Technological study and chemical- archaeometric characterization of Roman opaque red glass from opus sectile decoration in the Lucius Verus Villa, 2nd century AD

Opaque red glass has been manufactured since the begging of glassmaking technology. However, it can be considered one of the most difficult colours to produce. It has been widely investigated by both glass science and archaeometry fields, providing vast literature. However, several aspects concerning its production during the Roman age are still unclear such as: where it was produced, which raw materials were used, and overall, how it was made. Moreover, the absence of written technical sources for Roman glass makes the investigation more complex. This research aims to investigate the production technology of opaque red glass during the 2nd century AD in the Roman Empire, in order to: 1. Identify which types of opaque copper red glass were manufactured in the Roman Empire during the 2nd century AD. 2. Investigate, through a multi-analytical approach, which factors determine the origin of the different red and orange hues (chemical composition, the nature of the colouring agent as well as their number and sizes). 3. To shed light on the technological aspects involved in making copper-red glass hues during the 2nd century AD. To reach these goals the research faced opaque red glass from three main different points of view. Although they are focused on distinct aspects, they will be interconnected. First, a literature review was necessary to identify the main features of copper red glass from a glass science point of view to understand the colouring agent, the formation and production of the colour. On the other hand, chemical analyses from previous archaeometric investigations were collected from the literature to make the history of opaque red glass from the Late Bronze Age until the medieval period. After this first step, the core of this work is the archaeometric investigation of the glass sectilia (sheets of glass) which decorated the villa of the Roman Emperor Lucius Verus. The glass sectilia are part of the Gorga collection, which is stored in the Soprintendenza Archeologica di Roma, and they represent an exceptional opportunity to study Roman glass technology of the 2nd century AD. These sectilia were chosen for this case study for two main reasons: they are well dated, attested to the 2nd century AD; they show the presence of several red and orange hues. This made it possible to examine the origin of the different red hues (chemical composition, colouring agent and specific production technology). The scientific investigation was conducted through a multi-analytical approach, which included: FORS, OM, EPMA, FEG-SEM, LA-ICP-MS, μXRD and μRaman spectroscopy. The production technology of opaque red glass (in this case only red brown type) has been studied through systematic laboratory reproductions. Iron and copper were tested to understand which raw materials could be employed, in which oxidation state iron should be added and the concentration needed to produce opaque red glass. Several procedures were attempted to recognise the most probable method used by the Roman glassmakers. This study outlined the history of the production of opaque copper-red glass, which could be very useful to understand the technological development of the glassmaking industry. The red glass sectilia investigated in this work revealed the presence of four red hues and three orange hues. Beyond enriching the literature of chemical analyses of opaque red glass dated to the 2nd century AD, these results have highlighted the use of more than one recipe used by the Roman glassmaker to broaden the chromatic scale of opaque red glass. Each red hue weas obtained through the accurate control of the raw materials, glass composition and heat treatments. The difficulties in making opaque red glass that emerged through the laboratory reproductions underlined that the good results could be achieved through accurate control of the melt redox condition through the correct glass composition and use of the appropriate raw materials. Likely, opaque red glass was not the result of fortune but of several failed experiments which allowed to master the colouring technique.O vidro vermelho opaco tem sido produzido desde o início da tecnologia de produção vidreira. No entanto, esta pode ser considerada uma das cores mais difíceis de produzir. Tem vindo a ser amplamente investigado nas áreas da ciência do vidro e da arqueometria, fornecendo uma vasta literatura. Contudo, alguns aspetos relativos à sua produção durante a Idade Romana estão ainda por clarificar, tais como: onde era produzido, que matérias-primas era usadas, e no geral, como era preparado. Além disso, a ausência de fontes escritas técnicas sobre vidro Romano aumenta a complexidade desta investigação. O objetivo deste estudo é investigar a tecnologia de produção do vidro vermelho opaco durante o século II d.C. no Império Romano, de forma a: 1. Identificar que tipos de vidro vermelho opaco de cobre eram manufaturados no Império Romano durante o século II d.C. 2. Investigar, através de uma abordagem multi-analítica, quais os fatores que determinam a origem dos diferentes tons de vermelho e laranja (composição química, a natureza do agente colorante, bem como a sua quantidade e tamanho das partículas). 3. Esclarecer quais os aspetos tecnológicos envolvidos na produção de tons de vidro vermelho de cobre durante o século II d.C. Para alcançar estes objetivos, a investigação abordou o vidro vermelho opaco de três principais pontos de vista, que apesar de serem focados em aspetos distintos, estarão interligados. Em primeiro lugar foi necessária uma revisão da literatura para identificar as principais características do vidro vermelho opaco do ponto de vista da ciência do vidro para perceber qual o agente colorante e a formação e produção da cor. Por outro lado, as análises químicas de estudos arqueométricos anteriores foram recolhidas a fim de contruir uma espécie de história do vidro vermelho opaco deste a Idade do Bronze Final até ao período medieval. Após esta primeira etapa deu-se início à parte central deste projeto, a investigação arqueométrica do vidro sectilia (placas de vidro) que decorava a villa do Imperador Romano Lucius Verus. Estas amostras de vidro são parte da coleção Gorga que se encontra armazenada/preservada na Soprintendenza Archeologica di Roma, e representam uma oportunidade excecional de estudar a tecnologia de vidro Romano do século II d.C. Estes sectilia foram selecionados como caso de estudo por duas razões principais: encontram-se bem datados, atribuídos ao século II d.C.; apresentam diferentes tons vermelhos e laranjas. Isso, tornou possível o estudo da origem dos diversos tons vermelhos (composição química, agente colorante e tecnologia de produção específica). A investigação científica foi realizada recorrendo a uma abordagem multi-analítica, que incluiu FORS, OM, EPMA, FEG-SEM, LA-ICP-MS, μXRD e espetroscopia μRaman. A tecnologia de produção do vidro vermelho opaco (neste caso apenas o tipo vermelho-acastanhado) foi estudado através de reproduções sistemáticas em laboratório. Ferro e cobre foram testados de forma a perceber que matérias-primas podiam ser empregues, em que estado de oxidação o ferro podia ser adicionado e a concentração necessária para produzir vidro vermelho opaco. Foram testadas várias metodologias para identificar qual o método mais provavelmente utilizado pelos vidreiros Romanos. A presente investigação delineou a história da produção do vidro vermelho de cobre opaco, que pode ser muito útil para compreender o desenvolvimento tecnológico da indústria vidreira. O vidro vermelho sectilia estudado neste trabalho, revelou a presença de quatro tons vermelhos e três tons laranjas. Para além de enriquecer a literatura referente a análises químicas de vidro vermelho opaco datado do século II d.C., estes resultados salientam o uso de mais do que uma receita pelos vidreiros Romanos por forma a alargar a escala cromática do vidro vermelho opaco. Cada tonalidade vermelha foi conseguida através do controlo preciso das matérias-primas, composição do vidro e tratamentos de calor. As dificuldades na produção de vidro vermelho opaco que emergiram com as reproduções em laboratório reforçaram que os bons resultados podem ser alcançados mediante o controlo preciso das condições de fusão redox através da composição de vidro correta e do uso das matérias-primas adequadas. Provavelmente, o vidro vermelho opaco não resultou da sorte, mas sim de várias experiências falhadas que permitiram o domínio das técnicas de coloração

