214.4%. Hospitalizations costs represented 98.4% and 98.3% of the management costs in the 'with HD TIV' strategy and 'without HD TIV' strategy respectively. Hospitalizations and HD TIV relative vaccine efficacy vs SD TIV as a major cost driver were further confirmed in scenario analysis and DSA. HD TIV remained cost saving under all the scenarios. The model showed that HD TIV higher efficacy translated into increased averted health and economic outcomes. HD TIV represented a cost saving intervention from a payer perspective since its introduction. [ABSTRACT FROM AUTHOR]

Despite the progressive decline in tuberculosis mortality, strains resistant to our dated antibiotics remain a global threat, as are the emerging nontuberculous mycobacteria, ubiquitous in natural and human environments. This pressing situation boosted by debilitated immune systems, chronic illness and the aged population calls for efficient strategies to fight these successful organisms, and identifying pathways critical for their survival is a crucial step towards this goal. In this context, the glycoside glucosylglycerate (GG) has been implicated in the adaptation of mycobacteria to nitrogen starvation and to thermal stress, and the key gene for GG synthesis has been considered essential for Mycobacterium tuberculosis growth. The many organisms we now know to have genes for GG metabolism opened new exciting avenues of research into its functions, hinting for example at hypothetical roles as an inter-cellular messenger among bacteria and in microbe-plant interactions, or at key roles in the global nitrogen cycle beyond what cyanobacteria and mycobacteria have taught us so far. Indeed, the insights into GG biology gained over the last decade have changed the perception of GG from a rare polysaccharide constituent to a widespread molecule with multiple functions and biosynthetic origins. It is now possible to build upon this knowledge and further explore its physiological importance in both pathogenic and environmentally relevant microorganisms. In particular, the vital roles of GG and of its important derivative the mycobacterial methylglucose lipopolysaccharide (MGLP) discussed here are now evident, making their metabolic links attractive targets for the development of new urgently needed antimycobacterial therapies. [ABSTRACT FROM AUTHOR]

In Central Portugal (westernmost Eurasia) the transition from the traditional Pleistocene hunter–gatherer societies to the complex Mesolithic societies of the Holocene has been debated for decades. While some argue that these differences were a progressive phenomenon that started with the shift from the Pleistocene to the Holocene, others defend that the Late Pleistocene patterns were fairly similar to those of the Epipaleolithic and that the major shift was rapid, dramatic and triggered by the necessary adaptation to the 8.2 ka cal BP (8.09–8.25 ka cal BP) climatic event. The study of lithic raw material provenance might be useful for this discussion, since it has been suggested that the Magdalenian and Epipaleolithic populations from this region were collecting this resources within a close range territory, whereas the Mesolithic populations were acquiring them at longer distances. In this paper, we present the results from p-XRF, VP-SEM-EDS and μ-XRD analysis done on the Epipaleolithic lithic assemblage from Pena d'Água Rockshelter, and in some geological samples from secondary sources located ∼14 km from this site. This layer is of major relevance for this debate since it is dated from 8.19 ka cal BP. If the transition was gradual, it would be expected that this assemblage would show some traits of higher-complexity seen in the Mesolithic, namely of longer distance acquisition. However, our results indicate correspondence between the archaeological chert types and some of the geological sources. The differences seen between the archaeological specimens and geological samples are mostly present in traits that can be related with manufacture, handling and post-depositional phenomena. The results suggest that, in what concerns to the economy of abiotic resources, the Epipaleolithic populations living at the time of the dramatic 8.2 ka cal BP cold event, were performing a short range acquisition of lithic raw materials which reinforces the idea of continuity from the Late Pleistocene to the 8.2 ka cal BP event and an abrupt and dramatic shift soon after this phenomena. [ABSTRACT FROM AUTHOR]

