Synthetic Aspects of Nanoporous and Nanohybrid Materials Kazuyuki Kuroda

Department of Applied Chemistry and Kagami Memorial Research Institute for Materials Science and

Technology, Faculty of Science & Engineering, Waseda University, Ohkubo-3, Shinjuku-ku, Tokyo 169-8555,

JAPAN

kuroda@waseda.jp

Applications of nanomaterials depend on their functions that are governed by various

hierarchical factors from the electronic structure of atoms to macroscopic factors. Synthetic aspects of nanoporous and nanohybrid materials are essential to the development of nanotechnology. So called building block approaches are effective to design nanomaterials. While synthetic organic chemistry has established precise synthetic strategies for very complex organic and bioactive substances, precise synthetic chemistry of hybrid and porous nanomaterials has not yet been fully developed. Building block approaches should be further studied to establish the strategies for designing nanomaterials. The dimensionality and size of building blocks are important for such precise syntheses.1

Inorganic-organic nanohybrids are often used as precursors for nanoporous materials. By removing organic fractions inorganic nanoporous materials can be prepared. Much more opportunities will be expected by appropriate combination of inorganic and organic components. Mesoporous silica nanoparticles (MSN) should have high potentiality for various applications.2 Alkoxysilanes with different alkyl chain lengths have different hydrolysis rates, which can be used for the preparation of colloidal mesoporous silica nanoparticles with controlled particle diameters. Mesoporous silica thin films with ordered mesopores for possible optical applications can also be prepared under controlled conditions.3 Pt nanoparticles encapsulated in mesoporous silica was reported to be an excellent catalyst for ethylene oxidation,4 which is very useful for keeping the freshness of vegetables. Sub-10-nm patterning is also a hot topic and the preparation method via directed self-assembly is growing. These recent findings are useful and stimulating for future developments in nanomaterials.

References 1. K. Kuroda, A. Shimojima, K. Kawahara, R. Wakabayashi, Y. Tamura, Y. Asakura, M. Kitahara, Chem.

Mater. (2014), 26, 211-220. 2. E. Yamamoto, K. Kuroda, Bull. Chem. Soc. Jpn. (2016), 89, 501-539 (Open Access). 3. S. Kitamura, Y. Kanno, M. Watanabe, M. Takahashi, K. Kuroda, H. Miyata, ACS Photonics (2014), 1,

47-52. 4. C. Jiang, K. Hara, A. Fukuoka, Angew. Chem. Int. Ed. (2013), 52, 6265-6268.

Multifunctional Mesoporous Silica Nanoparticles Controlled by Nanomachines for Biomedical Targeting, Imaging and Drug Delivery

Jeffrey I. Zink Department of Chemistry and Biochemistry

University of California, Los Angeles (UCLA) Los Angeles, California 90095 USA

The subjects of this talk are multifunctional nanoparticles controlled by nanomachines for targeting, imaging and drug delivery in cells and in vivo. The nanoparticles are designed to 1) trap therapeutic molecules inside of nanocarriers, 2) carry therapeutics to the site of the disease with no leakage, 3) release a high local concentration of drugs, 4) release only on command either autonomous or external, and 5) kill the cancer or infectious organism. The most important functionality is the ability to trap molecules in the pores and release them in response to desired specific stimuli. Two types of external stimuli will be discussed: light and oscillating magnetic fields. Activation by internal biological stimuli such as pH changes, redox potential changes and enzymes will also be presented. Molecular machines based on molecules that undergo large amplitude motion when attached to mesoporous silica - impellers, snap-tops and valves will be described. Derivatized azobenzene molecules, attached to the interior pore walls function as impellers that can move other molecules through the pores. Nanoparticles containing anticancer drugs in the mesopores are taken up by cancer cells, and optical stimulation of the impellers drives out the toxic molecules and kills the cells. Snap-tops with cleavable stoppers release cargo molecules when the stopper is removed from the pore entrance. Nanovalves consisting of rotaxanes and pseudorotaxanes placed at pore entrances can trap and release molecules from the pores in response to stimuli. Activation of these nanodevices by the five types of stimuli in solution, in living cells, and in animal models will be discussed. Applications to treatments of cancers (including pancreatic and breast) and of intracellular infectious diseases (including tuberculosis and tularemia) will be presented.

Mesoporous oxide films as nano-reactors for building photoluminescent nanostructures

Diego A. Onna, Mara Luz Martnez-Ricci, Sara A. Bilmes

Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Qumica Inorgnica, Analtica y Qumica-Fsica (DQIAQF), Instituto de Qumica Fsica de los Materiales, Medio Ambiente y Energa(INQUIMAE,UBA-CONICET) Ciudad Universitaria Pab. II, Ciudad de Buenos Aires, Argentina

Luminescent materials in nanostructures are envisaged as scaffolds for the design of multifunctional devices. However, most of them are toxic for humans and involve the use of low-abundance elements with costly and environmental non-friendly mining. Here we propose the use of nanostructures made of reproducible ordered mesoporous oxides films (OMPO) containing luminescent nanoparticles as building blocks for more complex composite structures. The advantage of this approach is the reduced amount of heavy metals involved, as well as providing fixed nanoparticles in an inert matrix.

The main idea of this work is to obtain efficient luminescent materials using pores in a OMPO as nano-reactors for precipitation reactions, controlling the size of nanoparticles (NPs) grown inside pores.

Using each pore as a single nano-reactor, an environmentally friendly synthesis was carried out by successive immersions in solutions of the appropriate precursors. Special attention was paid to the role of solvent, precursors and pH in the nucleation and growth mechanism inside pores leading to optimized photoluminescence. This approach was successfully carried out for semiconductor (CdS and ZnS) Q-dots and YVO4:X (X= Eu; Yb:Er; Yb:Ho) nanophosphors embedded in a Silica, Zirconia or Titania matrices. Intense and tunable luminescence was achieved for Q-dots after aging and/or photoactivation, even the very low mass amounts. Nanophosphors synthesized inside pores also exhibit photoluminescence, as well as up-conversion.

In addition to probing the feasibility of building complex luminescent nanostructures, in this work we discuss the mechanism of nucleation and growth of NPs inside pores and how to control of photoluminescent emission.

Contrast media for multimodal imaging through MRI and spectral photon counting CT scanner

Frederic Lerouge1, Niki Halttunen1, Frederic Chaput1, Stephane Parola1,

Marlne Wiart2, Yves Berthezne3, Daniel Barness3, Monica Sigovan3, Salim Si-Mohamed3, Loic Boussel3, Philippe Douek3

1Univ Lyon, Ens de Lyon, CNRS UMR 5182, UCB Lyon 1, Laboratoire de Chimie, France

2CarMeN, Inserm U1070, CNRS, Universit de Lyon 3CREATIS, UMR CNRS 5220, U630 Inserm, Hpital Neuro-cardiologique, Lyon

Magnetic Resonance Imaging (MRI) is a powerful modality allowing accurate diagnostics thanks to its high resolution. Because of it lower sensitivity, it is oftenly combined with Computed Tomography scanner (CT Scan). Spectral Photon Counting Computed Tomography (SPCCT) is a new imaging modality, currently in development. The SPCCT scanner is an evolution of the conventional CT scanner, with a totally new type of detection chain designed to provide high count-rate capabilities while offering energy discrimination with high spatial resolution (fig 1).

Fig. 1 : Contrast agents discrimination between classical CT and K-edge.

Its main asset is the ability to map and quantify elements based on their K-edge. For that modality, the traditional iodine based contrast agents are not particularly suited due to iodines low K-edge, the use of new types of contrast agents is therefore necessary.

We are focussing our interest on the synthesis and the study of contrast agents suitable for both imaging modalities MRI and SPCCT. In that context, rare earth fluoride nanoparticles are of particular interest since they show good relaxivity making them suitable for MRI and their composition make them the tools of choice for k-edge imaging. This work focusses on the design of hybrid nanoparticles with a gadolinium or holmium fluoride core (GdF3 and HoF3) grafted with PEG ligands. These particles are currently used as blood pool imaging agents, sensitivity results and biodistribution studies after in vivo injection will also be described.

3D printing of hydrogels incorporating biomolecules: from cm towards nm Cline A. Mandon, Chlo D. Devillard, Loc J. Blum, Christophe A. Marquette

Univ Lyon, Universit Lyon1, CNRS, INSA, CPE-Lyon, ICBMS, UMR 5246, 43, Bd du 11 novembre 1918, 69622 Villeurbanne cedex, France;

celine.mandon@univ-lyon1.fr; Chloe.devillard@etu.univ-lyon1.fr; loic.blum@univ-lyon1.fr; christophe.marquette@univ-lyon1.fr

Additive manufacturing processes and more specifically 3D printing generate new paradigm within the biotechnology engineers community. Indeed, the availability of new printing technologies, new materials and processes, but more often the access to unprecedented sensing layer complex geometries, initiate profound mutation of the biosensor developers way of thinking. As exemplarities of these mutations, new possibilities in active biomolecule immobilization strategies, new biosensor designs, 3D complex cell culture and tissue engineering were identified [1]. Our group have been working on this new paradigm for the last 2 years, digging deeply into the 3D printing technologies and ink formulation to achieve complex 3D objects having interest in healthcare field such as biosensing systems and biochips development. These smart objects, having catalysis, recognition or fluidic abilities are then named 4D printed objects (figure 1). From a technological point of view, 4D objects were produced either composed of printed living cells evolving into human tissues [2] or printed using inks composed of photopolymers bearing active biomolecules, such as enzymes, antibodies or cell adhesion proteins; directly integrated into hydrogels. The integration of multiple additive manufacturing technologies (mainly 3D printing) is use to integrate bioactive molecules and demonstrate the capacity of the 4D printing to generate interesting objects having i) complex architectures unreachable using standard manufacturing techniques, ii) enhanced biorecognition abilities but also iii) new or multiple functions such as mobility, multicomponent complex structures. Examples will be given of multiple protein markers detection, glucose sensing, immunosensors, cell chip and microfluidic components.

Figure 1: From 1D to 4D concept.

