Inhalation studies are the gold standard for assessing the toxicity of airborne materials. They require considerable time, special equipment, and large amounts of test material. Intratracheal instillation is considered a screening and hazard assessment tool as it is simple, quick, allows control of the applied dose, and requires less test material. The particle-induced pulmonary inflammation and acute phase response in mice caused by intratracheal instillation or inhalation of molybdenum disulphide or tungsten particles were compared. End points included neutrophil numbers in bronchoalveolar lavage fluid, Saa3 mRNA levels in lung tissue and Saa1 mRNA levels in liver tissue, and SAA3 plasma protein. Acute phase response was used as a biomarker for the risk of cardiovascular disease. Intratracheal instillation of molybdenum disulphide or tungsten particles did not produce pulmonary inflammation, while molybdenum disulphide particles induced pulmonary acute phase response with both exposure methods and systemic acute phase response after intratracheal instillation. Inhalation and intratracheal instillation showed similar dose–response relationships for pulmonary and systemic acute phase response when molybdenum disulphide was expressed as dosed surface area. Both exposure methods showed similar responses for molybdenum disulphide and tungsten, suggesting that intratracheal instillation can be used for screening particle-induced acute phase response and thereby particle-induced cardiovascular disease.@en

Background: Acute phase response (APR) is characterized by a change in concentration of different proteins, including C-reactive protein and serum amyloid A (SAA) that can be linked to both exposure to metal oxide nanomaterials and risk of cardiovascular diseases. In this study, we intratracheally exposed mice to ZnO, CuO, Al2O3, SnO2 and TiO2 and carbon black (Printex 90) nanomaterials with a wide range in phagolysosomal solubility. We subsequently assessed neutrophil numbers, protein and lactate dehydrogenase activity in bronchoalveolar lavage fluid, Saa3 and Saa1 mRNA levels in lung and liver tissue, respectively, and SAA3 and SAA1/2 in plasma. Endpoints were analyzed 1 and 28 days after exposure, including histopathology of lung and liver tissues. Results: All nanomaterials induced pulmonary inflammation after 1 day, and exposure to ZnO, CuO, SnO2, TiO2 and Printex 90 increased Saa3 mRNA levels in lungs and Saa1 mRNA levels in liver. Additionally, CuO, SnO2, TiO2 and Printex 90 increased plasma levels of SAA3 and SAA1/2. Acute phase response was predicted by deposited surface area for insoluble metal oxides, 1 and 28 days post-exposure. Conclusion: Soluble and insoluble metal oxides induced dose-dependent APR with different time dependency. Neutrophil influx, Saa3 mRNA levels in lung tissue and plasma SAA3 levels correlated across all studied nanomaterials, suggesting that these endpoints can be used as biomarkers of acute phase response and cardiovascular disease risk following exposure to soluble and insoluble particles.@en

Tungsten is used in several applications and human exposure may occur. To assess its pulmonary toxicity, we exposed male mice to nose-only inhalation of tungsten particles at 9, 23 or 132 mg/m3 (Low, Mid and High exposure) (45 min/day, 5 days/week for 2 weeks). Increased genotoxicity (assessed by comet assay) was seen in bronchoalveolar (BAL) fluid cells at Low and High exposure. We measured acellular ROS production, and cannot exclude that ROS contributed to the observed genotoxicity. We saw no effects on body weight gain, pulmonary inflammation, lactate dehydrogenase or protein in BAL fluid, pathology of liver or kidney, or on sperm counts. In conclusion, tungsten showed non-dose dependent genotoxicity in the absence of inflammation and therefore interpreted to be primary genotoxicity. Based on genotoxicity, a Lowest Observed Adverse Effect Concentration (LOAEC) could be set at 9 mg/m3. It was not possible to establish a No Adverse Effect Concentration (NOAEC).@en

Stone-built cultural heritage faces threats from natural forces and anthropogenic pollutants, including local climate, acid rain, and outdoor conditions like temperature fluctuations and wind exposure, all of which impact their structural integrity and lead to their degradation. The development of a water-based, environmentally-friendly protective coatings that meet a combination of requirements posed by the diversity of the substrates, different environmental conditions, and structures with complex geometries remains a formidable challenge, given the numerous obstacles faced by current conservation strategies. Here we report the structural, electrical, and mechanical characterization, along with performance testing, of a nanostructured hydrophilic and self-healing hybrid coating based on hydroxyapatite (HAp) nanocrystals and polyelectrolyte multilayers (PEM), formed in-situ on Greek marble through a simple spray layer-by-layer surface functionalization technique. The polyelectrolyte-hydroxyapatite multilayer (PHM) structure resembled the design of naturally forming trabecular bone, attained at a short procedural time. It exhibited chemical affinity, aesthetical compatibility and resistance to weathering while offering reversibility. The proposed method is able to generate micron-sized coatings with controlled properties, such as adhesion and self-healing, leading to less weathered surfaces. Our results show that the PHM is a highly effective protective material that can be applied for stone protection and other similar applications.@en

We have investigated the feasibility of a new two-step protocol for the restoration of marbles. The process employs a polyelectrolyte multilayer film that enhances the chemical affinity between the treated stone and restorative material (hydroxyapatite nanocrystals), through functionalization, while at the same time it attributes an acid resistant property to the resulting system. Surface functionalization and material deposition is achieved through spraying; a simple and versatile application method suitable for objects of various sizes and geometries. Polyelectrolyte (polyethylenimine and polyacrylic acid) deposition was examined through Attenuated Total Reflection Fourier-Transform Infrared Spectroscopy (ATR-FTIR) and Atomic Force Microscopy (AFM), and tested through contact angle, water absorption and dissolution experiments. The hydroxyapatite nanocrystals were studied by ATR-FTIR, z-potential, AFM and Scanning Electron Microscopy (SEM), and characterized via contact angle and color alteration measurements. Our results show that the polyelectrolyte multilayer was stable in an aqueous environment with increased acid resistance (up to 46% decrease in mass weight loss when compared with untreated samples) and decreased water absorption (up to 39%). Color measurements of the outer hydroxyapatite layer showed a minimal color alteration for one type of the tested substrates showing low color difference values (ΔΕ* < 5). The results suggest that the proposed method holds great potential for marble restoration as it attributes multi-functionality and is easy to apply.@en