Exposure to nanoparticles derived from diesel particulate filter equipped engine increases vulnerability to arrhythmia in rat hearts.

Air pollution is well recognized as a central player in cardiovascular disease. Exhaust particulate from diesel engines (DEP) is rich in nanoparticles and may contribute to the health effects of particulate matter in the environment. Moreover, diesel soot emitted by modern engines denotes defective surfaces alongside chemically-reactive sites increasing soot cytotoxicity. We recently demonstrated that engineered nanoparticles can cross the air/blood barrier and are capable to reach the heart. We hypothesize that DEP nanoparticles are pro-arrhythmogenic by direct interaction with cardiac cells. We evaluated the internalization kinetics and the effects of DEP, collected from Euro III (DEPe3, in the absence of Diesel Particulate Filter, DPF) and Euro IV (DEPe4, in the presence of DPF) engines, on alveolar and cardiac cell lines and on in situ rat hearts following DEP tracheal instillation. We observed significant differences in DEP size, metal and organic compositions derived from both engines. DEPe4 comprised ultrafine particles (<100 nm) and denoted a more pronounced toxicological outcome compared to DEPe3. In cardiomyocytes, particle internalization is fastened for DEPe4 compared to DEPe3. The in-vivo epicardial recording shows significant alteration of EGs parameters in both groups. However, the DEPe4-instilled group showed, compared to DEPe3, a significant increment of the effective refractory period, cardiac conduction velocity, and likelihood of arrhythmic events, with a significant increment of membrane lipid peroxidation but no increment in inflammation biomarkers. Our data suggest that DEPe4, possibly due to ultrafine nanoparticles, is rapidly internalized by cardiomyocytes resulting in an acute susceptibility to cardiac electrical disorder and arrhythmias that could accrue from cellular toxicity. Since the postulated transfer of nanoparticles from the lung to myocardial cells has not been investigated it remains open whether the effects on the cardiovascular function are the result of lung inflammatory reactions or due to particles that have reached the heart.

Toxic metal sequential sequestration in water using new amido-aminoacid ligand as a model for the interaction with polyamidoamines.

Polyamidoamines are low cost and easily synthesized materials that may find applications in cations sequestration and water treatment. In this paper a new amido-aminoacid ligand containing methionine has been designed as a monomeric model of the corresponding polyamidoamine. The amido-aminoacid ligand has been synthesized in high yield, by reacting acrylamide and methionine via aza-Michael addition in water and mild temperature conditions. The reaction has been monitored by NMR and Raman spectroscopies and the crystal structure has been determined by X-ray diffraction analysis. The coordination ability of the ligand towards Cu2+ cations in water, as well as its affinity for Ni2+ and Co2+ has been studied by potentiometric and spectrophotometric techniques. The divalent metal cations sequestration from water may occur with sequential selection by changing the pH of the solution. The copper complex with two coordinated ligands has been fully characterized in the solid state by single crystal X-ray diffraction. The results are discussed with a view to use these materials in the treatment of water contaminated by toxic transition metal ions.

Ag-functionalized nanocrystalline cellulose for paper preservation and strengthening.

Waste paper is an environmentally friendly source of cellulosic material. Here we propose a new treatment based on nanocrystalline cellulose (CNC) for paper preservation and consolidation. Suspensions of CNC were prepared by sulfuric acid hydrolysis using waste paper as cellulose source (CNCWP) and compared with CNC from cotton linter (CNCCL). Both CNCs were obtained with good yield, showing high crystallinity index and comparable morphology, as demonstrated by DLS-ELS, XRD, FTIR, Raman and TEM analyses. CNCs were mixed with silver nanoparticles (CNC/Ag) and their biocidal activity was tested against Escherichia coli and Bacillus subtilis, measuring the minimum inhibitory concentration. CNCs were exploited as treatments for biocidal activity and consolidation on Whatman paper. The presence of silver nanoparticles doesn't affect aesthetic appearance of the original paper and prevents the growth of Aspergillus niger fungus. Mechanical tests demonstrated that the coatings by CNC based products improve stretch and toughness of the paper support.

3D printed chitosan scaffolds: A new TiO2 support for the photocatalytic degradation of amoxicillin in water.