The Segura mining field, the easternmost segment of the Góis–Panasqueira–Segura tin–tungsten metallogenic belt (north–central Portugal), includes Sn-W quartz veins and Li-Sn aplite-pegmatites, which are believed to be genetically related to Variscan Granites. Sediment geochemistry indicates granite-related Ti-enrichments, locally disturbed by mineralization, suggesting magmatic and metamorphic/metasomatic titaniferous phases. Therefore, Segura alluvial samples and the geochemistry of their TiO2 polymorphs (rutile, anatase, and brookite) were investigated, and their potential as exploration tools for Sn and W deposits was evaluated. The heavy-mineral assemblages proved to be good proxies for bedrock geology, and TiO2 polymorph abundances were found to be suitable indicators of magmatic and/or metasomatic hydrothermal processes. The trace element geochemistry of Segura's alluvial rutile, anatase, and brookite is highly variable, implying multiple sources and a diversity of mineral-forming processes. The main compositional differences between TiO2 polymorphs are related to intrinsic (structural) factors, and to the P-T-X extrinsic parameters of their forming environments. Anomalous enrichments, up to 9% Nb, 6% Sn and W, 3% Fe, 2% Ta, and 1% V in rutile, and up to 1.8% Fe, 1.7% Ta, 1.2% Nb, 1.1% W 0.5% Sn and V in anatase, were registered. Brookite usually has low trace element content (<0.5%), except for Fe (~1%). HFSE-rich and granitophile-rich rutile is most likely magmatic, forming in extremely differentiated melts, with Sn and W contents enabling the discrimination between Sn-dominant and W-dominant systems. Trace element geochemical distribution maps show pronounced negative Sn (rutile+anatase) and W (rutile) anomalies linked to hydrothermal cassiterite precipitation, as opposed to their hydrothermal alteration halos and to W-dominant cassiterite-free mineralized areas, where primary hydrothermal rutile shows enrichments similar to magmatic rutile. This contribution recognizes that trace element geochemistry of alluvial TiO2 polymorphs can be a robust, cost- and time-effective, exploration tool for Sn(W) and W(Sn) ore deposit systems. [ABSTRACT FROM AUTHOR]

This paper discusses results obtained from in situ analysis of the tesserae of the Roman mosaic of Los Amores (Cástulo site, Linares, Spain) dating back to the turn of the 1st to the 2nd century AD. Specifically, it focuses on the scene The Judgment of Paris. In view of the exceptional state of preservation of the mosaic, from which very few tesserae had fallen off, non-invasive methods with portable Micro Raman Spectroscopy (MRS) and hand-held X-ray fluorescence (hXRF) and data assessment by use of principal component analysis and binary representations were selected. The results obtained allow to evaluate both the analytical method and the portable equipment used, as well as to classify the raw materials, the colouring agents and the opacifiers used. MRS analysis proved crucial for the identification of stone tesserae (ironstones, carbonate and siliciclastic rocks) and for the identification of the type of glasses used (soda-lime-silicate and lead type glasses) based on the analysis of two detached tesserae. hXRF analysis of the glass tesserae identified both colouring agents (Co, Cu, Pb, Zn) and opacifiers (calcium antimonate). The data obtained lend themselves to an assessment of the degradation process that threaten the integrity of the mosaic. The identification of tessera made of specific stone materials (especially ironstone) and of lead glass tesserae suggest the existence of a mosaic workshop in the Upper Guadalquivir (Eastern Andalusia, Spain). [ABSTRACT FROM AUTHOR]

This paper discusses results obtained from in situ analysis of the tesserae of the Roman mosaic of Los Amores (Cástulo site, Linares, Spain) dating back to the turn of the 1st to the 2nd century AD. Specifically, it focuses on the scene The Judgment of Paris. In view of the exceptional state of preservation of the mosaic, from which very few tesserae had fallen off, non-invasive methods with portable Micro Raman Spectroscopy (MRS) and hand-held X-ray fluorescence (hXRF) and data assessment by use of principal component analysis and binary representations were selected. The results obtained allow to evaluate both the analytical method and the portable equipment used, as well as to classify the raw materials, the colouring agents and the opacifiers used. MRS analysis proved crucial for the identification of stone tesserae (ironstones, carbonate and siliciclastic rocks) and for the identification of the type of glasses used (soda-lime-silicate and lead type glasses) based on the analysis of two detached tesserae. hXRF analysis of the glass tesserae identified both colouring agents (Co, Cu, Pb, Zn) and opacifiers (calcium antimonate). The data obtained lend themselves to an assessment of the degradation process that threaten the integrity of the mosaic. The identification of tessera made of specific stone materials (especially ironstone) and of lead glass tesserae suggest the existence of a mosaic workshop in the Upper Guadalquivir (Eastern Andalusia, Spain). [ABSTRACT FROM AUTHOR]

