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1.
J Biophotonics ; 17(7): e202300475, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38866730

RESUMO

The study encompasses an investigation of optical, photothermal and biocompatibility properties of a composite consisting of golden cores surrounded by superparamagnetic CoFe2O4 nanoparticles. Accompanied with the experiment, the computational modeling reveals that each adjusted magnetic nanoparticle redshifts the plasmon resonance frequency in gold and nonlinearly increases the extinction cross-section at ~800 nm. The concentration dependent photothermal study demonstrates a temperature increase of 8.2 K and the photothermal conversion efficiency of 51% for the 100 µg/mL aqueous solution of the composite nanoparticles, when subjected to a laser power of 0.5 W at 815 nm. During an in vitro photothermal therapy, a portion of the composite nanoparticles, initially seeded at this concentration, remained associated with the cells after washing. These retained nanoparticles effectively heated the cell culture medium, resulting in a 22% reduction in cell viability after 15 min of the treatment. The composite features a potential in multimodal magneto-plasmonic therapies.


Assuntos
Cobalto , Compostos Férricos , Ouro , Nanocompostos , Terapia Fototérmica , Nanocompostos/química , Cobalto/química , Cobalto/farmacologia , Ouro/química , Ouro/farmacologia , Compostos Férricos/química , Humanos , Sobrevivência Celular/efeitos dos fármacos , Temperatura
2.
Small Methods ; 7(11): e2300647, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37649220

RESUMO

The crystal site occupancy of different divalent ions and the induction of lattice defects represent an additional tool for modifying the intrinsic magnetic properties of spinel ferrites nanoparticles. Here, the relevance of the lattice defects is demonstrated in the appearance of exchange-bias and in the improvement of the magnetic properties of doped ferrites of 20 nm, obtained from the mild oxidation of core@shell (wüstite@ferrite) nanoparticles. Three types of nanoparticles (Fe0.95 O@Fe3 O4 , Co0.3 Fe0.7 O@Co0.8 Fe2.2 O4 and Ni0.17 Co0.21 Fe0.62 O@Ni0.4 Co0.3 Fe2.3 O4 ) are oxidized. As a result, the core@shell morphology is removed and transformed in a spinel-like nanoparticle, through a topotactic transformation. This study shows that most of the induced defects in these nanoparticles and their magnetic properties are driven by the inability of the Co(II) ions at the octahedral sites to migrate to tetrahedral sites, at the chosen mild oxidation temperature. In addition, the appearance of crystal defects and antiphase boundaries improves the magnetic properties of the starting compounds and leads to the appearance of exchange bias at room temperature. These results highlight the validity of the proposed method to impose novel magnetic characteristics in the technologically relevant class of nanomaterials such as spinel ferrites, expanding their potential exploitation in several application fields.

3.
Nanomaterials (Basel) ; 13(10)2023 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-37242002

RESUMO

The increasing resistance of bacteria to conventional antibiotics represents a severe global emergency for human health. The broad-spectrum antibacterial activity of silver has been known for a long time, and silver at the nanoscale shows enhanced antibacterial activity. This has prompted research into the development of silver-based nanomaterials for applications in clinical settings. In this work, the synthesis of three different silver nanoparticles (AgNPs) hybrids using both organic and inorganic supports with intrinsic antibacterial properties is described. The tuning of the AgNPs' shape and size according to the type of bioactive support was also investigated. Specifically, the commercially available sulfated cellulose nanocrystal (CNC), the salicylic acid functionalized reduced graphene oxide (rGO-SA), and the commercially available titanium dioxide (TiO2) were chosen as organic (CNC, rGO-SA) and inorganic (TiO2) supports. Then, the antimicrobial activity of the AgNP composites was assessed on clinically relevant multi-drug-resistant bacteria and the fungus Candida albicans. The results show how the formation of Ag nanoparticles on the selected supports provides the resulting composite materials with an effective antibacterial activity.

