Ondřej Kaman

Dual imaging probes for magnetic resonance imaging and fluorescence microscopy based on perovskite manganite nanoparticles

The present study reveals the potential of magnetic nanoparticles based on the La0.75Sr0.25MnO3 perovskite manganite for magnetic resonance imaging (MRI). Moreover, it describes the development of the dual imaging probe where the magnetic cores are combined with a fluorescent moiety while the improved colloidal stability is achieved by a two-ply silica shell. At first, the magnetic cores of La0.75Sr0.25MnO3 are coated with a hybrid silica layer, comprising a covalently attached fluorescein moiety that is subsequently covered by a pure silica layer providing the enhanced stability. The detailed characterization of the intermediate and the final product reveals the importance of the complex two-ply shell. Viability tests show that the complete particles are suitable for biological studies. Internalization of the particles and their presence in intracellular vesicles are observed by fluorescence microscopy in different cell types. Further experiments prove no fatal interference with the vitality and insulin releasing ability of labeled pancreatic islets. Relaxometric measurements confirm high spin–spin relaxivities at magnetic fields of B0 = 0.5–3 T, while visualisation of in vitro labeled pancreatic islets by MRI is successfully tested.

Core–shell La1−xSrxMnO3 nanoparticles as colloidal mediators for magnetic fluid hyperthermia

Core–shell nanoparticles consisting of La0.75Sr0.25MnO3 cores covered by silica were synthesized by a procedure consisting of several steps, including the sol–gel method in the presence of citric acid and ethylene glycol, thermal and mechanical treatment, encapsulation employing tetraethoxysilane and final separation by centrifugation in order to get the required size fraction. Morphological studies revealed well-separated particles that form a stable water suspension. Magnetic studies include magnetization measurements and investigation of the ferromagnetic–superparamagnetic–paramagnetic transition. Magnetic heating experiments in ‘calorimetric mode’ were used to determine the heating efficiency of the particles in water suspension and further employed for biological studies of extracellular and intracellular effects analysed by tests of viability.

Silica‐coated La0.75Sr0.25MnO3 nanoparticles for magnetically driven DNA isolation

Magnetic La(0.75)Sr(0.25)MnO(3) nanoparticles possessing an approximately 20-nm-thick silica shell (LSMO(0.25)@SiO(2) ) were characterised and tested for the isolation of PCR-ready bacterial DNA. The results presented here show that the nanoparticles do not interfere in PCR. DNA was apparently reversibly adsorbed on their silica shell from the aqueous phase system (16% PEG 6000-2 M NaCl). The method proposed was used for DNA isolation from complex food samples (dairy products and probiotic food supplements). The isolated DNA was compatible with PCR. The main advantages of the nanoparticles tested for routine use were their high colloidal stability allowing a more precise dosage and therefore high reproducibility of DNA isolation.

Silica-coated manganite and Mn-based ferrite nanoparticles: a comparative study focused on cytotoxicity

Magnetic oxide nanoparticles provide a fascinating tool for biological research and medicine, serving as contrast agents, magnetic carriers, and core materials of theranostic systems. Although the applications rely mostly on iron oxides, more complex oxides such as perovskite manganites may provide a much better magnetic performance. To assess the risk of their potential use, in vitro toxicity of manganite nanoparticles was thoroughly analysed and compared with another prospective system of Mn–Zn ferrite nanoparticles. Magnetic nanoparticles of La0.63Sr0.37MnO3 manganite were prepared by two distinct methods, namely the molten salt synthesis and the traditional sol–gel route, whereas nanoparticles of Mn0.61Zn0.42Fe1.97O4 ferrite, selected as a comparative material, were synthesized by a new procedure under hydrothermal conditions. Magnetic cores were coated with silica and, moreover, several samples of manganite nanoparticles with different thicknesses of silica shell were prepared. The size-fractionated and purified products were analysed using transmission electron microscopy, dynamic light scattering, measurement of the zeta-potential dependence on pH, IR spectroscopy, and SQUID magnetometry. The silica-coated products with accurately determined concentration by atomic absorption spectroscopy were subjected to a robust evaluation of their cytotoxicity by four different methods, including detailed analysis of the concentration dependence of toxicity, analysis of apoptosis, and experiments on three different cell lines. The results, comparing two manganese-containing systems, clearly indicated superior properties of the Mn–Zn ferrite, whose silica-coated nanoparticles show very limited toxic effects and thus constitute a promising material for bioapplications.

Magnetic properties of rare-earth-doped La0.7Sr0.3MnO3

Rare-earth-doped ferromagnetic manganites La0.63RE0.07Sr0.30MnO3 (RE  =  Gd, Tb, Dy, and Ho) are synthesized in the form of sintered ceramics and nanocrystalline phases with the mean size of crystallites  ≈30 nm. The electronic states of the dopants are investigated by SQUID magnetometry and theoretically interpreted based on the calculations of the crystal field splitting of rare-earth energy levels. The samples show the orthorhombic perovskite structure of Ibmm symmetry, with a complete FM order of Mn spins in bulk and reduced order in nanoparticles. Non-zero moments are also detected at the perovskite A sites, which can be attributed to magnetic polarization of the rare-earth dopants. The measurements in external field up to 70 kOe show a standard Curie-type contribution of the spin-only moments of Gd3+ ions, whereas Kramers ions Dy3+ and non-Kramers ions Ho3+ contribute by Ising moments due to their doublet ground states. The behaviour of non-Kramers ions Tb3+ is anomalous, pointing to singlet ground state with giant Van Vleck paramagnetism. The Tb3+ doping leads also to a notably increased coercivity compared to other La0.63RE0.07Sr0.30MnO3 systems.

Tunneling magnetoresistance in nanogranular La1-xSrxMnO3 (x∼0.5)

Electric transport and magnetic studies were performed on the La1-xSrxMnO3 (x=0.45-0.55) perovskite manganites. The main focus was given to the nanogranular ceramics of average x=0.47 composition, compacted by spark plasma sintering of molten salt synthesized nanoparticles. This sample can be viewed as a two-phase composite where FM manganite granules are embedded in AFM manganite matrix. The magnetoconductance data observed on this sample reveal a coexistence of distinct low- and high-field contributions, related to the field-induced alignment of ferromagnetic (FM) granules and the spin canting in antiferromagnetic (AFM) matrix, respectively. Their analysis confirms the theoretically predicted scaling of the low-field effect with squared reduced magnetization and provides also a quantitative comparison between the linear coefficient of high-field magnetoconductance and paraprocess seen in the magnetization measurement.

Effects of Tb(3+) dopants in the La1-x Sr x MnO3 bulk and nanoparticle ferromagnets.

Three forms of La,Sr-manganites are synthesized and the role of Tb doping is investigated. First two systems are sol-gel nanoparticles and sintered ceramics of the composition La0.56Tb0.07Sr0.37MnO3, whereas the third system is formed by comparable nanoparticles La0.51Tb0.06Sr0.43MnO3 synthesized in molten salt. The samples show pseudocubic perovskite structure with only small tilts of MnO6 that point to Ibmm symmetry in the bulk and [Formula: see text] symmetry in nanoparticles. SQUID magnetometry and neutron diffraction reveal a complete FM order of Mn spins in bulk, a reduced order in nanoparticles, and non-zero moments at A sites. Detailed analysis suggests that the dodecahedral coordination of A sites adapts to small terbium size, and the resulting crystal field splitting of Tb(3+) yields a singlet ground state. The response to exchange and external fields is characterized as a giant Van Vleck paramagnetism in contrast to the Curie-type behaviour of Tb-based orthoaluminates and orthocobaltites with the quasi-doublet ground state.