TiO2-supported chitosan scaffolds (TiO2/CS) are here proposed as promising material for wastewater treatment, in particular for the removal of pharmaceutical compounds. TiO2/CS are tested for the amoxicillin photodegradation under UV/Vis irradiation. Amoxicillin (AMX) is an antibiotic of the beta-lactam family. Due to the release of antibiotics in wastewater and their persistence in the environment, harmful effects can develop on the aquatic and terrestrial organisms. TiO2 chitosan scaffolds with photocatalytic activity for wastewater remediation have been prepared by 3D printing using commercial P25-TiO2. The formulation for the 3D printer was prepared by dispersion of chitosan and TiO2 in powder form at the concentration 6% w/v and 1% w/v, respectively. The TiO2 particles (crystalline anatase and rutile phases) embedded in the chitosan have a size of about 20 nm, like in the starting material, as verified by X-ray diffraction and Raman spectroscopy and are homogeneously distributed in the scaffold, also after repeated photocatalytic tests, as revealed by SEM-EDS. The mechanical properties of the 3D structures are suitable for the targeted application as they can be easily handled without breakage. The AMX photodegradation efficiency under light irradiation by TiO2/CS made with scaffolds of different thicknesses (3, 5, 15 layers), was assessed in water by means of UV-Vis absorption and HPLC/UV measurements, at two different AMX:TiO2 molar ratios: 1/100 and 1/10. The 3D printed TiO2/CS system, even after repeated cycles, shows a high photodegradation efficiency, compared to the direct AMX photolysis. A zero-order kinetics for TiO2 supported photodegradation was found, whereas a pseudo-first order was observed for water dispersed TiO2. Mass spectrometry analysis revealed the presence of AMX degradates such as penilloic and penicilloic acids and diketopiperazine. The proposed 3D printed chitosan scaffolds may be used as reusable substrate for the TiO2 photocatalytic degradation of antibiotic pollutants in wastewater.

Bio-inspired consolidants derived from crystalline nanocellulose for decayed wood.

Novel bio-inspired materials derived from crystalline nanocellulose (CNC) have been tested as wood consolidants. A suspension of CNC, produced by acid hydrolysis of cellulose and used as such or mixed with lignin and/or siloxane derivatives (PDMS), was applied on rotted wood samples of Norway spruce. X-Ray diffraction analysis on CNC powder showed high crystallinity index. Dynamic light scattering (DLS) measurement indicated a nearly uniform particle size distribution with an average hydrodynamic diameter for pure CNC smaller than that in the mixtures. Raman and FTIR spectroscopies suggested interactions between lignin, PDMS and CNC components. The storage modulus of wood samples, measured by Dynamic Mechanical Analysis on the same specimen before and after consolidation, confirmed the efficiency of pure CNC, which displayed a considerable improvement of stiffness. A substantial increase of E' was observed particularly for most decayed classes. These results suggest a closer interaction between nanocellulose and decayed wood.

A comprehensive study of the magnetic properties of the pyroxenes series CaMgSi2O6-Co2Si2O6 as a function of Co content.

We report a detailed study on the magnetic properties of the pyroxene series M2M1Si2O6, with M2 = Ca and M1 = Mg, where magnesium and then calcium are progressively substituted by cobalt. For cobalt site occupancy larger than 0.7 at the M1 site, a collinear antiferromagnetic phase is detected for T < T N1 = 12 K with a monodimensional character (i.e. M1 site intra-chain order parallel to c axis). Moreover the magnetization easy axis has been estimated to lie roughly along the [1 0 1] direction. Cobalt content ⩾0.5 at the M2 site (overall content 1.5) determines the formation of a new independent antiferromagnetic order with higher Néel temperature, involving only the M2 site intra-chain interactions. The incoming M2 site order is accompanied by a lowering of the space symmetry which yields to a weakly ferromagnetic resultant due to spin canted distribution of the magnetic moments either along the M1 or M2 chains. Furthermore, metamagnetic transitions are observed for both M1 and M2 site intra-chain orders at relatively low critical magnetic fields, around 2 T, suggesting that this series of pyroxenes can be used as a model system for investigating the fundamental aspects of magnetism in the matter.

Raman spectroscopy as a PAT for pharmaceutical blending: Advantages and disadvantages.