4.
Dalton Trans ; 52(12): 3551-3562, 2023 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-36880505

RESUMO

In this perspective article, we present a short selection of some of the most significant case studies on magnetic nanoparticles for potential applications in nanomedicine, mainly magnetic resonance. For almost 10 years, our research activity focused on the comprehension of the physical mechanisms on the basis of the nuclear relaxation of magnetic nanoparticles in the presence of magnetic fields; taking advantage of the insights gathered over this time span, we report on the dependence of the relaxation behaviour on the chemico-physical properties of magnetic nanoparticles and discuss them in full detail. In particular, a critical review is carried out on the correlations between their efficiency as contrast agents in magnetic resonance imaging and the magnetic core of magnetic nanoparticles (mainly iron oxides), their size and shape, and the coating and solvent used for making them biocompatible and well dispersible in physiological media. Finally, the heuristic model proposed by Roch and coworkers is presented, as it was extensively adopted to describe most of the experimental data sets. The large amount of data analyzed allowed us to highlight both the advantages and limitations of the model.

5.
Nanomaterials (Basel) ; 13(5)2023 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-36903670

RESUMO

We present an investigation of the effects on BxPC3 pancreatic cancer cells of proton therapy combined with hyperthermia, assisted by magnetic fluid hyperthermia performed with the use of magnetic nanoparticles. The cells' response to the combined treatment has been evaluated by means of the clonogenic survival assay and the estimation of DNA Double Strand Breaks (DSBs). The Reactive Oxygen Species (ROS) production, the tumor cell invasion and the cell cycle variations have also been studied. The experimental results have shown that the combination of proton therapy, MNPs administration and hyperthermia gives a clonogenic survival that is much smaller than the single irradiation treatment at all doses, thus suggesting a new effective combined therapy for the pancreatic tumor. Importantly, the effect of the therapies used here is synergistic. Moreover, after proton irradiation, the hyperthermia treatment was able to increase the number of DSBs, even though just at 6 h after the treatment. Noticeably, the magnetic nanoparticles' presence induces radiosensitization effects, and hyperthermia increases the production of ROS, which contributes to cytotoxic cellular effects and to a wide variety of lesions including DNA damage. The present study indicates a new way for clinical translation of combined therapies, also in the vision of an increasing number of hospitals that will use the proton therapy technique in the near future for different kinds of radio-resistant cancers.

6.
Nanomaterials (Basel) ; 13(5)2023 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-36903682

RESUMO

We investigated the effect of different organic coatings on the 1H-NMR relaxation properties of ultra-small iron-oxide-based magnetic nanoparticles. The first set of nanoparticles, with a magnetic core diameter ds1 = 4.4 ± 0.7 nm, was coated with polyacrylic acid (PAA) and dimercaptosuccinic acid (DMSA), while the second set, ds2 = 8.9 ± 0.9 nm, was coated with aminopropylphosphonic acid (APPA) and DMSA. At fixed core diameters but different coatings, magnetization measurements revealed a similar behavior as a function of temperature and field. On the other hand, the 1H-NMR longitudinal r1 nuclear relaxivity in the frequency range ν = 10 kHz ÷ 300 MHz displayed, for the smallest particles (diameter ds1), an intensity and a frequency behavior dependent on the kind of coating, thus indicating different electronic spin dynamics. Conversely, no differences were found in the r1 relaxivity of the biggest particles (ds2) when the coating was changed. It is concluded that, when the surface to volume ratio, i.e., the surface to bulk spins ratio, increases (smallest nanoparticles), the spin dynamics change significantly, possibly due to the contribution of surface spin dynamics/topology.

7.
Nanoscale Horiz ; 8(6): 776-782, 2023 05 30.
Artigo em Inglês | MEDLINE | ID: mdl-36951189

RESUMO

Cellulose nanocrystal and gold nanoparticles are assembled, in a unique way, to yield a novel modular glyconanomaterial whose surface is then easily engineered with one or two different headgroups, by exploiting a robust click chemistry route. We demonstrate the potential of this approach by conjugating monosaccharide headgroups to the glyconanomaterial and show that the sugars retain their binding capability to C-type lectin receptors, as also directly visualized by cryo-TEM.


