Effect of mesoporous silica and its combination with hydroxyapatite on the regeneration of rabbit's bone defects: A pilot study.

BACKGROUND: Bone volume augmentation is a routine technique used in oral implantology and periodontology. Advances in the surgical techniques and the biomaterials field have allowed a greater accessibility to these treatments. Nevertheless, dehiscence and fenestrations incidence during dental implant procedures are still common in patients with bone loss. OBJECTIVE: The main objective is to evaluate in a pilot experimental study the biological response to mesoporous silica (MS) hybrid scaffolds and its regenerative capacity in different formulations. METHODS: Two defects per rabbit tibia were performed (one for control and other for test) and the biomaterials tested in this study have been used to fill the bone defects, prepared in two different formulations (3D hybrid scaffolds or powdered material, in 100% pure MS form, or 50% MS with 50% hydroxyapatite (HA). Euthanasia was performed 4 months after surgery for bone histopathological study and radiographic images were acquired by computerized microtomography. RESULTS: Results showed that radiographically and histopathologically pure MS formulations lead to a lower biological response, e.g when formulated with HA, the osteogenic response in terms of osteoconduction was greater. CONCLUSIONS: We observed tolerance and lack of toxicity of the MS and HA, without registering any type of local or systemic allergic reaction.

Versatile Mesoporous Nanoparticles for Cell Applications.

Mesoporous silica nanostructures are emerging as a promising platform able to deal with challenges of many different applications in fields such as biomedicine and nanotechnology. The versatile physical and functional properties of these materials like high specific surface area, ordered porosity, chemical stability under temperature and pH variations, and biocompatible performance, offers new approaches to many biomedical applications ranging from drug delivery systems to biosensing, cell applications and tissue engineering. Their morphology, size and textural properties can be easily tailored by means of chemical control, giving rise to a variety of nanostructures with hexagonal (SBA15, MCM41) or cubic (SBA16) arrangement of channels and pore size ranging from 1.3 to 10 nm. Based on the versatility of their silane surface, a plethora of hybrid mesoporous matrices can be prepared incorporating new functionalities like contrast enhancement for magnetic resonance imaging, magnetic/plasmonic hyperthermia, drug delivery or cell applications by the simple grafting of superparamagnetic metal oxides (Fe3O4, transition metal ferrites) nanoparticles, noble metal (Au, Ag) nanoparticles, fluorescent moieties (fluorescein, rhodamine) or biological agents (mAb, mRNA, etc). The goal of this work is to present the development, by a facile soft template method, of size tailored mesoporous silica nanospheres from 20 to 350 nm (by means of chemical control), and highlight its versatility for surface grafting (with rhodamine and polydopamine) and their biological compatibility and efficient uptake by cultured HeLa cells. The combined, physicochemical and biological, properties indicate that MSNs are good candidates for cell tagging, gene transfer or targeted therapies.

Hybrid mesoporous nanostructured scaffolds as dielectric biosimilar restorative materials.

BACKGROUND: The intricate structure of natural materials is in correspondence with its highly complex functional behaviour. The health of teeth depends, in a complex way, on a heterogeneous arrangement of soft and hard porous tissues that allow for an adequate flow of minerals and oxygen to provide continuous restoration. Although restorative materials, used in clinics, have been evolving from the silver amalgams to actual inorganic fillers, their structural and textural properties are scarcely biomimetic, hindering the functional recovery of the tissue. OBJECTIVE: The objective of this work is to compare and test the hybrid mesoporous silica-based scaffolds as candidates for dentine restoration applications. METHODS: In this work, we present the development and the physical properties study of biocompatible hybrid mesoporous nanostructured scaffolds with a chemically versatile surface and biosimilar architecture. We test their textural (BET) and dielectric permittivity (ac impedance) properties. RESULTS: These materials, with textural and dielectric properties similar to dentine and large availability for the payload of therapeutic agents, are promising candidates as functional restorative materials, suitable for impedance characterization techniques in dental studies. CONCLUSIONS: Structural, textural, morphological characterization and electrical properties of hybrid mesoporous show a large degree of similarity to natural dentin samples.

Electrodecoration and Characterization of Superparamagnetic Iron Oxide Nanoparticles with Bioactive Synergistic Nanocopper: Magnetic Hyperthermia-Induced Ionic Release for Anti-Biofilm Action.

The urgency for the availability of new antibacterial/disinfectant agents has become a worldwide priority. At the same time, along with the extensive use of other metal nanoparticles (NPs), the investigation of magnetic NPs (MNPs) in antibacterial studies has turned out to be an increasingly attractive research field. In this context, we present the preparation and characterization of superparamagnetic iron oxide NPs, electrodecorated with antimicrobial copper NPs, able to modulate the release of bioactive species not only by the NP's stabilizer, but also through the application of a suitable magnetic field. Antimicrobial synergistic CuNPs stabilized by benzalkonium chloride have been used in the current study. We demonstrate the successful preparation of Cu@Fe3O4 MNPs composites through morphological and spectroscopic results. Additionally, an extensive magnetic characterization is reported, along with hyperthermia-induced copper ionic release. On the basis of our results, we propose a new generation of antimicrobial magnetic nanomaterials, whose bioactivity can be also tuned by the application of a magnetic field.

