Titanium and iron titanium oxide nanoparticles in antennae of the migratory ant Pachycondyla marginata: an alternative magnetic sensor for magnetoreception?

The most accepted hypothesis of magnetoreception for social insects is the ferromagnetic hypothesis which assumes the presence of magnetic material as a sensor coupled to sensitive structures that transmit the geomagnetic field information to the nervous system. As magnetite is the most common magnetic material observed in living beings, it has been suggested as basic constituent of the magnetoreception system. Antennae and head have been pointed as possible magnetosensor organs in social insects as ants, bees and termites. Samples of three antenna joints: head-scape, scape-pedicel and pedicel-third segment joints were embedded in epoxi resin, ultrathin sectioned and analyzed by transmission electron microscopy. Selected area electron diffraction patterns and X-ray energy dispersive spectroscopy were obtained to identify the nanoparticle compound. Besides iron oxides, for the first time, nanoparticles containing titanium have been identified surrounded by tissue in the antennae of ants. Given their dimension and related magnetic characteristics, these nanoparticles are discussed as being part of the magnetosensor system.

Biomineralization of calcium carbonate in the cell wall of Lithothamnion crispatum (Hapalidiales, Rhodophyta): correlation between the organic matrix and the mineral phase.

Over the past few decades, progress has been made toward understanding the mechanisms of coralline algae mineralization. However, the relationship between the mineral phase and the organic matrix in coralline algae has not yet been thoroughly examined. The aim of this study was to describe the cell wall ultrastructure of Lithothamnion crispatum, a cosmopolitan rhodolith-forming coralline algal species collected near Salvador (Brazil), and examine the relationship between the organic matrix and the nucleation and growth/shape modulation of calcium carbonate crystals. A nanostructured pattern was observed in L. crispatum along the cell walls. At the nanoscale, the crystals from L. crispatum consisted of several single crystallites assembled and associated with organic material. The crystallites in the bulk of the cell wall had a high level of spatial organization. However, the crystals displayed cleavages in the (104) faces after ultrathin sectioning with a microtome. This organism is an important model for biomineralization studies as the crystallographic data do not fit in any of the general biomineralization processes described for other organisms. Biomineralization in L. crispatum is dependent on both the soluble and the insoluble organic matrix, which are involved in the control of mineral formation and organizational patterns through an organic matrix-mediated process. This knowledge concerning the mineral composition and organizational patterns of crystals within the cell walls should be taken into account in future studies of changing ocean conditions as they represent important factors influencing the physico-chemical interactions between rhodoliths and the environment in coralline reefs.

Structural and thermal analyses of zinc and lactose in homeopathic triturated systems.

BACKGROUND: A series of different experimental approaches was applied in Zincum metallicum (Zinc met.) samples and lactose controls. Experiments were designed to elucidate the effect of zinc trituration and dynamization on physicochemical properties of homeopathic formulations, using lactose as excipient. METHODS: Zinc met. potencies (Zinc met 1-3c) were triturated and dynamized using lactose as excipient, according to Brazilian Homeopathic Pharmacopoeia. Lactose samples (LAC 1-3c) were also prepared following the same protocol and used as controls. The samples were analyzed structurally by Atomic Absorption Spectroscopy (AAS), X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) with Energy Dispersive X-ray Spectroscopy (EDX) and Scanning Electron Microscopy (SEM), and thermodynamically by Thermogravimetry (TG) and Differential Scanning Calorimetry (DSC). RESULTS: AAS analysis detected 97.0 % of zinc in the raw material, 0.75 % (Zinc met 1c) and 0.02% (Zinc met 2c). XRD analysis showed that inter-atomic crystalline spacing of lactose was not modified by dynamization. Amorphous and crystalline lactose spheres and particles, respectively, were observed by TEM in all samples, with mean size from 200 to 800 nm. EDX obtained with TEM identified zinc presence throughout the amorphous matter but individualized zinc particles were not observed. SEM images obtained from dynamized samples (LAC 1c and Zinc met 1c) with electron backscattering could not identify zinc metal grains. The dynamization process induced Derivatives of Thermal Gravimetric (DTg) peak modification, which was previously centered near 158°C to lactose, to a range from 140 to 170°C, suggesting the dynamization process modifies the temperature range of water aggregation. Thermal phenomena were analyzed and visualized by Analysis of Variance (ANOVA) and Principal Component Analysis (PCA) statistics. Both indicated that fusion enthalpy of dynamized samples (DynLAC 1-3c; DynZn 1-3c) increased 30.68 J/g in comparison to non-dynamized lactose (LAC; p < 0.05). CONCLUSIONS: Our results suggested no structural changes due to the trituration and dynamization process. However, TG and DSC analyses permit the differentiation of dynamized and non-dynamized groups, suggesting the dynamization process induced a significant increase in the degradation heat. These results call for further calorimetric studies with other homeopathic dilutions and other methodologies, to better understand the dynamics of these systems.

