Cultural innovation and megafauna interaction in the early settlement of arid Australia.

Elucidating the material culture of early people in arid Australia and the nature of their environmental interactions is essential for understanding the adaptability of populations and the potential causes of megafaunal extinctions 50-40 thousand years ago (ka). Humans colonized the continent by 50 ka, but an apparent lack of cultural innovations compared to people in Europe and Africa has been deemed a barrier to early settlement in the extensive arid zone. Here we present evidence from Warratyi rock shelter in the southern interior that shows that humans occupied arid Australia by around 49 ka, 10 thousand years (kyr) earlier than previously reported. The site preserves the only reliably dated, stratified evidence of extinct Australian megafauna, including the giant marsupial Diprotodon optatum, alongside artefacts more than 46 kyr old. We also report on the earliest-known use of ochre in Australia and Southeast Asia (at or before 49-46 ka), gypsum pigment (40-33 ka), bone tools (40-38 ka), hafted tools (38-35 ka), and backed artefacts (30-24 ka), each up to 10 kyr older than any other known occurrence. Thus, our evidence shows that people not only settled in the arid interior within a few millennia of entering the continent, but also developed key technologies much earlier than previously recorded for Australia and Southeast Asia.

Traditional Yellow Dyes Used in the 21st Century in Central Iran: The Knowledge of Master Dyers Revealed by HPLC-DAD and UHPLC-HRMS/MS.

This work provides new knowledge on natural yellows used in Iran. Seven biological sources were selected based on interviews with dye masters in Isfahan workshops (Iran). Delphinium semibarbatum, Eremostachys laevigata, Prangos ferulacea, Morus alba, Pistacia vera, Punica granatum, and Vitis vinifera are currently used in these workshops. Aiming to study the dye composition of wool samples dyed with the extracts of the selected biological sources and the changes induced by the dyeing procedures in the original chemical composition of the plant extract, raw materials and dyed wool (by us and in the workshops) were analyzed by HPLC-DAD and UHPLC-HRMS/MS. The main yellows for E. laevigata are luteolin-O-glycosides. In the other plant sources, the main chromophores are based on 3-O-glycosides of kaempferol, quercetin, and isorhamnetin. In pistachio hulls, myricitin derivatives were detected and we propose their use as markers. Generally, the solutions extracted from the wool displayed a higher amount of more polar compounds, but also a higher amount of aglycones. Importantly, the chromatographic profiles of the samples we prepared compared well with 17th c. yellows in Persian carpets, and therefore can be considered highly characterized references for the study of Persian yellows.

Influence of pigments and protein aging on protein identification in historically representative casein-based paints using enzyme-linked immunosorbent assay.

A systematic study on the influence of pigments and sample aging on casein identification was performed on 30 reconstructed paints. The protein in all the paints was extracted into solution for analysis. The amount of protein that can be retrieved for solution-based analysis in each of the reconstructed paints was studied with a well-developed NanoOrange method before and after artificial aging. The results showed that in the paints with calcium phosphate (in bone black) and copper carbonate, hydroxide, or acetate (in verdigris and azurite), the amount of protein that can be retrieved for liquid-phase analysis is much smaller than the other paints, indicating that the protein degradation was accelerated significantly in those paints. Carbon (in vine black), calcium carbonate (in natural chalk), and calcium sulfate (terra alba gypsum and ground alabaster) did not affect much the amount of protein that can be retrieved in the paints compared to non-pigmented binder, meaning that the protein degradation rate was not affected much by those pigments. Artificial aging was observed to decrease the amount of retrievable protein in all the reconstructed paints that were studied. The enzyme-linked immunosorbent assay (ELISA) method was applied to the 28 reconstructed paints (except two verdigris paints) to assess the protein identification. The ELISA responses from the different paints were compared at fixed protein concentrations. Natural chalk, bone black, raw sienna, stack lead white, and cochineal red-violet lake had the lowest ELISA signal in this study, which indicated that the binding sites (epitopes) on the target protein in these paints are likely to deteriorate more than those in the other paints. Artificial aging did not influence the ELISA response as much as the pigments when the protein concentration was kept the same for the paints that were studied.

Analytical and microbiological characterization of paper samples exhibiting foxing stains.

