Synthesis, Characterization and Antimicrobial Activity of Multiple Morphologies of Gold/Platinum Doped Bismuth Oxide Nanostructures.

Bismuth oxides were synthesized from bismuth carbonate using the sol-gel method. Studies have described the formation of Bi2O3, as a precursor of HNO3 dissolution, and intermediate oxides, such as BixOy when using H2SO4 and H3PO4. The average size of the crystallite calculated from Scherrer's formula ranged from 9 to 19 nm, according to X-ray diffraction. The FTIR analysis showed the presence of specific Bi2O3 bands when using HNO3 and of crystalline phases of "bismuth oxide sulphate" when using H2SO4 and "bismuth phosphate" when using H3PO4. The TG curves showed major mass losses and specific thermal effects, delimited in four temperature zones for materials synthesized with HNO3 (with loss of mass between 24% and 50%) and H2SO4 (with loss of mass between 45% and 76%), and in three temperature zones for materials synthesized with H3PO4 (with loss of mass between 13% and 43%). Further, the thermal stability indicates that materials have been improved by the addition of a polymer or polymer and carbon. Confocal laser scanning microscopy showed decreased roughness in the series, [BixOy]N > [BixOy-6% PVA]N > [BixOy-C-6% PVA]N, and increased roughness for materials [BixOy]S, [BixOy-6% PVA]S, [BixOy-C-6% PVA]S, [BixOy]P, [BixOy-6% PVA]P and [BixOy-C-6% PVA]P. The morphological analysis (electronic scanning microscopy) of the synthesized materials showed a wide variety of forms: overlapping nanoplates ([BixOy]N or [BixOy]S), clusters of angular forms ([BixOy-6% PVA]N), pillars ([BixOy-6% PVA]S-Au), needle particles ([BixOy-Au], [BixOy-6% PVA]S-Au, [BixOy-C-6% PVA]S-Au), spherical particles ([BixOy-C-6% PVA]P-Pt), 2D plates ([BixOy]P-Pt) and 3D nanometric plates ([BixOy-C-6% PVA]S-Au). For materials obtained in the first synthesis stage, antimicrobial activity increased in the series [BixOy]N > [BixOy]S > [BixOy]P. For materials synthesized in the second synthesis stage, when polymer (polyvinyl alcohol, PVA) was added, maximum antimicrobial activity, regardless of the microbial species tested, was present in the material [BixOy-6% PVA]S. For the materials synthesized in the third stage, to which graphite and 6% PVA were added, the best antimicrobial activity was in the material [BixOy-C-6% PVA]P. Materials synthesized and doped with metal ions (gold or platinum) showed significant antimicrobial activity for the tested microbial species.

Study of Interactions between Titanium Dioxide Coating and Wood Cell Wall Ultrastructure.

Titanium dioxide (TiO2) is used as a UV light absorber to protect wood matter from photodegradation. In this paper, interactions between wood and TiO2 coating are studied, and the efficiency of the coating is evaluated. For the experiments, two wood species were chosen: beech (Fagus sylvatica) and pine (Pinus sylvestris). Molecular and physical modifications in coated and uncoated wood exposed to UV radiation were investigated with Fourier transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR) and transmission electron microscopy (TEM). UV-VIS spectroscopy was used to describe the absorption of UV light by the TiO2 planar particles chosen for the experiment. It was demonstrated that TiO2 coating protects wood against photodegradation to a limited extent. TEM micrographs showed fissures in the wood matter around clusters of TiO2 particles in beech wood.

Long-chain mercury carboxylates relevant to saponification in oil and tempera paintings: XRPD and ssNMR complementary study of their crystal structures.

Saponification, resulting from pigment-binder interactions, is one of the most endangering phenomena affecting the appearance and stability of painted works of art. The crystallization of metal carboxylates (soaps) in paint layers is recently assumed as the most critical point for the development of undesirable changes induced by saponification, however, the factors triggering it are not fully understood. The red pigment cinnabar (HgS) has been suspected of contributing to saponification, however, the paucity of reliable reference structural data limited the experimental research of its effect at the molecular level. Within this study we synthesized mercury(II) carboxylates of the formula Hg(C16)x(C18)2-x (x = 0.0; 0.2; 0.5; 0.8; 1.0; 1.2; 1.5; 1.8; 2.0) where C16 and C18 are hexadecanoate (palmitate) and octadecanoate (stearate), respectively, and characterize them by combination of X-ray powder diffraction (XRPD) and 13C and 199Hg solid state NMR (ssNMR). For a more detailed interpretation of their structural and thermal behavior, Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) were used. The crystal structure of the studied mercury carboxylates was described on the basis of complementary ssNMR and XRPD measurements, Rietveld refinement and DFT calculations. All the subjected compounds crystallize in a monoclinic lattice of the C2/c symmetry. Mercury atoms are arranged in a slightly distorted square antiprismatic geometry and are monodentatically bonded to carboxylate anions. The structural disorder at the aliphatic end of the stearic acid chains was detected in the mixed carboxylates. Within the paper, the structural (dis)similarity with the corresponding lead carboxylates is discussed. The synthesized and characterized mercury carboxylates were applied to describe neo-formed mercury soaps in a model experiment simulating an egg-based paint system.