Assuntos
Nanopartículas Metálicas , Nanopartículas Metálicas/química , Ouro/química , Celulose/química , Química Click , Lectinas Tipo C
8.
ACS Appl Nano Mater ; 5(10): 14871-14881, 2022 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-36338325

RESUMO

In this work, we demonstrate that the reduction of the local internal stress by a low-temperature solvent-mediated thermal treatment is an effective post-treatment tool for magnetic hardening of chemically synthesized nanoparticles. As a case study, we used nonstoichiometric cobalt ferrite particles of an average size of 32(8) nm synthesized by thermal decomposition, which were further subjected to solvent-mediated annealing at variable temperatures between 150 and 320 °C in an inert atmosphere. The postsynthesis treatment produces a 50% increase of the coercive field, without affecting neither the remanence ratio nor the spontaneous magnetization. As a consequence, the energy product and the magnetic energy storage capability, key features for applications as permanent magnets and magnetic hyperthermia, can be increased by ca. 70%. A deep structural, morphological, chemical, and magnetic characterization reveals that the mechanism governing the coercive field improvement is the reduction of the concomitant internal stresses induced by the low-temperature annealing postsynthesis treatment. Furthermore, we show that the medium where the mild annealing process occurs is essential to control the final properties of the nanoparticles because the classical annealing procedure (T > 350 °C) performed on a dried powder does not allow the release of the lattice stress, leading to the reduction of the initial coercive field. The strategy here proposed, therefore, constitutes a method to improve the magnetic properties of nanoparticles, which can be particularly appealing for those materials, as is the case of cobalt ferrite, currently investigated as building blocks for the development of rare-earth free permanent magnets.

9.
Nano Lett ; 22(22): 9036-9044, 2022 Nov 23.
Artigo em Inglês | MEDLINE | ID: mdl-36346871

RESUMO

Active modulation of the plasmonic response is at the forefront of today's research in nano-optics. For a fast and reversible modulation, external magnetic fields are among the most promising approaches. However, fundamental limitations of metals hamper the applicability of magnetoplasmonics in real-life active devices. While improved magnetic modulation is achievable using ferromagnetic or ferromagnetic-noble metal hybrid nanostructures, these suffer from severely broadened plasmonic response, ultimately decreasing their performance. Here we propose a paradigm shift in the choice of materials, demonstrating for the first time the outstanding magnetoplasmonic performance of transparent conductive oxide nanocrystals with plasmon resonance in the near-infrared. We report the highest magneto-optical response for a nonmagnetic plasmonic material employing F- and In-codoped CdO nanocrystals, due to the low carrier effective mass and the reduced plasmon line width. The performance of state-of-the-art ferromagnetic nanostructures in magnetoplasmonic refractometric sensing experiments are exceeded, challenging current best-in-class localized plasmon-based approaches.

