In this study, we investigated biodeterioration of materials used in tempera painting by analyzing the structure of the microbiome in ancient tempera paintings exhibited in State Tretyakov Gallery, Moscow, Russia. Samples were obtained from 16 th-century paintings, including a grand Russian Orthodox icon "The Church Militant" (all exhibits were without visible signs of biodeterioration), and from surrounding walls and ceilings (with vast zones of visible microbial growth). A number of microorganisms isolated from visible signs of environmental bio-damage were also detected in tempera paintings kept in temperature-and humidity-controlled conditions unfavorable for the growth of microflora. To determine the biodegrading potential of the microbiome for tempera paintings, we developed a set of mock layers from paintwork materials used in tempera painting of 16 th century and their modern analogues and inoculated them with cultures containing filamentous fungi and bacteria. The susceptibility to microbial degradation of individual tempera painting materials was examined by micro-Fourier Transform Infrared (FTIR) spectroscopy, which enabled detection of even invisible signs of biodeterioration. The results indicate that the microorganisms isolated from paintings and surrounding areas in the museum are capable of causing significant damage of various tempera materials, among which varnishes were the most resistant; however, the addition of antiseptic (sodium pentachlorophenolate) can inhibit microbial growth on sturgeon glue.
Information about the surrounding atmosphere at a real timescale significantly relies on available gas sensors to be efficiently combined into multisensor arrays as electronic olfaction units. However, the array’s performance is challenged by the ability to provide orthogonal responses from the employed sensors at a reasonable cost. This issue becomes more demanded when the arrays are designed under an on-chip paradigm to meet a number of emerging calls either in the internet-of-things industry or in situ noninvasive diagnostics of human breath, to name a few, for small-sized low-powered detectors. The recent advances in additive manufacturing provide a solid top-down background to develop such chip-based gas-analytical systems under low-cost technology protocols. Here, we employ hydrolytically active heteroligand complexes of metals as ink components for microplotter patterning a multioxide combinatorial library of chemiresistive type at a single chip equipped with multiple electrodes. To primarily test the performance of such a multisensor array, various semiconducting oxides of the p- and n-conductance origins based on pristine and mixed nanocrystalline MnO x , TiO2, ZrO2, CeO2, ZnO, Cr2O3, Co3O4, and SnO2 thin films, of up to 70 nm thick, have been printed over hundred μm areas and their micronanostructure and fabrication conditions are thoroughly assessed. The developed multioxide library is shown to deliver at a range of operating temperatures, up to 400 °C, highly sensitive and highly selective vector signals to different, but chemically akin, alcohol vapors (methanol, ethanol, isopropanol, and n-butanol) as examples at low ppm concentrations when mixed with air. The suggested approach provides us a promising way to achieve cost-effective and well-performed electronic olfaction devices matured from the diverse chemiresistive responses of the printed nanocrystalline oxides.
The application of gas sensors in breath analysis is an important trend in the early diagnostics of different diseases including lung cancer, ulcers, and enteric infection. However, traditional methods of synthesis of metal oxide gas-sensing materials for semiconductor sensors based on wet sol-gel processes give relatively high sensitivity of the gas sensor to changing humidity. The sol-gel process leading to the formation of superficial hydroxyl groups on oxide particles is responsible for the strong response of the sensing material to this factor. In our work, we investigated the possibility to synthesize metal oxide materials with reduced sensitivity to water vapors. Dry synthesis of SnO2 nanoparticles was implemented in gas phase by spark discharge, enabling the reduction of the hydroxyl concentration on the surface and allowing the production of tin dioxide powder with specific surface area of about 40 m2/g after annealing at 610 °C. The drop in sensor resistance does not exceed 20% when air humidity increases from 40 to 100%, whereas the response to 100 ppm of hydrogen is a factor of 8 with very short response time of about 1 s. The sensor response was tested in mixtures of air with hydrogen, which is the marker of enteric infections and the marker of early stage fire, and in a mixture of air with lactate (marker of stomach cancer) and ammonia gas (marker of Helicobacter pylori, responsible for stomach ulcers).
In this work, we studied the formation of conductive silver lines with high aspect ratios (AR = thickness/width) > 0.1 using the modernized method of aerosol jet printing on a heated silicon substrate. The geometric (AR) and electrical (resistivity) parameters of the formed lines were investigated depending on the number of printing layers (1–10 layers) and the temperature of the substrate (25–300 °C). The AR of the lines increased as the number of printing layers and the temperature of the substrate increased. An increase in the AR of the lines with increasing substrate temperature was associated with a decrease in the ink spreading as a result of an increase in the rate of evaporation of nano-ink. Moreover, with an increase in the substrate temperature of more than 200 °C, a significant increase in the porosity of the formed lines was observed, and as a result, the electrical resistivity of the lines increased significantly. Taking into account the revealed regularities, it was demonstrated that the formation of silver lines with a high AR > 0.1 and a low electrical resistivity of 2–3 μΩ∙cm is advisable to be carried out at a substrate temperature of about 100 °C. The adhesion strength of silver films formed on a heated silicon substrate is 2.8 ± 0.9 N/mm2, which further confirms the suitability of the investigated method of aerosol jet printing for electronic applications.
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