Achieving metal-organic frameworks (MOFs) in the form of nanoparticles (NanoMOFs) represents a re... more Achieving metal-organic frameworks (MOFs) in the form of nanoparticles (NanoMOFs) represents a recent challenge due to the possibility to combine the intrinsic porosity of these materials with the nanometric dimension, a fundamental requirement for strategic biomedical applications. In this outlook we envision the current/future opportunities of the NanoMOFs in the field of biomedicine, with particular emphasis on (i) biocompatible MOFs composition; (ii) MOFs miniaturization and (iii) nanoMOFs applications.
Artificial nano-heterostructures (NHs) with controlled morphology, obtained by combining two or m... more Artificial nano-heterostructures (NHs) with controlled morphology, obtained by combining two or more components in several possible architectures, make them suitable for a wide range of applications. Here, we propose an oleate-based solvothermal approach to design silver-spinel ferrite flower-like NHs. Small oleate-coated silver nanoparticles were used as seeds for the growth of magnetic spinel ferrite (cobalt ferrite and spinel iron oxide) nanodomains on their surface. With the aim of producing homogeneous flower-like heterostructures, a careful study of the effect of the concentration of precursors, the reaction temperature, the presence of water, and the chemical nature of the spinel ferrite was carried out. The magnetic and optical properties of the NHs were also investigated. A heterogeneous growth of the spinel ferrite phase on the silver nanoparticles, through a possible defect-assisted mechanism, was suggested in the light of the high concentration of stacking faults (intrin...
The effect of the annealing temperature Tann on the magnetic properties of cobalt ferrite nanopar... more The effect of the annealing temperature Tann on the magnetic properties of cobalt ferrite nanoparticles embedded in an amorphous silica matrix (CoFe2O4/SiO2), synthesized by a sol-gel auto-combustion method, was investigated by magnetization and AC susceptibility measurements. For samples with 15% w/w nanoparticle concentration, the particle size increases from ~2.5 to ~7 nm, increasing Tann from 700 to 900 °C. The effective magnetic anisotropy constant (Keff) increases with decreasing Tann, due to the increase in the surface contribution. For a 5% w/w sample annealed at 900 °C, Keff is much larger (1.7 × 106 J/m3) than that of the 15% w/w sample (7.5 × 105 J/m3) annealed at 700 °C and showing comparable particle size. This indicates that the effect of the annealing temperature on the anisotropy is not only the control of the particle size but also on the core structure (i.e., cation distribution between the two spinel sublattices and degree of spin canting), strongly affecting the ...
As a contribution to understand the interactions between mineral surfaces and organic molecules, ... more As a contribution to understand the interactions between mineral surfaces and organic molecules, this study reports an accurate characterization of the bis-(2-ethylhexyl) phthalate (DEHP)-Hydrozincite (DEHP-HY), that has been conduced combining the following techniques: FTIR, NMR, XAS spectroscopies and XRD. XRD patterns indicate that the HY is made of nanocrystals whose size is not influenced by the presence of DEHP. The (1)H NMR analysis of DEHP-HY samples points out the presence of interactions of DEHP with HY. CPMAS NMR analysis suggests that the interaction is operated by ester carbonyl groups while the aliphatic chain, as expected, is not involved. MAS and CPMAS NMR measurements, performed on (13)C ester carbonyl enriched DEHP, allow to demonstrate that there are two ester carbonyl linkage sites interacting at the HY surface: an acid site with a strong link and a second one with weak chemical interactions. Zn K-edge XAS spectroscopy demonstrates that the local atomic structure around Zn in DEHP-HY sample remains essentially unchanged with respect to that of HY. Such a weak structural effect suggests that HY interaction with DEHP is limited to the nanoparticle surface.
A series of Fe2O3-SiO2 nanocomposites (25 weight % of Fe2O3) has been prepared using a sol-gel me... more A series of Fe2O3-SiO2 nanocomposites (25 weight % of Fe2O3) has been prepared using a sol-gel method. Samples showing different features were obtained by varying the evaporation conditions acting on the surface / volume ratio of the starting sol. The samples were investigated using Mössbauer spectroscopy at low temperature. The Fe2O3 nanoparticles have been identified as maghemite ( γ-Fe2O3) particles. The samples show a superparamagnetic behavior with a blocking temperature that depends on the average particle size.
A series of Fe2O3 -SiO2 nanocomposites (9 -33 wt% of Fe2O3) has been prepared by a sol-gel method... more A series of Fe2O3 -SiO2 nanocomposites (9 -33 wt% of Fe2O3) has been prepared by a sol-gel method and submitted to thermal treatments at 300 -900 °C. The samples were characterized by X-ray diffraction and Mössbauer Spectroscopy measurements. Superparamagnetic behavior is exhibited by all the samples, indicating that the size of iron oxide grains is in the nanometer range (4-6 nm). Increase of iron content and temperature treatment give rise to a small particle growth, while the spread of sizes around the average value increases with the iron concentration. The Mössbauer spectra, at all the explored compositions, show a very steep increase of the peak width by treatment temperature at 900 °C, indicating the formation of the ferrimagnetic γ-Fe2O3 phase from the antiferromagnetic amorphous Fe2O3 phase, which dominates in the samples treated at lower temperatures. The samples at 28.5% and 33.2%, treated at 900 °C, also show a component of γ-Fe2O3 in the blocked state at room temperatur...
