Aquivion-Based Spray Freeze-Dried Composite Materials for the Cascade Production of γ-Valerolactone.

The development of multifunctional catalysts is a necessary step to effectively carry out one-pot cascade reactions, such as that from furfural to γ-valerolactone. This research effort faces the challenge posed by the intrinsic limit of how many kinds of catalytic sites a single material can bear. In this work, the application of Spray-Freeze Drying (SFD) as a synthetic technique for the preparation of a wide range of innovative composite multi-functional catalysts is reported. Herein we show that by the proper combination of Aquivion as a highly active Brønsted acid catalyst and metal oxides as both support materials and Lewis acids (LAS) enable to achieve highly unique efficient and effective dual acid composite catalysts that are able to carry out the cascade reaction from furfural to γ-valerolactone. The dual catalytic system comprised of Aq/ZrO2 with 30 % polymer content prepared via spray-freeze drying exhibited GVL yields of 25 % after only 2 h at 180 °C and a remarkably high productivity of 4470 µmolGVL gCat -1 h-1, one of the highest reported results. Mechanistic studies based on experimental and advanced characterisation and spectroscopic techniques, such as, SEM, TEM, 15N MAS NMR and 19F MAS NMR indicate that activity arises from the proper tuning of BAS/LAS (Brønsted Acid Site/Lewis Acid Site) acidic properties.

Design rules applied to silver nanoparticles synthesis: A practical example of machine learning application.

The synthesis of silver nanoparticles with controlled physicochemical properties is essential for governing their intended functionalities and safety profiles. However, synthesis process involves multiple parameters that could influence the resulting properties. This challenge could be addressed with the development of predictive models that forecast endpoints based on key synthesis parameters. In this study, we manually extracted synthesis-related data from the literature and leveraged various machine learning algorithms. Data extraction included parameters such as reactant concentrations, experimental conditions, as well as physicochemical properties. The antibacterial efficiencies and toxicological profiles of the synthesized nanoparticles were also extracted. In a second step, based on data completeness, we employed regression algorithms to establish relationships between synthesis parameters and desired endpoints and to build predictive models. The models for core size and antibacterial efficiency were trained and validated using a cross-validation approach. Finally, the features' impact was evaluated via Shapley values to provide insights into the contribution of features to the predictions. Factors such as synthesis duration, scale of synthesis and the choice of capping agents emerged as the most significant predictors. This study demonstrated the potential of machine learning to aid in the rational design of synthesis process and paves the way for the safe-by-design principles development by providing insights into the optimization of the synthesis process to achieve the desired properties. Finally, this study provides a valuable dataset compiled from literature sources with significant time and effort from multiple researchers. Access to such datasets notably aids computational advances in the field of nanotechnology.

Safe and sustainable by design Ag nanomaterials: A case study to evaluate the bio-reactivity in the environment using a soil model invertebrate.

Safe-and-sustainable-by-design (SSbD) nanomaterials (NMs) or NM-containing products are a priority. Silver (Ag) NMs have a vast array of applications, including biomedical and other products, even as nanopesticides. Thus, their release to the environment is expected to increase. The aim of the present study was to assess the ecotoxicity of the SSbD Ag NM to the soil model species Enchytraeus crypticus (Oligochaeta). The Ag NM tested consists in a SSbD Ag with biomedical applications, a hydroxyethyl cellulose (HEC) coated Ag NMs (AgHEC) and its toxicity was compared to the naked Ag NMs (Ag-Sigma), an Ag-based biomedical product (PLLA-Ag: Poly l-Lactide microfibers doped with Ag), and AgNO3. Effects were assessed both in soil and aqueous media, following the standard OECD guideline in soil (28 days) and the OECD extension (56 days), and short-term pulse (5 days) in aqueous media: reconstituted water (ISO water) and soil:water (S:W) extracts, followed by a 21-days recovery period in soil. Ag materials were thoroughly characterized as synthesized and during the test in media and animals. Results in S:W showed AgHEC was more toxic than Ag-Sigma (ca. 150 times) and PLLA-Ag (ca. 2.5 times), associated with a higher Ag uptake. Higher toxicity was related to a smaller hydrodynamic size and higher suspension stability, which in turn resulted in a higher bioavailability of Ag NMs and released ions, particularly in S:W. Toxicity was correlated with the main physicochemical features, providing useful prediction of AgNMs bioactivity. The ability to test E. crypticus in a range of media with different and/or increasing complexity (water, S:W extracts, soil) provided an excellent source to interpret results and is here recommended.

