A framework for health-related nanomaterial grouping.

BACKGROUND: Nanotechnology has been in the limelight since its emergence and its products affect everyday lives. Nanomaterials are characterized by features such as size and shape, thus rendering their possible number essentially unlimited, which in turn makes them difficult to study and categorize regarding possible dangers. This work suggests that grouping could allow studying them with limited testing efforts without endangering safety. METHODS: Initially, the materials are identified and grouped according to their applications in health/medicine, as well as on their environmentally-friendly potential. The materials are then categorized using various toxicity classification methods to identify those with highest risks and group them with others that demonstrate similar behavior. RESULTS: The materials studied show promising uses in diagnostics, drug delivery, biosensors, water purification, oil spill cleaning, emission control and other fields. The toxicity risk assessment shows that the majority pose little to moderate risk, however there are certain materials that can be extremely hazardous or even cause death under specific circumstances. A risk mitigation plan was also developed. CONCLUSIONS: Nanomaterials applications, including drug delivery, cancer treatment, waste treatment, solar energy generation etc. can be very beneficiary, but at the same time, these materials can be extremely harmful or even cause death, thus making the need to prioritize research on high risk materials crucial. A clear regulatory framework that addresses both benefits and risks and communicates that information effectively should play an important part in European and worldwide efforts. GENERAL SIGNIFICANCE: The risk analysis validated the impression that there is limited research on nanomaterial toxicity risks, which calls for a more organized approach. The framework outlined in this work can be utilized by researchers as well as government bodies, in order to form regulatory policies and adopt a universally accepted labeling system. This article is part of a Special Issue entitled "Recent Advances in Bionanomaterials" Guest Editor: Dr. Marie-Louise Saboungi and Dr. Samuel D. Bader.

On the Formation of Nanobubbles in Vycor Porous Glass during the Desorption of Halogenated Hydrocarbons.

Vycor porous glass has long served as a model mesoporous material. During the physical adsorption of halogenated hydrocarbon vapours, such as dibromomethane, the adsorption isotherm exhibits an hysteresis loop; a gradual ascent is observed at higher pressures during adsorption, and a sharp drop is observed at lower pressures during desorption. For fully wetting fluids, an early hypothesis attributed the hysteresis to mechanistic differences between capillary condensation (adsorption) and evaporation (desorption) processes occurring in the wide bodies and narrow necks, respectively, of 'ink-bottle' pores. This was later recognized as oversimplified when the role of network percolation was included. For the first time, we present in-situ small angle x-ray scattering measurements on the hysteresis effect which indicate nanobubble formation during desorption, and support an extended picture of network percolation. The desorption pattern can indeed result from network percolation; but this can sometimes be initiated by a local cavitation process without pore blocking, which is preceded by the temporary, heterogeneous formation of nanobubbles involving a change in wetting states. The capacity of the system to sustain such metastable states is governed by the steepness of the desorption boundary.

New TiO2/MgAl-LDH nanocomposites for the photocatalytic degradation of dyes.

In this study we report the synthesis of a series of composite nanostructures comprising LDH and TiO2 phases. The materials characterization showed that the LDH crystallites are encapsulated inside the TiO2 matrix after the anatase seeds are deposited on MgxAl-LDHs. The structure in which LDH phase is embedded into anatase matrix is unique bringing important advantages to the photocatalytic performances of the nanocomposites. The photocatalytic activity of the prepared nanocomposites was tested on the degradation of the methylene blue (MB) in aqueous solution. The photocatalytic activities of the nanocomposites were compared with commercial TiO2 nanoparticles Degussa P25. The nanocomposites exhibited superior photocatalytic activity in basic environment because the negatively charged surface of TiO2 nanoparticles at high pH attracts the positively charged methylene blue species.

Multistep loading of titania nanoparticles in the mesopores of SBA-15 for enhanced photocatalytic activity.

A multistep deposition of anatase nanoparticles was employed to incorporate high amounts of titania into the mesopores of SBA-15. Anatase nanoparticles were synthesized and deposited following the Acid Catalyzed Sol Gel method. With this method, the size of the anatase nanoparticles can be controlled and therefore, the titania loading into the mesopores of SBA-15 can be controlled. Through multistep deposition of anatase nanoparticles, a further increase of titania loading into the mesoporous channels can be obtained. For the degradation of Rhodamine-6G, the samples synthesized by multistep deposition showed an enhanced photocatalytic activity.

Preparation and characterization of vanadium oxide deposited on thermally stable mesoporous titania.