10.
ACS Appl Mater Interfaces ; 14(25): 29087-29098, 2022 Jun 29.
Artigo em Inglês | MEDLINE | ID: mdl-35708301

RESUMO

Here, we synthesize a Au@Fe3O4 core@shell system with a highly uniform unprecedented star-like shell morphology with combined plasmonic and magnetic properties. An advanced electron microscopy characterization allows assessing the multifaceted nature of the Au core and its role in the growth of the peculiar epitaxial star-like shell with excellent crystallinity and homogeneity. Magnetometry and magneto-optical spectroscopy revealed a pure magnetite shell, with a superior saturation magnetization compared to similar Au@Fe3O4 heterostructures reported in the literature, which is ascribed to the star-like morphology, as well as to the large thickness of the shell. Of note, Au@Fe3O4 nanostar-loaded cancer cells displayed magneto-mechanical stress under a low frequency external alternating magnetic field (few tens of Hz). On the other hand, such a uniform, homogeneous, and thick magnetite shell enables the shift of the plasmonic resonance of the Au core to 640 nm, which is the largest red shift achievable in Au@Fe3O4 homogeneous core@shell systems, prompting application in photothermal therapy and optical imaging in the first biologically transparent window. Preliminary experiments performing irradiation of a stable water suspension of the nanostar and Au@Fe3O4-loaded cancer cell culture suspension at 658 nm confirmed their optical response and their suitability for photothermal therapy. The outstanding features of the prepared system can be thus potentially exploited as a multifunctional platform for magnetic-plasmonic applications.


Assuntos
Óxido Ferroso-Férrico , Terapia Fototérmica , Óxido Ferroso-Férrico/química , Ouro/química , Campos Magnéticos , Magnetismo
11.
Small ; 18(16): e2107426, 2022 04.
Artigo em Inglês | MEDLINE | ID: mdl-35274450

RESUMO

Nanometric core@shell wüstite@ferrite (Fe1-x O@Fe3 O4 ) has been extensively studied because of the emergence of exchange bias phenomena. Since their actual implementation in modern technologies is hampered by the low temperature at which bias is operating, the critical issue to be solved is to obtain exchange-coupled antiferromagnetic@ferrimagnetic nanoparticles (NPs) with ordering temperature close to 300 K by replacing the divalent iron with other transition-metal ions. Here, the effect of the combined substitution of Fe(II)  with Co(II)  and Ni(II)  on the crystal structure and magnetic properties is studied. To this aim, a series of 20 nm NPs with a wüstite-based core and a ferrite shell, with tailored composition, (Co0.3 Fe0.7 O@Co0.8 Fe2.2 O4  and Ni0.17 Co0.21 Fe0.62 O@Ni0.4 Co0.3 Fe2.3 O4 ) is synthetized through a thermal-decomposition method. An extensive morphological and crystallographic characterization of the obtained NPs shows how a higher stability against the oxidation process in ambient condition is attained when divalent cation doping of the iron oxide lattice with Co(II)  and Ni(II)  ions is performed. The dual-doping is revealed to be an efficient way for tuning the magnetic properties of the final system, obtaining Ni-Co doped iron oxide core@shell NPs with high coercivity (and therefore, high energy product), and increased antiferromagnetic ordering transition temperature, close to room temperature.


Assuntos
Imãs , Nanopartículas , Compostos Férricos , Compostos Ferrosos , Nanopartículas/química , Tamanho da Partícula , Temperatura
12.
Nanomaterials (Basel) ; 12(3)2022 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-35159647

RESUMO

In this study, we report the realization of drug-loaded smart magnetic nanocarriers constituted by superparamagnetic iron oxide nanoparticles encapsulated in a dual pH- and temperature-responsive poly (N-vinylcaprolactam-co-acrylic acid) copolymer to achieve highly controlled drug release and localized magnetic hyperthermia. The magnetic core was constituted by flower-like magnetite nanoparticles with a size of 16.4 nm prepared by the polyol approach, with good saturation magnetization and a high specific absorption rate. The core was encapsulated in poly (N-vinylcaprolactam-co-acrylic acid) obtaining magnetic nanocarriers that revealed reversible hydration/dehydration transition at the acidic condition and/or at temperatures above physiological body temperature, which can be triggered by magnetic hyperthermia. The efficacy of the system was proved by loading doxorubicin with very high encapsulation efficiency (>96.0%) at neutral pH. The double pH- and temperature-responsive nature of the magnetic nanocarriers facilitated a burst, almost complete release of the drug at acidic pH under hyperthermia conditions, while a negligible amount of doxorubicin was released at physiological body temperature at neutral pH, confirming that in addition to pH variation, drug release can be improved by hyperthermia treatment. These results suggest this multi-stimuli-sensitive nanoplatform is a promising candidate for remote-controlled drug release in combination with magnetic hyperthermia for cancer treatment.

