Supporting Information

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1 Submitted as an article to Phys. Chem. Chem. Phys., February Revised April 2010 Supporting Information Synthesis and Studies of Water Soluble Prussian Blue-Type Nanoparticles into Chitosan Beads. Benjamin Folch, a Joulia Larionova,* a Yannick Guari, a Karine Molvinger, b Carlos Luna, c& Claudio Sangregorio,* c,d Claudia Innocenti, c Andrea Caneschi c and Christian Guérin. a a Institut Charles Gerhardt Montpellier, UMR 5253 CNRS-UM2-ENSCM-UM1, Chimie Moléculaire et Organisation du Solide, Université Montpellier II, Place E. Bataillon, Montpellier cedex 5, France. Fax: (33) , joulia@univmontp2.fr. b Institut Charles Gerhardt Montpellier, UMR 5253 CNRS-UM2-ENSCM-UM1, Matériaux Avancés pour la Catalyse et la Santé, ENSCM, 8 rue de l Ecole Normale, Montpellier cedex 5, France. c INSTM Research Unit-Dipartimento di Chimica, Università di Firenze, via della Lastruccia 3, Sesto F.no, Firenze, Italy. claudio.sangregorio@unifi.it d C.N.R,-I.S.T.M. Milano, via C. Golgi 19, Milano, Italy. & Present adress: Facultad de Ciencias Físico-Matemáticas, Universidad Autónoma de Nuevo León. Av. Pedro de Alba s/n, San Nicolás de los Garza, Nuevo León, México. / Centro de Innovación, Investigación y Desarrollo en Ingeniería y Tecnología, Universidad Autónoma de Nuevo León, Parque de Investigación e Innovación Tecnológica (PIIT), Autopista Aeropuerto Km. 10, C.P Apodaca, Nuevo León, Mexico.

2 Table 1S. Magnetic data for the samples 1 4. Supplementary Material (ESI) for PCCP Samples T max a, Vogel-Fulcher law 2D model (T g =0K) K ι 0, s E a /k B, T 0, K τ 0, s E a /k B, K zν K 1a (5) 2.0± (3) 0.5 1b (9) 1.9± (10) 0.3 1c (3) 2.1± (8) 0.3 2a (2) 1.7± (6) 3.2 2b (8) 1.1± (1) 0.5 3a (1) 1.3± (4) 1.4 4a < a maximum value on the ZFC curve.

3 1 Abs. / Arb. units Wavelength / nm Figure 1S. UV-Vis spectra for the composite beads M 2+ /chitosan (M 2+ = Ni 2+, Cu 2+, Co 2+, Mn 2+ ). (- -) for Ni 2+ /chitosane, (-o-) for Cu 2+ /chitosane, (-Δ-) for Co 2+ /chitosan and ( x-) for Mn 2+ /chitosane.

4 a) Pristine chitosane beads Cu 2+ /[Fe(CN) 6 ] 3- /chitosan Co 2+ /[Fe(CN) 6 ] 3- /chitosan Fe 2+ /[Fe(CN) 6 ] 3- /chitosan Ni 2+ /[Fe(CN) 6 ] 3- /chitosan b) Fe 2+ /[Fe(CN) 6 ] 3- / chitosan Cu 2+ /[Fe(CN) 6 ] 3- / chitosan Ni 2+ /[Fe(CN) 6 ] 3- / chitosan Co 2+ /[Fe(CN) 6 ] 3- / chitosan Figure 2S. a) Photographical images of the pristine chitosan beads and the nanocomposite beads 1a 4a and b) of the nanocomposite beads 1a-4a along with the respective aqueous colloids 1b-4b.

5 5 nm Figure 3S. HRTEM image of sample 1b showing the cyano-bridged metallic core of a nanoparticle surrounded with an eye-guide.

6 Figure 4S. The nitrogen physisorption isotherms of the pristine chitosan and after cyanobridged networks incorporation in the case of nanocomposite 4a.

7 c H B 6 8 : N i - F e / C h i t o s a n H z Supplementary Material (ESI) for PCCP Co-Fe/ Chitosan χ, (Arbitrary Units) 6.0x x x10-4 HB64: Co-Fe/Chitosan Hz Hz 262 Hz 424 Hz Hz Hz Hz 2912 Hz 4714 Hz 7632 Hz 12,355 Hz 20,000 Hz χ,, (Arbitrary Units) 8.0x10-5 HB64: Co-Fe/Chitosan 6.0x x x Hz 424 Hz Hz Hz Hz 2912 Hz 4714 Hz Hz Hz χ, (emu/mol) χ, (Arbitrary Units) χ, (Arbitrary Units) HB66: Fe-Fe/Chitosan Hz 262 Hz Hz Hz Hz Hz 2912 Hz 4714 Hz 7632 Hz Hz Hz HB68: Ni-Fe/Chitosan HB65: Cu-Fe/Chitosan Hz Hz 3,039 Hz 10,673 Hz 20,000 Hz Hz Hz Hz 3,039 Hz 20,000 Hz Ni-Fe/ Chitosan χ,, (emu/mol) Fe-Fe/ Fe/ Chitosan χ,, (Arbitrary Units) 2.5x x x x x x10-4 HB66: Fe-Fe/Chitosan 6.0x x x Cu-Fe/ Chitosan (Arbitrary Units),, HB65: Cu-Fe/Chitosan Hz Hz 3,039 Hz 10,673 Hz 20,000 Hz Hz 262 Hz Hz Hz Hz Hz 2912 Hz 4714 Hz 7632 Hz Hz Hz Hz Hz Hz 3039 Hz Hz 20000Hz

8 Mn-Cr/chitosan 0,10 x', x'' emu/g 0,08 0,06 0, Hz 997 Hz 498 Hz 125 Hz 1 Hz 0.25 Hz 0,02 0, T / K Frequencies: 0.25 Hz (-ο-), 1 Hz (- -), 125 Hz (- -), 498 ( ), 997 (- -) and 1488 (- -). Ni-Cr/chitosan χ' / emu g χ'' / emu g T / K T / K Frequencies: 0.25 Hz (-ο-), 1 Hz (- -), 125 Hz (- -), 498 ( ). Figure 5S. a) Temperature dependences of in-phase, χ, (left) component of the ac susceptibility and out-of-phase, χ, component of the ac susceptibility of 2-6 with zero dc magnetic field.

9 ln(1/(2pf)) /T max Figure 6S. Arrhenius fit for the samples 1a ( ), 1b (ο) and 1c ( ).

10 ln(1/(2pf)) /(T-T ) 0 Figure 7S. a) Thermal variation of the relaxation time according to the Vogel-Fulcher law for 1a ( ), 1b (ο) and 1c ( ) samples.

11 M / emu/mol T / K Figure 8S. ZFC/FC curve for the bulk compound Ni 3 [Fe(CN) 6 ] 2.

12 Figure 9S. IR spectra of (a) the pristine chitosan, (b) composite bead Ni 2+ /chitosan, c) sample 1a.

13 A α T (K) 1.0 B 0.8 α T (K) C α T (K) Figure 10S. Thermal dependence of the α parameter obtained from fit to equation (4) for 1a (A), 5a (B) and 6a (C)..

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