The technology of copper-based red glass sectilia from the 2nd century ad lucius verus villa in rome

PD/BD/135053/2017This work aimed to investigate the origin of different red hues of Roman copper-based red opaque glass sectilia, to shed light on the production technology behind them. This objective was achieved by the depth study of the samples of glass sectilia, which decorated the villa of co-Emperor Lucius Verus (161–169 AD). These were selected for analysis due to their abundance, the certainty of their date and of their different red and orange hues. Using OM (optical microscopy), colourimetry and FORS (fibre optical reflectance spectroscopy) spectroscopy, four red and four orange hues were individuated. A set of representative samples for each hue was analysed by EPMA (electron probe microanalyses) to detect any correlation between colour and chemical composition. Crystalline phases were investigated through high-resolution FEG–SEM (field emission gun scanning electron microscope), µRaman spectroscopy and XRD, for the identification of colouring and opacifying agents and to understand how the different hues are affected by their shape, concentration and dimension. Sub-micrometric particles of metallic copper and cuprite crystals were identified as both the colouring and opacifying agents. These were not present in the same samples and were manufactured by two distinct colouring techniques, corresponding to two different glass chemical compositions. The size and the number of the colouring particles were the main factors that distinguished one hue from another. Although produced through different colouring techniques, some red samples appeared to be very similar to each other. These data enrich a period of the Roman age through some analyses and allow the identification of the type, as well as some of the production conditions of opaque red glass produced during 2nd century AD, which could be considered to be a period of transition from one technology to another.publishersversionpublishe