Raman spectroscopy has been positively evaluated as a tool for the in-line and real-time monitoring of powder blending processes and it has been proved to be effective in the determination of the endpoint of the mixing, showing its potential role as process analytical technology (PAT). The aim of this study is to show advantages and disadvantages of Raman spectroscopy with respect to the most traditional HPLC analysis. The spectroscopic results, obtained directly on raw powders, sampled from a two-axis blender in real case conditions, were compared with the chromatographic data obtained on the same samples. The formulation blend used for the experiment consists of active pharmaceutical ingredient (API, concentrations 6.0% and 0.5%), lactose and magnesium stearate (as excipients). The first step of the monitoring process was selecting the appropriate wavenumber region where the Raman signal of API is maximal and interference from the spectral features of excipients is minimal. Blend profiles were created by plotting the area ratios of the Raman peak of API (AAPI) at 1598cm-1 and the Raman bands of excipients (AEXC), in the spectral range between 1560 and 1630cm-1, as a function of mixing time: the API content can be considered homogeneous when the time-dependent dispersion of the area ratio is minimized. In order to achieve a representative sampling with Raman spectroscopy, each sample was mapped in a motorized XY stage by a defocused laser beam of a micro-Raman apparatus. Good correlation between the two techniques has been found only for the composition at 6.0% (w/w). However, standard deviation analysis, applied to both HPLC and Raman data, showed that Raman results are more substantial than HPLC ones, since Raman spectroscopy enables generating data rich blend profiles. In addition, the relative standard deviation calculated from a single map (30 points) turned out to be representative of the degree of homogeneity for that blend time.

Raman and NMR kinetics study of the formation of amidoamines containing N-hydroxyethyl groups and investigations on their Cu(II) complexes in water.

Three amidoamines containing the N-hydroxyethyl group (HOEt), namely (HOEt)2N(CH2)2C(O)NH2 (1), [(HOEt)2N(CH2)2C(O)NH]2CH2 (2) and HOEtN[(CH2)2C(O)NH2]2 (3) have been synthesized by reacting diethanolamine HOEt2NH with acrylamide and N,N'-methylenebisacrylamide (respectively 1 and 2) and ethanolamine HOEtNH2 with acrylamide (3). Four other compounds corresponding to 1 and 2, but derived from sec-amines Me2NH (4 and 5) and Et2NH (6 and 7) have been prepared for the sake of comparison of the spectroscopic features. All compounds have been obtained by the well-known aza-Michael addition between an N-nucleophile and an activated vinyl group. The reaction in water between diethanolamine and acrylamide leading to 1 has been monitored in situ by Raman and NMR spectroscopy, both techniques confirming second order kinetics and giving values for kinetic constants in excellent agreement. The coordination ability of 1 and 2 towards Cu2+ in water has been studied by the Job's plot method. Spectroscopic data indicate that ligand 1 prevalently forms a 4:1 Ligand/Metal complex with a (N,O3) coordination set on the equatorial plane of Cu2+, whereas ligand 2, containing two amide functionalities bridged by a methylene group, appears able to form a 1:1 Ligand/Metal chelate species, again with a (N,O3) donor set around copper.

Raman Investigation of Precious Jewelry Collections Preserved in Paolo Orsi Regional Museum (Siracusa, Sicily) Using Portable Equipment.

This work is a part of a large scientific project aimed at highlighting the potential of portable Raman equipment in characterizing jewelry materials preserved in museums, carried out in collaboration with gemologists and archeologists. In detail, we report the results of a measurement campaign performed for the study of gems and jewels preserved in the well-known Medagliere section at the Paolo Orsi Regional Museum of Siracusa (Sicily). The studied materials consist of exquisite examples of engraved loose gems and really rare examples of Hellenistic-Roman jewels, mainly coming from relevant Sicilian archaeological sites. Portable Raman measurements have been carried out using two instruments equipped with different excitation wavelengths. The obtained results have allowed for a complete characterization of the studied gemological materials, also suggesting sometimes misclassification for some valuable objects and gems.

Oxidative and pro-inflammatory effects of cobalt and titanium oxide nanoparticles on aortic and venous endothelial cells.

Ultra-fine particles have recently been included among the risk factors for the development of endothelium inflammation and atherosclerosis, and cobalt (CoNPs) and titanium oxide nanoparticles (TiNPs) have attracted attention because of their wide range of applications. We investigated their toxicity profiles in two primary endothelial cell lines derived from human aorta (HAECs) and human umbilical vein (HUVECs) by comparing cell viability, oxidative stress, the expression of adhesion molecules and the release of chemokines during NP exposure. Both NPs were very rapidly internalised, and significantly increased adhesion molecule (ICAM-1, VCAM-1, E-selectin) mRNA and protein levels and the release of monocyte chemoattractant protein-1 (MCP-1) and interleukin 8 (IL-8). However, unlike the TiNPs, the CoNPs also induced time- and concentration-dependent metabolic impairment and oxidative stress without any evident signs of cell death or the induction of apoptosis. There were differences between the HAECs and HUVECs in terms of the extent of oxidative stress-related enzyme and vascular adhesion molecule expression, ROS production, and pro-inflammatory cytokine release despite the similar rate of NP internalisation, thus indicating endothelium heterogeneity in response to exogenous stimuli. Our data indicate that NPs can induce endothelial inflammatory responses via various pathways not involving only oxidative stress.