13.
Nanomaterials (Basel) ; 12(2)2022 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-35055222

RESUMO

Today, public health is one of the most important challenges in society. Cancer is the leading cause of death, so early diagnosis and localized treatments that minimize side effects are a priority. Magnetic nanoparticles have shown great potential as magnetic resonance imaging contrast agents, detection tags for in vitro biosensing, and mediators of heating in magnetic hyperthermia. One of the critical characteristics of nanoparticles to adjust to the biomedical needs of each application is their polymeric coating. Fatty acid coatings are known to contribute to colloidal stability and good surface crystalline quality. While monolayer coatings make the particles hydrophobic, a fatty acid double-layer renders them hydrophilic, and therefore suitable for use in body fluids. In addition, they provide the particles with functional chemical groups that allow their bioconjugation. This work analyzes three types of self-assembled bilayer fatty acid coatings of superparamagnetic iron oxide nanoparticles: oleic, lauric, and myristic acids. We characterize the particles magnetically and structurally and study their potential for resonance imaging, magnetic hyperthermia, and labeling for biosensing in lateral flow immunoassays. We found that the myristic acid sample reported a large r2 relaxivity, superior to existing iron-based commercial agents. For magnetic hyperthermia, a significant specific absorption rate value was obtained for the oleic sample. Finally, the lauric acid sample showed promising results for nanolabeling.

14.
Int J Mol Sci ; 22(17)2021 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-34502176

RESUMO

Hybrid materials composed of superparamagnetic iron oxide nanoparticles (SPIONs) and lipid self-assemblies possess considerable applicative potential in the biomedical field, specifically, for drug/nutrient delivery. Recently, we showed that SPIONs-doped lipid cubic liquid crystals undergo a cubic-to-hexagonal phase transition under the action of temperature or of an alternating magnetic field (AMF). This transition triggers the release of drugs embedded in the lipid scaffold or in the water channels. In this contribution, we address this phenomenon in depth, to fully elucidate the structural details and optimize the design of hybrid multifunctional carriers for drug delivery. Combining small-angle X-ray scattering (SAXS) with a magnetic characterization, we find that, in bulk lipid cubic phases, the cubic-to-hexagonal transition determines the magnetic response of SPIONs. We then extend the investigation from bulk liquid-crystalline phases to colloidal dispersions, i.e., to lipid/SPIONs nanoparticles with cubic internal structure ("magnetocubosomes"). Through Synchrotron SAXS, we monitor the structural response of magnetocubosomes while exposed to an AMF: the magnetic energy, converted into heat by SPIONs, activates the cubic-to-hexagonal transition, and can thus be used as a remote stimulus to spike drug release "on-demand". In addition, we show that the AMF-induced phase transition in magnetocubosomes steers the realignment of SPIONs into linear string assemblies and connect this effect with the change in their magnetic properties, observed at the bulk level. Finally, we assess the internalization ability and cytotoxicity of magnetocubosomes in vitro on HT29 adenocarcinoma cancer cells, in order to test the applicability of these smart carriers in drug delivery applications.


Assuntos
Sistemas de Liberação de Medicamentos , Nanopartículas Magnéticas de Óxido de Ferro/química , Adenocarcinoma/tratamento farmacológico , Antineoplásicos/administração & dosagem , Liberação Controlada de Fármacos , Células HT29 , Humanos , Transição de Fase , Espalhamento a Baixo Ângulo , Difração de Raios X
15.
ACS Appl Nano Mater ; 4(2): 1057-1066, 2021 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-33778418