Nanotechnology in Roman Opaque Red Glass from the 2nd Century AD. Archaeometric Investigation in Red Sectilia from the Decoration of the Lucius Verus Villa in Rome

PD/BD/135053/2017 UID/EAT/00729/2019This work aims to characterise the chemical composition of Roman opaque red glass sectilia dated to the 2nd century A.D and to shed light on Roman glassmaking production of different shades of red, from red to reddish-brown. Due to the lack of technical historical sources for this period many questions about technological aspects still remain. In this project a multi-disciplinary approach is in progress to investigate the red glass sectilia with several red hues from the Imperial Villa of Lucius Verus (161–169 A.D.) in Rome. First, colorimetric measurements were taken to identify the various red hues. The second step was chemical characterization of the samples and the identification of crystalline colouring phases. Particle Induced X-Ray Emission (PIXE) analysis was used to investigate the chemical composition of these glass samples, while the crystalline phases were identified by Raman Spectroscopy and Scanning Electrons Microscope with Energy Dispersive X-ray Spectrometry (SEM-EDS). Using SEM-EDS nanoparticles were detected as a colouring agent, the chemical composition and the morphology of which has been studied in depth. This information has been compared with the colorimetric analysis to establish any correlation with the different colour hues.publishersversionpublishe

Apoptosis in spermatozoa of infertile men, clinical correlations

The methods for evaluation of male infertility include not only routine investigations, standardized by the WHO, but also complementary techniques, developed over the last years, in order to improve the predictive value of seminal analysis for natural conception and assisted reproduction. With reference to these new methods, studies suggest that sperm with certain levels of DNA fragmentation serve as a strong predictor of reduced male fertility. We studied subjects who underwent seminal fluid evaluation, because of an infertility condition, at the Department of Biomedical Sciences of the University of Sassari.The samples collected by masturbation were evaluated according to the World Health Organisation (1999).The samples was washed twice in PBS and cytocentrifuged for 10 min at 1800 rpm on polylysine-coated slides that were fixed in methanol at room temperature. The apoptosis was evaluated using the TUNEL (In Situ Cell Death Detection Kit, Fluorescein, Roche, Cat.No. 1 684 795). At fluorescent miscroscopy are counted at least 300 cells. Quantitative evaluation of apoptosis by the TUNEL method confirmed that apoptosis did not seem to be correlated with sperm concentration or morphology; however, we found a higher apoptotic rate in semen from patients affected by andrologic diseases, such as varicocele, than from those with alteration of semen characteristics. Apoptosis analysis might be used in infertile patients in order to understand the etiology of unexplained infertility and to improve therapeutic effectiveness

MaaS modelling: a review of factors, customers’ profiles, choices and business models