References 1. C.A. Mandon, L.J. Blum, and C.A. Marquette, Adding Biomolecular Recognition Capability to 3D Printed

Objects Anal. Chem., 2016, 88 (21), pp 1076710772 2. L. J. Pourchet, A. Thepot, M. Albouy, E. J. Courtial, A. Boher, L. J. Blum, C. A. Marquette, Human Skin 3D

Bioprinting Using Scaffold-Free Approach Adv. Healthcare Mater. (2017), Volume 6, Issue 4, 1601101

mailto:celine.mandon@univ-lyon1.frmailto:Chloe.devillard@etu.univ-lyon1.frmailto:loic.blum@univ-lyon1.frmailto:christophe.marquette@univ-lyon1.frhttp://pubs.acs.org/doi/abs/10.1021/acs.analchem.6b03426http://pubs.acs.org/doi/abs/10.1021/acs.analchem.6b03426http://onlinelibrary.wiley.com/doi/10.1002/adhm.201601101/abstracthttp://onlinelibrary.wiley.com/doi/10.1002/adhm.201601101/abstract

Combining DNA Nanotechnology with High-Throughput Materials Screening to

Generate New Biomedical Devices J.D. Brennan,1 C. Carrasquilla,1 E. Kapteyn,1 M. Liu,1,2 Y. Li,1,2

1 Biointerfaces Institute, McMaster University, Hamilton, ON, L8S 0A3, Canada;

brennanj@mcmaster.ca 2 Department of Biochemistry and Biomedical Sciences, McMaster University, Hamilton, ON, L8S

4L7, Canada

Fabrication of porous sol-gel derived biocomposites has been an active field of research for over 25 years. While substantial progress has been made in the development of porous materials bearing entrapped biomolecules, the route to discovery and optimization of such materials has generally been slow and labour intensive. Recently, our group has pioneered the use of high throughput synthesis and screening of porous sol-gel derived materials using robotic liquid handing, microarray and microwell plate based assays, and advanced characterization tools to rapidly produce new biologically doped materials for a range of health based applications ranging from small molecule screening to bioaffinity chromatography and point-of-care diagnostics. In this presentation, I will highlight the workflow used to produce a high-throughput method for materials discovery and optimization. I will then provide a summary of our recent work involving the production of high molecular weight DNA nanoflowers produced by rolling circle amplification of functional nucleic acids (DNA aptamers and DNA enzymes), including formation mechanism and ways to control DNA nanoflower size and shape. Finally, I will discuss the integration of functional DNA nanoflowers into porous and non-porous composite materials for development of new biosensor coatings and bio-chromatography columns.

Tailoring magnetic properties in composite oxide films: nanoscale effects N. Jedrecy1,*, M. Hamieh1, C. Hebert1, J. Perriere1, T. Aghavnian2, J.-B. Moussy2, H. Magnan2, D.

Stanescu2, Ph. Ohresser3, A. Barbier2 1 INSP, UPMC-Sorbonne Universits, CNRS UMR7588, 4 Place Jussieu, 75252 Paris Cedex 05, France

2 SPEC, DSM/IRAMIS/SPEC, CEA-CNRS UMR 3680, CEA-Saclay, 91191 Gif-sur-Yvette, France 3Synchrotron-SOLEIL, Saint-Aubin, BP48, 91192 Gif sur Yvette Cedex, France

*jedrecy@insp.jussieu.fr Two main research directions for energy saving in magnetic/spintronic applications are currently investigated: manipulation of magnetization by an electrical field and carrier transport enhancement by a small magnetic field. Oxide thin films are a playground for such effects. We will discuss two representative examples with unique properties involving the nanometer scale.

The first system is a multiferroic one which involves ultra-thin layers (2-15 nm thick) of ferromagnetic CoFe2O4 and ferroelectric BaTiO3, grown on SrTiO3(001) substrate. Unexpectedly, the strain state of the BaTiO3 layers evolves as a function of the CoFe2O4 thickness on top, and vice versa. As a result, the ferroelectric properties depend on the CoFe2O4 thickness and the ferromagnetic properties depend on the BaTiO3 thickness. This interdependence of the two properties is crucial for the thinnest films.

The second system is a composite film which involves small ferromagnetic Co clusters in a ZnO host matrix. If the size of the Co clusters is in the 10-20 nm range, the system behaves as ferromagnetic and semiconducting at room temperature, and results in small values of the magnetoresistance, below -3 %. Very differently, if the in-plane size of the Co clusters is reduced to 1.3 nm, the system behaves as paramagnetic at room temperature, but it results in large values of the magnetoresistance, ranging from 11 % at 300 K to - 19 % at 50 K, with a steep decrease at low magnetic field. This enhanced magnetoresistance response is linked to the high number of ZnO/Co interfaces, through which an efficient spin-dependent tunneling of the charge carriers occurs.

Engineering of smart anisotropic magnetic nano-objects towards an image-guided

therapy G. Cotin1, C. Blanco-Andujar1, D. Mertz1, B. Pichon1, F. Meyer2, D. Felder-Flesch1 and S. Begin-

Colin1

1Institut de Physique et Chimie des Matriaux, UMR 7504, CNRS- University of Strasbourg, 23 Rue du Loess,

BP 43, 67034 Strasbourg, France. Sylvie.begin@unistra.fr 2INSERM, UMR 1121, 11 rue Humann, 67085 Strasbourg, France. fmeyer@unistra.fr

In the field of the synthesis and functionalization of inorganic nanoparticles (NPs) for

biomedical applications, most researches aim at developing multifunctional theranostic NPs which can both identify disease states and deliver therapy and allow thus following the effect of therapy by imaging. The current challenge for iron oxide based NPs is the design of NPs able to combine in one nano-objects both magnetic hyperthermia (MH) and MRI with the best efficiency in order to reduce the dose injected in the patient. Ultra small iron oxide NPs are already commercially used as T2 contrast agent for MRI. The use of MH as a stand-alone or an adjacent therapy for cancer is closer to be a reality in every hospital thanks to the positive results achieved by the clinical trials carried out by MagforceTM(Germany) treating glioblastoma. Nonetheless, the need for direct intratumoral injection of large amounts of NPs to achieve a therapeutic effect only points out at the need of improving the available nanomaterials for MH. Different parameters may be varied to increase the effective heat loss of a ferrofluid such as size, shape anisotropy or composition, among others. Shape and aspect ratio may offer interesting possibilities as chain formation has been previously reported to increase heat loss. Furthermore there is also a need for evaluating the heating efficiency in cellular media as it may be different from that in solution and of course in in vivo conditions.

On that basis, plate-like, cubic and octopod shape NPs were prepared by thermal decomposition of home-made iron stearate, functionalised with dendron ligands to achieve aqueous suspensions and proved suitable for in vivo injection. MH performance was found to be shape-dependent with octopod-shaped NPs exhibiting the highest SAR values of 260 W.g-1 (f = 579 kHz, 8 kAm-1, ILP = 7.1 nHm2kg-1) or 960 W.g-1 (f = 796 kHz, 16 kAm-1, ILP = 4.8 nHm2kg-1). At the same time, their performance in MRI was investigated leading to relaxivity values of 16.9 and 405.5 mM-1 s-1 for r1 and r2, respectively, which was superior to that of commercial products like Resovist. Cell response was studied as a function of NP concentration and morphology, as well as under MH treatment. The in vivo MRI and MH experiments have allowed evaluating their biodistribution and their therapeutic properties. The obtained results open the possibility of using these systems as theranostic platform thanks to the exhibited performance in hyperthermia and MRI at both in vitro and in vivo levels. A start-up company is currently under construction.

Magnetic nanostructures with added functionalities for future magnetic and medical

applications

Kristina uek Roman1*, Darja Peko1, Muhammad Shahid Arshad1, pela Trafela1, Xuan Xu1, Sao

turm1, M. P. Mariana Proenca2, Manuel Vazquez2, U. Wolff3, V. Neu3, M. Erdani Kreft4, S.

Hudoklin4, S. Kobe1, N. Kostevek1

1Jozef Stefan Institute, Department for nanostructured materials, Ljubljana, Slovenia 2 Instituto de Ciencia de Materiales de Madrid, CSIC, Madrid, Spain

3Institute for Solid state and Materials research, IFW, Dresden, Germany 4Institute for cell biology, Medical Faculty, University of Ljubljana, Ljubljana, Slovenia

Magnetic nanostructures in 0, 1 and 2D dimensions show size dependent unique potentials when talking about their applications either in magnetic storage and magnetic-based nanodevices for medical purposes. First we introduce 0D nanostructures suitable for advanced medical therapies, where with combining the magnetic (FePt) and plasmonic (Au) entity in a single nanoparticle we are able to produce multifunctional NPs enabling both the diagnostic (MRI) and the therapeutic (phototermal ablation) action[1], that got confirmed also in in vitro-studies on three cell lines: normal porcine urothelial cells (NPU), low-grade (RT4) and high-grade (T24) cancer urothelial cells. The ICP-MS analysis showed that the uptake of the NPs to normal cells is minor (1%) however significant in RT4 and T24 cells where it has reached around 13 %, which shows that we can target the cancer cells passively but effectively, as after the laser treatment the cell viabilities have dropped in accordance to the overall NPs uptake. In order to investigate different anisotropy contributions the magnetization distribution and switching study was performed on fcc Fe-Pd 1D nanowires (NWs)[2] and Co-rich hcp Co-Pt NWs[3]. For the in-field MFM measurements on electroplated Fe-Pd and Co-Pt NWs a home-made stage was used. Magnetic force microscopy on a single Fe-Pd NW revealed single-domain behavior with the easy axis of magnetization along the long axis of the NW. In the case of the Co-Pt NWs the texturing of the direction [001] was observed that suggests the uniaxial anisotropy perpendicular to NW long axis. This was found further to result in a unique periodic domain structure observed with MFM. Such type of domain pattern is the state with the lowest energy that can be applicable in the newest version of race track memory devices with perpendicular anisotropy. We are also investigation novel processing of Nd-Fe-based 2D films via electrodeposition from ionic liquid-based 1-ethyl-3-methylimidazolium dicyanamide from the permanent magnet recycling perspective. References

1. N. Kostevsek, J. Phys. Chem. C. (2015) 119, 1674-1682 2. D. Pecko, IEEE Trans. Magn. (2015) 51, 9600204 -1-9600204-4 3. M. S. Arshad, J. of Phys. D., Applied Physics (2016) 49, 1-13