Vanadium oxide was deposited on mesoporous titania by the molecular designed dispersion method to investigate the potential properties of these catalysts. Mesoporous titania was synthesized following the evaporation-induced self-assembly (EISA) method with a subsequent treatment with ammonia to increase the thermal stability. As a result, the mesoporous titania obtained shows a high surface area (approximately 350 m2/g) and high stability. Vanadium oxide was deposited by the MDD method using a vanadyl acetylacetonate complex that was transformed into VOx after a controlled calcination in air flow at 300 degrees C. The mesostructure and porosity characteristics of titania remain even until the maximum V-loading was reached (0.4 mmol/g), as it was shown by N2 sorption measurements at -196 degrees C. The catalysts were characterized by chemical analysis, Fourier transform infrared-photoacoustic spectroscopy (FTIR-PAS), UV-vis diffuse reflectance (DR), and Fourier transform Raman spectroscopy. Raman spectra showed isolated V species for the different V-containing catalysts. Furthermore, UV-vis-DR revealed a higher contribution of polymeric species as the V loading increases. The VOx/mesoporous titania catalysts were highly active in the selective catalytic reduction of NOx. A high activity in the NO conversion was observed, which increases with increasing metal loading.

Characterization of vanadium and titanium oxide supported SBA-15.

Supported vanadium and titanium oxide catalysts were prepared by adsorption and subsequent calcination of the vanadyl and titanyl acetylacetonate complexes, respectively, on mesoporous SBA-15 by the molecular designed dispersion (MDD) method. Liquid and gas phase depositions at different temperatures were carried out with vanadyl acetylacetonate, and the different results together with those of titanyl acetylacetonate in the liquid phase deposition were discussed. The bonding mechanism, the influence of the metal interaction with the support material, and differences due to the way of deposition and the temperature were investigated by TGA, chemical analysis, FTIR, and Raman spectroscopy. Elevated dissolving temperatures in the liquid phase led to higher final loadings on the SBA-15 without the formation of clusters, even at high loadings. The decomposition of the anchored vanadium and titanium complexes, their thermal stability, and the conversion to the covalently bound VO(x) and TiO(x) species on SBA-15 were studied and investigated by in situ transmission IR spectroscopy. In general, the titanium complex is more reactive than the vanadium complex toward the surface of SBA-15 and has a higher thermal stability. The MDD method of the VO(acac)2 and TiO(acac)2 enables to create a dispersed surface of supported VO(x) and TiO(x), respectively. The structure configurations of VO(x) and TiO(x) oxide catalysts obtained at different metal loadings were studied by Raman spectroscopy. Pore size distributions, XRD, and N2 sorption confirmed the structural stability of these materials after grafting. VO(x)/SBA-15 and TiO(x)/SBA-15 samples, with different metal loadings, were also catalytically tested for the selective catalytic reduction (SCR) of NO with ammonia.

Design and applications of a home-built in situ FT-Raman spectroscopic cell.

In the field of heterogeneous catalysis, in situ spectroscopy is one of the topics with growing interest. The characterization of a catalyst under working conditions is essential to identify the catalytic active site and to study the relation between the surface structure of a catalyst and its catalytic performance. For the first time, the design of an in situ spectroscopic cell for FT-Raman is presented and its performance is demonstrated by monitoring the thermal conversion of as synthesized mesoporous titanium and by characterizing the molecular surface structure of the vanadium oxides grafted on MCM-48 after exposure to a probe molecule. The results in both cases indicate that the in situ FT-Raman cell is a promising technique for characterizing the molecular surface structure of catalyst materials.

Post-synthesis deposition of V-zeolitic nanoparticles in SBA-15.

A post-synthesis deposition of vanadium silicalite-1 zeolite nanoparticles in the pores of SBA-15 results in a highly ordered hexagonal templated silica material with V-silicalite zeolitic plugs, giving rise to an increased crystallinity of the amorphous mesoporous walls.

Influence of polymer matrix and adsorption onto silica materials on the migration of alpha-tocopherol into 95% ethanol from active packaging.

