Exploratory research project, funded by CNCSIS, program PN II ‘Idei’ Title: Multilayer Hybrid Nanoparticles. Synthesis, Characterisation, Properties and Potential Applications in Supramolecular Chemistry, Biochemistry, Catalysis. Director: Dr. Petre Ionita Lenght: 01.10.2007-30.09.2010

Budget: Nr. Crt Budget chapter 2007 2008 2009 2010 Total (lei) 1. Personnel 27000 108000 81000 324000 2. Indirect costs 14600 58400 43800 175200 3 Mobilities 20000 25600 80000 60000 185600 4. Logistics 11400 100000 45600 34200 191200 5. 73000 292000 219000 876000

Summary: The project aims the obtaining of nanometric size hybrid assemblies by controlled synthesis; these assemblies are made by successive deposition of different concentric layers of organic or inorganic type on a metallic core (gold) or on metal oxide core (iron oxides). Each layer (including the core surface) may be functionalized in a different (individual) way, leading thus to a spatial (regional) accumulation of the significant properties; in a cumulative way, it may be possible that a co-operation between different layers to led to new interesting properties, leading to the acquisition of nanomaterials with remarkable multifunctional properties. We aim also the labeling of such materials with different organic compounds, with optical, fluorescence, complexing, paramagnetic and biological active compounds. The multilayer hybrid nanoparticles will be characterized by different general physico-chemical measurements (UV-Vis, IR, NMR, TEM) and also by particular measurements (as function of the label, such as fluorescence, magnetism, etc.). The properties of the new hybrid multilayer nanoparticles will be studied involving them in different physical, chemical or biological processes, using the methods and the procedures of supramolecular chemistry, biochemistry and heterogeneous catalysis. Joining together different properties and different behaviors (as each layer has its own characteristics) open the way of interesting applications of these materials.

Objectives: 1. Synthesis of gold, magnetite and hematite nanoparticles; 2. Deposition of a silica layer on these nanoparticles; 3. Derivatization of the hybrid nanoparticles with different (bio)chemical compounds; 4. Involvement of the hybrid derivatized nanoparticles into different (bio)chemical processes.

Team: Name Birth date Job Ph. D. Petre Ionita 1967 CS II yes Luminita Patron 1947 CS I Elena Gabriela Ionita 1969 Reseacher Gabriela Marinescu 1972 CS III Daniela Culita 1979 student Marioara Bem 1977

CV Petre Ionita The Director of this project gain his organic chemistry license from University of Bucharest in 1992; in 1993 he enrolled into a Ph. D. program at Polytechnic University of Bucharest, defending his thesis (Diphenyl-picryl-hydrazyl derivatives as modeling compounds in interphasic acid-base and redox processes) in 1997; since his license till today he is working in the Institute of Physical Chemistry. Advanced knowledge in: Structural physico-chemical investigations (UV-VIS, IR, NMR, EPR, MS, CV, HPLC, GC, Chromatography;. Organic synthesis of free stable radical;. Spin labeling of gold nanoparticles. Laboratory experience and main areas of research interests: -organic and analytical skills; -synthesis of free stable radicals and diradicals; -generation of short-lived and of persistent free radicals; -electronic paramagnetic resonance (EPR); -spin-trapping of short-lived free radicals; -unconventional nitration, ipso-substitution and mechanistic studies; -spin-labeling and labeling with stable isotopes; -experience with spectro-chemical and physico-chemical analysis; -interphase transport of cations, protons, electrons, and amino-acids using crown compounds; -pKa determinations; -extraction and molar ratio determination of supramolecular complexes; -experimental and theoretical determination of lipophilicities; -chromatographic techniques (TLC, RPTLC); -spin-labeled nanoparticles. 1. C. Ghica, P. Ionita, J. Mat. Sci, 2007, 42, 10058-10064. 2. P. Ionita, F. Tuna, M. Andruh, T. Constantinescu, A. T. Balaban, Aust. J. Chem., 2007, 60, 173-179. 3. P. Ionita, Free Radic. Res., 2006, 40, 59-65. 4. V. Chechik, P. Ionita, B. C. Gilbert, A. Caragheorgheopol, H. Caldararu, H. Wellsted, A. Korte, Faraday Discuss., 2004, 125, 279-91. 5. P. Ionita, A. Caragheorgheopol, V. Chechik, and B. C. Gilbert, J. Am Chem. Soc., 2002, 124, 9048-9.

