Coordination Polymer Nanoparticles: New bjects and New Trends. Joulia Larionova - A new type of inorganic nanoparticles - Multifunctional magneto-optical nanoparticles - New contrast agents for MRI and biolabeling
A New type of Inorganic Nanoparticles: Coordination Polymer Nanoparticles Porous Iron Carboxilates Frameworks Nanoparticles ~2 nm Cyano-Bridged Metallic Nanoparticles 1-1 nm Nanocubs of Fe III 4[Fe II (CN) 6 ] 3 G. Ferey, Nature Materials 21, 9, 172 S. Mann, Angew. Chem. Int. Ed., 2, 39, 1793
Cyano-Bridged Metallic Coordination Polymer Nanoparticles The oldest bulk coordination polymers Prussian Blue: Fe III 4[Fe II (CN) 6 ] 3 Discovered in174 M x [M (CN) n ] y M and M = transition metal ions or lanthanides Johann Conrad Dippel - a pigment; - magnetic properties: molecular magnets; - photo-magnetic properties; - host-guest properties: molecular sieves;
Cyano-Bridged Metallic Coordination Polymer Nanoparticles Determined and modified properties Determined structure numerous structures are available Controlled size, shape and organization Multifunctional nanoparticles Coordination Polymer Nanoparticles (CPNs) Controlled physical and chemical properties. Porous nanoparticles Biocompatibility? Appearance of new properties? Ultra-small nanoparticles (< 1 nm)
Nanoparticles into mesostructured silica Nanoparticles into chitosan N N N N N N H New J. Chem., 28 H NH 2 n Nanoparticles of cyano-bridged coordination polymers Chem Commun. 26; Dalton Trans. 28 Angew. Chem. 29 Nanoparticles into Ionic Liquids N R + N, BF - 4 N + N 11, BF - 4 Nanoparticles with Ligands M(An) n.6h 2 + [N(C 4 H 9 ) 3 ] 3 [M'(CN) 6 ] R 3 N R'CH THF Chem: Eur. J., 26; Inorg. Chim. Acta 27, 28 Chem.Mater., 27
Water Soluble Cyano-Bridged Metallic Nanoparticles enwrapped by biopolymer chitosan Why we use the chitosan beads? - a porous structure - diffusion of precursors; - NH 2 groups able to coordinate metal ions - H - high water solubility; - biocompatibility. H NH 2 n SEM SEM
Water Soluble Cyano-Bridged Metallic Nanoparticles enwrapped by biopolymer chitosan H H NH 2 n M n+ Chitosan [M (CN) n ] m- Nanocomposite beads Colloïdal solutions M 2+ = Fe, Ni, Co, Mn, Cu and M 3+ = Gd, Yb, Eu M = Fe, Cr, Co (n = 6); Ni, Pt (n = 4), Mo (n = 8) Chem Commun. 26; Dalton Trans. 28, Angew. Chem. 29, PCCP 21
ccurence ccurence Ni 2+ /[Fe(CN) 6 ] 3- /chitosan Nanoparticles Beads of Ni 2+ /[Fe(CN) 6 ] 3- /chitosan 12 1 8 6 4 2 Aqueous colloid of Ni 2+ /[Fe(CN) 6 ] 3- /chitosan 1 8 6 4 2 1 2 3 4 6 7 8 9 1 Diameter / nm 2.8 nm 1 2 3 4 6 7 8 9 1 Diameter / nm 2.8 ±.8 nm 4.2 ± 1. nm
Magnetic Properties as a probe to study nanoparticles behavior 1 Dynamic analysis: Colloids Ni 2+ /[Fe(CN) 6 ] 3- /chitosan.8 3 2 Diluted sample: T max =9.K FC T max =11.K.6.4.2 M / emu L -1 2 1 1 T max =11.K M/M Tmax ZFC 1 1 2 2 T / K H = 1 e.12.1.8.6.4.2 1 Hz 12 Hz 498 Hz 998 Hz 1488 Hz 8 12 16 2 24 T / K ' / emu L -1 Diluted sample '' / emu L -1 Diluted sample 4 8 12 16 2 T / K
log(1/(2 f)) Magnetic Properties as a probe to study nanoparticles behavior Critical slowing down: = [T g /(T max T g )] zv -. -1 Concentrated Colloid T g, K, s z Colloids Ni 2+ /[Fe(CN) 6 ] 3- /chitosan 11.2 3.6 1-12 12.4 Diluted Ni 2+ /[Fe(CN) 6 ] 3- /chitosan 9. 7.29 1-11 11.7 z = 4 12; = 1-8 1-13 s -1. -2-2. -3-3. Diluted Colloid Beads -4..6.7.8.9 1 1.1 log(t /(T-T )) g g Superspin-glass behavior due to the presence of interparticle interactions and surface spin frustration
Coordination Polymer Nanoparticles as Contrast Agent for Magnetic Resonance Imaging: Paramagnetic Gd 3+ complexes: positives CA Porous Iron Carboxilates Frameworks Nanoparticles mniscan, Gadoteridol, Dotarem SPINs: negatives CA Fe 3 4 Resovist, Combidex, Endorem G. Ferey, Nature Materials 21, 9, 172
r 1p (mm -1 s -1 ) Gd[Fe(CN) 6 ]/chitosan Nanoparticles H H NH 2 n Longitudinal relaxivity 4 T =2 C 3 2 1 mniscan ( ) and Gd-DTPA ( ) nm Aqueuse solution.1.1 1 1 1 Size: 4(.4) nm nm (MHz) r ip = [(1/T i ) meas (1/T i ) dia ]/c i=1,2 (1/T i ) meas is the measured value on the sample with concentration c = 4 mmol L -1 of Gd 3+ (1/T i ) dia is the nuclear relaxation rate of water Dalton Trans. 28.