Functionalized Carbon Nanotubes Filled with Metal Oxide Nanoparticules for

Hyperthermia, Imaging, Therapy and Magnetic Manipulation

D. Bgin1 X.Liu1, D. Mertz2, A. Bianco3 , C. Mnard-Moyon3 F. Gazeau4, S. Bgin-Colin2 1 ICPEES CNRS-Universit de Strasbourg, 25 rue Becquerel, 67087 Strasbourg cedex 2 France dominique.begin@unistra.fr 2 IPCMS - CNRS-Universit de Strasbourg, 23 rue du Loess, BP 34 67034 Strasbourg cedex 2, France sylvie.begin@ipcms.unistra.fr 3 IBMC , CNRS, , Universit de Strasbourg 67000 Strasbourg, France a.bianco@ibmc-cnrs.unistra.fr 4 MSC CNRS/Universit Paris-Diderot, PRES Sorbonne Paris Cit, 75205 Paris cedex 13, France florence.gazeau@univ-paris-diderot.fr, Nanocomposites combining multiple functionalities in one single nanoobject hold a lot of promises for biomedical applications. In this work carbon nanotubes (CNTs) were filled with ferrite nanoparticles (NPs) to develop the magnetic manipulation of the nanotubes, their theranostic applications and also in hyperthermia. The challenges were both the filling of CNTs with a high amount of magnetic NPs and their functionalization to form biocompatible water suspensions. We are here proposing a filling process using CNTs as nanoreactors for high yield in situ growth of ferrite NPs into the inner carbon cavity. At first, NPs were formed inside the nanotubes by thermal decomposition of an iron stearate precursor. A second filling step was then performed with iron or cobalt stearate precursors to enhance the encapsulation yield and block the formed NPs inside the tubes. Water suspensions were then obtained by addition of amino groups via the covalent functionalization of the external surface of the nanotubes. Microstructural and magnetic characterizations confirmed the confinement of NPs into the anisotropic structure of CNTs making them suitable for magnetic manipulations and MRI detection. We shall show also the behavior of such nano-composites (from an hyperthermic consideration) under an NIR wavelength : A 50 L water suspension of CNTs was irradiated using a fiber optic laser device operating at the NIR wavelength of 808 nm. Soon after laser irradiation, the nanotube suspension started to heat and attained boiling temperature in less than one minute. Works are actually in progress to shorten the CNTs in order to decrease their aspect ratio (and their potential toxicity) and to increase the filling ratio with NPs . However, during the manipulation of those nano-composites an important removal of the NPs out of the CNTs channel can be observed, and to avoid such problem, we recently succeeded to encapsulate such nano-composites with an homogeneous layer of porous silica : this protection layer presents many advantages : Nps are stabilized inside the CNT channel, its hydrophilic character stabilize the nano-composites in suspension in aqueous media, and specific proteins or medicines can be grafted on their surface making them very interesting as vectorisation agents Liu X., Marangon I., Melinte G., Wilhelm C., Mnard-Moyon C., Vacchi I. A., Pichon B., Ersen O., Baaziz W., Pham-Huu C., Bgin-Colin S., Bianco A., Gazeau F., Bgin D. ACS Nano, 2014 , 8,1129011304

mailto:dominique.begin@unistra.frmailto:a.bianco@ibmc-cnrs.unistra.frmailto:a.bianco@ibmc-cnrs.unistra.frmailto:florence.gazeau@univ-paris-diderot.fr

Design of self-healing silica-based nanomaterials A. Shimojima

Department of Applied Chemistry, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555, Japan,

Email: shimojima@waseda.jp

Self-healing materials are useful for a wide range of applications [1-3]. Recently, design of self-healing materials by utilizing reversible bonds such as hydrogen bonds and dynamic covalent bonds has attracted increasing attention. In contrast to many reports on the self-healing soft materials, research on self-healing of relatively hard inorganic solids has been limited [3]. Siloxane networks are expected to exhibit an intrinsic self-healing ability because of the reversibility of the SiOSi bonds. It is reported that cross-linked polydimethylsiloxane (PDMS) with silanolate end groups has the ability to rejoin cut surfaces by restructuring the siloxane networks below 100 C [4]. The high mobility of the PDMS chains should play a crucial role in the efficient self-healing; therefore, similar self-healing mechanism is hardly applied for silica (SiO2)-based materials with more rigid structures. Design of silica-based materials that can repair themselves under mild conditions is an important subject of research.

In this paper, we report the self-healing ability of lamellar silica-based thin films[5] formed by evaporation-induced self-assembly of silicate species and quaternary ammonium-type surfactants. Artificial cracks with submicrometer widths were spontaneously healed at 6080 C under humid conditions. These conditions are much milder than those required for crack healing of soda-lime glass (typically > 500 C) [6]. TEM observation and EDS mapping of the cross-section of the healed area suggested that new siloxane networks were formed between the fracture surfaces. The randomly oriented lamellar structures with increased Q3 ((SiO)3SiOH) sites were found essential for the crack closure and rearrangement of the siloxane networks. Nanoindentation tests revealed that these materials were much harder than a PDMS elastomer. These findings will lead to the creation of a variety of self-healing silica-based materials. References 1. Y. Yang and M. W. Urban, Chem. Soc. Rev. (2013) 42, 7446. 2. C. E. Diesendruck, N. R. Sottos, J. S. Moore, and S. R. White, Angew. Chem. Int. Ed.

(2015) 54, 10428. 3. M. D. Hager, P. Greil, C. Leyens, S. van der Zwaag, and U. S. Schubert, Adv. Mater.

(2010) 22, 5424. 4. P. Zheng and T. J. McCarthy, J. Am. Chem. Soc. (2012) 134, 2024. 5. M. Ogawa, Langmuir (1997) 13, 1853. 6. M. K. C. Holden and V. Frechette, J. Am. Ceram. Soc. (1989) 72, 2189.

Polysaccharides derivatised with amino-acids R. Kargl1,2, T. Elschner1, A. Bratua1 and K. Stana Kleinschek1,2

1Laboratory for Characterization and Processing of Polymers (LCPP), Faculty of Mechanical Engineering,

University of Maribor, Smetanova ulica 17, 2000 Maribor, Slovenia. (rupert.kargl@um.si) 2Institute for Chemistry and Technology of Materials (ICTM), Graz University of Technology, Stremayrgasse 9,

8010 Graz, Austria.

Polysaccharides and proteins are the main polymers determining and influencing the structure and function of living biological systems. Understanding and utilizing the interaction of both biopolymers is prerequisite for designing new and efficient biomaterials for tissue engineering or biosensor applications. Polysaccharide-amino acid conjugates are materials that possess properties and function of both biopolymers. These materials are intended to mimic natures proteoglycans, glycoproteins and glycosylated enzymes in form and function. Development of derivatization strategies for the conjugation of polysaccharides with amino acids are the crucial step for obtaining these materials. Further processing into two and three-dimensional objects (particles, coatings, foams, fibers) allows for their use in bio-medical applications. Studying interactions of living cells with the described biomaterials gives insights into the mechanisms and applicability of this relatively unexplored group of semi-synthetic polymers. This project has received funding from the European Unions Horizon 2020 research and innovation programme under grant agreement No 665172

mailto:rupert.kargl@um.si

Synthesis, isolation, and transformation of orthosilicic acid and its oligomers Masayasu Igarashi, Tomohiro Matsumoto, Fujio Yagihashi, Kazuhiko Sato, Shigeru Shimada

National Institute of Advanced Industrial Science and Technology (AIST) (1-1-1 Higashi, Tsukuba, Ibaraki 305-

8565, Japan. e-mail address: s-shimada@aist.go.jp)

Orthosilicic acid, Si(OH)4, and its small condensation compounds are among the most important silicon compounds. These compounds have long been known, but have never been isolated due to their instability. They would be highly useful compounds for advanced materials synthesis if they become available at high purity. We succeeded in developing a simple procedure to selectively synthesize orthosilicic acid 1, its dimer 2 (disilicic acid), cyclic trimer 3, and tetramer 4 (Scheme 1) by the hydrogenolysis reaction of benzyloxysilanes, as well as appropriate conditions to stabilize these species in organic solvents. Isolation of 1, dimer 2 and the cyclic tetramer 4 as hydrogen-bonded crystals with tetrabutylammonium halides and of the cyclic trimer 3 as solvent-containing crystals was achieved. The solid-state structures of these compounds were unambiguously clarified by single crystal X-ray diffraction analysis. Based on these results, we also developed a more practical synthetic procedure for high concentrations of orthosilicic acid stably in organic solvents by a simple hydrolysis of tetraalkoxysilanes. The results make the family of silicic acid compounds available as building blocks for material synthesis. Some selective transformations of these silicic acid compounds will also be presented.

Si

OH

OHHO

HOSi O Si

OHHO

OHHO

OHHOO

SiO

Si

OSi

O

Si

HO OH

OH

OH

OHHO

HO

HOSiO

SiO

Si

O

HO OH

OHOH

HOHO

1 23

4 Scheme 1. Structure of orthosilicic acid 1 and its condensation oligomers 2, 3, and 4

This work was supported by the "Development of Innovative Catalytic Processes for Organosilicon Functional Materials" project (PL: K. Sato) from the New Energy and Industrial Technology Development Organization (NEDO).

Elaboration of silicon carbide with controlled porosity by soft-templating approaches

T. Nardin1, B. Gouze1, M. Cognet1, M. Carboni1, M. Wong Chi Man2, O. Diat1 and J. Cambedouzou1

1 Institut de Chimie Sparative de Marcoule UMR 5257 CEA-CNRS-ENSCM-UM, BP17171, F-

30207 Bagnols-sur-Cze, France 2 ENSCM, Institut Charles Gerhardt Montpellier, UMR 5253 CNRS-UM-ENSCM, Lab. Architectures

Mol. & Mat. Nanostruct., F-34296 Montpellier, France

Silicon carbide (SiC) constitutes an appealing material for high-tech applications ranging from catalysis in high temperature conditions to innovative battery materials. The unique properties of SiC, combining mechanical resistance and high thermal conductivity are indeed desirable for such applications. However, controlling the porosity in such cohesive materials remains challenging, and requires innovative approaches. We present a bottom-up approach based on the use of molecular and polymeric silane precursors for the elaboration of SiC of controlled porosity. The porosity is generated by the use of removable molecular aggregates during the elaboration process through a so-called soft-templating approach (see Fig. 1). Depending on the sought porosity, semifluorinated alkanes[1] (leading to macroporosity), or triblock copolymers[2] (leading to mesoporosity) can be used. For each case, a careful characterization of the material is provided at each step of the elaboration process. Finally, we present new SiC composites preloaded with materials of interest for applications in catalysis and for energy storage.