This work comprises the use of a multi-analytical approach combined with microbiological studies to characterize six paper samples, containing foxing stains, from the 20th century, regarding their cellulose matrix, fillers, and sizing materials, and to evaluate possible paper degradation that might have occurred during the foxing stains. Photography under different illuminations and optical microscopy were used for morphological characterization of the paper samples and foxing stains. Scanning electron microscopy coupled energy dispersive spectroscopy (SEM-EDS) was of particular importance for defining the presence of fiber disorder and disruption on the surface of some of the stains, and localized accumulations of mineral-like particles on the surface of others. SEM-EDS, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT-IR), and energy dispersive X-ray fluorescence (EDXRF) were used for the identification of mineral fillers, whereas sizing agents were analyzed using ATR-FT-IR. EDXRF results showed that no differences, within the standard deviation, were found in iron and copper contents between the foxed and unfoxed areas. Fungi belonging to the genus Penicillium spp. were found in all the paper samples. Unfoxed areas presented lower contamination than the foxed areas.

More than just a color: Archaeological, analytical, and procedural aspects of Late Bronze Age purple-dye production at Cape Kolonna, Aegina.

Excavations in the Eastern Suburb of Bronze Age Aegina Kolonna revealed the destruction deposit of two sequenced Early Mycenaean buildings (phase Late Helladic IIA; 16th century BC). The older building is interpreted as a widely undisturbed production site of purple-dye based on indicative finds such as ceramic sherds containing analyzable quantities of pigment, high amounts of mollusk shells, and a few functional facilities. Chemical analysis by HPLC and malacological determination revealed that the banded dye-murex (Hexaplex trunculus) was used almost exclusively. The presence of crushing tools and a waste disposal pit provide insight into the technical process of dye production. Additionally, skeletal remains of heavily burnt infantile and juvenile piglets, kids, or lambs were found in the purple workshop area. The evidence may be better explained by ritual activities aimed at promoting the highly meaningful event of purple production, rather than by normal food consumption practices.

Tyrian purple: the first four thousand years.

Some of the long history ofshellfish purple is recounted Understanding how the dye is produced from molluscs, the composition of the pigment and the chemistry involved has only been achieved as a result of the advances in analytical chemistry in the twentieth century, but some mysteries remain. Other diverse aspects such as the taste of the molluscs, the actual colour of the dye, the smell associated with the production and even the application in photography contribute to the fascination of the subject.

Early human use of marine resources and pigment in South Africa during the Middle Pleistocene.

Genetic and anatomical evidence suggests that Homo sapiens arose in Africa between 200 and 100 thousand years (kyr) ago, and recent evidence indicates symbolic behaviour may have appeared approximately 135-75 kyr ago. From 195-130 kyr ago, the world was in a fluctuating but predominantly glacial stage (marine isotope stage MIS6); much of Africa was cooler and drier, and dated archaeological sites are rare. Here we show that by approximately 164 kyr ago (+/-12 kyr) at Pinnacle Point (on the south coast of South Africa) humans expanded their diet to include marine resources, perhaps as a response to these harsh environmental conditions. The earliest previous evidence for human use of marine resources and coastal habitats was dated to approximately 125 kyr ago. Coincident with this diet and habitat expansion is an early use and modification of pigment, probably for symbolic behaviour, as well as the production of bladelet stone tool technology, previously dated to post-70 kyr ago. Shellfish may have been crucial to the survival of these early humans as they expanded their home ranges to include coastlines and followed the shifting position of the coast when sea level fluctuated over the length of MIS6.

Cosmetics, categories, and the future.

Cosmetics is an interesting unregulated category of over-the-counter products designed to enhance appearance and skin health. The coloring agents used in cosmetics are regulated along with their preservative constituents. New understandings of skin physiology have allowed cosmetics to advance beyond appearance issues into the functional arena. Cosmeceuticals is an unrecognized term from a regulatory perspective that conveys the new cosmetic formulations ability to improve skin health.

Digital indocyanine green videoangiography and choroidal neovascularization. 1992.

This report describes a new system for digital indocyanine green videoangiography (ICGV) that provides enhanced imaging of the choroidal circulation. This newly assembled system was used to study a consecutive series of 129 patients with exudative age-related macular degeneration (AMD), and ill-defined or occult choroidal neovascularization (CNV). Overall, 39% of the patients in this study with occult CNV could be reclassified as having well-delineated or so-called classic CNV by virtue of the additional findings provided by ICGV. In this series, ICGV was particularly useful in identifying occult CNV in eyes with a large, serous pigment epithelial detachment (PED) and in eyes with recurrent CNV after previous laser photocoagulation treatment. Some of these patients were selected for laser photocoagulation of the abnormal choroidal vessels in order to evaluate the feasibility of this form of treatment on the basis of combined clinical, fluorescein angiographic, and ICGV findings. The results of this study suggest that ICGV is an important adjunct in the evaluation, classification, and laser treatment of patients with occult CNV secondary to AMD.

