Characterization of aluminum, aluminum oxide and titanium dioxide nanomaterials using a combination of methods for particle surface and size analysis B. Krause, T. Meyer, H. Sieg, C. Kästner, P. Reichardt, J. Tentschert, H. Jungnickel, I. Estrela-Lopis, A. Burel, Soizic Chevance, et al. To cite this version: B. Krause, T. Meyer, H. Sieg, C. Kästner, P. Reichardt, et al.. Characterization of aluminum, alu- minum oxide and titanium dioxide nanomaterials using a combination of methods for particle sur- face and size analysis. RSC Advances, Royal Society of Chemistry, 2018, 8 (26), pp.14377 - 14388. 10.1039/c8ra00205c. anses-01787430 HAL Id: anses-01787430 https://hal-anses.archives-ouvertes.fr/anses-01787430 Submitted on 7 May 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Distributed under a Creative Commons Attribution - NonCommercial| 4.0 International License RSC Advances View Article Online PAPER View Journal | View Issue Characterization of aluminum, aluminum oxide and titanium dioxide nanomaterials using Cite this: RSC Adv.,2018,8,14377 a combination of methods for particle surface and size analysis† a b c d a a B. Krause, * T. Meyer, H. Sieg, C. Kastner,¨ P. Reichardt, J. Tentschert, H. Jungnickel,a I. Estrela-Lopis,b A. Burel,e S. Chevance, f F. Gauffre, f P. Jalili,g h c c d i J. Meijer, L. Bohmert,¨ A. Braeuning, A. F. Thunemann,¨ F. Emmerling, V. Fessard,g P. Laux, a A. Lampenc and A. Luch a The application of appropriate analytical techniques is essential for nanomaterial (NM) characterization. In this study, we compared different analytical techniques for NM analysis. Regarding possible adverse health effects, ionic and particulate NM effects have to be taken into account. As NMs behave quite differently in physiological media, special attention was paid to techniques which are able to determine the biosolubility Creative Commons Attribution-NonCommercial 3.0 Unported Licence. and complexation behavior of NMs. Representative NMs of similar size were selected: aluminum (Al0) and aluminum oxide (Al2O3), to compare the behavior of metal and metal oxides. In addition, titanium dioxide (TiO2) was investigated. Characterization techniques such as dynamic light scattering (DLS) and nanoparticle tracking analysis (NTA) were evaluated with respect to their suitability for fast characterization of nanoparticle dispersions regarding a particle's hydrodynamic diameter and size distribution. By application of inductively coupled plasma mass spectrometry in the single particle mode (SP-ICP-MS), individual nanoparticles were quantified and characterized regarding their size. SP-ICP-MS measurements were correlated with the information gained using other characterization techniques, i.e. This article is licensed under a transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). The particle surface as an important descriptor of NMs was analyzed by X-ray diffraction (XRD). NM impurities and their co- Received 8th January 2018 localization with biomolecules were determined by ion beam microscopy (IBM) and confocal Raman Accepted 22nd March 2018 ff Open Access Article. Published on 17 April 2018. Downloaded 07/05/2018 13:52:49. microscopy (CRM). We conclude advantages and disadvantages of the di erent techniques applied and DOI: 10.1039/c8ra00205c suggest options for their complementation. Thus, this paper may serve as a practical guide to particle rsc.li/rsc-advances characterization techniques. Introduction may result from a high surface area,3,4 specic surface coatings5 or a surface charge.6–8 An important factor for increasing their The specic properties of NMs depend on their physicochemical activity is the self-assembly of NMs. Here, NMs associate via non- characteristics. Optical properties build upon the size, the shape covalent interactions resulting in organized structures of higher- and the surface structure,1,2 while higher reactivity, for example, order. Different applications based on advanced functions were aGerman Federal Institute for Risk Assessment (BfR), Department of Chemical and hFelix Bloch Institute for Solid State Physics, Faculty of Physics and Geosciences, Product Safety, Max-Dohrn-Straße 8-10, 10589 Berlin, Germany. E-mail: Division of Nuclear Solid State Physics, University of Leipzig, Linn´estraße 5, [email protected] 04103 Leipzig, Germany bInstitute of Medical Physics and Biophysics, University of Leipzig, Hartelstrasse€ 16- iFederal Institute for Materials Research and Testing (BAM), Richard-Willstatter-¨ 18, 04275 