Fig. 1. Schematic representation of the soft-templating strategy involving TSCH as SiC precursor and organogelator molecules as templating agent. References 1. T. Nardin et al. J. Mater. Chem. A (2015) 3, 3082-3090.

2. T. Nardin et al., Mater. Lett. (2016) 185, 425-427.

Hierarchically Structured Assembly of Inorganic Nanosheets for Tailored Fusion

Materials

Minoru Osada

International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials

Science (NIMS), Tsukuba, Ibaraki 305-0044, Japan osada.minoru@nims.go.jp

Hierarchical selfassembly is a ubiquitous process in nature where it underlies the formation

of complex biological structures. Over the past decades, scientists have aspired to exploit

biomimetic approaches to create new artificial materials with hierarchical structures and

tailored properties. However, de-novo design of such hierarchical structured materials is still a

major challenge. In this Focus Review, we provide an overview on new design principles for

hierarchical nanoarchitectures using a layer-by-layer (LbL) assembly of two-dimensional

(2D) oxide nanosheets. 2D oxide nanosheets have remarkable potential as building blocks for

tailoring fusion materials combined with a range of foreign materials such as organic

molecules, gels, polymers, and inorganic and metal nanoparticles. The ability to create

functionalized 2D hierarchical systems will lead to various applications in optoelectronics,

spinelectronics, energy and environment technologies [1-6].

References

1. M. Osada, T. Sasaki, Adv. Mater. (2012) 24, 209.

2. B-W. Li, M. Osada et al., ACS Nano (2010) 4, 6673.

3. M. Osada et al., ACS Nano (2011) 5, 6871.

4. C-X. Wang, M. Osada et al., ACS Nano (2014) 8, 2658.

5. Y. S. Kim et al., Nature Mater. (2015) 14, 1002.

6. B-W. Li, M. Osada et al., J. Am. Chem. Soc. (2016) 138, 7621.

Hierarchically Porous Hybrid Materials Derived from Nanocomposite Foams Sebastijan Kovai1,2, Matja Mazaj1, Nataa Zabukovec Logar1, Ema agar1

1National Institute of Chemistry, Hajdrihova 19, 1001 Ljubljana, Slovenia sebastijan.kovacic@ki.si 2University of Maribor, Faculty of Chemistry and Chemical Engineering, Smetanova 17, SI-2000 Maribor,

Slovenia

Controllable integration of microporous nanocrystals into macroporous functional polymeric materials results in creation of new multifunctional hierarchically porous hybrids with the properties superior to those of the individual components. Embedding microporous nanocrystals (e.g. MOFs) into the organic (polymeric) matrices is an appealing combination since the resulting hybrids maintain the shape and flexibility of the polymeric support and exhibit microporosity and high surface area of MOFs as well. Particularly interesting are microcellular polymeric foams as matrices since their macropores serve as highways, providing an unobstructed flow towards the active-sites within the microporous MOF's. Among the methodologies available for preparing polymeric foams, high internal phase emulsion (HIPE) templating and polyHIPEs thereof are especially intriguing.1

Herein, the solid-to-MOF transformation will be shown as a feasible and effective technique for preparation of MOF@polyHIPE hybrid materials (Figure 1).2 MOF phase within the hybrid materials exhibits superior structure hydrostability and CO2 adsorption capacity even at 50% humidity.

Figure 1. Scanning electron micrograph of HKUST-1@polyHIPE.

References: 1. Cameron, N. R.; Krajnc, P.; Silverstein, M. S. Colloidal Templating, in: M. S. Silverstein,

N. R. Cameron, M. A. Hillmyer (Eds.) Porous Polymers, Wiley & Sons, 2011. 2. Matja Mazaj, Natasa Zabukovec Logar, Ema agar, Sebastijan Kovai, J. Mater. Chem.

A, 2017, 5, 19671971.

mailto:sebastijan.kovacic@ki.si

The immobilization of cryptophane derivatives onto silica and gold

substrates

Elise Siurdyban1, Karine Heuz1, Thierry Brotin2, Thierry Buffeteau1 and Luc Vellutini1

1UNIVERSITE DE BORDEAUX, Institut des Sciences Molculaires (UMR-5255), 351 cours de la libration, TALENCE, France

2Laboratoire de Chimie, Ecole Normale Suprieure de Lyon, 46 Alle dItalie, 69364, Lyon, France

luc.vellutini@u-bordeaux.fr Cryptophanes are nearly spherical cage molecules composed of two cyclo-triveratrylene bowls connected by three aliphatic linkers. The rigid bowl-shaped structure of the cryptophane cavity generates a lipophilic cavity suitable for the encapsulation of guest species, such as halogenomethanes, ammonium salts, or even xenon in organic or aqueous solutions. Recently, we have shown that cryptophanes bearing hydroxyl functions could also efficiently encapsulate cesium and thallium cations in water under basic conditions.1-3 The immobilization of cryptophane molecules onto surfaces could be an original and clever approach for extraction of toxic cations such as cesium or thallium. Therefore, we have investigated the grafting of cryptophane derivatives onto SiO2/Au and Au substrates.4

References 1 Brotin T., Montserret R., Bouchet A., Cavagnat D., Linares M., Buffeteau T. (2012), J. Org. Chem., 77, 1198-1201 2 Brotin T., Cavagnat D., Berthault P., Montserret R., Buffeteau T. (2012), J. Phys. Chem. B, 116, 10905-10914 3 Brotin T., Goncalves S., Berthault P., Cavagnat D., Buffeteau T. (2013), J. Phys. Chem. B, 117, 12593-12601 4 Siurdyban E., Brotin T., Heuz K., Vellutini T., Buffeteau T. (2014), Langmuir, 30, 14859-14867.

Figure 1. Schematic representation of cryptophane derivatives immobilized

onto SiO2/Au or Au substrates.

pH-operated functionalized hybrid silica nanoparticles for drug delivery

C. Carcel1 1Institut Charles Gerhardt Montpellier UMR-5253 CNRS-ENSCM-UM, Ecole Nationale Suprieure de Chimie

de Montpellier, 8 rue de lcole normale, 34296 Montpellier Cedex 05, France, carole.carcel@enscm.fr

In the past decades, several smart nanomaterials have been developed for application in medical fields in particular as drug delivery systems. Appropriately designed drug carriers with controlled delivery triggered by stimuli, without premature release, to the targeted cells can overcome some issues of conventional therapy (limited side-effects) and enhance the therapeutic performance of a specific drug. Among several strategies, silica nanoparticles (SNP) appear as one of the most promising drug carrier [1].

Following our work on the development of pH-responsive hybrid silicas [2] we have considered the possibility to prepare new hybrid silica nanoparticles as pH-operating nanomachines for drug release. The key challenge is to develop an autonomous system with a self-triggered release liable to occur inside the infected cells without external control. Since SNP can enter in infected cells due to EPR effect and via endocytosis route to the acidic lysosome compartment, a mild pH operating strategy may afford such autonomy to prevent leakage and avoid premature release of the drug. The strategy presented here will describe the preparation of hybrid mesoporous silica nanoparticles with pH-operated stoppers [3] and the improvements done to get combination therapy [4] and more efficient targeting.

References 1. S. Giret, M.Wong Chi Man, C. Carcel, Chem. Eur. J., (2015) 40, 13850. 2. L. Fertier, C. Thron, C. Carcel, P. Trens, M. Wong Chi Man, Chem. Mater., (2011) 23,

2100. 3. C. Thron, A. Gallud, .S.Giret, M. Maynadier, P. Puche, E. Jacquet, G. Pop, O. Sgarbura,

V. Bellet, J. Zink, M. Garcia, M. Wong Chi Man, C. Carcel and M. Gary-Bobo, RSC Adv. , (2015) 5, 64932

4. S. Giret, C. Thron, A. Gallud, M. Maynadier, M. Gary-Bobo, M. Garcia, M. Wong Chi Man, C. Carcel, Chem. Eur. J., (2013) 19, 12806.

Protein Nanocages: A Versatile Molecular Carrier Sierin Lim1,2

1School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 637457 2NTU-Northwestern Institute for Nanomedicine, Singapore 637553

SLim@ntu.edu.sg Protein nanocages can be engineered to tailor their functions as carriers for health (e.g. therapeutic and diagnostic agents)[1], molecular electronic, as well as consumer care applications (e.g. cosmetics and food). They are formed by the self-assembly of multiple subunits forming hollow cage-like structures of nanometer size. Due to their proteinaceous nature, the protein nanocages allow facile modifications on its internal and external surfaces, as well as the subunit interfaces. In this presentation, I will focus on two applications that are health and electronic.

For health application, we have shown that protein nanocages can be loaded with metal as MRI contrast agent[2] or with drug as drug carrier. Modifications at the interface of the subunits can render the nanocages sensitive to environmental changes, such as pH[3]. Engineering of the external surface allows for the display of targeting ligands for selective accumulation on cancer cells[4,5] as well as epitopes for modulation of the immune system. Figure 1 summarizes the modifications and potential health applications of the protein nanocages.

For molecular electronic application, protein nanocages serves a dual function as a reaction container and as facilitator in the deposition of monodispersed platinum nanoparticles on graphene surfaces for electrocatalysis in fuel cells[6]. Long-range electron tunneling across metal-loaded protein nanocages has also been shown to be promising in the development of memristive devices and future molecular electronics[7,8].

Figure 1 Modifications resulting in multifunctional protein nanocages and their potential applications [1].

References 1. Bhaskar SM, Lim S, NPG Asia Materials (2017), accepted.

2. Sana B, Poh CL, Lim S, Chemical Communications (2012) 48(6):862-864.

3. Peng T, Lee H, Lim S, Biomaterials Science (2015) 3:627-635.

4. Bcheler J, Howard C, de Bakker CJ, Goodall S, Jones ML, Win T, Peng T, Tan CH, Chopra A, Mahler S, Lim S, Journal of Chemical Technology & Biotechnology (2015) 80(7):1230-1236.