Streptococcus dysgalactiae subsp. dysgalactiae (SDSD) are considered exclusive animal pathogens; however, a putative zoonotic upper limb cellulitis, a prosthetic joint infection and an infective endocarditis were described in humans. To unravel if bovine SDSD isolates are able to infect human cells, the adherence and internalization to human primary keratinocytes of two bovine SDSD strains isolated from milk collected from udder were analyzed. Bacterial adhesion assays and confocal microscopy indicate a high adherence and internalization of SDSD isolates to human cells, suggesting for the first time the ability of bovine isolates to infect human cells. [ABSTRACT FROM AUTHOR]

[Display omitted] • Roman blue glass samples from Palatine hill were analysed. • A step-by-step geochemical organized protocol is proposed for provenance studies. • Optical Microscopy, SEM-EDS, EMPA and LA-ICP-MS results are discussed. • REE were fundamental to identify ancient compositional groups. Glass is one of the ancient human products most often traded for long distances from the place of raw material supply. Provenance studies on this kind of artefact are mainly based on the comparison of major and trace elements among archaeological samples. The paper proposes a step-by-step geochemical organized protocol that considers the elements with prominent influence on glass composition, helping in a fine discrimination of compositional groups and, consequently, an easier identification of provenance in archaeological artefacts. The proposed approach is presented through the case study of Roman blue glass samples, dated from the 1st century to Late Antiquity and coming from the Palatine Northeast archaeological site. Optical Microscopy, SEM-EDS, EMPA and LA-ICP-MS results are discussed to gather information on network former, flux, colourants and decolourants. In addition, the comparison with literature provides additional information on chemical groups of ancient glass spanning from the 1st to the 5th century. [ABSTRACT FROM AUTHOR]

The approach for selective growth of 1D nanostructured oxide materials using poly (dimethylsiloxane) (PDMS) stamp consists of using microcontact printing, as such the soft lithography technique, for transferring the pattern of ZnO film on a substrate, followed by the hydrothermal growth of 1D nanowires on patterned areas. The nanowires have been grown in aqueous solutions of zinc nitrate at temperature at 95°C. The wettability of the glass and of the Si/SiO2 substrates was investigated by contact angle measurements. The morphology of the nanostructures obtained was characterized by optical microscopy and scanning electron micoscopy. [ABSTRACT FROM AUTHOR]