peer reviewedMobility-as-a-Service (MaaS) system is regarded as one of the emerging solutions to offer integrated, seamless, and flexible multi-modal mobility services as an alternative to privately owned mobility resources. MaaS is expected to change the way users will choose their modes of transport to reach their daily activities, and how service providers will generate profits, cooperate, and compete. To successfully deploy MaaS to reach the intended goals, it is critical to develop feasible and sustainable models that capture the diverse needs of customers as well as the diverse and often competing objectives of service providers. This paper aims to provide a general modelling framework and a critical and descriptive analysis of the relevant literature relating all main actors in the MaaS ecosystem, and identify and discuss all factors that are considered relevant, focusing on the actor’s decision-making processes and their correlations. This review shows the large variety and interaction of factors influencing MaaS adoption and their impact on forecasting MaaS appeal. It is also observed that current travel behaviour and multi-modal transport models are not fully capturing the diverse travel needs and choices of potential MaaS users. Recent advancements in agent-based simulation and discrete choice modelling offer potential solutions to address this gap, and future research should aim in that direction. Finally, the review analyses the interaction between MaaS actors, including customers, service providers, the government, and the MaaS Broker, highlighting the complexity of the modelling process comprising all actors of the MaaS ecosystem. Therefore, it is recommended to prioritise future research in exploring these areas.R-AGR-3625 - BRIDGES/19/13769009 MaaS4All - ACL (15/10/2019 - 14/10/2022) - CONNORS Richard11. Sustainable cities and communitie

reelaboración experimental de recetas históricas e influencia del proceso de vidriado en el análisis in situ de obras de arte históricas

Funding Information: Funding has been provided by the Fundação para a Ciência e a Tecnologia (FCT); The work was carried out at the Associated Laboratory for Green Chemistry – Clean Technologies and Processes (LA/P/0008/2020). Publisher Copyright: © 2023 The AuthorsNaples yellow was widely used across different types of artwork. Technical studies identified a binary Pb–Sb type as well as modified ternary variants with either zinc or tin in the structure. Although these variants were the object of previous experimental studies, a better understanding of the impact of the glazing procedure on the chromatic, chemical and crystallographic characteristics of the pigment is still lacking. In this work, several historical Naples yellow recipes were re-worked and subsequently applied and fired on test tiles, over a white glaze. The results show that the interaction between pigment and glaze produces important modifications to the colour, chemistry and structure of the pigment. Such modifications will strongly impact the reconstruction of historical recipes, with major consequences for identifying Naples yellow variants on artwork and investigating artistic practices.publishersversioninpres

Stigma, Discrimination and Disclosure of the Diagnosis of Multiple Sclerosis in the Workplace: A Systematic Review

The objective of the study was to describe and analyze the stigma, discrimination and the disclosure of the diagnosis of Multiple Sclerosis (MS) in the workplace. The protocol was registered in PROSPERO (CRD42022320437). We systematically searched four scientific databases with key search terms. We included any original peer-reviewed articles reporting the stigma or discrimination experienced at work due to MS or the disclosure of the diagnosis of MS in the workplace. No time limits were set for the search. An appraisal of the individual study quality was performed with the JBI critical appraisal checklist. Overall, 26 studies were deemed to fulfil all the eligibility criteria. The total number of participants in this review was 9571. The prevalence of people with MS who experience some degree of stigma in the workplace can be as high as 79.2%. Those who report greater feelings of discrimination are more likely to be unemployed. The prevalence of employers' and co-workers' awareness of the diagnosis varies from 31.7 to 90.2%. The main reason for non-disclosure is the fear of being discriminated against. The psychosocial work environment needs to be taken into consideration as part of public and individual policies to promote the health of patients with MS

Spatial and temporal distribution of the prevalence of unemployment and early retirement in people with multiple sclerosis: A systematic review with meta-analysis

BackgroundWe aimed to summarise the prevalence of unemployment and early retirement among people with MS and analyze data according to a spatio-temporal perspective.MethodsWe undertook a systematic search of PubMed/MEDLINE, Scopus, SciVerse ScienceDirect, and Web of Science. We included any peer-reviewed original article reporting the prevalence of unemployment and early retirement in the working-age population with MS. We excluded articles off-topic, with other study designs, whose study sample were unlikely to be representative of the MS population and in case of unavailability of the full text or essential information. A random-effects meta-analysis was used to measure overall prevalence estimates of unemployment and early retirement. We used meta-regression and subgroup analysis to evaluate potential moderators of prevalence estimates and the leave-one-out method for sensitivity analyses.ResultsOur research identified 153 studies across 29 countries encompassing 188436 subjects with MS. The pooled overall effect size for unemployment and early retirement was 35.6% (95% CI 32.8-38.4; I-2 = 99.31) and 17.2% (95% CI 14.6-20.2; I-2 = 99.13), respectively. The prevalence of unemployment varied according to the year of publication (p < 0.001) and there was a statistically significant decrease in the prevalence of unemployment over time (p = 0.042). Regarding early retirement, only seven (31.8%) estimates obtained from studies that were published before 2010 were below the overall effect size in comparison to 27 (60.0%) estimates extracted from data published between 2010 and 2021 (p = 0.039). There was a significant difference in prevalence according to countries (p < 0.001). Psychiatric illness was an important clinical feature responsible for patients leaving the workforce in regions with a high MS prevalence.ConclusionsUnemployment and early retirement due to MS remain highly prevalent, despite a slight decline in the last decade. The prevalence of unemployment and early retirement varies globally