5. Walsh EG, Mills DR, Lim S, Sana B, Brilliant KE, Park WKC, Journal of Nanoparticle Research (2013) 15:1409-1418.

6. Qiu H, Dong X, Sana B, Peng T, Paramelle D, Chen P, Lim S, ACS Applied Materials and Interfaces (2013) 5(3):782-787.

7. Meng F, Sana B, Li Y, Liu Y, Lim S, Chen X, Small (2014) 10(2):277-283.

8. Kumar KS, Pasula RR, Lim S, Nijhuis CA, Advanced Materials (2016) 28(9):1824-1830.

Self-assembling through H bonds in urea and thiourea based bridged silsesquioxanes

R. Le Parc1, V. Freitas1,2, A. F. Sbardelotto1, M. Wong Chi Man3, X. Catton4, R. A. S.

Ferreira2, L. D. Carlos2, J.R. Bartlett5, J-L. Bantignies1 1Laboratoire Charles Coulomb, UMR5521 CNRS et Universit de Montpellier, place Eugne Bataillon, 34095

Montpellier, France, 2Physics Department and CICECO Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro,

Portugal, Institut Charles Gerhardt Montpellier, UMR 5253 CNRS-UM-ENSCM, 34296 Montpellier, France

4Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast, Maroochydore DC, QLD 4558 Australia

5Inst. NEEL, CNRS and Univ Grenoble-Alpes, 38042 Grenoble, France rozenn.le-parc@umontpellier.fr

The control of structuring and morphology in hybrid solids is a key parameter for the design of functional materials. In particular, it has been shown that structure and morphology could be tuned through sol gel synthesis conditions in bridged silsesquioxanes (BS). As a matter of fact, during sol-gel process, the competition between self-assembing through non covalent interactions between the organic sub-structures and condensation of the inorganic siliceous sub-structure can lead to the formation of crystalline compounds or amorphous materials.

In order to go further with the understanding of the control of the nanostructuring in bridged silsequioxane, we designed the organic moieties of the precursors with either 2 symetrical through hydrogen bond and the strength of these hydrogen bonds is studied through vibrational spectroscopies in-situ at low temperature or at high pressure. The results are analyzed and discussed in terms of H bond strength and geometric factors.

In the second part of this talk, we will focus on the influence of the central subunit lying between the two urea/thiourea groups_either a long flexible alkyl chain or rigid phenyl group_ on the self-assembling properties through H bonds.

Figure 1 : self-assembly through covalent Si-O-Si bridges and through urea-urea bifurcated H-bonds. The central group is either a long flexible alkyl chain (CH2)12 or rigid aryl ring.

mailto:rozenn.le-parc@umontpellier

Polymer-stabilized nanoparticles of metal hydroxides and oxides: an efficient

preparation route in water N. Sanson1, G. Layrac1, N. Sanchez-Ballester1, A. Mezy1, S. Harrison2, M. Destarac2,

D. Tichit1 and C. Grardin1 1 Institute Charles Gerhardt Montpellier, ENSCM-UM-CNRS, 34296 Montpellier, France

2 IMRCP Universit de Toulouse, 31062 Toulouse, France

Nanoparticles are used, or being evaluated for use, in many fields including biology, medicine, environment protection, energy, optics, electronics, tissue engineering and manufacturing materials. In the field of nanomaterials and nanosciences, particle size control, dispersion and stability in diverse media are among the major challenges to be overcome. We have been mainly interested in colloidal hybrid organic-inorganic systems, and more specifically in metal hydroxide or oxide phases finely subdivided in aqueous media because of their wide interest in many applications. Among the different methods for stabilizing colloids (electrostatic, steric and depletion stabilization), we have been focusing on steric stablization by addition of polymers. In the last decade, we have developed an original route for preparing aqueous suspensions of metal hydroxide or oxide nanoparticles directly in water with an efficient control of the size and of the aggregation degree and with a maximum yield. We use double hydrophilic block copolymers (DHBC), constituted of a metal complexing polymer block and a neutral block; the role of such polymers is double : control the particle growth and ensure steric stabilization in aqueous suspension. DHBC polymers of different chemical nature and with varying polymer block lengths were synthesized and used for the polymer-mediated synthesis of the particles with the intention of understanding the mechanisms of particle formation as a function of the system parameters. We have first studied the case of simple metal hydroxides such as Al, Cu, Fe and La hydroxides and of simple metal oxides such as ZnO. More recently we have extended our approach to double metal hydroxides such as the well-known layered double hydroxides (LDH) phases and to other more complex multicationic metal hydroxide compounds. For the different systems, we have established a unique relation between the size of the obtained particles and the amount of polymer stabilizing units, allowing to predict the size of the colloidal particles using a polymer whose structure and block lengths are known. References 1. C. Grardin, N. Sanson, F. Bouyer, F. Fajula, J.-L. Putaux, M. Joanicot and T. Chopin Angew.Chem.Int.Ed. (2003) 42, 3681. 2. A. Mezy, C. Gerardin, D. Tichit, D. Ravot, S. Suwanboon, J.C. Tedenac Journal of the Ceramic Society of Japan (2008), 116 (1351) 369. 3. F. Bouyer, N. Sanson, M. Destarac and C. Grardin New Journal of Chemistry, (2006), 30, 399. 4. G. Layrac, M. Destarac, C. Grardin and D. Tichit Langmuir (2014) 30, 9663.

Multiple functionalization of silica-based materials

by click chemistry

Achraf Noureddine, Jonas Croissant, Magali Gary-Bobo, Marcel Garcia, Marie Maynadier, Jean-Olivier

Durand, Michel Wong Chi Man and Xavier Catton

Silica-based materials constitute very interesting platforms for application such as catalysis, optics, or

nanomedicine. While the grafting of organo-alkoxysilanes is a widely used technique to endow the

materials with the targeted organic functionality, this technique is not suitable to bring multiple

functionalities in a controlled manner. Recently, click reactions have emerged to link together two

independent moieties simply and reliably. Among them, the copper-catalyzed azide to alkyne

cycloaddition has proven to be extremely powerful and compatible with a wide scope of moieties,

enabling for example the controlled functionalization of silica materials with biomolecules [1].

In this presentation, we will see how clickable groups can be included in controlled loadings into a

silica material by co-condensation, and easily derivatized with (bio)organic moieties to bring the

desired functionality [2]. In particular, we will discuss the bis(functionalization) of silica materials with

functional groups either separated in space, or placed in close vicinity and able to communicate with

each other [3,4]. Application of such bi-functional mesoporous silica nanoparticles for nanomedicine

will be exemplified.

[1] S. ShenoiPerdoor, A. Noureddine, F. Dubois, M. Wong Chi Man, X. Catton (2016), "Click

Functionalization of SolGel Materials" in Handbook of SolGel Science and Technology, Springer

International Publishing DOI: 10.1007/9783319194547_951

[2] A. Noureddine, M. GaryBobo, L. Lichon, M. Garcia, J. I. Zink, M. Wong Chi Man, X. Catton.

Chem. Eur. J., 2016, 22, 96249630.

[3] A. Noureddine, L. Lichon, M. Maynadier, M. Garcia, M. GaryBobo, X. Catton, M. Wong Chi Man.

Nanoscale, 2015, 7, 1144411452.

[4] J. G. Croissant, S. Picard, D. Aggad, M. Klausen, C. MaurielloJimenez, et al. J. Mater. Chem. B,

2016, 4, 55675574.

TEM image of bifunctional mesoporous silica nanoparticles and principle of energy transfer between

a donor and an acceptor.

Tuning the Interfacial Properties of Mesoporous Ionosilicas: Effect of Cationic Precursor and Counter Anion

Ut Dong Thach, Benedicte Prelot, Jerzy Zajac, Peter Hesemann, Philippe Trens

Institut Charles Gerhardt, UMR-5253 CNRS-UM-ENSCM 8 rue de lEcole Normale, 34296 Montpellier cedex 5, France Ionosilica are mesoporous silica-based hybrid materials containing covalently bound ionic groups.[1,2] The mixed ionic mineral nature confers particular properties to these materials. Here, we focus on the tailoring of the interfacial properties of ionosilicas. Three materials were synthesized from three different oligosilylated ammonium precursors. Furthermore, anion exchange allowed replacing the halide in the parent ionosilicas against more hydrophobic anions e.g. thiocyanate (SCN) and bis-trifluoromethanesulfonimide (NTf2). Both the constitution of the ammonium substructure of the precursor and the nature of the counter anion allow controlling the interfacial properties in terms of hydrophilicity modulation and affinity towards solvents. Although all studied ionosilica are highly hydrophilic mesoporous materials, significant differences between the materials were observed. The hydrophilicity can be fine tuned either by the use of more hydrophobic ammonium precursors or the incorporation of hydrophobic anions. We show that ionosilicas combine high porosity, regular architecture on the mesoscopic level with an unmatched chemical versatility, induced by the high variability and the high number of homogeneously distributed ionic species. Ionosilicas appear as highly adaptable materials and can be considered as designer materials.[3] Immersion as well as titration calorimetry will be used for evaluating the hydrophilic/hydrophobic balance of the materials as a function of nature of the cationic precursor used. The influence of the counter anion will be also discussed and it will be proved to be crucial for the hydrothermal stability of the materials. Volumetric adsorption of probes of increasing polarity will illustrate their versatility. These porous phases are therefore interesting for their potential for applications in catalysis, sorption and separation.

References [1] B. Gadenne, P. Hesemann, J.J.E. Moreau, Chem. Commun. (2004) 17681769. [2] P. Hesemann, T. Nguyen, S. Hankari, Materials (Basel). 7 (2014) 2978. [3] U.D. Thach, P. Trens, B. Prelot, J. Zajac, P. Hesemann, J. Phys. Chem. C 120 (2016)

27412.

Synthesis and Design of Iron Oxide Nanostructures for

Spintronic and Energy Storage Applications

Benoit P. Pichon & Sylvie Begin-Colin

Universit de Strasbourg, CNRS, Institut de Physique et Chimie des Matriaux de Strasbourg, UMR 7504, F-

67000 Strasbourg, France

Nanostructures with controlled size, morphology, and composition represent a main

challenge in materials science because controlling these parameters is fundamental to

optimizing the subsequent functional properties. Aggregated nanostructures, combining

both individual and collective properties of nanocrystals, offer interesting perspectives to

design new nanomaterials. In that context, original porous raspberry shaped

nanostructures (RSN) consisting of oriented aggregates of ferrite nanocrystals have been

synthesized by an one-pot polyol solvothermal method. Synthesis conditions have been optimized to obtain nanostructures featured by similar sizes of about 250 nm and

nanocrystal sizes modulated from 5 to 60 nm, leading to porous structures with tunable

specific surface area. The formation mechanism of RSN was deeply investigated by a wide

panel of characterization techniques including in situ TEM, EELS, SEM, TGA, FTIR

Their physical properties were investigated as collective magnetism, magneto dielectrics

diluted in a polymer matrix and electrode materials for energy storage.