RESUMO

Plasmon resonance modulation with an external magnetic field (magnetoplasmonics) represents a promising route for the improvement of the sensitivity of plasmon-based refractometric sensing. To this purpose, an accurate material choice is needed to realize hybrid nanostructures with an improved magnetoplasmonic response. In this work, we prepared core@shell nanostructures made of an 8 nm Au core surrounded by an ultrathin iron oxide shell (≤1 nm). The presence of the iron oxide shell was found to significantly enhance the magneto-optical response of the noble metal in the localized surface plasmon region, compared with uncoated Au nanoparticles. With the support of an analytical model, we ascribed the origin of the enhancement to the shell-induced increase in the dielectric permittivity around the Au core. The experiment points out the importance of the spectral position of the plasmonic resonance in determining the magnitude of the magnetoplasmonic response. Moreover, the analytical model proposed here represents a powerful predictive tool for the quantification of the magnetoplasmonic effect based on resonance position engineering, which has significant implications for the design of active magnetoplasmonic devices.

16.
Nanoscale Adv ; 3(6): 1612-1623, 2021 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-36132565

RESUMO

Multifunctional nano-heterostructures (NHSs) with controlled morphology are cardinal in many applications, but the understanding of the nanoscale colloidal chemistry is yet to be fulfilled. The stability of the involved crystalline phases in different solvents at mid- and high-temperatures and reaction kinetics considerably affect the nucleation and growth of the materials and their final architecture. The formation mechanism of manganese ferrite-based core-shell NHSs is herein investigated. The effects of the core size (8, 10, and 11 nm), the shell nature (cobalt ferrite and spinel iron oxide) and the polarity of the solvent (toluene and octanol) on the dissolution phenomena of manganese ferrite are also studied. Noteworthily, the combined use of bulk (powder X-ray diffraction, 57Fe Mössbauer spectroscopy, and DC magnetometry) and nanoscale techniques (HRTEM and STEM-EDX) provides new insights into the manganese ferrite dissolution phenomena, the colloidal stability in an organic environment, and the critical size below which dissolution is complete. Moreover, the dissolved manganese and iron ions react further, leading to an inverted core-shell in the mother liquor solution, paving the way to novel synthetic pathways in nanocrystal design. The MnFe2O4@CoFe2O4 core-shell heterostructures were also employed as heat mediators, exploiting the magnetic coupling between a hard (CoFe2O4) and a soft phase (MnFe2O4).

17.
Nanomaterials (Basel) ; 10(10)2020 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-32993001

RESUMO

A combination of carbon ions/photons irradiation and hyperthermia as a novel therapeutic approach for the in-vitro treatment of pancreatic cancer BxPC3 cells is presented. The radiation doses used are 0-2 Gy for carbon ions and 0-7 Gy for 6 MV photons. Hyperthermia is realized via a standard heating bath, assisted by magnetic fluid hyperthermia (MFH) that utilizes magnetic nanoparticles (MNPs) exposed to an alternating magnetic field of amplitude 19.5 mTesla and frequency 109.8 kHz. Starting from 37 °C, the temperature is gradually increased and the sample is kept at 42 °C for 30 min. For MFH, MNPs with a mean diameter of 19 nm and specific absorption rate of 110 ± 30 W/gFe3o4 coated with a biocompatible ligand to ensure stability in physiological media are used. Irradiation diminishes the clonogenic survival at an extent that depends on the radiation type, and its decrease is amplified both by the MNPs cellular uptake and the hyperthermia protocol. Significant increases in DNA double-strand breaks at 6 h are observed in samples exposed to MNP uptake, treated with 0.75 Gy carbon-ion irradiation and hyperthermia. The proposed experimental protocol, based on the combination of hadron irradiation and hyperthermia, represents a first step towards an innovative clinical option for pancreatic cancer.