The Key Role of Tin (Sn) in Microstructure and Mechanical Properties of Ti2SnC (M2AX) Thin Nanocrystalline Films and Powdered Polycrystalline Samples.

Layered ternary Ti2SnC carbides have attracted significant attention because of their advantage as a M2AX phase to bridge the gap between properties of metals and ceramics. In this study, Ti2SnC materials were synthesized by two different methods-an unconventional low-energy ion facility (LEIF) based on Ar+ ion beam sputtering of the Ti, Sn, and C targets and sintering of a compressed mixture consisting of Ti, Sn, and C elemental powders up to 1250 °C. The Ti2SnC nanocrystalline thin films obtained by LEIF were irradiated by Ar+ ions with an energy of 30 keV to the fluence of 1.1015 cm-2 in order to examine their irradiation-induced resistivity. Quantitative structural analysis obtained by Cs-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) confirmed transition from ternary Ti2SnC to binary Ti0.98C carbide due to irradiation-induced ß-Sn surface segregation. The nanoindentation of Ti2SnC thin nanocrystalline films and Ti2SnC polycrystalline powders shows that irradiation did not affect significantly their mechanical properties when concerning their hardness (H) and Young's modulus (E). We highlighted the importance of the HAADF-STEM techniques to track atomic pathways clarifying the behavior of Sn atoms at the proximity of irradiation-induced nanoscale defects in Ti2SnC thin films.

Synthesis and Catalytic Properties of New Polymeric Monometallic Composites Based on Copolymers of Polypropylene Glycol Maleate Phthalate with Acrylic Acid.

Metal-polymer composites based on copolymers of polypropylene glycol maleate phthalate with acrylic acid and metallic nickel and silver were synthesized for the first time. The objects obtained were characterized by infrared (IR) and Raman spectroscopies, thermogravimetry, a scanning electron microscope with energy dispersive spectroscopy, and atomic emission spectrometry. The catalytic activity of new metal-polymer composites that exhibited a rather high efficiency in the reactions of electrocatalytic hydrogenation of pyridine was studied. It is shown that nanoparticles of metals are evenly distributed in the volume of the polymer matrix; more than 80% of nanoparticles are in the range from 25 to 40 nm and have spherical and rhombic shapes. The reusability of the obtained composites is shown.

Uncovering lead formate crystallization in oil-based paintings.

Lead carboxylates are an extensive group of compounds studied for their promising industrial applications and for their risky behavior when they are formed in oil paintings as corrosion products of lead-based pigments, leading to serious deterioration of paintings. Although the processes leading to the formation of aggregates, protrusions or inclusions, affecting undesirably the appearance of paintings, are assumed to be long term, neo-formed lead carboxylates are detectable in the early stage of paint drying. To uncover the chemical changes in lead pigments during the drying of oil paint films, model systems consisting of minium (Pb3O4) and four common drying oils were studied by X-ray powder diffraction (XRPD), 13C and 207Pb solid state NMR (ssNMR) spectroscopy and Fourier-transformed infrared spectroscopy (FTIR). For the first time, a degradation mechanism of Pb3O4via the crystallization of lead formate (Pb(HCOO)2), at the end of oxidative polymerization of oil paint films, was uncovered. The formation of formic acid in oils was proved by gas chromatography-mass spectrometry (GC-MS). Vapor experiments evidenced the susceptibility of Pb3O4 to react with volatile formic acid released during the autoxidation of oils comparably to the direct pigment-binder interactions in paint films. The investigation of the local environment of lead atoms in the paint film by 207Pb WURST-CPMG NMR spectroscopy showed that Pb(ii) atoms reacted with linseed oil preferentially to form highly crystalline Pb(HCOO)2, while the local chemical environment of Pb(iv) atoms did not change. The results proved the co-existence of (i) highly crystalline Pb(HCOO)2, (ii) a highly mobile amorphous phase corresponding to free carboxylic acids or a nascent lead soap phase and (iii) the remaining Pb3O4 in the polymeric/ionomeric network. Pb(HCOO)2 is assumed to be an intermediate for the conversion of Pb3O4 to lead soaps and/or lead carbonates.

Mixed lead carboxylates relevant to soap formation in oil and tempera paintings: the study of the crystal structure by complementary XRPD and ssNMR.