Titanium dioxide nanoparticles promote arrhythmias via a direct interaction with rat cardiac tissue.

BACKGROUND: In light of recent developments in nanotechnologies, interest is growing to better comprehend the interaction of nanoparticles with body tissues, in particular within the cardiovascular system. Attention has recently focused on the link between environmental pollution and cardiovascular diseases. Nanoparticles <50 nm in size are known to pass the alveolar-pulmonary barrier, enter into bloodstream and induce inflammation, but the direct pathogenic mechanisms still need to be evaluated. We thus focused our attention on titanium dioxide (TiO2) nanoparticles, the most diffuse nanomaterial in polluted environments and one generally considered inert for the human body. METHODS: We conducted functional studies on isolated adult rat cardiomyocytes exposed acutely in vitro to TiO2 and on healthy rats administered a single dose of 2 mg/Kg TiO2 NPs via the trachea. Transmission electron microscopy was used to verify the actual presence of TiO2 nanoparticles within cardiac tissue, toxicological assays were used to assess lipid peroxidation and DNA tissue damage, and an in silico method was used to model the effect on action potential. RESULTS: Ventricular myocytes exposed in vitro to TiO2 had significantly reduced action potential duration, impairment of sarcomere shortening and decreased stability of resting membrane potential. In vivo, a single intra-tracheal administration of saline solution containing TiO2 nanoparticles increased cardiac conduction velocity and tissue excitability, resulting in an enhanced propensity for inducible arrhythmias. Computational modeling of ventricular action potential indicated that a membrane leakage could account for the nanoparticle-induced effects measured on real cardiomyocytes. CONCLUSIONS: Acute exposure to TiO2 nanoparticles acutely alters cardiac excitability and increases the likelihood of arrhythmic events.

Synthesis and characterization of nanocrystalline TiO2 with application as photoactive coating on stones.

UNLABELLED: Self-cleaning photocatalytic coatings for biocalcarenite stones, based on TiO2 nanoparticles obtained by sol-gel processes at different pH values and also adding gold particles, have been investigated. The selected test material is a biocalcarenite named "pietra di Lecce" (Lecce stone), outcropping in Southern Italy. Scanning electron microscopy with energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray diffraction, and Raman investigations were carried out to characterize the TiO2 nanoparticles and coatings. Nanocrystalline anatase and, to a lesser extent, brookite phases are obtained. Photocatalytic activity of the TiO2 sols and of the coatings on "pietra di Lecce" was assessed under ultraviolet irradiation, monitoring methyl orange (MeO) dye degradation as a function of time. To evaluate the harmlessness of the treatment, colorimetric tests and water absorption by capillarity were performed. The results show good photodegradation rates for titania nanosols, particularly when putting in Au particles, whereas a satisfactory chromatic compatibility between the sol and the surface of the calcarenite is found only without Au addition. HIGHLIGHTS: Sols of nanocrystalline titania at different pH values and with Au particles were prepared and characterized. Satisfactory photodegradation of MeO by the sols in solution and on calcarenite-coated surfaces is obtained. The addition of Au particles improves the photodegradation activity but gives poor chromatic results on "pietra di Lecce."

Micro-Raman study of copper hydroxychlorides and other corrosion products of bronze samples mimicking archaeological coins.

Three bronze samples created by CNR-ISMN (National Research Council-Institute of Nanostructured Materials) to be similar to Punic and Roman coins found in Tharros (OR, Sardinia, Italy) were studied to identify the corrosion products on their surfaces and to evaluate the reliability of the reproduction process. Micro-Raman spectroscopy was chosen to investigate the corroded surfaces because it is a non-destructive technique, it has high spatial resolution, and it gives the opportunity to discriminate between polymorphs and to correlate colour and chemical composition. A significant amount of green copper hydroxychlorides (Cu(2)(OH)(3)Cl) was detected on all the coins. Their discrimination by Raman spectroscopy was challenging because the literature on the topic is currently confusing. Thus, it was necessary to determine the characteristic peaks of atacamite, clinoatacamite, and the recently discovered anatacamite by acquiring Raman spectra of comparable natural mineral samples. Clinoatacamite, with different degrees of order in its structure, was the major component identified on the three coins. The most widespread corrosion product, besides hydroxychlorides, was the red copper oxide cuprite (Cu(2)O). Other corrosion products of the elements of the alloy (laurionite, plumbonacrite, zinc carbonate) and those resulting from burial in the soil (anatase, calcite, hematite) were also found. This study shows that identification of corrosion products, including discrimination of copper hydroxychlorides, could be accomplished by micro-Raman on valuable objects, for example archaeological findings or works of art, avoiding any damage because of extraction of samples or the use of a destructive analytical technique.