Mesoporous metal oxide anodes for Li-ion batteries G.A. Seisenbaeva1,V. G. Pol2

1Department of Molecular Sciences, SLU, Box 7015, 75007 Uppsala, Sweden, Gulaim.Seisenbaeva@slu.se; 2School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, USA, vpol@purdue.edu

Porous metal oxide nanomaterials are of great interest due to their attractive properties and a broad range of applications. Most attractive characteristic of mesoporous materials is their high surface area and capacity to enhanced surface reactivity, which are of greatest interest for such applications as adsorbents, heterogeneous catalysts, and electrodes for Li-ion batteries and solar cells. Mesoporous transition metal oxides with high surface area (over 200 m2/g) can efficiently be produced by a new approach from solid metal alkoxide precursors through surfactant-free quick hydrothermal synthesis [1, 2]. This technique allows to obtain a broad range of metal oxide materials, comprising TiO2, ZrO2, HfO2, SnO2, Nb2O5, Ta2O5 etc., possessing unusual structure and properties high crystallinity associated with ordered mesoporosity the properties highly requested for electrode materials in alkali ion batteries. Lithium-ion batteries are today most attractive rechargeable batteries due to high energy storage per unit volume and weight. However, their performance still needs further development for use in high energy density applications, e.g., cars and large scale energy storage. Thus an important direction is improvement of anode materials. Tin oxide is a material that attracted a lot of interest because of its high theoretical capacity. It was demonstrated that mesoporous anodes composed of nano sized SnO2 particles (NP) show substantially higher specific capacities, rate performance, coulombic efficiency, and cycling stabilities compared to available commercial tin oxide. A discharge capacity of 778 mAh g 1, close to the theoretical limit of 781 mAh g 1, was achieved [3]. To make batteries cheaper and more environmentally friendly, materials with low toxicity, abundant in the nature, and low in cost are required. In this sense iron oxide is ideal for next generation anode materials. NP of -Fe2O3 are successfully prepared via facile hydrolysis of iron iodide complex precursor with following oxidation under mild conditions. Electrodes of -Fe2O3 NPs initially deliver capacities of 1100 mAh g-1 and increase by up to 300 mAh g-1 by following an activation step of the electrodes [4]. References 1. G.A. Seisenbaeva, G. Daniel et al., J. Mater. Chem. (2012) 22, 20374-20380. 2. G. A. Seisenbaeva, J.M. Nedelec et al., Chem. Eur. J. (2013) 19, 17439 17444. 3. V. Etacheri, G.A. Seisenbaeva, V.G. Pol et al., Adv. Energy Mater. (2015) 5:1401289. 4. J. Tang, G. A. Seisenbaeva, V.G. Pol et al., J. Mater. Chem. A (2016) 4, 18107-18115.

mailto:Gulaim.Seisenbaeva@slu.semailto:vpol@purdue.edu

Elaboration of an aqueous sol-gel method for the synthesis of g-Al2O3 supports V. Claude1, C. Wolfs1 and S. D. Lambert1

1Department of Chemical Engineering Nanomaterials, Catalysis, Electrochemistry, University of Liege, B6a,

B-4000 Liege, Belgium. E-mail : Stephanie.lambert@ulg.ac.be

-Al2O3 material appears to be the best catalytic support for applications at high temperatures such as CH4 reforming, biomass gazification into Syngas,... Instead of using commercially available -Al2O3 materials, this work presents the synthesis of alumina supports by the sol-gel process, in order to be able to tailor the micro- and meso-structure of -Al2O3 supports. The cogelation (realized by organic path) and coprecipitation (realized by aqueous path) methods allow the synthesis of homogenous supports from the hydrolysis and condensation of different kind of precursors.

The cogelation syntheses can be realized with precursors being both alkoxides of the same element, for example the formation of SiO2 with tetramethoxysilane (Si(OCH3)4) and tetraethoxysilane (TEOS, Si(OC2H5)4) [1, 2]. It is also possible to start from one alkoxide and one salt, for example the synthesis of Al2O3 with a mix of Al-isopropoxide (Al(OC3H7)3)/aluminum nitrate (Al(NO3)3) [3] or Al-isopropoxide/aluminum acetylacetonate (Al(C5H7O2)3) [4]. The more interesting aspect of the cogelation lies in the possibility to create homogeneous inorganic materials with different elements. Similar materials can be obtained by coprecipitation by using a combination of TEOS and aluminum salts (Al(NO3)3, Al(Cl3)3) [5].

Cogelation with a functionalized precursor is also possible in order to tailor the morphology of the material. In this way, the use of silicon alkoxide containing a functional organic group made of one or several amino groups, which are able to form a chelate with a metallic ion, has proved to be an innovative and efficient way to improve the performances of catalytic materials. Indeed, the amino-metal complex of the functional chain allows an efficient dispersion of the metallic nanoparticles inside the inorganic support, thus improving the activity and lifetime of the catalyst. In this way, Lambert et al. [1, 2] synthesized finely dispersed Ni and Ni-Cu/SiO2 by the homogeneous cogelation of a common silicon alkoxide (TEOS) and an amino-group functionalized silicon alkoxide (N-[3-(trimethoxysilyl)propyl]ethylenediamine, (CH3O)3-Si-(CH2)3-NH-(CH2)2-NH2; called EDAS).

Since no functionalized aluminum precursors are commercially available, the functionalization of alumina supports is usually realized via grafting methods. The usual methods consist in the mixing of a functionalized silica precursor with an alumina support in an organic solvent. Thereafter, a small quantity of water is added to hydrolyze the alkoxy groups and form silanol groups which graft onto the alumina support by condensation reactions [6]. Though showing interesting results for the dispersion of metallic active sites, these methods are nevertheless not convenient and difficult to scale up, principally because of the required synthesis conditions (inert and dry atmosphere, toxic solvents such as toluene).

One goal of this work was to develop an easy synthesis procedure for the cogelation between a functionalized silicon alkoxide (EDAS) and alumina hydroxide. Furthermore, the influences of the organosilane nature on the physico-chemical properties of alumina supports were realized. References 1. J. G. Mahy, V. Claude, L. Sacco, S. D. Lambert, Journal of Sol-Gel Science and

Technology (2017) 81, 59. 2. S. Pirard, J. Mahy, J.-P. Pirard, B. Heinrichs, L. Raskinet, S. D. Lambert, Microporous and

Mesoporous Materials (2015) 209, 197. 3. J. Delgado, M. P. Aznar, J. Corella, Industrial and Engineering Chemistry Research

(1997) 36, 1535. 4. B. Acharya, A. Dutta, P. Basu, International Journal of Hydrogen Energy (2010) 35, 1582. 5. L. Zhang, X. Wang, B. Tan, U.S. Ozkan, Journal of Molecular Catalysis A: Chemical

(2009) 297, 26. 6. D. Y. C. Leung, X. Wu, M. K. H. Leung, Applied Energy (2010) 87, 1083.

Confinement of organic dyes inside carbon nanotubes

J.L. Bantignies Laboratoire Charles Coulomb (L2C), UMR 5221 CNRS, Universit de Montpellier, F-34000 Montpellier, France, Jean-louis.bantignies@umontepllier.fr Opto-electronic properties of single-walled carbon nanotubes can be significantly modified by

chromophore confinement into their hollow core. This presentation deals with

quaterthiophene derivatives encapsulated into nanotubes displaying different diameter

distributions. We show that the supramolecular organizations of the confined chromophores

depend on the nanocontainer size. The Raman radial breathing mode frequency is monitored

by both the number of confined molecules into a nanotube section and the competition

between dye/dye and dye/tube wall interactions. The confinement properties lead also to an

exaltation of the infrared absorption response1 in single-walled carbon nanotubes from dye

molecule interactions due to a symmetry breaking, allowing us, thanks to the complementarity

of DFT calculations and experimental IR investigations to study interactions between both

subsystems. Significant electron transfer from the confined molecules to the nanotubes is also

reported from Raman investigations. This charge transfer leads to an important enhancement

of the photoluminescence intensity by a factor of nearly five depending on the tube diameter.

In addition, close to the molecule resonance, the magnitude of the Raman G-band shifts is

modified and the intensity loss is amplified, indicating a photo-induced electron transfer.

Results are discussed in the frame of electron-phonon coupling. Thus, confinement species

into nanotubes allow moving the Fermi level and consequently to monitor their opto-

electronic properties.

Reference 1. A. Belhboub et al., J. phys. Chem. C (2016) 120, 28802-28807.

New tools for the risk assessment and risk management of engineered nanomaterials Fito, C1 , Domat.M1, Palau.J.L2, Mantilla.E2

1Instituto Tecnolgico del Embalaje, Transporte y Logstica. ITENE. 46980. Albert Eistein, 1. Paterna (Spain) /

cfito@itene.com 2Centro De Estudios Ambientales Del Mediterrneo. CEAM. 46980. Charles Robert Darwin, 14. Paterna (Spain)

/ joseluis@ceam.es The use of engineered nanomaterials (ENMs) is growing continuously due to the increasing number of applications of nanotechnology, promoting the development of a new generation of smart and innovative products and processes that have created tremendous growth potential for a large number of industrial sectors [1)] Due to its potential to develop new added value products, a staggering number of ENMs is already available on the market, however, along with the benefits, there is an on-going debate about their potential effects on the human health or the environment. In the occupational context, it has been demonstrated that workers have the potential to be exposed to uniquely ENMs with novel sizes, shapes, and chemical properties, at levels far exceeding ambient concentrations [2]. Recent studies show how the most extensive exposures to ENPs likely occur in the workplace, particularly research laboratories, start-up companies, pilot production facilities, and operations where ENMs are processed, used, disposed, or recycled. To cope with this situation, two novel tools developed under the framework of the LIFE NanoRISK and LIFE NanoMONITOR are presented. A new interactive library of risk management measures to select proven engineering controls and personal protective equipment has been developed within LIFE NanoRISK. Similarly, a new monitoring system based on the combination particle measurement devices, exposure libraries and data acquisition technologies has been developed within LIFE NanoMONITOR. References 1. Savolainen et al, 2013. Nanosafety in Europe 2015-2025. Finnish Institute of

Occupational Health / EU NanoSafety Cluster. 2. Y. RA, Engineered nanomaterials: exposures, hazards, and risk prevention, Journal of

Occupational Medicine and Toxicology, vol. 6:7, 2011.