Critical aspects in occupational exposure assessment with different aerosol metrics in an industrial spray coating process.

Engineered Nanomaterials (ENMs) have several uses in various industrial fields and are embedded in a myriad of consumer products. However, there is continued concern over the potential adverse health effects and environmental impacts of ENMs due to their unique physico-chemical characteristics. Currently, there are no specific international regulations for various ENMs. There are also no Occupational Exposure Limits (OEL) regulated by the European Union (EU) for nanomaterials in the form of nano-objects, their aggregates or agglomerates (NOAA). For ENMs the question of which metric to be used (i.e., mass, surface area, number concentrations) to determine the exposure is still not resolved. The aim of this work is to assess the worker exposure by inhalation in an industrial spray coating process by using all three metrics mentioned above. Two target ENMs (N-doped TiO2, TiO2N and AgNPs capped with a quaternized hydroxyethyl-cellulose, AgHEC) generated for industrial-scale spraying processes were considered. Results showed that the averaged particle number concentration (10-100 nm) was below 2.7 104 cm-3 for both materials. The Lung Deposited Surface Area (LDSA) was in the range between 73 and 98 µm2cm-3 and the particle mass concentration (obtained by means of ICP-EOS off-line analysis) resulted below 70 µg m-3 and 0.4 µg m-3 for TiO2 and Ag, respectively. Although, the airborne particles concentration compared well with the NIOSH Recommended Exposure Level (REL) limits the contribution to the background, according to EN 17058 (Annex E) was significant (particularly in the particle number and PM1 mass concentrations). We successfully evaluated the worker exposure by means of the different airborne particles' metrics (number, surface and mass concentrations). We concluded that worker exposure assessment involving ENMs is a complex procedure with requires both real time and off-line measurements and a deep investigation of the background.

Design of TiO2-Surfactin Hybrid Systems with Multifunctional Properties.

In recent years, multifunctional inorganic-organic hybrid materials have been widely investigated in order to determine their potential synergetic, antagonist, or independent effects in terms of reactivity. The aim of this study was to design and characterize a new hybrid material by coupling well-known photocatalytic TiO2 nanoparticles with sodium surfactin (SS), a biosurfactant showing high binding affinity for metal cations as well as the ability to interact with and disrupt microorganisms' cell membranes. We used both chemical and colloidal synthesis methodologies and investigated how different TiO2:SS weight ratios affected colloidal, physicochemical, and functional properties. We discovered a clear breaking point between TiO2 and SS single-component trends and identified different ranges of applicability by considering different functional properties such as photocatalytic, heavy metal sorption capacity, and antibacterial properties. At low SS contents, the photocatalytic properties of TiO2 are preserved (conversion of organic dye = 99% after 40 min), and the hybrid system can be used in advanced oxidation processes, taking advantage of the additional antimicrobial SS properties. At high SS contents, the TiO2 photoactivity is inhibited, and the hybrid can be usefully exploited as a UV blocker in cosmetics, avoiding undesired oxidative effects (UV adsorption in the range between 300-400 nm). Around the breaking point (TiO2:SS 1:1), the hybrid material preserves the high surface area of TiO2 (specific surface area around 180 m2/g) and demonstrates NOx depletion of up to 100% in 80 min, together with improved adhesion of hybrid antibacterial coating. The last design demonstrated the best results for the concurrent removal of inorganic, organic, and biological pollutants in water/soil remediation applications.

Native Study of the Behaviour of Magnetite Nanoparticles for Hyperthermia Treatment during the Initial Moments of Intravenous Administration.