Applications of Raman spectroscopy to gemology.

Being nondestructive and requiring short measurement times, a low amount of material, and no sample preparation, Raman spectroscopy is used for routine investigation in the study of gemstone inclusions and treatments and for the characterization of mounted gems. In this work, a review of the use of laboratory Raman and micro-Raman spectrometers and of portable Raman systems in the gemology field is given, focusing on gem identification and on the evaluation of the composition, provenance, and genesis of gems. Many examples are shown of the use of Raman spectroscopy as a tool for the identification of imitations, synthetic gems, and enhancement treatments in natural gemstones. Some recent developments are described, with particular attention being given to the semiprecious stone jade and to two important organic materials used in jewelry, i.e., pearls and corals.

The effect of water on particle size, porosity and the rate of drug release from implanted titania reservoirs.

The implantation of controlled drug release devices represents a new strategy in the treatment of neurodegenerative disorders. Sol-gel titania implants filled with valproic acid, have been used for this purpose to treat induced epilepsy in rats. The kinetics of the drug release depend on: (a) porosity, (b) chemical interactions between valproic acid and surface hydroxyl groups of titania, (c) particle size, and (d) particle size agglomerates. The concentration of water used in the hydrolysis reaction is an important variable in the degree of porosity, hydroxylation, and structural defects of the nanostructured titanium oxide reservoir. The titanium n-butoxide/water ratio was systematically varied during the sol-gel synthesis, while maintaining the amount of valproic acid constant. Characterization studies were performed using DTA-TGA, FTIR, Raman, TEM, SEM, BET, and in vitro release kinetic measurements. The particle agglomerate size and porosity were found to depend on the amount of water used in the sol-gel reaction.

Micro-Raman spectroscopy as a routine tool for garnet analysis.

A rapid system to obtain molar compositions of minerals belonging to the garnet group by means of Raman spectroscopy is illustrated here. A series of standard garnets, whose composition was determined by means of Wavelength Dispersive System (WDS) electron microprobe measurements, was used to correlate the wavenumbers of the different Raman peaks with chemical composition. A simple software routine was then developed in order to obtain garnet molar composition starting from the Raman spectrum, based on the assumption that in a solid solution belonging to the garnet family the Raman wavenumbers are linear combinations of end member wavenumbers, weighted by their molar fraction. The choice of the Raman bands used for the calculations and their behaviour are also discussed. The method, called MIRAGEM (Micro-Raman Garnets Evaluation Method), was then tested on a second series of garnets with satisfactory results.

Green pigments of the Pompeian artists' palette.

Green colored samples on wall paintings and green powder from a pigment pot found in Pompeii area are investigated by micro-Raman, FT-IR and, for one sample, SEM-EDX. To obtain the green color, green earths and malachite were used, together with mixture of Egyptian blue and yellow ochre. The mineralogical identification of the green earths has been attempted through the comparison of the vibrational features, discriminating between celadonite and glauconite spectra. Traces of a modern synthetic pigment containing copper phthalocyanine were found in a fresco fragment.

Polarization holographic gratings in hybrid solgel films doped with Disperse Red 1.

Polarization holographic gratings in sp configuration are written at 488 nm in photorefractive organic-inorganic films based on SiO2. The films, prepared by a solgel technique, contain Disperse Red 1, carbazole units, and 2,4,7-trinitro-9-fluorenone. The gratings are characterized by their diffraction efficiency for a 632.8-nm probe. The polarization gratings act as a half-wave plate, and the diffraction efficiency is independent of the polarization direction of the probe.

Raman microspectrometric investigation of wall paintings in S. Giovanni Evangelista Abbey in Parma: a comparison between two artists of the 16th century.

Micro-Raman spectroscopy, combined with gas chromatography and ultra-violet fluorescence photography, was used to study some wall paintings in the S. Giovanni Evangelista Abbey in Parma, Italy. The restoration of some painted chapels enabled a comparison between two painters of the 16th century: Parmigianino (Girolamo Francesco Maria Mazzola, 1503-1540) and Michelangelo Anselmi (1492?-1556?). Micro-Raman spectroscopy determined the palette used by the artists, leading to the identification of different white, yellow, red, brown, green, blue and black pigments. Some pigments are evidence of later restorations. Gas chromatography combined with mass spectroscopy revealed the presence of organic binding media and enabled to distinguish between fresco and secco paintings.