CV Patron Luminita Over 112 papers, 13 patents (5 in use), 1 book, 1 monography, over 20 national and international conferences. Gas-cromatography and complexes chemistry. Synthesis and characterization of mono- and poly-nuclear compounds. Coordinative chemistry and application of patents in practical purposes. Oxidic materials and precursors in complex coordinative chemistry. 1) Daniela C. Culita, G. Marinescu, L. Patron and N. Stanica, Rev. Roum. Chim., 2006, 51(6), 503-508. 2) G. Marinescu, L. Patron, Daniela C. Culita, C. Neagoe, C. I. Lepadatu, I. Balint, L. Bessais and C. Bazil Cizmas, Journal of Nanoparticle Research, 2006, 8(6), 1045-1052. 3) D. Gingasu, I. Mîndru, L. Patron, O. Carp, D. Matei, C. Neagoe, I. Balint, J. Alloys Compd., 2006, 425, 357-361. 4) O. Carp, D. Gingaşu, I. Mîndru, L. Patron, Thermochim. Acta, 2006, 449, 55-60. 5) Daniela C. Culita, L. Patron, V. S. Teodorescu, I. Balint, Journal of Alloys and Compounds, 2007, 432, 211-216.

CV Elena Gabriela Ionita 1993-2002, University of Pitesti; since 2002 researcher at Institute of Physical Chemistry Bucharest. Expertise: EPR, IR, UV-Vis spectroscopy, cyclic voltammetry, TLC, organic synthesis, cyclodextrins, spin labelling. International fellowships: - NATO/Royal Society (2004-5): “Spin-Labelled Cyclodextrins: Novel Supramolecular Receptor/Reporter Units” at York University, UK; -September – December 2005, Royal Society -Short visit fellowship (York University, UK); -February-August 2006, study visit at York University CEEX 2/2005; -COST P15 – STSM, January-March 2007 (York University, UK), COST P15 – STSM June 2007, (Institute Weizmann, Rehovot). 1. Gabriela Ionita, Viorica Meltzer, Elena Pincu, Victor Chechik, Org. Biomol. Chem, 2007, 5, 1910. 2. Victor Chechik, Gabriela Ionita, Organic & Biomolecular Chemistry, 2006, 3(17), 3505. 3. Gabriela Ionita, Victor Chechik, Organic & Biomolecular Chemistry, 2005, 3(17), 3096. 4. Agneta Caragheorgheopol, Horia Caldararu, Gabriela Ionita, and Florenta Savonea, Langmuir 2005, 21, 2591 5. Gabriela Ionita, V. Sahini, J. Incl. Phenom. Macrocycl. Chem., 2004, 50, 183.

CV Gabriela Marinescu Bucharest University degree-Faculty of Chemistry (1996), master (1997), Ph. D. diploma (2003). Post-doctoral fellowship, France (2005-2006); other short visits (several months) in France and Spain. 24 published papers. Competence: Thermo-chromism. Reactions in solid state. Poly-nuclear complexes. Synthesis of complex homo- and hetero-polynuclear derivatives (poly-metallic self-assemblies). Poly-metallic supramolecular architectures. Advanced materials, nanomaterials; synthesis and characterization. 1) G. Marinescu, M. Andruh, M. Julve, F. Lloret, R. Llusar, S. Uriel, J. Vaissermann, Cryst. Growth & Design 2004, 5, 261-267. 2) L. Patron, O. Carp, I. Mindru, G. Marinescu, N. Stanica, I. Balint, J. Serb. Chem. Soc., 2005, 70(8), 1049-1056. 3) Daniela C. Culita, G. Marinescu, L. Patron and N. Stanica, Rev. Roum. Chim., 2006, 51(6), 503-508. 4) G. Marinescu, L. Patron, Daniela C. Culita, C. Neagoe, C. I. Lepadatu, I. Balint, L. Bessais and C. Bazil Cizmas, Journal of Nanoparticle Research, 2006, 8(6), 1045-1052. 5) G. Marinescu, S. Ferlay, N. Kyritsakas, Mir W. Hosseini, Dalton Transction, 2008, in press.