Magnetic nanoparticles (MNPs) present outstanding properties making them suitable as therapeutic agents for hyperthermia treatments. Since the main safety concerns of MNPs are represented by their inherent instability in a biological medium, strategies to both achieve long-term stability and monitor hazardous MNP degradation are needed. We combined a dynamic approach relying on flow field flow fractionation (FFF)-multidetection with conventional techniques to explore frame-by-frame changes of MNPs injected in simulated biological medium, hypothesize the interaction mechanism they are subject to when surrounded by a saline, protein-rich environment, and understand their behaviour at the most critical point of intravenous administration. In the first moments of MNPs administration in the patient, MNPs change their surrounding from a favorable to an unfavorable medium, i.e., a complex biological fluid such as blood; the particles evolve from a synthetic identity to a biological identity, a transition that needs to be carefully monitored. The dynamic approach presented herein represents an optimal alternative to conventional batch techniques that can monitor only size, shape, surface charge, and aggregation phenomena as an averaged information, given that they cannot resolve different populations present in the sample and cannot give accurate information about the evolution or temporary instability of MNPs. The designed FFF method equipped with a multidetection system enabled the separation of the particle populations providing selective information on their morphological evolution and on nanoparticle-proteins interaction in the very first steps of infusion. Results showed that in a dynamic biological setting and following interaction with serum albumin, PP-MNPs retain their colloidal properties, supporting their safety profile for intravenous administration.

Fate of engineered nanomaterials at the human epithelial lung tissue barrier in vitro after single and repeated exposures.

The understanding of the engineered nanomaterials (NMs) potential interaction with tissue barriers is important to predict their accumulation in cells. Herein, the fate, e.g., cellular uptake/adsorption at the cell membrane and translocation, of NMs with different physico-chemical properties across an A549 lung epithelial tissue barrier, cultured on permeable transwell inserts, were evaluated. We assessed the fate of five different NMs, known to be partially soluble, bio-persistent passive and bio-persistent active. Single exposure measurements using 100 µg/ml were performed for barium sulfate (BaSO4), cerium dioxide (CeO2), titanium dioxide (TiO2), and zinc oxide (ZnO) NMs and non-nanosized crystalline silica (DQ12). Elemental distribution of the materials in different compartments was measured after 24 and 80 h, e.g., apical, apical wash, intracellular and basal, using inductively coupled plasma optical emission spectrometry. BaSO4, CeO2, and TiO2 were mainly detected in the apical and apical wash fraction, whereas for ZnO a significant fraction was detected in the basal compartment. For DQ12 the major fraction was found intracellularly. The content in the cellular fraction decreased from 24 to 80 h incubation for all materials. Repeated exposure measurements were performed exposing the cells on four subsequent days to 25 µg/ml. After 80 h BaSO4, CeO2, and TiO2 NMs were again mainly detected in the apical fraction, ZnO NMs in the apical and basal fraction, while for DQ12 a significant concentration was measured in the cell fraction. Interestingly the cellular fraction was in a similar range for both exposure scenarios with one exception, i.e., ZnO NMs, suggesting a potential different behavior for this material under single exposure and repeated exposure conditions. However, we observed for all the NMs, a decrease of the amount detected in the cellular fraction within time, indicating NMs loss by cell division, exocytosis and/or possible dissolution in lysosomes. Overall, the distribution of NMs in the compartments investigated depends on their composition, as for inert and stable NMs the major fraction was detected in the apical and apical wash fraction, whereas for partially soluble NMs apical and basal fractions were almost similar and DQ12 could mainly be found in the cellular fraction.

Measuring TiO2N and AgHEC Airborne Particle Density during a Spray Coating Process.