18.
Mater Sci Eng C Mater Biol Appl ; 117: 111338, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32919687

RESUMO

The systemic delivery of composite nanoparticles remains an outstanding challenge in cancer nanomedicine, and the principal reason is a complex interplay of biological barriers. In this regard, adaptive cell transfer may represent an alternative solution to circumvent these barriers down to the tumor microenvironment. Here, tumor-tropic macrophages are proposed as a tool to draw and vehiculate modular nanoparticles integrating magnetic and plasmonic components. The end result is a bionic shuttle that exhibits a plasmonic band within the so-called therapeutic window arising from as much as 40 pg Au per cell, magnetization in the order of 150 pemu per cell, and more than 90% of the pristine viability and chemotactic activity of its biological component, until at least two days of preparation. Its synergistic combination of plasmonic, magnetic and tumor-tropic functions is assessed in vitro for applications as magnetic guidance or sorting, with a propulsion around 4 µm s-1 for a magnetic gradient of 0.8 T m-1, the optical hyperthermia of cancer, with stability of photothermal conversion to temperatures exceeding 50∘C, and the photoacoustic imaging of cancer under realistic conditions. These results collectively suggest that a bionic design may be a promising roadmap to reconcile the efforts for multifunctionality and targeted delivery, which are both key goals in nanomedicine.


Assuntos
Hipertermia Induzida , Nanopartículas , Neoplasias , Biônica , Ouro , Humanos , Magnetismo , Neoplasias/terapia , Fototerapia , Microambiente Tumoral
19.
Inorg Chem ; 59(17): 12086-12096, 2020 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-32805986

RESUMO

We present for the first time a method for the preparation of magnetic halloysite nanotubes (HNT) by loading of preformed superparamagnetic magnetite nanoparticles (SPION) of diameter size ∼6 nm with a hydrodynamic diameter of ∼10 nm into HNT. We found that the most effective route to reach this goal relies on the modification of the inner lumen of HNT by tetradecylphosphonic acid (TDP) to give HNT-TDP, followed by the loading with preformed oleic acid (OA)-stabilized SPION. Transmission electron microscopy evidenced the presence of highly crystalline magnetic nanoparticles only in the lumen, partially ordered in chainlike structures. Conversely, attempts to obtain the same result by exploiting either the positive charge of the HNT inner lumen employing SPIONs covered with negatively charged capping agents or the in situ synthesis of SPION by thermal decomposition were not effective. HNT-TDP were characterized by infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), and ζ-potential, and all of the techniques confirmed the presence of TDP onto the HNT. Moreover, the inner localization of TDP was ascertained by the use of Nile Red, a molecule whose luminescence is very sensitive to the polarity of the environment. The free SPION@OA (as a colloidal suspension and as a powder) and SPION-in-HNT powder were magnetically characterized by measuring the ZFC-FC magnetization curves as well as the hysteresis cycles at 300 and 2.5 K, confirming that the super-paramagnetic behavior and the main magnetic properties of the free SPION were preserved once embedded in SPION-in-HNT.

20.
Nanomaterials (Basel) ; 10(9)2020 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-32825748

RESUMO

Heterodimeric nanoparticles comprising materials with different functionalities are of great interest for fundamental research and biomedical/industrial applications. In this work, Fe3O4-Au nano-heterostructures were synthesized by a one-step thermal decomposition method. The hybrid nanoparticles comprise a highly crystalline 12 nm magnetite octahedron decorated with a single noble metal sphere of 6 nm diameter. Detailed analysis of the nanoparticles was performed by UV-visible spectroscopy, magnetometry, calorimetry and relaxometry studies. The cytotoxic effect of the nanoparticles in the human hepatic cell line Huh7 and PLC/PRF/5-Alexander was also assessed. These Fe3O4-Au bifunctional nanoparticles showed no significant cytotoxicity in these two cell lines. The nanoparticles showed a good theranostic potential for liver cancer treatment, since the r2 relaxivity (166.5 mM-1·s-1 and 99.5 mM-1·s-1 in water and HepG2 cells, respectively) is higher than the corresponding values for commercial T2 contrast agents and the Specific Absorption Rate (SAR) value obtained (227 W/gFe) is enough to make them suitable as heat mediators for Magnetic Fluid Hyperthermia. The gold counterpart can further allow the conjugation with different biomolecules and the optical sensing.

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