Crystallographic orientation and concentric layers in spicules of calcareous sponges.

In this work, the crystallography of calcareous sponges (Porifera) spicules and the organization pattern of the concentric layers present in their inner structure were investigated in 10 species of the subclass Calcaronea and three species of the subclass Calcinea. Polished spicules had specific concentric patterns that varied depending on the plane in which the spicules were sectioned. A 3D model of the concentric layers was created to interpret these patterns and the biomineralization process of the triactine spicules. The morphology of the spicules was compared with the crystallographic orientation of the calcite crystals by analyzing the Kikuchi diffraction patterns using a scanning electron microscope. Triactine spicules from the subclass Calcinea had actines (rays) elongated in the 〈210〉 direction, which is perpendicular to the c-axis. The scale spicules of the hypercalcified species Murrayona phanolepis presented the c-axis perpendicular to the plane of the scale, which is in accordance with the crystallography of all other Calcinea. The triactine spicules of the calcaronean species had approximately the same crystallographic orientation with the unpaired actine elongated in the ∼[211] direction. Only one Calcaronea species, whose triactine was regular, had a different orientation. Three different crystallographic orientations were found in diactines. Spicules with different morphologies, dimensions and positions in the sponge body had similar crystallographic directions suggesting that the crystallographic orientation of spicules in calcareous sponges is conserved through evolution.

Embryotoxicity and visual-motor response of functionalized nanostructured hydroxyapatite-based biomaterials in zebrafish (Danio rerio).

Hydroxyapatite (HA) is a biomaterial widely used in biomedical applications. Many studies have shown that ionic substituents can be incorporated into HA to produce a mineral composition more similar to natural bone tissue with more favorable biological characteristics for application in bone regeneration. However, its potentially toxic effects need to be evaluated before full approval for human use. For this purpose, an embryotoxicity test was performed on zebrafish according to OECD guideline 236. Zebrafish embryos were exposed to 1 or 3 microspheres of alginate containing nanoparticles of HA and carbonate (CHA), strontium (SrHA), and zinc-substituted HA (ZnHA) from 4 to 120 h post-fertilization (hpf). Lethality and developmental endpoints were evaluated. In addition, larval behavior at 168 hpf was also analyzed to observe whether biomaterials adversely affect optomotor and avoidance responses (neurotoxicity), as well as the oxidative stress pattern through qPCR. After 120 h exposure to all microspheres with different patterns of crystallinity, porosity, nanoparticle size, surface area, and degradation behavior, there was no mortality rate greater than 20%, indicating the non-embryotoxic character of these biomaterials. All experimental groups showed positive optomotor and avoidance responses, which means that embryo exposure to the tested biomaterials had no neurotoxic effects. Furthermore, larvae exposed to one SrHA microsphere showed a better optomotor response than the control. Furthermore, the biomaterials did not change the pattern of mRNA levels of genes related to oxidative stress even after 120 hpf. The growing number of new HA-based biomaterials produced should be accompanied by increased studies to understand the biosafety of these compounds, especially in alternative models, such as zebrafish embryos. These results reinforce our hypothesis that ion-substituted HA biomaterials do not impose toxicological effects, cause development and neuromotor impairment, or increase oxidative stress in zebrafish embryos being useful for medical devices and in the process of bone regeneration.

Cellulose nanocrystals from grape pomace and their use for the development of starch-based nanocomposite films.