Effective particle density is a key parameter for assessing inhalation exposure of engineered NPs in occupational environments. In this paper, particle density measurements were carried out using two different techniques: one based on the ratio between mass and volumetric particle concentrations; the other one based on the ratio between aerodynamic and geometric particle diameter. These different approaches were applied to both field- and laboratory-scale atomization processes where the two target NPs (N-doped TiO2, TiO2N and AgNPs capped with a quaternized hydroxyethylcellulose, AgHEC) were generated. Spray tests using TiO2N were observed to release more and bigger particles than tests with AgHEC, as indicated by the measured particle mass concentrations and volumes. Our findings give an effective density of TiO2N particle to be in a similar range between field and laboratory measurements (1.8 ± 0.5 g/cm3); while AgHEC particle density showed wide variations (3.0 ± 0.5 g/cm3 and 1.2 + 0.1 g/cm3 for field and laboratory campaigns, respectively). This finding leads to speculation regarding the composition of particles emitted because atomized particle fragments may contain different Ag-to-HEC ratios, leading to different density values. A further uncertainty factor is probably related to low process emissions, making the subtraction of background concentrations from AgHEC process emissions unreliable.

Dissolution Rate of Nanomaterials Determined by Ions and Particle Size under Lysosomal Conditions: Contributions to Standardization of Simulant Fluids and Analytical Methods.

Dissolution of inhaled engineered nanomaterials (ENM) under physiological conditions is essential to predict the clearance of the ENM from the lungs and to assess their biodurability and the potential effects of released ions. Alveolar macrophage (AM) lysosomes contain a pH 4.5 saline brine with enzymes and other components. Different types of artificial phagolysosomal simulant fluids (PSFs) have been developed for dissolution testing, but the consequence of using different media is not known. In this study, we tested to which extent six fundamentally different PSFs affected the ENM dissolution kinetics and particle size as determined by a validated transmission electron microscopy (TEM) image analysis. Three lysosomal simulant media were consistent with each other and with in vivo clearance. These media predict the quick dissolution of ZnO, the partial dissolution of SiO2, and the very slow dissolution of TiO2. The valid media use either a mix of organic acids (with the total concentration below 0.5 g/L, thereof citric acid below 0.15 g/L) or another organic acid (KH phthalate). For several ENM, including ZnO, BaSO4, and CeO2, all these differences induce only minor modulation of the dissolution rates. Only for TiO2 and SiO2, the interaction with specific organic acids is highly sensitive, probably due to sequestration of the ions, and can lead to wrong predictions when compared to the in vivo behavior. The media that fail on TiO2 and SiO2 dissolution use citric acid at concentrations above 5 g/L (up to 28 g/L). In the present selection of ENM, fluids, and methods, the different lysosomal simulant fluids did not induce changes of particle morphology, except for small changes in SiO2 and BaSO4 particles most likely due to ion dissolution, reprecipitation, and coalescence between neighboring particles. Based on the current evidence, the particle size by TEM analysis is not a sufficiently sensitive analytical method to deduce the rate of ENM dissolution in physiological media. In summary, we recommend the standardization of ENM dissolution testing by one of the three valid lysosomal simulant fluids with determination of the dissolution rate and halftime by the quantification of ions. This recommendation was established for a continuous flow system but may be relevant as well for static (batch) solubility testing.

Particles Emission from an Industrial Spray Coating Process Using Nano-Materials.

Industrial spray coating processes are known to produce excellent coatings on large surfaces and are thus often used for in-line production. However, they could be one of the most critical sources of worker exposure to ultrafine particles (UFPs). A monitoring campaign at the Witek s.r.l. (Florence, Italy) was deployed to characterize the release of TiO2 NPs doped with nitrogen (TiO2-N) and Ag capped with hydroxyethyl cellulose (AgHEC) during automatic industrial spray-coating of polymethyl methacrylate (PMMA) and polyester. Aerosol particles were characterized inside the spray chamber at near field (NF) and far field (FF) locations using on-line and off-line instruments. Results showed that TiO2-N suspension produced higher particle number concentrations than AgHEC in the size range 0.3-1 µm (on average 1.9 102 p/cm3 and 2.5 101 p/cm3, respectively) after background removing. At FF, especially at worst case scenario (4 nozzles, 800 mL/min flow rate) for TiO2-N, the spray spikes were correlated with NF, with an observed time lag of 1 minute corresponding to a diffusion speed of 0.1 m/s. The averaged ratio between particles mass concentrations in the NF position and inside the spray chamber was 1.7% and 1.5% for TiO2-N and for AgHEC suspensions, respectively. The released particles' number concentration of TiO2-N in the size particles range 0.3-1 µm was comparable for both PMMA and polyester substrates, about 1.5 and 1.6 102 p/cm3. In the size range 0.01-30 µm, the aerosol number concentration at NF for both suspensions was lower than the nano reference values (NRVs) of 16·103 p/cm-3.

