Deamidation at Asparagine and Glutamine As a Major Modification upon Deterioration/Aging of Proteinaceous Binders in MuralPaintings

Proteomic strategies are herein proved to be a complementary approach to the well established amino acid composition analysis for the characterization of the aging and deterioration phenomena occurring to proteinaceous materials in works-of-art. Amino acid analyses on several samples demonstrated that proteins in the frescoes from the Camposanto Monumentale in Pisa are deteriorated as revealed by the decrease in Met, Lys, and Tyr content and by the presence in all the samples of amino malonic acid as a result of Ser, Phe, and Cys oxidation. Proteomic analysis identified deamidation at Asn and Gln as a further major event occurred. This work paves the way to the exploitation of proteomic strategies for the investigation of the molecular effects of aging and deterioration in historical objects. Results show that proteomic searches for deamidation by liquid chromatography-tandem mass spectrometry (LC-MS/MS) could constitute a routine analysis for paintings or any artistic and historic objects where proteins are present. Peptides that can be used as molecular markers when casein is present were identified

A mass spectrometric study on tannin degradation within dyed woolen yarns

Natural tannins from various plants have been used throughout human history in textile dyeing, often as mordant dyes. The ageing behavior of these dyes is a challenge in conservation science, requiring a thorough knowledge of the textile–mordant-dye system. In this work, we analyzed reference wool yarns dyed with natural tannins from oak gallnuts, walnut (Juglans regia), and catechu (Acacia catechu), after artificial ageing. To gain insights on the composition of the dyestuffs and on how they aged, an analytical procedure based on extraction with Na2EDTA/DMF (ethylenediaminetetraacetic acid/dimethylformamide) and high-performance liquid chromatography (HPLC) analysis using high-resolution mass spectrometry detection was used. Since conventional reversed-phase (RP) columns usually show poor retention efficiency of highly polar compounds such as tannins, an RP-amide embedded polar group stationary phase was used to achieve optimal retention of the most polar compounds. Tannins from oak gallnuts showed little degradation after ageing, while a significant increase in the content of hydroxybenzoic acids was observed for tannins from walnut and catechu. Finally, the analytical procedure was applied to characterize the tannin dyes in historical tapestries from the 15th to 16th century, and the results were discussed in comparison with the reference yarns

The analysis of the Saltzman Collection of Peruvian dyes by high performance liquid chromatography and ambient ionisation mass spectrometry

Yarn samples from the Saltzman Collection of Peruvian dyes were characterized by several different analytical techniques: high performance liquid chromatography with both diode array detection (HPLC-DAD) and electrospray ionisation with tandem mass spectrometry (HPLC-ESI-Q-ToF), direct analysis in real time (DART) mass spectrometry and paper spray mass spectrometry. This report serves primarily as a database of chemical information about the colorants in these dye materials for those studying ancient South American textiles and their colorants. We also provide a comparison of the results obtained by currently widespread HPLC techniques with those of two different ambient ionisation direct mass spectrometry methods to highlight the advantages and disadvantages of these approaches

High entropy alloys obtained by field assisted powder metallurgy route: SPS and microwave heating

The aim of this work was to investigate the field assisted powder metallurgy route for producing HEAs at equimolar composition, i.e. FeCoNiCrAl, starting from metal powders. Both mixed, mechanically activated and mechanically alloyed powders have been used. The powders obtained by mechanical alloying were synthesized only by SPS, whereas the remaining ones were sintered by SPS or microwave heating. The investigated field assisted sintering techniques allowed an extremely short alloying time, high energy density on the load and negligible contamination by the surrounding environment. Both the conducted sintering-synthesis technology resulted not definitive to produce chemical homogeneity and to obtain a single stable structure. Thus a subsequently heat treatment was required. The post heat treatment, indeed, led to a single crystalline structure (FCC) and the material was fully recrystallized. After heat treatment samples are isomorphic: they exhibit two different phases with the same FCC cell, but different chemical composition, in detail Fe-Cr richer and Al-Ni richer. SPS-ed samples present a reduced porosity, while microwave processed ones are much more porous and this is reflected in the mechanical properties

SPS-assisted Synthesis of SICp reinforced high entropy alloys: reactivity of SIC and effects of pre-mechanical alloying and post-annealing treatment

In this work a traditional high entropy alloy (FeCoNiCrAl) was reinforced by uniformly distributed reactive silicon carbide (SiC) particles by a powder metallurgy synthetic route, using as precursors simply mixed powders or mechanically prealloyed ones. The reactive sintering produced a single isomorphic BCC structure. The sample microstructure resulted equiassic, more homogenous in samples based on prealloyed powders. The instability of SiC in the presence of metal precursors resulted in the formation of more stable carbides and silicides, as well as in carbon diffusion in the high entropy alloy matrix and partially unreacted SiC particles. The formation of these newly formed fine precipitates, as well as the presence of residual SiC were useful to increase the hardness of the alloy

Influence of Different Filler Metals on the Mechanical and Microstructural Characteristics of Arc-Welded Joints Made of Dissimilar Titanium Alloys

In the motorsport industry, the choice of material for manufacturing the heat resistant components often falls on titanium alloys. In most cases, the production flow for this kind of part involves CNC machining and subsequent assembly by welding process, to other parts obtained by cold plastic forming and possibly made using different titanium alloys. Hence, the alloying element-content in the joint area can be extremely heterogeneous and variable point-by-point. To investigate this topic further, dissimilar welding of the alpha/beta alloy Ti6Al4V and of the oxidation-resistant alpha alloy KS-Ti 1.2 ASN-EX was made by GTAW technology and using different filler metals. Chemical and mechanical properties of the welds were investigated by XRD, SEM-EDS, microhardness maps, and tensile and bending tests. Results show that, despite the different alloying elements present in the two filler wires investigated, static properties of the welds are similar. Results also show that the local V/Al content ratio affects the microhardness as it is responsible for the creation of supersaturated alpha phases during the cooling of the weld beads