Nanocomposite films prepared from starch (ST) in the presence of cellulose nanocrystals (CNCs) was performed using grape pomace as raw material. CNCs were obtained by acid hydrolysis and added to filmogenic solutions (1, 2, 5, 10 and 15 g/100 g of ST). Cellulose, CNCs and Nanocomposites were characterized. Amorphous non-cellulosic materials were removed from the grape pomace presented values for CrI 64% and 71% and yield 12 and 70% in Cellulose and CNCs, respectively. Nanocomposites showed smaller permeability and the addition of 5 to 15% CNCs formed more opaque films and had improved tensile strength and Young's modulus. The addition of CNCs from 5 to 15% proved to be effective in improving mechanical properties and decreasing water vapor permeability, important characteristics in food packaging materials. This study provided an effective method to obtain CNCs from the agroindustrial waste and open the way to produce high-value starch based nanocomposites.

Effects of a biomimetic analog-based experimental bonding system on caries-affected and sound dentin.

This study compared the ultrastructure, chemical composition, and proteases activity (PA) of sound (SD) and caries-affected dentin (CAD) in the dentin hybrid layer after using an experimental bonding system containing pyromellitic dianhydride glycerol methacrylate and biomimetic analogs. The bonding system used a three step and a total-etch procedure. Polyacrylic acid (5%) and sodium trimetaphosphate (5%) were added to the primer and monocalcium phosphate monohydrate (9%), beta-tricalcium phosphate (10.5%), and calcium hydroxide (0.5%) were added to the adhesive. Transmission electron microscopy (TEM) was used to evaluate the resultant structure, particularly the adhesive-dentin and the demineralized-SD interfaces. The chemical composition was evaluated through energy-dispersive X-ray spectroscopy (EDS) and selected area electron diffraction (SAED). The PA was measured with the Coomassie Blue-G250 coloring test, and the PA data were analyzed by ANOVA. EDS identified the presence of isolated calcium phosphate nanoparticles in the demineralized region; however, the SAED analysis did not show any evidences of hydroxyapatite (HA) neoformation in SD and CAD. The biomimetic analog-based adhesive system inhibited the activities of dentin proteases immediately after treatment. Additionally, the proteolytic activity on the affected dentin resembled that of the SD. In conclusion, no HA formed in the demineralized SD and CAD although there were calcium and phosphate deposits. The experimental adhesive system inhibited dentin proteases. The present study uses a new approach to investigate the hybrid layer behavior in dentin. The experimental adhesive system was synthesized and used on sound and affected-caries dentin as the substrate to reproduce real clinical conditions.

Remineralizing potential of dental composites containing silanized silica-hydroxyapatite (Si-HAp) nanoporous particles charged with sodium fluoride (NaF).

OBJECTIVES: To synthesize and evaluate the enamel remineralizing potential of dental composites containing silanized silica-hydroxyapatite (Si-HAp) nanoporous particles charged with sodium fluoride (NaF). METHODS: Si-HAp particles were synthesized using a solid-state method. Dental composites were prepared by incorporating 70 wt.% of Si-HAp particles into a 70/30 wt.% Bis-GMA/TEGDMA organic matrix. Four dental composites were produced: SilF, Sil, F, and NT (nontreated). For SilF and F, Si-HAp particles were previously treated with 10% NaF (F). Afterwards, SilF and Sil composites had their particles silanized (Sil) with α-methacryloxypropyl-1-trimethoxysilane (α-MPS). The remineralizing potential was evaluated in caries-like enamel lesions induced byS. mutans biofilm for seven days and after pH-cycling for fifteen days using X-ray microtomography (micro-CT). Z350 was used as a commercial control for remineralizing potential evaluation Degree of conversion (DC%), flexural strength (FS), and Knoop hardness (KHN) were characterized. Data were analyzed using one-way ANOVA and Tukey's HSD post-hoc test (α = 0.05). RESULTS: F presented the highest enamel remineralizing potential, followed by SilF. Alternatively, Sil and NT were not capable of totally recovering the enamel mineral loss. NT showed the highest DC%, followed by Sil, F, and SilF. Sil and NT showed the highest FS when compared to SilF and F. No statistical significance in KHN was found among the composites. CONCLUSIONS: Dental composites with Si-HAp nanoporous particles charged with NaF presented a remineralizing potential for human enamel. However, this ability underwent a subtle reduction after particle silanization. CLINICAL SIGNIFICANCE: Si-HAp nanoporous particles charged with NaF may be an alternative for producing dental composites with an improved remineralizing potential for enamel affected by caries.