Indocyanine green angiography-guided photodynamic therapy for treatment of chronic central serous chorioretinopathy: a pilot study. 2003.

BACKGROUND: Most patients with central serous chorioretinopathy (CSC) have spontaneous resolution of exudative macular detachments and a good visual prognosis. Patients with CSC have a primary choroidal hyperpermeability problem evident as multifocal areas of hyperpermeability during indocyanine green (ICG) angiography. A small percentage of patients develop chronic or progressive disease with widespread decompensation of the retinal pigment epithelium and severe vision loss. There is no known treatment for this variant of the disorder. PURPOSE: To study ICG-guided photodynamic therapy (PDT) with verteporfin as a potential treatment for patients with chronic CSC. METHODS: Twenty eyes of 15 patients were studied with fluorescein angiography, optical coherence tomography, and ICG angiography to diagnose the maculopathy, monitor the detachments, and localize the choroidal hyperpermeability of the disorder. PDT with ICG guidance was applied to areas of choroidal hyperpermeability, and the patients were observed to determine the anatomic and functional outcomes. RESULTS: Photodynamic therapy guided by ICG was associated with complete resolution of exudative macular detachments in 12 patients and incomplete resolution in the remaining eight eyes. The vision improved in six eyes and remained unchanged in 14 eyes during a mean follow-up of 6.8 months. Six weeks after treatment, the mean visual acuity improved by 0.55 lines, an amount that was marginally significant. There was a significant inverse correlation between the baseline visual acuity and the amount of improvement in acuity at 6 weeks. No patient had any treatment-related side effects. CONCLUSIONS: Indocyanine green angiography-guided PDT with verteporfin seems to aid in the resolution of exudative detachments in patients with chronic CSC. This treatment was associated with a rapid reduction in subretinal fluid and improvement in visual acuity. Although the follow-up time and number of patients in this pilot study were limited, the encouraging results and lack of complications suggest that further study is indicated.

On the production of ancient Egyptian blue: Multi-modal characterization and micron-scale luminescence mapping.

The ancient pigment Egyptian blue has long been studied for its historical significance; however, recent work has shown that its unique visible induced luminescent property can be used both to identify the pigment and to inspire new materials with this characteristic. In this study, a multi-modal characterization approach is used to explore variations in ancient production of Egyptian blue from shabti statuettes found in the village of Deir el-Medina in Egypt (Luxor, West Bank) dating back to the New Kingdom (18th-20th Dynasties; about 1550-1077 BCE). Using quantitative SEM-EDS analysis, we identify two possible production groups of the Egyptian blue and demonstrate the presence of multiple phases within samples using cluster analysis and ternary diagram representations. Using both macro-scale non-invasive (X-rays fluorescence and multi-spectral imaging) and micro-sampling (SEM-EDS and Raman confocal microspectroscopy) techniques, we correlate photoluminescence and chemical composition of the ancient samples. We introduce Raman spectroscopic imaging as a means to capture simultaneously visible-induced luminesce and crystal structure and utilize it to identify two classes of luminescing and non-luminescing silicate phases in the pigment that may be connected to production technologies. The results presented here provide a new framework through which Egyptian blue can be studied and inform the design of new materials based on its luminescent property.

Phytochemical analysis of young fustic (Cotinus coggygria heartwood) and identification of isolated colourants in historical textiles.

Young fustic (Cotinus coggygria Scop.; Anacardiaceae) has been used as a dyestuff since antiquity. Phytochemical investigation of the methanol extract of the heartwood has led to the isolation and structure elucidation by nuclear magnetic resonance and mass spectrometry (MS) of 3',4',6-trihydroxyaurone (sulfuretin) and 3',4',7-trihydroxyflavonol (fisetin) as well as 3',4',7-trihydroxyflavanol (fustin), 3',4',5,7-tetrahydroxyflavonol (quercetin), 3',4',5,7-tetrahydroxyflavanol (taxifolin), 4',7-dihydroxyflavanol, 3',4',7-trihydroxyflavanone (butin), 4',7-dihydroxyflavanone (liquiritigenin), trans-2',3,4,4'-tetrahydroxychalcone (butein), 4',5,7-trihydroxyflavanone and trans-2',4,4'-trihydroxychalcone (isoliquiritigenin). The isolated compounds were used as reference materials for the development of a high-performance liquid chromatography-diode array detector-MS method, which was then applied to analyse (1) fresh silk samples dyed with young fustic, (2) dyed silk subjected to artificially accelerated light ageing and (3) historical silk micro-samples, extracted from ecclesiastical post-Byzantine garments (fifteenth to eighteenth century), which belong to monasteries of Mount Athos. Sulfuretin and fisetin, which are usually used as markers for the identification of the yellow dye and, for the first time, some of the aforementioned flavonoid components of young fustic were identified in the historical extracts. Furthermore, preliminary experiments suggested that although the amounts of the dye components decrease with light ageing, the relative ratio of fisetin and sulfuretin, after a first step of ageing, seems to be almost unaffected by such degradation processes raised by light. The effect of the latter on the morphology of the dyed silk fibres is briefly investigated by scanning electron microscopy.