Carbon-Coated Superparamagnetic Nanoflowers for Biosensors Based on Lateral Flow Immunoassays.

Superparamagnetic iron oxide nanoflowers coated by a black carbon layer (Fe3O4@C) were studied as labels in lateral flow immunoassays. They were synthesized by a one-pot solvothermal route, and they were characterized (size, morphology, chemical composition, and magnetic properties). They consist of several superparamagnetic cores embedded in a carbon coating holding carboxylic groups adequate for bioconjugation. Their multi-core structure is especially efficient for magnetic separation while keeping suitable magnetic properties and appropriate size for immunoassay reporters. Their functionality was tested with a model system based on the biotin-neutravidin interaction. For this, the nanoparticles were conjugated to neutravidin using the carbodiimide chemistry, and the lateral flow immunoassay was carried out with a biotin test line. Quantification was achieved with both an inductive magnetic sensor and a reflectance reader. In order to further investigate the quantifying capacity of the Fe3O4@C nanoflowers, the magnetic lateral flow immunoassay was tested as a detection system for extracellular vesicles (EVs), a novel source of biomarkers with interest for liquid biopsy. A clear correlation between the extracellular vesicle concentration and the signal proved the potential of the nanoflowers as quantifying labels. The limit of detection in a rapid test for EVs was lower than the values reported before for other magnetic nanoparticle labels in the working range 0-3 × 107 EVs/µL. The method showed a reproducibility (RSD) of 3% (n = 3). The lateral flow immunoassay (LFIA) rapid test developed in this work yielded to satisfactory results for EVs quantification by using a precipitation kit and also directly in plasma samples. Besides, these Fe3O4@C nanoparticles are easy to concentrate by means of a magnet, and this feature makes them promising candidates to further reduce the limit of detection.

Tribological Behavior of Nanolubricants Based on Coated Magnetic Nanoparticles and Trimethylolpropane Trioleate Base Oil.

The main task of this work is to study the tribological performance of nanolubricants formed by trimethylolpropane trioleate (TMPTO) base oil with magnetic nanoparticles coated with oleic acid: Fe3O4 of two sizes 6.3 nm and 10 nm, and Nd alloy compound of 19 nm. Coated nanoparticles (NPs) were synthesized via chemical co-precipitation or thermal decomposition by adsorption with oleic acid in the same step. Three nanodispersions of TMPTO of 0.015 wt% of each NP were prepared, which were stable for at least 11 months. Two different types of tribological tests were carried out: pure sliding conditions and rolling conditions (5% slide to roll ratio). With the aim of analyzing the wear by means of the wear scar diameter (WSD), the wear track depth and the volume of the wear track produced after the first type of the tribological tests, a 3D optical profiler was used. The best tribological performance was found for the Nd alloy compound nanodispersion, with reductions of 29% and 67% in friction and WSD, respectively, in comparison with TMPTO. On the other hand, rolling conditions tests were utilized to study friction and film thickness of nanolubricants, determining that Fe3O4 (6.3 nm) nanolubricant reduces friction in comparison to TMPTO.

Development of Superparamagnetic Nanoparticles Coated with Polyacrylic Acid and Aluminum Hydroxide as an Efficient Contrast Agent for Multimodal Imaging.

Early diagnosis of disease and follow-up of therapy is of vital importance for appropriate patient management since it allows rapid treatment, thereby reducing mortality and improving health and quality of life with lower expenditure for health care systems. New approaches include nanomedicine-based diagnosis combined with therapy. Nanoparticles (NPs), as contrast agents for in vivo diagnosis, have the advantage of combining several imaging agents that are visible using different modalities, thereby achieving high spatial resolution, high sensitivity, high specificity, morphological, and functional information. In this work, we present the development of aluminum hydroxide nanostructures embedded with polyacrylic acid (PAA) coated iron oxide superparamagnetic nanoparticles, Fe3O4@Al(OH)3, synthesized by a two-step co-precipitation and forced hydrolysis method, their physicochemical characterization and first biomedical studies as dual magnetic resonance imaging (MRI)/positron emission tomography (PET) contrast agents for cell imaging. The so-prepared NPs are size-controlled, with diameters below 250 nm, completely and homogeneously coated with an Al(OH)3 phase over the magnetite cores, superparamagnetic with high saturation magnetization value (Ms = 63 emu/g-Fe3O4), and porous at the surface with a chemical affinity for fluoride ion adsorption. The suitability as MRI and PET contrast agents was tested showing high transversal relaxivity (r2) (83.6 mM-1 s-1) and rapid uptake of 18F-labeled fluoride ions as a PET tracer. The loading stability with 18F-fluoride was tested in longitudinal experiments using water, buffer, and cell culture media. Even though the stability of the 18F-label varied, it remained stable under all conditions. A first in vivo experiment indicates the suitability of Fe3O4@Al(OH)3 nanoparticles as a dual contrast agent for sensitive short-term (PET) and high-resolution long-term imaging (MRI).