Monitoring and Optimisation of Ag Nanoparticle Spray-Coating on Textiles.

An automatic lab-scaled spray-coating machine was used to deposit Ag nanoparticles (AgNPs) on textile to create antibacterial fabric. The spray process was monitored for the dual purpose of (1) optimizing the process by maximizing silver deposition and minimizing fluid waste, thereby reducing suspension consumption and (2) assessing AgNPs release. Monitoring measurements were carried out at two locations: inside and outside the spray chamber (far field). We calculated the deposition efficiency (E), finding it to be enhanced by increasing the spray pressure from 1 to 1.5 bar, but to be lowered when the number of operating sprays was increased, demonstrating the multiple spray system to be less efficient than a single spray. Far-field AgNPs emission showed a particle concentration increase of less than 10% as compared to the background level. This finding suggests that under our experimental conditions, our spray-coating process is not a critical source of worker exposure.

Use of single particle ICP-MS to estimate silver nanoparticle penetration through baby porcine mucosa.

Children are potentially exposed to products that contain nanoparticles (NPs). In particular, silver NPs are commonly present both in products used by and around children, primarily due to their antibacterial properties. However, very few data are available regarding the ability of silver NPs to penetrate through the oral mucosa in children. In the present work, we used baby porcine buccal mucosa mounted on vertical Franz diffusion cells, as an in vitro model to investigate penetration of silver NPs (19 ± 5 nm). Permeability experiments were performed using pristine physiologically-relevant saline solution in the receiver chamber and known concentrations of NPs or ions in the donor chamber; conditions mimicked the in vivo physiological pH conditions. After physicochemical characterization of silver nanoparticles dispersed in physiological solution, we evaluated the passage of ions and NPs through the mucosa, using single particle inductively coupled plasma mass spectrometry. A flux of 4.1 ± 1.7 ng cm-2 min-1 and a lag time of 159 ± 17 min were observed through mucosa exposed to silver nanoparticles. The latter suggests nanoparticle penetration through the baby porcine mucosa and release Ag+ ions in the receptor fluid, as confirmed by computational model. Due to physiological similarity between human and pig membranes it is reasonable to assume that a trans-oral mucosa penetration could occur in children upon contact with silver nanoparticles.

Polyvinyl alcohol/silver electrospun nanofibers: Biocidal filter media capturing virus-size particles.

In response to the nowadays battle against SARS-CoV-2, we designed a new class of high performant filter media suitable to advance the facemask technology and provide new efficient widespread solutions against virus propagation. By means of the electrospinning technology we developed filter media based on polyvinyl alcohol (PVA) nanofibers doped with AgNPs combining three main performance requirements: high air filtration efficiency to capture nanometer-size particles, low airflow resistance essential to ensure breathability and antimicrobial activity to inactivate aerosolized microorganisms. PVA/AgNPs electrospun nanofibers were produced by electrospinning the dispersion of colloidal silver into the PVA water solution. A widespread physicochemical characterization was addressed to the Ag colloidal suspension. The key functional performances of the electrospun nanofibers were proven by water stability, antibacterial activity, and filtration efficiency and pressure drop measurements performed under conditions representative of facemasks. We assessed a total bacterial depletion associated to a filtering efficiency towards nano-aerosolized particles of 97.7% higher than required by the EN149 standard and a pressure drop in line with FFP1 and FFP2 masks, even at the highest filtration velocity. Such results pave the way to the application of PVA/AgNPs electrospun nanofibers in facemasks as advanced filtering media for protecting against airborne microorganisms.