CV Daniela Culita Design and Synthesis of Coordination Compounds; Supramolecular Chemistry; Synthesis of functionalized iron oxide nanoparticles for biomedical applications. 1. Daniela C. Culita, L. Patron, V. S. Teodorescu, I. Balint, Journal of Alloys and Compounds, 2007, 432, 211-216. 2. G. Marinescu, L. Patron, Daniela C. Culita, C. Neagoe, C. I. Lepadatu, I. Balint, L. Bessais and C. B. Cizmas, Journal of Nanoparticle Research, 2006, 8, 1045-1051. 3. Daniela C. Culita, G. Marinescu, L. Patron and N. Stanica, Rev. Roum. Chim., 2006, 51(6), 503-508. 4. Daniela C. Culita, L. Patron, G. Marinescu, T. Constantinescu, R. Alexandrova and G. Rashkova, Rev. Roum. Chim., 2005, 50(9-10), 745-749. 5. J. Stoyloff, R. Alexandrova, Daniela C. Culita, L. Patron and S. Ivanov, Experimental Pathology and Parasitology, 2005, 8/3, 3-12.

CV Marioara Bem Professional experience: the supramolecular chemistry areas (catalysis through interphase transfer), fine synthesis of organic compounds (through SNAr and SN2 mechanism), the projection of structural molecular design for specific physical-chemical properties (dynamic and covalent chemistry) purifycation of organic compounds (selective extractions, preparative chromatography) physical-chemical characterizations (UV-Vis, IR, 1H- and 13C-NMR, experimental determination of hydrophobic/hydrophilic balance by HPTLC and, the calculation of this properties respectively using the influence parameters of the different molecular groups. 1. M. Bem, F. Badea, C. Draghici, M.T. Caproiu, M. Vasilescu, M. Voicescu, A. Beteringhe, A. Caragheorgheopol, M. Maganu, T. Constantinescu and A.T. Balaban, Arkivoc, 2007, XIII, 87-104. 2. M. Bem, M.Vasilescu, M.T.Caproiu, C. Draghici, A. Beteringhe, T. Constantinescu, M.D. Banciu, A.T. Balaban, Central European Journal of Chemistry, 2004, 2(4), 672-685. 3. M. Bem, M.T. Caproiu, M.Vasilescu, M. Tudose, R. Socoteanu, A. Nicolae, T. Constantinescu and M.D. Banciu, Revue Roumaine de Chimie, 2003, 48(9), 709-715. 4. M. Bem, M.T. Caproiu, D. Stoicescu, T. Constantinescu and A.T. Balaban, Central European Journal of Chemistry, 2003, 3, 260-276. 5. M. Bem, D. C. Culita, M.T. Caproiu, T. Constantinescu and M. D. Banciu, Revue Roumaine de Chimie, 2003, 48(5), 387-392.

Results: No. Journal Year Vol. Pages Description 1 Mat. Sci. (Poland) 2007 25 1011-1017 Gold nanoparticles, labeled or not with spins (stable free radicals), were synthesized and deposited on cellulose (labeled or not with spins), and interaction between spins studied. 2 J. Inorg. Organomet. Polym. 2008 18 414-419 Hybrid metal-inorganic (gold-silica) nanoparticles were synthesized and characterized; these were derivatized with different spins (spins attached to gold, silica, or both). 3 Rev. Roum. Chim. 53 The interaction between stable biradicals and cyclodextrins has been studied, in order to get preliminary data for nanoparticles studies. 4 J. Mat. Sci. 43 6571-6574 The dual behavior of Au nanoparticles, as generators and scavengers of short-lived radicali species has been proved. 5 Arkivoc xiv 158-165 Di-, tri- and tetra-radicals were synthesized and characterized, as well as their interaction with gold nanoparticles.