Analysis of the Temple Scroll reveals another technology used to produce the Dead Sea Scrolls and potential preservation concerns. The miraculously preserved 2000-year-old Dead Sea Scrolls, ancient texts of invaluable historical significance, were discovered in the mid-20th century in the caves of the Judean desert. The texts were mainly written on parchment and exhibit vast diversity in their states of preservation. One particular scroll, the 8-m-long Temple Scroll is especially notable because of its exceptional thinness and bright ivory color. The parchment has a layered structure, consisting of a collagenous base material and an atypical inorganic overlayer. We analyzed the chemistry of the inorganic layer using x-ray and Raman spectroscopies and discovered a variety of evaporitic sulfate salts. This points toward a unique ancient production technology in which the parchment was modified through the addition of the inorganic layer as a writing surface. Furthermore, understanding the properties of these minerals is particularly critical for the development of suitable conservation methods for the preservation of these invaluable historical documents.

This work follows the recent discovery of a zinc-bearing Egyptian blue (EB) pigment widely used for the production of the early medieval mural paintings cycle in Santa Maria foris portas Church at Castelseprio (Lombardy Region, Italy). The inclusion of zinc in the synthesis of EB has been studied for the first time trying to evaluate whether its addition could be casual or deliberate. Historical reconstructions of the pigment have been carried out with a special focus on the use of zinc besides copper, using the different production methods. The influence of zinc on the pigment’s NIR photoluminescence and VIS-NIR reflectance has been characterized using FORS spectroscopy, X-ray diffraction, optical microscopy, and scanning electron microscopy-energy dispersive X-ray spectroscopy. A comparison of the production methods including salt-flux, solid-state, and Zn-rich syntheses showed that the solid-state synthesis results in particularly efficient NIR photoluminescence and VIS-NIR reflectance. Modern replicas were compared with an ancient sample in order to understand the zinc environment inside the structure of the Zn-enriched EB. Zn was found to be concentrated in a glass-based matrix surrounding cuprorivaite crystals, the main mineral associated with the EB pigment, and not included in a hypothetical Zn-doped cuprorivaite with formula CaCu1−xZnxSi4O10. The Zn-rich synthesis opens up the possibility of producing EB from brass and demonstrates that EB used in Castelseprio’s mural paintings could have been produced in this way. The relationship between the microstructure and the NIR photoluminescence of cuprorivaite-like pigments is of interest also for applications in modern and future technologies.

Aberrant lipid accumulation and marked changes in cellular lipid profiles are related to breast cancer metabolism and disease progression. In vitro, these phenomena are primarily studied using cells cultured in monolayers (2D). Here, we employ multicellular spheroids, generated using the MCF10A cell line series of increasing malignancy potential, to better recapitulate the 3D microenvironmental conditions that cells experience in vivo. Breast cancer cell lipid compositions were assessed in 2D and 3D culture models as a function of malignancy using liquid chromatography coupled with mass spectrometry. Further, the spatial distribution of lipids was examined using Raman chemical imaging and lipid staining. We show that with changes in the cellular microenvironment when moving from 2D to 3D cell cultures, total lipid amounts decrease significantly, while the ratio of acylglycerols to membrane lipids increases. This ratio increase could be associated with the formation of large lipid droplets (>10 μm) that are spatially evident throughout the spheroids but absent in 2D cultures. Additionally, we found a significant difference in lipid profiles between the more and less malignant spheroids, including changes that support de novo sphingolipid production and a reduction in ether-linked lipid fractions in the invasive spheroids. These differences in lipid profiles as a function of cell malignancy and microenvironment highlight the importance of coupled spatial and lipidomic studies to better understand the connections between lipid metabolism and cancer.

There has been significant progress in recent years aimed at the development of new analytical techniques for investigating structure-function relationships in hierarchically ordered materials. Inspired by these technological advances and the potential for applying these approaches to the study of construction materials from antiquity, we present a new set of high throughput characterization tools for investigating ancient Roman concrete, which like many ancient construction materials, exhibits compositional heterogeneity and structural complexity across multiple length scales. The detailed characterization of ancient Roman concrete at each of these scales is important for understanding its mechanics, resilience, degradation pathways, and for making informed decisions regarding its preservation. In this multi-scale characterization investigation of ancient Roman concrete samples collected from the ancient city of Privernum (Priverno, Italy), cm-scale maps with micron-scale features were collected using multi-detector energy dispersive spectroscopy (EDS) and confocal Raman microscopy on both polished cross-sections and topographically complex fracture surfaces to extract both bulk and surface information. Raman spectroscopy was used for chemical profiling and phase characterization, and data collected using EDS was used to construct ternary diagrams to supplement our understanding of the different phases. We also present a methodology for correlating data collected using different techniques on the same sample at different orientations, which shows remarkable potential in using complementary characterization approaches in the study of heterogeneous materials with complex surface topographies.

Nanocrystalline domains can be used to create robust anti-fatigue-fracture hydrogels for artificial cartilages and soft robots. The emerging applications of hydrogels in devices and machines require hydrogels to maintain robustness under cyclic mechanical loads. Whereas hydrogels have been made tough to resist fracture under a single cycle of mechanical load, these toughened gels still suffer from fatigue fracture under multiple cycles of loads. The reported fatigue threshold for synthetic hydrogels is on the order of 1 to 100 J/m2. We propose that designing anti-fatigue-fracture hydrogels requires making the fatigue crack encounter and fracture objects with energies per unit area much higher than that for fracturing a single layer of polymer chains. We demonstrate that the controlled introduction of crystallinity in hydrogels can substantially enhance their anti-fatigue-fracture properties. The fatigue threshold of polyvinyl alcohol (PVA) with a crystallinity of 18.9 weight % in the swollen state can exceed 1000 J/m2.

In recent years, great strides have been taken in the characterization of complex, heterogeneous ancient materials to gain a better understanding of their structure-function relationships. In this work, we apply a new set of high throughput characterization tools to study ancient Roman concrete, which is a particularly interesting material that shows heterogeneities and complexity across multiple scales, each of which are important for understanding its mechanics, its resilience, how it degrades, and for making informed decisions regarding its preservation.

AbstractPromoting the use of naturally available materials as a partial substitute to portland cement can be a viable solution for producing low carbon footprint and durable cements. This work asse...