TiO2@BSA nano-composites investigated through orthogonal multi-techniques characterization platform.

Biocompatible coating based on bovine serum albumin (BSA) was applied on two different TiO2 nanoparticles (aeroxide P25 and food grade E171) to investigate properties and stability of resulting TiO2@BSA composites, under the final perspective to create a "Safe-by-Design" coating, able to uniform, level off and mitigate surface chemistry related phenomena, as naturally occurring when nano-phases come in touch with proteins enriched biological fluids. The first step towards validating the proposed approach is a detailed characterization of surface chemistry with the quantification of amount and stability of BSA coating deposited on nanoparticles' surfaces. At this purpose, we implemented an orthogonal multi-techniques characterization platform, providing important information on colloidal behavior, particle size distribution and BSA-coating structure of investigated TiO2 systems. Specifically, the proposed orthogonal approach enabled the quantitative determination of bound and free (not adsorbed) BSA, a key aspect for the design of intentionally BSA coated nano-structures, in nanomedicine and, overall, for the control of nano-surface reactivity. In fact, the BSA-coating strategy developed and the orthogonal characterisation performed can be extended to different designed nanomaterials in order to further investigate the protein-corona formation and promote the implementation of BSA engineered coating as a strategy to harmonize the surface reactivity and minimize the biological impact.

Understanding the impact of more realistic low-dose, prolonged engineered nanomaterial exposure on genotoxicity using 3D models of the human liver.

BACKGROUND: With the continued integration of engineered nanomaterials (ENMs) into everyday applications, it is important to understand their potential for inducing adverse human health effects. However, standard in vitro hazard characterisation approaches suffer limitations for evaluating ENM and so it is imperative to determine these potential hazards under more physiologically relevant and realistic exposure scenarios in target organ systems, to minimise the necessity for in vivo testing. The aim of this study was to determine if acute (24 h) and prolonged (120 h) exposures to five ENMs (TiO2, ZnO, Ag, BaSO4 and CeO2) would have a significantly different toxicological outcome (cytotoxicity, (pro-)inflammatory and genotoxic response) upon 3D human HepG2 liver spheroids. In addition, this study evaluated whether a more realistic, prolonged fractionated and repeated ENM dosing regime induces a significantly different toxicity outcome in liver spheroids as compared to a single, bolus prolonged exposure. RESULTS: Whilst it was found that the five ENMs did not impede liver functionality (e.g. albumin and urea production), induce cytotoxicity or an IL-8 (pro-)inflammatory response, all were found to cause significant genotoxicity following acute exposure. Most statistically significant genotoxic responses were not dose-dependent, with the exception of TiO2. Interestingly, the DNA damage effects observed following acute exposures, were not mirrored in the prolonged exposures, where only 0.2-5.0 µg/mL of ZnO ENMs were found to elicit significant (p ≤ 0.05) genotoxicity. When fractionated, repeated exposure regimes were performed with the test ENMs, no significant (p ≥ 0.05) difference was observed when compared to the single, bolus exposure regime. There was < 5.0% cytotoxicity observed across all exposures, and the mean difference in IL-8 cytokine release and genotoxicity between exposure regimes was 3.425 pg/mL and 0.181%, respectively. CONCLUSION: In conclusion, whilst there was no difference between a single, bolus or fractionated, repeated ENM prolonged exposure regimes upon the toxicological output of 3D HepG2 liver spheroids, there was a difference between acute and prolonged exposures. This study highlights the importance of evaluating more realistic ENM exposures, thereby providing a future in vitro approach to better support ENM hazard assessment in a routine and easily accessible manner.

Use of Cotton Textiles Coated by Ir(III) Tetrazole Complexes within Ceramic Silica Nanophases for Photo-Induced Self-Marker and Antibacterial Application.