In this study, the effect of polymer materials with different polarity, namely low density polyethylene (LDPE) and ethylene vinyl acetate (EVA), on the migration behaviour of alpha-tocopherol from active packaging was investigated. The antioxidant was also adsorbed onto silica materials, namely SBA-15 (Santa Barbara-15) and Syloblock, in order to protect the antioxidant during extrusion and to ensure a controlled and sufficient release during the shelf-life of the food product. Migration experiments were performed at 7.0 +/- 0.5 degrees C and 95% ethanol was used as fatty food simulant. All films contained a high concentration of alpha-tocopherol, approximately 2000 mg kg(-1), to obtain an active packaging. Polymer matrix had a small influence on the migration profile. The migration of 80% of total migrated amount of antioxidant was retarded for 2.4 days by using LDPE instead of EVA. When alpha-tocopherol was adsorbed onto both silica materials, the migration of 80% of total migrated amount of antioxidant was retarded for 3.4 days in comparison to pure alpha-tocopherol. No difference was seen between the migration profiles of alpha-tocopherol adsorbed onto both silica materials. In the case of pure alpha-tocopherol, 82% of the initial amount of alpha-tocopherol in the film migrated into the food simulant at a rather fast migration rate. In the case of adsorption on silica materials, a total migration was observed. These antioxidative films can have positive food applications.

A new strategy towards ultra stable mesoporous titania with nanosized anatase walls.

A new and generally applicable synthesis procedure is developed in order to synthesise micelle-templated mesoporous titania built up of nanosized anatase walls with thermal stability up to 600 degrees C.

Mesoporous templated silicates: an overview of their synthesis, catalytic activation and evaluation of the stability.

The most recent developments in the formation of new mesoporous templated zeolitic materials, characterized by surfaces of more than 1000 m(2)/g, are discussed in this paper. By adapting the synthesis parameters, such as type of silicium source, type of template, pH, temperature, em leader different materials can be synthesized with varying porosity and crystallinity. Besides the synthesis, much attention is focused on the activation of their surfaces by incorporation methods or deposition processes towards catalytic applications. Finally, the stability of the different materials, one of the critical parameters to potential industrial applications, is compared and evaluated.

Improvement of the hydrothermal stability of SAPO-34.

Hydrothermal stability of SAPO-34 is greatly improved by the treatment of the acidic form of the SAPO-34 with NH3.

Plugged hexagonal templated silica: a unique micro- and mesoporous composite material with internal silica nanocapsules.

We describe in this paper the development of plugged hexagonal templated silicas (PHTS) which are hexagonally ordered materials, with internal microporous silica nanocapsules; they have a combined micro- and mesoporosity and a tuneable amount of both open and encapsulated mesopores and are much more stable than other tested micellar templated structures.

The influence of humidity on the overall mass transfer coefficient of the Wheeler-Jonas equation.

The Wheeler-Jonas model is well known for its good prediction of breakthrough times for organic vapors on activated carbon beds. However, it is valid only in dry conditions: no prewetting of the filter and no humidity in the ambient air during use. One of the parameters that is likely to be influenced is the overall mass transfer coefficient kv. By measuring over 200 breakthrough times, with 7 different vapors on 4 different types of activated carbon, a simple but satisfactory model for the influence of moisture on kv was established. The only items of information needed, compared with the application of the Wheeler-Jonas equation under dry circumstances, are the water isotherm and the total pore volume of the activated carbon.

Estimating the overall mass transfer coefficient k(v) of the Wheeler-Jonas equation: a new and simple model.

The modified Wheeler-Jonas model is well known for its good prediction of breakthrough times for organic vapors on activated carbon beds. To use this model adequately one must estimate the overall adsorption rate coefficient kv. In this work a new equation is proposed to calculate kv. The relevant parameters of this equation are the airstream velocity, the affinity constant beta of the organic vapor, and the mean diameter of the carbon particles. Very accurate predictions were obtained for breakthrough times on a wide range of carbons using the calculated values of kv. Compared with other models, this model shows a higher accuracy and a lower degree of uncertainty.

Derangement of composite filler distribution inside syringe-type delivery systems.

Used and almost emptied syringes of two brands of composites contained material close to the pestle-head that appeared to be more granular and dry, as compared to the composite obtained from unused syringes. The present results suggest that a derangement of filler and matrix phases occurred inside the used syringes when compared to unused controls. Stress imposed on the composite material inside the unused syringes resulted in a comparable derangement of filler and matrix phases. Although this derangement was limited, the effect could contribute to intra- and interlaboratory scattering of data.

Waste water analysis by purge and trap capillary GC-FTIR spectrometry.

Gas chromatography with Fourier transform infra-red spectroscopic detection (GC-FTIR) is used for the analysis of waste water samples. Compared to GC-MS, this technique offers a more complete identification of organic compounds. Lower concentrations of organic volatiles however require preconcentration techniques such as a Purge and Trap (P&T) preconcentrator. Using this combination, concentrations of organic volatiles in the ppb range can be detected and positively identified.

The selectivity of a macrotetrolide electrode towards organic onium ions.

The selectivity for ammonium and some of its alkyl derivatives has been experimentally determined for a liquid-membrane ammonium electrode.