Long-chain lead carboxylates, on the one hand, represent compounds for versatile industrial applications in high-tech industries, while on the other hand, they are predominant constituents of secondary products of saponification of paint layers in works of art. Affecting significantly the appearance and stability of painted works of art, saponification is one of the most serious problems of preservation of cultural heritage objects. Despite their versatility as well as hazardousness, there is a paucity of single-crystal X-ray structures of long-chain carboxylates, due to difficulties in preparing single crystals of sufficient quality. We studied the crystal structure of polycrystalline mixed lead carboxylates of the formula Pb(C16)2-x(C18)x (x = 0; 0.25; 0.5; 0.75; 1; 1.5; 2), where C16 and C18 stand for hexadecanoate (palmitate) and octadecanoate (stearate) anions, respectively, by complementary X-ray powder diffraction (XRPD) and 13C and 207Pb solid state NMR (ssNMR). Mixed lead carboxylates consisting of hexadecanoate and octadecanoate are relevant to the formation of soaps in egg yolk and/or oil-based binders combined with lead-based pigments, which belong to the most common pigments in history. Combining an advanced XRPD analysis with a comparative analysis of ssNMR parameters, we described the structural model of mixed lead carboxylates. We revealed that both hexadecanoate (C16) and octadecanoate (C18) chains are present in one crystal structure, creating the statistical disorder at the ethyl end of the chains. Based on the 207Pb ssNMR spectra, we revealed two distinct local environments of lead atoms, corresponding to the symmetrically (i.e., (C16)-Pb-(C16) and/or (C18)-Pb-(C18) and asymmetrically (i.e., (C16)-Pb-(C18)) substituted lead carboxylates, and we confirmed the formation of a holo-directed structure for both the structural motifs. The structural models were applied to identify the neo-formed crystalline lead soap in a model experiment simulating the simplified historic paint consisting of the pigment lead tin yellow type I and emulsion binder prepared from egg yolk and linseed oil. We identified the secondary product as a mixed lead carboxylate of the composition Pb(C16)(C18).

New comprehensive approach for airborne asbestos characterisation and monitoring.

High concentrations of airborne asbestos in the ambient air are still a serious problem of air quality in numerous localities around the world. Since 2002, elevated concentrations of asbestos minerals of unknown origin have been detected in the ambient air of Pilsen, Czech Republic. To determine the asbestos fibre sources in this urban air, a systematic study was conducted. First, 14 bulk dust samples were collected in Pilsen at nine localities, and 6 bulk samples of construction aggregates for gravel production were collected in a quarry in the Pilsen-Litice district. The quarry is the largest quarry in the Pilsen region and the closest quarry to the built-up urban area. X-ray diffraction of the asbestos minerals revealed that monoclinic amphibole (MA, namely actinolite based on subsequent SEM-EDX analysis) in the bulk samples accounted for < 1-33% of the mass and that the highest values were found in the bulk dust samples from the railway platform of the Pilsen main railway station. Simultaneously, 24-h samples of airborne particulate matter (PM) at three localities in Pilsen were collected. Actinolite was identified in 40% of the PM samples. The relationship between the meteorology and presence of actinolite in the 24 PM10 samples was not proven, probably due to the long sampling integration time. Therefore, highly time-and-size-resolved PM sampling was performed. Second, sampling of size-segregated aerosols and measurements of the wind speed (WS), wind direction (WD), precipitation (P) and hourly PM10, PM2.5 and PM1 were conducted in a suburban locality near the quarry in two monthly highly time-resolved periods (30, 60, 120 min). Three/eight PM size fractions were sampled by a Davis Rotating-drum Uniform-size-cut Monitor (3/8DRUM) and analysed for the presences of asbestos fibres by scanning electron microscopy with energy dispersive x-ray spectroscopy (SEM-EDX). Asbestos fibre detection in highly time-resolved PM samples and current WD and WS determination allows the apportionment directionality of asbestos fibre sources. The number of critical actinolite asbestos fibres (length ≥ 5 µm and width < 3 µm, 3:1) increased with the PM1-10/PM10 and PM2.5-10/PM10 ratios, WS > 2 m s-1 and precipitation < 1 mm. Additionally, the number of critical actinolite asbestos fibres was not related to a specific WD. Therefore, we conclude that the sources of airborne critical actinolite asbestos fibres in Pilsen's urban area are omnipresent. Frequent use of construction aggregates and gravel from the metamorphic spilite quarries in the Pilsen region and in many localities around the urban area is a plausible explanation for the omnipresence of the critical actinolite asbestos fibres concentration in Pilsen's ambient air. Mitigation strategies to reduce the concentrations of critical actinolite asbestos fibres must be developed. Continuous monitoring and performing SEM-EDX analysis of highly time-and-size-resolved PM samples, correlated with fast changing WS and WD, seems to be a strong tool for efficiently controlling the mitigation strategies of critical actinolite asbestos fibres.