Leipzig, Germany Straße 11, 12489 Berlin, Germany cGerman Federal Institute for Risk Assessment (BfR), Department of Food Safety, † Electronic supplementary information (ESI) available: NTA size distributions 0 0 Max-Dohrn-Straße 8-10, 10589 Berlin, Germany for Al ,Al2O3, NM103, NM104, DLS number-based distribution for Al ,Al2O3, d 0 Federal Institute for Materials Research and Testing (BAM), Unter den Eichen 87, NM103, NM104, TEM measurement of TiO2 NMs in DMEM, SAXS data for Al , 12205 Berlin, Germany Al2O3 and AlCl3 in BSA and DMEM aer 24 and 48 h, impurities of used NMs eMRIC TEM BIOSIT, Universit´e de Rennes 1, 2 av pro Leon Bernard, France determined by IBM, aluminium aqua complexes at different pH values, CRM fUniv Rennes, CNRS, ISCR UMR6226, F-35000 Rennes, France surface investigations, colocalization pattern by IBM for Al2O3, CRM spectra gANSES, French Agency for Food, Environmental and Occupational Health and displaying protein modi cations, ToF-SIMS measurements of Al and Al2O3 Safety, Foug`eres Laboratory, 10B rue Claude Bourgelat, 35306, Foug`eres Cedex, NMs in DMEM, ToF-SIMS measurements of TiO2 NMs in DMEM. See DOI: France 10.1039/c8ra00205c This journal is © The Royal Society of Chemistry 2018 RSC Adv.,2018,8,14377–14388 | 14377 View Article Online RSC Advances Paper reported, for example formation of mesoporous TiO2 mediated investigation, XRD was used to test whether the aluminum was 0 by ionic liquids for solar cell conversion, catalysis or electronic already oxidized. The core diameter of Al ,Al2O3 and both TiO2 devices.9–11 Another application is the self-assembly of biomole- NMs was measured by SP-ICP-MS. These results were compared cules, like lipids and proteins, mediating inner-particle meso- to TEM measurements. As a further technique for estimation of 12 porosity in a macroporous TiO2 structure. the core diameter, SAXS was applied. Additionally, IBM and TiO2 NMs are classied as granular biodurable particles CRM were performed to analyze the interaction of NMs with (GBPs) of low toxicity.13 They occur in the form of anatase or biomolecules as well as to quantify impurities in the NM rutile as well as in mixtures thereof. While signicant accu- composition. ToF-SIMS is capable of visualizing the formation 0 mulation was shown in the liver of rats in the case of orally of complexes out of Al and Al2O3 NMs with components of the 14 ff 0 administered TiO2 NMs, this was di erent in studies with Al environmental media. This allows investigation of the behavior NMs in mice, in which predominant accumulation in the brain, of NMs within physiological uids such as CCM. thymus and lung was revealed.15 Characterization is important With respect to uptake, the dissolution of NMs in different for both in vitro and in vivo studies. Currently, the human health media is of high importance. For example, during an articial risk assessment of NMs is mainly based on in vivo experiments digestion procedure, different pH values, as well as proteins, in rodents.16,17 However, due to the high number of new NMs,18 enzymes and other compounds, mimic the oral uptake route for 0 it is not ethical or feasible to conduct such studies for each NMs. For Al and Al2O3 NMs, an increased dissolution within individual NM. On the other hand, in vitro systems proved the gastric environment was noticed.24 However, to properly useful, e.g. to generate high throughput data.19 Extrapolation to interpret and compare the results, precise knowledge of the the in vivo situation remains limited, in particular due to the properties of the starting materials and of their state in CCM is insufficient comparability of applied dose and particle required. Although there are a lot of studies dealing with silver biotransformation.20,21 An accurate characterization of NMs in and copper-containing NMs and their dissolution behavior in in vitro systems by the application of up-to-date analytical biological media,25–27 to our knowledge, no study accounts for 0 Creative Commons Attribution-NonCommercial 3.0 Unported Licence. methods may therefore help to establish reliable methods for Al NMs. Furthermore, the dissolution behavior of aluminum- determination of nanomaterial uptake and translocation as key containing nanomaterials may be very different since parameters that affect NM-related toxicity. Such an approach aluminum ions already have a different complexation behavior would therefore help to reduce the number of materials that compared to silver or copper ions. By means of the methods need to