Achieving metal-organic frameworks (MOFs) in the form of nanoparticles (NanoMOFs) represents a re... more Achieving metal-organic frameworks (MOFs) in the form of nanoparticles (NanoMOFs) represents a recent challenge due to the possibility to combine the intrinsic porosity of these materials with the nanometric dimension, a fundamental requirement for strategic biomedical applications. In this outlook we envision the current/future opportunities of the NanoMOFs in the field of biomedicine, with particular emphasis on (i) biocompatible MOFs composition; (ii) MOFs miniaturization and (iii) nanoMOFs applications.
Artificial nano-heterostructures (NHs) with controlled morphology, obtained by combining two or m... more Artificial nano-heterostructures (NHs) with controlled morphology, obtained by combining two or more components in several possible architectures, make them suitable for a wide range of applications. Here, we propose an oleate-based solvothermal approach to design silver-spinel ferrite flower-like NHs. Small oleate-coated silver nanoparticles were used as seeds for the growth of magnetic spinel ferrite (cobalt ferrite and spinel iron oxide) nanodomains on their surface. With the aim of producing homogeneous flower-like heterostructures, a careful study of the effect of the concentration of precursors, the reaction temperature, the presence of water, and the chemical nature of the spinel ferrite was carried out. The magnetic and optical properties of the NHs were also investigated. A heterogeneous growth of the spinel ferrite phase on the silver nanoparticles, through a possible defect-assisted mechanism, was suggested in the light of the high concentration of stacking faults (intrin...
The effect of the annealing temperature Tann on the magnetic properties of cobalt ferrite nanopar... more The effect of the annealing temperature Tann on the magnetic properties of cobalt ferrite nanoparticles embedded in an amorphous silica matrix (CoFe2O4/SiO2), synthesized by a sol-gel auto-combustion method, was investigated by magnetization and AC susceptibility measurements. For samples with 15% w/w nanoparticle concentration, the particle size increases from ~2.5 to ~7 nm, increasing Tann from 700 to 900 °C. The effective magnetic anisotropy constant (Keff) increases with decreasing Tann, due to the increase in the surface contribution. For a 5% w/w sample annealed at 900 °C, Keff is much larger (1.7 × 106 J/m3) than that of the 15% w/w sample (7.5 × 105 J/m3) annealed at 700 °C and showing comparable particle size. This indicates that the effect of the annealing temperature on the anisotropy is not only the control of the particle size but also on the core structure (i.e., cation distribution between the two spinel sublattices and degree of spin canting), strongly affecting the ...
As a contribution to understand the interactions between mineral surfaces and organic molecules, ... more As a contribution to understand the interactions between mineral surfaces and organic molecules, this study reports an accurate characterization of the bis-(2-ethylhexyl) phthalate (DEHP)-Hydrozincite (DEHP-HY), that has been conduced combining the following techniques: FTIR, NMR, XAS spectroscopies and XRD. XRD patterns indicate that the HY is made of nanocrystals whose size is not influenced by the presence of DEHP. The (1)H NMR analysis of DEHP-HY samples points out the presence of interactions of DEHP with HY. CPMAS NMR analysis suggests that the interaction is operated by ester carbonyl groups while the aliphatic chain, as expected, is not involved. MAS and CPMAS NMR measurements, performed on (13)C ester carbonyl enriched DEHP, allow to demonstrate that there are two ester carbonyl linkage sites interacting at the HY surface: an acid site with a strong link and a second one with weak chemical interactions. Zn K-edge XAS spectroscopy demonstrates that the local atomic structure around Zn in DEHP-HY sample remains essentially unchanged with respect to that of HY. Such a weak structural effect suggests that HY interaction with DEHP is limited to the nanoparticle surface.
A series of Fe2O3-SiO2 nanocomposites (25 weight % of Fe2O3) has been prepared using a sol-gel me... more A series of Fe2O3-SiO2 nanocomposites (25 weight % of Fe2O3) has been prepared using a sol-gel method. Samples showing different features were obtained by varying the evaporation conditions acting on the surface / volume ratio of the starting sol. The samples were investigated using Mössbauer spectroscopy at low temperature. The Fe2O3 nanoparticles have been identified as maghemite ( γ-Fe2O3) particles. The samples show a superparamagnetic behavior with a blocking temperature that depends on the average particle size.
A series of Fe2O3 -SiO2 nanocomposites (9 -33 wt% of Fe2O3) has been prepared by a sol-gel method... more A series of Fe2O3 -SiO2 nanocomposites (9 -33 wt% of Fe2O3) has been prepared by a sol-gel method and submitted to thermal treatments at 300 -900 °C. The samples were characterized by X-ray diffraction and Mössbauer Spectroscopy measurements. Superparamagnetic behavior is exhibited by all the samples, indicating that the size of iron oxide grains is in the nanometer range (4-6 nm). Increase of iron content and temperature treatment give rise to a small particle growth, while the spread of sizes around the average value increases with the iron concentration. The Mössbauer spectra, at all the explored compositions, show a very steep increase of the peak width by treatment temperature at 900 °C, indicating the formation of the ferrimagnetic γ-Fe2O3 phase from the antiferromagnetic amorphous Fe2O3 phase, which dominates in the samples treated at lower temperatures. The samples at 28.5% and 33.2%, treated at 900 °C, also show a component of γ-Fe2O3 in the blocked state at room temperatur...
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Papers by Carla Cannas