Background: Calcium‐phosphate bioactive coatings have been suggested to improve the biological response of titanium. We have developed a new manufacturing protocol that enables integration of these bioactive materials in a titanium scaffold, overcoming the mechanical limitations of coatings. However, the biological behavior of these new materials is not yet described. Aim/Hypothesis: The aim of this study was to evaluate the behavior of human fetal osteoblasts and human gingival fibroblasts in contact with Titanium (Ti), Ti with 5% hydroxyapatite (TiHA) or Ti with 5% beta tricalcium phosphate (Ti‐TCP). Material and Methods: Ti, TiHA and Ti‐TCP discs were produced with homogeneous surface roughness. Human fetal osteoblasts and human gingival fibroblasts were cultured on discs for 14 days using previously established methods. Morphology and cellular adhesion were analyzed using scanning electron microscopy (SEM) after 1 and 7 days. Cell viability and proliferation were evaluated at pre‐defined time‐points (1, 3, 7 and 14 days) using a commercial resazurin‐based method. Alkaline phosphatase (ALP) activity was evaluated at 7 and 14 days for osteoblasts. All results were presented as mean fluorescence intensity (AU) ± standard deviation (SD). Mineralization patterns were evaluated using hydroxyapatite fluorescence staining. Group comparisons were tested using Anova (Tukey's post‐hoc) using appropriate statistical software and significance was set _I_P_i_ < 0.05. Results: The results showed similar cells adhesion on all materials. Osteoblast viability was higher on Ti‐TCP (114.47 ± 15.56 AU) when comparing to TiHA (54.11 ± 4.05 AU) and Titanium (41.52 ± 2.86 AU) group at 14 days of culture (_I_P_i_ < 0.05). However, cell proliferation was not statistically different between study groups. A higher fibroblast viability and proliferation on Ti specimens was observed compared to other groups, although without statistically significant. A significant higher ALP activity was observed on Ti‐TCP samples, suggesting higher differentiation of osteoblasts cultured on this type of surface. Conclusions and Clinical Implications: Titanium implant surfaces incorporated with bioactive materials, in particular TCP, were associated to improved osteoblast proliferation and differentiation comparing to pure titanium. However, gingival fibroblast responses did not present an enhanced viability and proliferation on contact with these bioactive materials, suggesting an important difference behavior of human hard and soft tissue cells along calcium phosphate bioactive materials. [ABSTRACT FROM AUTHOR]

Background: Zirconia dental implants have been proposed as an option for oral rehabilitation. Hydroxyapatite and calcium phosphate based coatings have been described to improve the bioactivity of zirconia, however, there is a need for alternate solutions since these coatings may delaminate. Aim/Hypothesis: The aim of this study was to compare the in vitro response of human fetal osteoblasts and human gingival fibroblasts in contact with Zirconia based implant surfaces‐ Zirconia (control), Zirconia containing hydroxyapatite (ZrHA) or beta tricalcium phosphate (ZrTCP). Material and Methods: Zirconia discs (control, 5% HA or 5% TCP) were produced by a novel pressing‐sintering technique under appropriate and similar conditions to achieve controlled surfaces. Human osteoblasts and gingival fibroblasts were cultured for 15 days by previously described methods. Morphology and cellular adhesion were observed using scanning electron microscopy (SEM) after 1 and 7 days. Cell viability and proliferation were evaluated at pre‐defined time‐points (1, 3, 7 and 14 days) using a commercial resazurin‐based method. Alkaline phosphatase (ALP) activity of human osteoblasts was evaluated at 7 and 14 days. All results were presented as mean fluorescence intensity (AU) ± standard deviation (SD). Group comparisons were tested using Anova (Tukey's post‐hoc) using appropriate statistical software and significance was set _I_P_i_ < 0.05. Results: SEM presented a good cell spreading in all groups on osteoblasts and fibroblasts. Cell viability and proliferation increased over time for all groups on the two types of cells, with osteoblasts viability being significantly higher on ZrHA group (211.32 ± 39.04 AUs) comparing to Zr (90.82 ± 29.95 AUs) and Zr‐TCP (125.51 ± 36.92 AUs) at 14 days of culture. However, when assessing fibroblast viability, the Zr group (249.98 ± 60.40 AUs, 595.98 ± 69.40 AUs) presented significantly higher values when compared to the remaining groups at 7 and 14 day culture, respectively. ALP results on osteoblasts suggested a higher activity in ZrHA group compared to the others at 7 and 14 days (_I_P_i_ < 0.05). Conclusions and Clinical Implications: All groups presented increasing cell viability and proliferation over time. Human osteoblasts presented higher viability, proliferation and differentiation on ZrHA surfaces when compared to Zr and Zr‐TCP. However, human gingival fibroblasts revealed an enhanced behavior on pure Zr surface compared to other groups. These results suggest different behaviors of representative cell models of bone and gingival connective tissue. Further in vitro studies are needed. [ABSTRACT FROM AUTHOR]