LUMINESCENT NANOTHERMOMETERS: WHATS NEXT?

L. D. Carlos

Departamento de Fsica and CICECO-Aveiro Institute of Materials, Universidade de Aveiro, 3810193 Aveiro, Portugal

lcarlos@ua.pt

Luminescent ratiometric thermometers combining high spatial and temporal resolution at the micro and nanoscale, where the conventional methods are ineffective, have emerged over the last decade as an effervescent field of research, essentially motivated by their potential applications in nanotechnology, photonics and biomedicine [1]. Among the distinct luminescent thermal probes, Ln3+-based materials play a central role in the field due to their unique thermometric response and intriguing emission features (e.g., high quantum yield, narrow bandwidth, long-lived emission, large Stokes shifts, and ligand-dependent luminescence sensitization). One of the main challenge that is currently facing scientists in the field is to use luminescent thermometry for unveiling thermometers local surrounding properties, as, for instance, heat transfer in heater-thermometer nanoplatforms [2], the absorption coefficient and thermal diffusivity of tissues in small animals [3] and the measurement of the instantaneous ballistic velocity of Brownian nanocrystals suspended in both aqueous and organic solvents based on upconversion nanothermometry [4]. This lecture presents a general revision of the work done in the last couple of years on ratiometric luminescent nanothermometers and on heater-thermometer nanoplatforms capable of measuring the light-, magnetic- and plasmonic-induced local temperature increase of nanoheaters (e.g., nanoparticles based on Nd3+, Au or Fe2O3) via ratiometric luminescence thermometry. [1] C. D. S. Brites, A. Milln, L. D. Carlos, in Handbook on the Physics and Chemistry of Rare Earths, J.-C. Bnzli, V. K. Pecharsky, Eds., Amsterdam: Elsevier Science B.V., Vol. 49 (2016), 339. [2] R. Piol, C. D. S. Brites, R. Bustamante, A. Martnez, N. J. O. Silva, J. L. Murillo, R. Cases, J. Carrey, C. Estepa, C. Sosa, F. Palacio, L. D. Carlos, A. Milln, ACS Nano 9 (2015) 3134 [3] E. C. Ximendes, W. Q. Santos, U. Rocha, U. K. Kagola, F. Sanz-Rodrguez, N. Fernndez, A. da Silva Gouveia-Neto, D. Bravo, A. Martn Domingo, B. del Rosal, C. D. S. Brites, L. D. Carlos, D. Jaque, C. Jacinto, Nano Lett. 16 (2016) 1695. [4] C. D. S. Brites, X. Xie, M. L. Debasu, X. Qin, R. Chen, W. Huang, J. Rocha, X. Liu, L. D. Carlos, Nature Nanotech. 11 (2016) 851.

Tunning Plasmonic-Photonic nanocomposites for Electromagnetic Field Enhancement Rodrigo Martnez Gazoni1, Martn Bellino2,. Mara Cecilia Fuertes1,3, Gustavo Gimenez 4, Galo Soler-

Illia, Mara Luz Martnez Ricci

1 Gerencia Qumica, Centro Atmico Constituyentes, Comisin Nacional de Energa Atmica, Avenida General

Paz 1499, B1428KNA, San Martn, Argentina 2Departamento de Micro y Nanotecnologa, Centro Atmico Constituyentes, Comisin Nacional de Energa

Atmica, Avenida General Paz 1499, B1428KNA, San Martn, Argentina 3Instituto Sbato, UNSAM-CNEA, Avenida General Paz 1499, B1428KNA, San Martn, Argentina

4CMNB, Instituto Nacional de Tecnologa Industrial, Avenida General Paz 5445, B1650WAB, San Martn,

Argentina 5DQIAQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab.

II, C1428EHA, Ciudad Autnoma de Buenos Aires, Argentina 6Instituto de Nanosistemas, Universidad Nacional de General San Martn, Av. 25 de Mayo y Francia, 1650, San

Martn, Argentina 7INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria,

Pab. II, C1428EHA, Ciudad Autnoma de Buenos Aires, Argentina

Nanocomposites are nowadays one of the most promising architectures for the production of highly tunable systems. Adjusting the composite scale with optical wavelengths gives the possibility to confine and enhance the electromagnetic (EM) density field inside the structures. Among the appropriate diverse structures for this aim, photonic crystals and plasmonic structures are known as good architectures for confining light.

In this work[1] we present the designed production of a nanocomposite multilayer architecture, able to control de EM density field and spatial location. For this purpose, a one-dimensional mesoporous photonic crystal (MPC) was designed and synthesized aiming to tune the band gap edges with the plasmon resonance position of the silver nanoparticles (SNP) that were infiltrated inside the multilayer. These SNP-MPC structures are expected to enhance the EM field as a dual-consequence of the periodicity of the photonic crystal architecture and the plasmon resonance. To achieve this objective, mesoporous SiO2-TiO2 multilayers were first numerically designed and then synthesized by a successive dip-coating process. The 1D-MPC were then infiltrated with Ag+, followed by mild reduction that leads to very well-defined localization of Ag NPs in the TiO2 layers. The EM field distribution was simulated to assess its spatial localization. Raman studies using an active probe (thiopyridyne) were carried out to monitor the EM field. An increase in the enhancement of the thiopyridyne Raman signals was observed in the SNP-MPC systems, which was several times higher than the one obtained with Ag NP embedded in mesoporous films with equivalent thickness (stacks) and Ag loading (Figure 1). The combined photonic-plasmonic effect observed proves

that NP@MPC structures lead to an extra enhancement due to the photonic structure, and opens the gate to SERS-active substrates with increased signal.

[1] Gazoni, Rodrigo Martnez, et al, (2017). DOI:10.1039/C6TC05195B

Figure 1: Raman signal for Ag nanoparticles in stacks and MPCs. A clear enhancement is observed as a consequence of a plasmonic-photonic coupling

Shaping the pores for enhancing Raman detection: Graphene Enhanced Raman Scattering meets molecular imprinting

Luca Malfatti

Laboratory of Materials Science and Nanotechnology, D.A.D.U., CR-INSTM, University of Sassari, Palazzo Pou Salit, Piazza Duomo 6, 07041 Alghero (Sassari),

Italy

luca.malfatti@uniss.it Abstract The first report on Graphene Enhanced Raman Scattering (GERS) of molecules deposited onto

graphene layer has arisen a great deal of interest in the scientific community boosting the need of

developing new graphene-based substrates capable of improving this property. [1] However, one issue

that hampers the use of graphene-based substrates is the low enhancement factor associated with the

GERS effect. This, in general, is several orders of magnitude lower than conventional Surfaced

Enhanced Raman Scattering (SERS) based on plasmonic nanoparticles. Highly porous films are able to

improve the enhancement factor because of the large number of molecules which can be adsorbed into

the high surface-to-volume matrix. [2,3] In addition, hybrid organic-inorganic matrices can also be

specifically designed to provide a selective GERS response. More in detail, a molecular imprinting

approach can be used to enhance the molecular recognition properties of the hybrid substrates.[4] This

has allowed developing a general strategy for the detection of specific analytes based on selective

enhanced Raman scattering, exploiting the GERS effect (Figure 1). As a proof of concept, we have

recently developed a GERS-based sensor for organophosphates. These compounds are a class of

pesticides which is widely used in agricultural production although being a dangerous source of water

pollution.

Figure 1. a) Schematic of the MIGERS sensing platform. b) Enhancement of Rh6G Raman mode (1510 cm1) deposited on molecularly-imprinted graphene hybrid matrix (blue bar), not-imprinted graphene hybrid matrix (red bar), molecular imprinted

hybrid matrix (green bar) and flat silica surface (black bar).

References [1] P. Innocenzi, L. Malfatti, D. Carboni. Nanoscale, 7, (2015) 12759 [2] D. Carboni, B. Lasio, V. Alzari, A. Mariani, D. Loche, M. F. Casula, L. Malfatti and P. Innocenzi.

Phys. Chem. Chem. Phys., 16 (2014) 25809. [3] D. Carboni, B. Lasio, D. Loche, M. F. Casula, A. Mariani, L. Malfatti and P. Innocenzi. J. Phys.

Chem. Lett., 6 (2015) 3149. [4] D. Carboni, Y. Jiang, M. Faustini, L. Malfatti, P. Innocenzi ACS App. Mater. Interfaces, 8

(2016),34098.

Quantitative Scanning Transmission Electron Microscopy of Cu3Pt based catalyst

nanomaterials G. Drai1, F. Ruiz Zepeda1, M. Bele1, P. Jovanovi1, M. Gatalo1, N. Hodnik2, M. Gaberek1

1. Department for Materials Chemistry, National Institute of Chemistry, Hajdrihova 19, Ljubljana, Slovenia,

goran.drazic@ki.si 2. Department of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19,

Ljubljana, Slovenia

The activity of the cathode catalyst material for oxygen reduction reaction (ORR) influences strongly the efficiency of proton exchange membrane fuel cells (PEMFC). Various metals, intermetallic alloys, carbon-based supports, metal chalcogenides and carbides could be used as catalysts. Among the most promising materials are C-supported CuPt-based intermetallic nanoparticles where activity is enhanced due to structural ordering resulting in crystal lattice strain and core-shell morphology. Additional lattice strain could be induced with the twinning of the structure. In this work we investigated the local structure and chemistry of the Cu3Pt nanoparticles prepared by modified sol-gel synthesis. Using High-Angle Annular Dark-Field imaging in Cs corrected Scanning Transmission Electron Microscope (HAADF-STEM) in conjunction with the image simulations a study at the atomic level was performed. Detailed analysis of Cu-Pt showed a core-shell type of structure. The core consisted of disordered Fm3-m cubic phase where Pt and Cu atoms were statistically distributed. Around disordered core an ordered Pm3-m shell was formed during the annealing procedures. Furthermore a Pt-rich outer layer, 1- 2 nm thick, called skin, was observed on the surface of particles. Polysynthetic twinning was observed and using quantitative approach to column intensities, measured from HAADF images we were able to determine local strain and local variations of chemical composition. The influence of the nanostructure and the morphology of the Cu3Pt nanoparticles on the dissolution in the acidic media will be presented and discussed.

