Abstract: Amyloid fibrils, which are closely associated with various neurodegenerative
diseases, are the final products in many protein aggregation pathways. The identification of fibrils at low concentration is, therefore, pivotal in disease diagnosis and development of therapeutic strategies. We report a methodology for the specific identification of amyloid fibrils using chiroptical effects in plasmonic nanoparticles. The formation of amyloid fibrils based on α-synuclein was probed using gold nanorods, which showed no
apparent interaction with monomeric proteins but effective adsorption onto fibril structures via noncovalent interactions. The amyloid structure drives a helical nanorod arrangement, resulting in intense optical activity at the surface plasmon resonance wavelengths. This sensing technique was successfully applied to human brain homogenates of patients affected by Parkinson’s disease,
wherein protein fibrils related to the disease were identified through chiral signals from Au nanorods in the visible and near IR, whereas healthy brain samples did not exhibit any meaningful optical activity. The technique was additionally extended to the specific detection of infectious amyloids formed by prion proteins, thereby confirming the wide potential of the technique. The intense chiral response driven by strong dipolar coupling in helical Au nanorod arrangements allowed us to detect amyloid fibrils down to nanomolar concentrations.

Abstract: A hitherto unknown composition is highlighted in the red and black inks preserved on ancient Egyptian papyri from the Roman period (circa 100 to 200 CE). Synchrotron-based macro-X-ray fluo-rescence (XRF) mapping brings to light the presence of iron (Fe) and lead (Pb) compounds in the majority of the red inks inscribed on 12 papyrus fragments from the Tebtunis temple library. The iron-based compounds in the inks can be assigned to ocher, notably due to the colocalization of Fe with aluminum, and the detection of hematite (Fe2O3) by micro-X-ray diffraction. Using the same techniques together with micro-Fourier transform infrared spectroscopy, Pb is shown to be associated with fatty acid phosphate, sulfate, chloride, and carboxylate ions. Moreover, microXRF maps reveal a peculiar distribution and colocalization of Pb, phosphorus (P), and sulfur (S), which are present at the micrometric scale resembling diffused “coffee rings” surrounding the ocher particles imbedded in the red letters, and at the submicrometric scale concentrated in the papyrus cell walls. A similar Pb, P, and S composition was found in three black inks, suggesting that the same lead components were employed in the manufacture of carbon-based inks. Bearing in mind that pigments such as red lead (Pb3O4) and lead white (hydrocerussite [Pb-3(CO3)(2)(OH)(2)] and/or cerussite [PbCO3]) were not detected, the results presented here suggest that the lead compound in the ink was used as a drier rather than as a pigment. Accordingly, the study calls for a reassessment of the composition of lead-based components in ancient Mediterranean pigments.

Abstract: Mesosiderite meteorites consist of a mixture of crustal basaltic or gabbroic material and metal. Their formation process is still debated due to their unexpected combination of crust and core materials, possibly derived from the same planetesimal parent body, and lacking an intervening mantle component. Mesosiderites have experienced an extremely slow cooling rate from ca. 550 degrees C, as recorded in the metal (0.25-0.5 degrees C/Ma). Here we present a detailed investigation of exsolution features in pyroxene from the Antarctic mesosiderite Asuka (A) 09545. Geothermobarometry calculations, lattice parameters, lamellae orientation, and the presence of clinoenstatite as the host were used in an attempt to constrain the evolution of pyroxene from 1150 to 570 degrees C and the formation of two generations of exsolution lamellae. After pigeonite crystallization at ca. 1150 degrees C, the first exsolution process generated the thick augite lamellae along (100) in the temperature interval 1000-900 degrees C. By further cooling, a second order of exsolution lamellae formed within augite along (001), consisting of monoclinic low-Ca pyroxene, equilibrated in the temperature range 900-800 degrees C. The last process, occurring in the 600-500 degrees C temperature range, was likely the inversion of high to low pigeonite in the host crystal, lacking evidence for nucleation of orthopyroxene. The formation of two generations of exsolution lamellae, as well as of likely metastable pigeonite, suggest non-equilibrium conditions. Cooling was sufficiently slow to allow the formation of the lamellae, their preservation, and the transition from high to low pigeonite. In addition, the preservation of such fine-grained lamellae limits long-lasting, impact reheating to a peak temperature lower than 570 degrees C. These features, including the presence of monoclinic low-Ca pyroxene as the host, are reported in only a few mesosiderites. This suggests a possibly different origin and thermal history from most mesosiderites and that the crystallography (i.e., space group) of low-Ca pyroxene could be used as parameter to distinguish mesosiderite populations based on their cooling history.