Occupational outcomes of people with multiple sclerosis: a scoping review

Objectives To update the knowledge on the occupational outcomes associated with multiple sclerosis (MS), systematically examine the extent, scope and nature of the pre-existing literature and identify research gaps in the existing literature. Design Scoping review. Data sources A comprehensive database search of PubMed/MEDLINE, Scopus, SciVerse ScienceDirect and Web of Science was performed. There were no time limits. Eligibility criteria We included any peer-reviewed original article reporting the occupational outcomes of people with MS between the ages of 18 and 65 years. We excluded those off-topic and with insufficient information. Methods This review was conducted following the Joanna Briggs Institute recommendations and the Preferred Reporting Items for Systematic Reviews and Meta-Analyses for scoping review checklist. Screening, reading of full-texts and data extraction was performed in a standardised way by expert reviewers from 14 July 2021 to 31 October 2021. We provided a narrative synthesis and an overview of findings. Results The initial systematic search yielded 104 228 results. After removing duplicates and applying the exclusion criteria, 403 articles were included in the review. In total, the studies evaluated 492 062 subjects with MS. One hundred fifty-four (38.2%) articles were published in the last 5 years, mostly from Europe and North America (50.9% and 33.0%, respectively). Concerning the occupational outcomes, studies mostly addressed unemployment (311, 77.2%), early retirement (120, 29.8%), disability pension (117, 29.0%), sick leave (77, 19.1%), the indirect cost of MS (74, 18.4%) and work characteristics (57, 14.1%). The results were categorised into seven subtopics: 'Changes in work and occupational status due to MS', 'work-related socio-economic consequences of MS', 'risk factors for unfavourable occupational outcomes', 'reported barriers to employment', 'reported job accommodations and vocational rehabilitation strategies', 'job satisfaction, stigma, and disclosing the diagnosis in the workplace' and 'rating clinical scales'. Conclusions There are several issues that deserve further in-depth study by the scientific community in order to improve the occupational outcomes of people with MS

Cadmium modifies the cell cycle and apoptotic profiles of human breast cancer cells treated with 5-fluorouracil

Industrialisation, the proximity of factories to cities, and human work activities have led to a disproportionate use of substances containing heavy metals, such as cadmium (Cd), which may have deleterious effects on human health. Carcinogenic effects of Cd and its relationship with breast cancer, among other tumours, have been reported. 5-Fluorouracil (5-FU) is a fluoropyrimidine anticancer drug used to treat solid tumours of the colon, breast, stomach, liver, and pancreas. The purpose of this work was to study the effects of Cd on cell cycle, apoptosis, and gene and protein expression in MCF-7 breast cancer cells treated with 5-FU. Cd altered the cell cycle profile, and its effects were greater when used either alone or in combination with 5-FU compared with 5-FU alone. Cd significantly suppressed apoptosis of MCF-7 cells pre-treated with 5-FU. Regarding gene and protein expression, bcl2 expression was mainly upregulated by all treatments involving Cd. The expression of caspase 8 and caspase 9 was decreased by most of the treatments and at all times evaluated. C-myc expression was increased by all treatments involving Cd, especially 5-FU plus Cd at the half time of treatment. Cd plus 5-FU decreased cyclin D1 and increased cyclin A1 expression. In conclusion, our results indicate that exposure to Cd blocks the anticancer effects of 5-FU in MCF-7 cells. These results could have important clinical implications in patients treated with 5-FU-based therapies and who are exposed to high levels of Cd