Organic dyes anchoring in anatase photocatalysts to

decontaminate water with solar light Ludivine Tasseroul, Sophie Pirard, Stephanie Lambert, Carlos Pez and Benot Heinrichs

Nanomaterials, Catalysis & Electrochemistry - NCE, Department of Chemical Engineering, University of Lige Building B6a - Quartier Agora, Alle du six Aot 13, 4000 Lige - Belgium (b.heinrichs@ulg.ac.be)

Since the discovery of photocatalytic decomposition of water on TiO2 electrodes by Fujishima and Honda (1972), heterogenous photocatalysis has been widely studied for environmental applications. Advanced oxidative processes are new technologies for waste water treatments because many compounds in effluents are not readily degraded by the conventional treatments. Oxidative processes can completely destroy organic pollutants like alkanes, pesticides, dyes, etc. and microorganisms like bacteria, viruses, fungi, etc.

The commercial catalyst Degussa P25 is very efficient but it is activated with UV light only. To extend the TiO2 activation to visible light, various atoms such as N, P, or metallic nanoparticles (Pt, Cu, Ag, ) are added. Another way to activitate TiO2 with visible light is the dye-sensitization with porphyrins or phtalocyanins for example. In that case, dyes are grafted on TiO2. However, these kinds of catalysts are not stable.

To obtain a good stability and to extend its photocatalytic activity to visible light, TiO2 has been doped in situ through the cogelation sol-gel proces with two dyes : free metal tetra(4-carboxyphenyl)porphyrin and nickel tetra(4-carboxyphenyl)porphyrin. UV-Vis diffuse reflectance and FT-IR spectroscopies have been performed to determine the interaction between porphyrins and TiO2. Cristallinity and specific surface area have been measured by XRD and N2 adsorption. The photoactivity of the doped TiO2 xerogels has been evaluated for p-nitrophenol (a model water pollutant) degradation under visible light and a kinetic study has been performed. The samples allow the degradation of 40% of p-nitrophenol in 6 h which makes them very promising for water decontamination under natural light. A kinetic study of p-nitrophenol degradation with the Ni-doped catalyst has shown that the best kinetic model involves one type of active site corresponding to the hole h+ of electron-hole pairs created at the TiO2 surface by light. The rate determining step consists of the surface reaction between adsorbed p-nitrophenol and adsorbed OH radicals.

mailto:b.heinrichs@ulg.ac.be

Catalytic air cleaning using nanomaterials Nataa Novak Tuar1,2

1National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia natasa.novak.tusar@ki.si 2University of Nova Gorica, Vipavska 13, 5000 Nova Gorica, Slovenia

Volatile organic compounds (VOCs), emitted mainly from industrial processes,

transportation and consumer products, represent the main class of air pollutants. Two principle methods are available for improving air quality: source control and air cleaning. The European Union has issued directives to limit VOC emissions (50100 mgC/Nm3),[1] but they still remain a problem due to their highly toxic and carcinogenic nature. In this work, we focus on a possible way to manage VOC exhaust by treating industrial waste gases with catalysts. Transition metal oxides immobilized on a suitable support are a low-cost alternative to currently used noble metal-containing catalysts. The nature of the support and the method of immobilization are critical as the surface area and functionality determine the nature and dispersion of the metal oxide nanoparticles and hence their catalytic activity. Mesoporous silica supports have been of particular interest because of their high specific surface areas. We have recently demonstrated the nature and reducing properties of silica supported copper oxide nanoparticles and found out that these are influenced by the peculiarity of silica with interparticle mesoporosity and the presence of iron as a second metal in the silica matrix.2,3,4 An overview on the design and development of bimetal nanostructured catalyst with superior catalytic activity for removal of VOCs from industrial waste gases will be presented. References 1. VOC Solvent Emissions Directives of European Union, Council Directive 1999/13/EC,

Paint directive 2004/42/EC. 2. M. Popova, A. Risti, K. Lazar, D. Mauec, M. Vassileva, N. Novak Tuar,

ChemCatChem (2013) 5, 986. 3. M. Popova, A. Risti, M. Mazaj, D. Mauec, M. Dimitrov, N. Novak Tuar,

ChemCatChem (2014) 6, 271. 4. M. Rangus, M. Popova, G. Drai, M. Mazaj, A. Risti, V. D. B. C Dasireddy, B. Likozar,

N. Zabukovec Logar, N. Novak Tuar, ACS Catalysis (2017), in preparation.

mailto:natasa.novak.tusar@ki.si

Molten salt colloidal synthesis towards rare compositions at the nanoscale D. Portehault1

1 Sorbonne Universits UPMC Univ Paris 06 - CNRS - Collge de France, UMR 7574 Chimie de la Matire

Condense de Paris Collge de France, 11 place Marcelin Berthelot, 75231 Paris Cedex 05, France,

david.portehault@upmc.fr

Liquid phase materials syntheses provide exquisite control of crystal, nano-, meso- and micro-structures. Although such pathways are studied since three decades for nanostructured metals, chalcogenides and simple metal oxides, other compounds families were only scarcely, if ever, reported at the nanoscale. These systems include complex multicationic oxides and alloys containing heteroelements (e.g. boron). They show at the bulk scale mechanical, catalytic, optical and electronic properties without equivalent among usual compounds. The design of corresponding nanostructures, especially nanoparticles with large versatility in size, shape and dispersion, could therefore lead to important changes or enhancement of existing properties and emergence of new behaviors. This presentation will highlight recent developments in original liquid-phase syntheses based on inorganic molten salts as solvents. The aim is to design functional nanomaterials with innovative elemental compositions. Several cases showing different properties than bulk phases will be presented: (1) nanoscale metal-boron alloys for thermoelectricity, catalysis, and hard materials,[14] (2) multicationic perovskite oxide nanocrystals (Figure), showing unprecedented spin transport properties.[5]

1. D. Portehault, S. Devi, P. Beaunier, C. Gervais, C. Giordano, C. Sanchez, M. Antonietti,

Angew. Chem. Int. Ed. (2011) 50, 3262. 2. W. Lei, D. Portehault, R. Dimova, M. Antonietti, J. Am. Chem. Soc. (2011) 133, 7121. 3. S. Carenco, D. Portehault, C. Boissire, N. Mzailles, C. Sanchez, Chem. Rev. (2013) 113,

7981. 4. G. Gouget, P. Beaunier, D. Portehault, C. Sanchez, Faraday Discuss. (2016) 191, 511. 5. H. Le Thi NGoc, L. D. N. Mouafo, C. Etrillard, A. Torres-Pardo, J.-F. Dayen, S. Rano,

G. Rousse, C. Laberty-Robert, J. G. Calbet, M. Drillon, et al., Adv. Mater. (2016) 10.1002/adma.201604745.

Figure. Scanning transmission electron microscopy of a nanoparticle of La0.67Sr0.33MnO3 perovskite recorded in high angle annular dark field mode, showing atom columns.

Development of indicator dyes for smart sensor textiles and non-wovens G. J. Mohr

JOANNEUM RESEARCH Forschungsgesellschaft mbH Materials, Franz-Pichler-Strasse 30

A-8160 Weiz, Austria, e-mail: gerhard.mohr@joanneum.at The design of indicator dyes to be used with textiles and non-wovens is challenging, because the requirements for textiles and non-wovens are challenging. The flexibility of textiles and non-wovens must not be compromised. Textiles are washed at up to 90 C and are ironed at even higher temperatures. Non-wovens are frequently sterilized. We design and synthesize new indicator dyes which exhibit a vinylsulfonyl group for covalent linkage to cellulose-based textile materials. Thus, leaching is prevented even when washing the sensor materials in conventional washing machines using alkaline laundry detergents. Furthermore, the dyes exhibit receptor functions to recognize ions such as sodium or magnesium ion. By immobilising indicator dyes to cellulose particles and proper use of polymer matrix materials, sensors for biogenic amines can be obtained. Furthermore, the possible combination of indicator dyes with cellulose nanofibres is discussed. Several examples for sensor textiles and non-wovens are given, e.g. indicator cotton swabs for detecting pH in wounds or a T-shirt with sensitivity to sodium ions. They are characterised in terms of colour changes as well as sensitivity and selectivity.

Potential of -cyclodextrin@guest compound inclusion complexes as key units for molecular

exchange based sensing layers T. Szab*, A. Shaban, T. Marek, B. Csupor, Zs. Keresztes

Research Centre for Natural Sciences, Hungarian Academy of Sciences,

Magyar tudsok krtja 2., Budapest, 1117 Hungary, *szabo.84.tamas@ttk.mta.hu

Cyclodextrins (CDs) are hollow supramolecular structures with the ability of hosting hydrophobic molecules or fragments, forming inclusion complexes. This feature makes them suitable for molecular separation and sensing. In our work we are focusing on the applicability of exchange reactions (guest- or host exchange) in sensor developments. pH response of amphoteric indicators (i.e. methyl red) in aqueous environment in the presence of CDs can depend on the extent of hydrophobic inclusion. Covalently linked switchable CD-indicator inclusion complexes has been already used[1] to detect solvation effects by colour change. Recently, we have used different CD derivatives to realize tunable solvation effect detection. Solid thin layer of CD-indicator inclusion complexes were formed by drop casting method. Occupancy of solid state CDs by the indicator were recorded with positron annihilation technique. Extraction of indicator by different solvents has been followed by UV-Vis spectrophotometry. CD-indicator inclusion complexes were also applied as thin layers on the surface of quartz crystal microbalance (QCM) when detected mass change could be correlated to the exchange of guest molecules. Ferrocene (Fc) is a hydrophobic compound often used as mediator in electrochemical systems. Encapsulation, thus water solubilisation of ferrocene can be achieved with amphiphilic carriers, such as protein capsules or cyclodextrines. Host exchange can be a concept to detect the sensitivity of capsules to different environmental effects, in case of degradation the capsules release the host molecules giving electrochemical signal. CDs can be used as secondary hosts to validate the signal. Effect of proteolytic enzyme system on casein capsules have been verified is such a way. References 1. A. Hashidzume, Y. Takashima, H. Yamaguchi, A. Harada; Molecular Sciences and Chemical

Engineering Elsevier Inc. (2017)

1D nanostructures and 3D vertically aligned nanostructured arrays for sensing

applications K. agar Sodernik1, L. Suhadolnik1, C. Fabrega2, F. Hernandez-Ramirez2,3, J. D. Prades3, J. R.

Morante2,3 and M. eh1 1Department for Nanostructured Materials, Joef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia

2Catalonia Institute for Energy Research (IREC), Jardins de les Dones de Negre 1, 08930 Sant Adri de Bess,