Novel Magnetic Nanostructured Beads for Cadmium(II) Removal.

This study presents an effective magnetic separation method for cadmium removal, based on the use of a novel nanostructured material as an adsorbent. This adsorbent involves the incorporation of magnetite nanoparticles (Fe3O4-NPs), synthesized by the reverse coprecipitation method, into sodium alginate and activated carbon to form spherical structures by crosslinking Ca2+ ions with the charged alginate chains, referred to as magnetic alginate activated carbon (MAAC) beads. The effect of the experimental parameters, such as pH, contacting time, adsorbent dosage, agitation type, and rotating speed were investigated and optimized for an efficient removal of Cd(II) ions at an initial concentration of 250 mg/L. The amount of adsorbed Cd(II) by MAAC beads increased at a pH of 6 with a removal efficiency over 90%. The maximum adsorption capacity reached was 70 mg/g of adsorbent at an initial Cd(II) concentration of 150 mg/L, whereas at 250 mg/L the adsorption capacity lowered until 60 mg/g. Sorption isotherms were calculated using Langmuir, Freundlich, Temkin, and Dubinin⁻Radushkevich equations, and were better described by the Freundlich and Temkin models. These results proved the removal efficiency and the potential use under real environmental conditions of the MAAC beads, due to their easy recovery from contaminated aqueous solutions.

Coexistence of Three Ferroic Orders in the Multiferroic Compound [(CH3 )4 N][Mn(N3 )3 ] with Perovskite-Like Structure.

The perovskite azido compound [(CH3 )4 N][Mn(N3 )3 ], which undergoes a first-order phase change at Tt =310 K with an associated magnetic bistability, was revisited in the search for additional ferroic orders. The driving force for such structural transition is multifold and involves a peculiar cooperative rotation of the [MnN6 ] octahedral as well as order/disorder and off-center shifts of the [(CH3 )4 N](+) cations and bridging azide ligands, which also bend and change their coordination mode. According to DFT calculations the latter two give rise to the appearance of electric dipoles in the low-temperature (LT) polymorph, the polarization of which nevertheless cancels out due to their antiparallel alignment in the crystal. The conversion of this antiferroelectric phase to the paraelectric phase could be responsible for the experimental dielectric anomaly detected at 310 K. Additionally, the structural change involves a ferroelastic phase transition, whereby the LT polymorph exhibits an unusual and anisotropic thermal behavior. Hence, [(CH3 )4 N][Mn(N3 )3 ] is a singular material in which three ferroic orders coexist even above room temperature.

Role of Temperature and Pressure on the Multisensitive Multiferroic Dicyanamide Framework [TPrA][Mn(dca)3] with Perovskite-like Structure.

A multistimuli response to temperature and pressure is found in the hybrid inorganic-organic perovskite-like [TPrA][Mn(dca)3] compound, which is related to a first-order structural phase transition near room temperature, Tt ≈ 330 K. This phase transition involves a transformation from room temperature polymorph I, with the noncentrosymmetric space group P4̅21c, to the high temperature polymorph II, with the centrosymmetric space group I4/mcm, and it implies ionic displacements, order-disorder phenomena, and a large and anisotropic thermal expansion (specially along the c-axis). As a consequence, [TPrA][Mn(dca)3] exhibits a dielectric anomaly, associated with the change from a cooperative to a noncooperative electric behavior (antiferroelectric (AFE)-paraelectric (PE) transition). The former implies an AFE distribution of electric dipoles in polymorph I, related to the described off-shift of the apolar TPrA cations and the order-disorder of the polar dca ligands mechanisms, that are different from those reported, up to now, for others perovskite-type hybrid compounds. Such cooperative electric order, below Tt ≈ 330 K, coexisting with long-range antiferromagnetic ordering below T = 2.1 K render the [TPrA][Mn(dca)3] a new type-I multiferroic material. In addition, the obtained experimental results reveal that this compound is also a multistimuli-responsive material, with a very large sensitivity toward temperature and applied external pressure, δTt/δP ≈ 24 K kbar(-1), even for small values of pressure (P < 2 kbar). Therefore, this material opens up a potential interest for future technological applications, such as temperature/pressure sensing.