Number of nanoparticles / n Multifunctional Gd. Ln. [Mo(CN) 8 ]/chitosan (Ln = Eu, Tb) Nanoparticles Aqueous colloidal solutions: TEM image 2 Crystal structure of bulk Gd. Ln. [Mo(CN) 8 ] 1 1 HRTEM image 3.6(.9) 1, 2, 2, 3, 3, 4, 4, Diameter / nm
1/ emu -1 g r 2 (mm -1 s -1 ) r 1 (mm -1 s -1 ) Relaxometry of Gd. Ln. [Mo(CN) 8 ]/chitosan (Ln = Eu, Tb) Nanoparticles M / emu g -1 1 8 6 4 2 ' emu g -1..4.3.2.3.3.2.2.1.1.1. 1 1 2 2 3 T / K H = 1 e 1 1 2 2 3 T / K '' emu g -1 6 4 3 2 1 1 1 longitudinal Eu.Gd.[Mo(CN)8] Gd-DTPA T =2 C.1.1 1 1 1 frequency (MHz) Long Scan Std Dev 1/X emu-1 mol r ip = [(1/T i ) meas (1/T i ) dia ]/c i=1,2 transvers Eu.Gd.[Mo(CN)8] mniscan 1 1 frequency (MHz)
(b) (a) Intensity (arb. units) Luminescence of Gd. Ln. [Mo(CN) 8 ]/chitosan (Ln = Eu, Tb) Nanoparticles Excitation wavelengths 28-34 nm: D 7 F -4 (Eu 3+ ) D 4 7 F 6- (Tb 3+ ) Excitation wavelengths 3-464 nm: Gd. Tb. [Mo(CN) 8 ]/chitosan 2 1 2 D4 7 F 6 3 D 4 7 F 4 D 7 F D4 7 F 6 D 7 F 1 D4 7 F 6 D 4 7 F 2-2 3 1 D 7 F 2 64 66 68 x D 7 F 3 D 7 F 4 Gd. Eu. [Mo(CN) 8 ]/chitosan 1 38 43 49 4 6 6 71 Wavelength (nm)
Localization of Gd. Eu. [M (CN) m ] z /chitosan in living colon and pancreatic cancer cells by confocal microscopy. Incubation: 6h at 37 C 1 ng ml -1 Excitation at 489 nm Nuclei Sample 3 Lysosomes Merged HCT116 HCT-116 colon 4 µm Capan-1 pancreatic Capan-1 cancer cells 4 µm
Living fibroblasts (% control) Living HUVEC cells (% control) Living HCT116 cells (% control) Living Capan-1 cells (% control) Toxicity Tests A 12 1 B 12 1 4 days, Concentration: (2, and 1 ng ml -1 ) 8 6 4 8 6 4 (A) Human colorectal cancer cells (HCT116), (B) (B) human pancreatic cancer cells (Capan-1) C 2 12 2 1 Sample 3 (ng/ml) D 2 12 2 1 Sample 3 (ng/ml) 1 1 (C) human fibroblasts (D) human umbilical endothelial HUVEC cells 8 6 4 8 6 4 2 2 2 1 2 1 Sample 3 (ng/ml) Sample 3 (ng/ml)
Summary: Coordination Polymer Nanoparticles Gd[Fe(CN) 6 ]/chitosan Multifunctional Gd. Ln. [Mo(CN) 8 ]/chitosan (Ln = Eu, Tb) Relaxivity Relaxivity, Luminescence
ur group: ICG-CMS, Montpellier PAC-ICG, Montpellier Pr. Ch. Guérin Dr. Y. Guari E. Chelebaeva Dr. B. Folch Dr. A. Tokarev C. Reibel ur partners: Dr. A. Caneschi, Dr. C. Sangregorio INSTM, Florence, Itlay Dr. C. Luna UANL, Mexico Dr. A. Lascialfari, K. Tangawel, M. Marione, IFGCB, Milano, Italy Pr. Luis Carlos, Dr. R. Fereira CICEC, Portugal, Dr. N. Baril LNIA, Marseille, France Dr. M. Garcia, Dr. M. Gary-Bobo IRC, Montpellier, France Dr. K. Molvinger, MACS, ICG, Montpellier