[Corneal tatoo--art or science?]. / Tatuajul corneean--arta sau stiinta?

The permanent colouring of disfigured corneal scars is known for almost 200 years. Because of improvement in surgical reconstructive techniques, corneal tattoing is used today only with a restricted group on carefully chosen patients, and merely for esthetique reasons.

Coloring plastinated specimens.

In the early days of plastination, plastinate Color was the usual grey/brown familiar to formalin-fixed biological specimens. Initially, trials with Kaiserling's, Klotz, Jore's and McCormick's fixative solutions were disappointing. Vascular injections with Colored epoxy were a great breakthrough in the 1980s. Biodur AC10® stain was the first stain of note to be applied to gross specimens to be plastinated and was applied in the last acetone bath. As plastination became more popular, specimen Color became an important and necessary aspect. Reactivation of the normal Color of red blood cells within a formalin-fixed specimen was introduced as a mechanism to restore Color to plastinated specimens. Painting of plastinated vessels was tried with some success, and finally, a superior new proprietary type of silicone coloration was developed. More recently, a versatile red pigment stain was developed. All of these have added aesthetically to the plastination processes and will certainly be a reality in the years to come. The various methodologies to Color plastinates are presented. Time will tell how effective these may or may not be.

A new multi analytical approach for the identification of synthetic and natural dyes mixtures. The case of orcein-mauveine mixture in a historical dress of a Sicilian noblewoman of nineteenth century.

In this paper, the application of a multi-analytical approach for the characterisation of synthetic and natural dyes in a historical textile is presented. The work is focused on a historical dress of a Sicilian noblewoman, dating from about 1865-1870. Firstly, SERS on fibre was performed, in order to individuate the classes of dyes employed. The SERS spectra suggested the presence of two main dyes: mauveine and orcein. In order to confirm these preliminary results, two different extraction protocols were applied. The extracts obtained were analysed by ESI-MS, MALDI-ToF and UHPCL-MS analyses, confirming the SERS results. In particular, the application of the ammonia mild extraction technique allowed to selectively extract the phenoxazonic dyes, separating them already in the extraction step from the synthetic ones. Thanks to this multi-analytical approach, this dress could be considered as one of the first examples of employment of synthetic dyes in association with natural ones.

Congo Red and amyloids: history and relationship.

Staining with Congo Red (CR) is a qualitative method used for the identification of amyloids in vitro and in tissue sections. However, the drawbacks and artefacts obtained when using this dye can be found both in vitro and in vivo Analysis of scientific data from previous studies shows that CR staining alone is not sufficient for confirmation of the amyloid nature of protein aggregates in vitro or for diagnosis of amyloidosis in tissue sections. In the present paper, we describe the characteristics and limitations of other methods used for amyloid studies. Our historical review on the use of CR staining for amyloid studies may provide insight into the pitfalls and caveats related to this technique for researchers considering using this dye.

Historical aspects and evolution of the application of vital dyes in vitreoretinal surgery and chromovitrectomy.

Lobeck and coworkers performed the first intravitreal application of vital dyes to visualize preretinal structures in 1932. Since then numerous investigators in the 20th century examined the use of biological stains through the endovenous, subretinal and intravitreal delivery route in order to identify vitreoretinal tissues and breaks. However, in the year 2000, a new surgical approach, recently coined chromovitrectomy, has arisen, which consists in the intraoperative application of vital dyes during vitrectomy. Initially fluorescein, and more recently indocyanine green, trypan blue, bromophenol blue, triamcinolone acetonide and patent blue have been used for the staining of preretinal membranes and tissues. Currently, many vital stains are under evaluation in animals for future clinical application during chromovitrectomy such as indigo carmine or light green. In this paper, several historical considerations in regard to the application of vital dyes in chromovitrectomy are discussed.