This study was aimed at the production and characterization of coated cotton textiles with luminescent ceramic nanophases doped with cationic Ir(III) tetrazole complexes. We confirmed that SiO2 nanoparticles (NPs) do not affect the phosphorescent properties of the complexes that maintain their emission (610 and 490 nm). For the first time we transferred the luminescence feature from nanosol to textile surface, highlighting the advantages of using nanosilica as an encapsulating and stabilizing matrix. The optimized Ir@SiO2 suspensions were homogenously applied onto the cotton surface by dip-pad-dry-cure technique, as proved by the 2p-fluorescence microscope analysis. Once we verified the self-marker properties of the Ir(III) complex, we observed an excellent washing fastness of the coating with a very limited release. SiO2 in the washing water was quantified at maximum around 1.5 wt% and Ir below the inductively coupled plasma optical emission spectrometry (ICP-OES) detection limit of 1 ppm. A Franz cell test was used to evaluate any possible ex-vivo uptake of Ir@SiO2 nanoparticles across human skin tissues, showing that epidermis and dermis stop over 99% of Ir, implying a reduced impact on human health. The light-induced antimicrobial potential of the Ir@SiO2 were assessed toward both Gram(-) and Gram(+) bacteria. The results encouraged further developments of such functional textiles coated by self-markers and antibacterial active nanophases.

NanoTiO2@DNA complex: a novel eco, durable, fire retardant design strategy for cotton textiles.

A strategy for the design of cotton flame retardant coatings is described, exploiting the natural intumescent formulation of nucleic acids, the intrinsic thermal inertia of TiO2 ceramic phase and the strong affinity that TiO2 nanoparticles shows for amphiphilic biomolecules (e.g. proteins, nucleic acids) and hydrophilic substrates. Two different self-assembled TiO2@DNA systems are obtained by mixing two opposite charged TiO2 nanoparticles suspensions with DNA solution. The colloidal behavior of separate and mixed phases was investigated, as well as the morphological, chemical structure and thermal properties of resulting coatings, in order to make some hypothesis on the observed synergic effects. Scanning electron microscopy (SEM) and Attenuated Total Reflectance (ATR) spectroscopy demonstrated the homogeneous distribution of nano-TiO2@DNA based coatings on the treated fabrics. The washing fastness tests evidenced the highly improved performance of hybrid coatings if compared with DNA alone. The flammability and cone calorimetry test results confirmed this positive synergy that resulted quite effective in slowing down (or even blocking) the propagation of a flame within the treated substrates and in improving the resistance of the fabrics to the applied heat flux, these latter leaving increased residues at the end of the test.

Methylation of Ir(iii)-tetrazolato complexes: an effective route to modulate the emission outputs and to switch to antimicrobial properties.

Two neutral cyclometalated Ir(iii)-tetrazolato complexes that differ by variations of the substituents on either the phenylpyridine or the tetrazolate ligand have been converted into the corresponding methylated and cationic analogues. NMR (1H and 13C) characterization of the Ir(iii) complexes provided the results in agreement with the chemo- and regioselective character of methylation at the N-3 position of the Ir(iii)-coordinated tetrazolato ring. This evidence was further corroborated by the analysis of the molecular structures of the cationic complexes obtained by X-ray diffraction. In view of the photophysical properties, the addition of a methyl moiety to neutral Ir(iii) tetrazolates, which behave as sky-blue or orange phosphors, caused a systematic red shift of their phosphorescence output. The transformation of neutral Ir(iii) tetrazolates into cationic Ir(iii)-tetrazole complexes was screened for any eventual antimicrobial activity in vitro against Gram negative (E. coli) and Gram positive (D. radiodurans) microorganisms. While both kinds of complexes were not active against E. coli, the conversion of the neutral Ir(iii) tetrazolates into the corresponding methylated and cationic Ir(iii)tetrazole derivatives determined the turn-on of a good to excellent antimicrobial activity toward Gram positive Deinococcus radiodurans, a non-pathogenic bacterium that is listed as one of the toughest microorganisms in light of its outstanding resistance to radiation and oxidative stress.