Fabrication and Properties of the Montmorillonite/Nanobioglass Hybrid Reinforcement from Agroindustrial Waste for Bone Regeneration.

Nowadays, bone systems have a series of consequences that compromise the quality of life mainly due to wear and decreased bioactivity, generally in elderly people and children. In this context, the combination of montmorillonite (MMT-NPs) in a vitreous system such as nanobioglass facilitates the adsorption of biomolecules on the surface and within the interlamellar spaces, enabling the entry of ions by a cation exchange process focusing on increasing the rate of bone formation. This work aims to synthesize and characterize an eco-friendly hybrid reinforcement containing MMT-NPs with nanobioglass doped with magnesium nanoparticles (MgNPs-BV). In this way, MMT-NPs@MgNPs-BV was synthesized by the impregnation method, where an experimental design was used to verify the synthesis conditions. The ideal condition by experimental design was carried out in terms of the characterization and biological activity, where we demonstrated MMT-NPs of 30% w w-1, MgNPs-BV of 6% w w-1, and a calcination temperature of 1273.15 K with a cell viability around 66.87%, an average crystallite diameter of 12.5 nm, and a contact angle of 17.7°. The characterizations confirmed the impregnation method with an average particle size of 51.4 ± 13.1 nm. The mechanical tests showed a hardness of 2.6 GPa with an apparent porosity of 22.2%, similar to human bone. MMT-NPs@MgNPs-BV showed a cell proliferation of around 96% in osteoblastic cells (OFCOL II), with the formation of the apatite phase containing a relation of Ca/P of around 1.63, a biodegradability of 82%, and rapid release of ions with a Ca/P ratio of 1.42. Therefore, the eco-friendly hybrid reinforcement with MMT-NPs and MgNPs-BV shows potential for application with a matrix for biocompatible nanocomposites for bone regeneration.

Magnetic layered double hydroxides with carbamazepine for breast cancer treatment.

Current cancer chemotherapy is associated with many side effects and, in some cases, drug resistance, which makes the search for new active molecules and drug delivery strategies imperative. Carbamazepine is an antiepileptic compound that has shown efficacy against breast cancer cell lines. In this study, it was incorporated into layered double hydroxide nanoclays, the percentage of drug loading was increased compared to previous research, and the clays were impregnated with magnetic Fe3O4 nanoparticles. The goal of the magnetic Fe3O4-impregnation was to direct the nanocomposites to the therapeutic target with an external magnetic field. The nanoclay-carbamazepine composites had a carbamazepine loading of 51 %, and the nanoclay-carbamazepine-nanoparticles had a drug loading of 13 % due to the addition of more ingredients. The structure of the composites was analyzed by X-ray diffraction and Scherrer equation, showing a layered double hydroxide organization with crystal sizes of 9-15 nm; from transmission electron microscopy, the final compounds showed a particle size of 97-158 nm, small enough for systemic circulation. In vibrating sample magnetization studies, the composites showed a superparamagnetic behavior with high magnetic saturation (9-17 emu/gr), which should allow a good material attraction by an external magnetic field located near the tumor. In vitro drug release studies were done in Franz cells and measured by UV/Vis spectrophotometry; they showed that carbamazepine release from the nanocomposites responds to the media pH: a good drug release at the lysosome pH and slow release at the blood pH. Finally, the efficacy was tested in vitro in MDA-MB-231 breast cancer cells, and the composites showed an enhanced efficacy in comparison with that produced by the free drug (96 % and 62 % of cell inhibition respectively). Carbamazepine administered with magnetic clays as a carrier is a promising treatment for breast cancer, and further studies should be done to measure the arrival time and the efficacy in vivo.

Improvements of thermal and mechanical properties of achira starch/chitosan/clay nanocomposite films.

Thermoplastic biofilms were developed from achira starch, chitosan and nanoclays using the solvent-casting method. To obtain the filmogenic solutions, different sonication times (0, 10, 20 and 30 min) were considered in order to evaluate the incidence of this parameter on the chemical and physico-mechanical properties of the bionanocomposite films. The chemical analysis using FTIR spectroscopy showed strong intermolecular interactions between the components with increasing sonication times. The results for tensile strength and elongation were satisfactory for films with 20 min of sonication with increases of 154% and 161%, respectively. Morphological analysis showed greater homogeneity, while thermal analysis showed that sonication favoured the plasticization process and thus, the production of homogeneous materials. The water absorption and wettability tests showed less hydrophilic materials allowing these new materials to be considered for use as coatings or packaging for the food sector.

Hydrogel Based on Nanoclay and Gelatin Methacrylate Polymeric Matrix as a Potential Osteogenic Application.

A nanocomposite hydrogel has potentially applicability in the induction of osteogenesis. The hydrogel was synthesized using 1% gelatin methacrylate (GelMA), a biodegradable and bioactive polymer containing the structure of gelatin, denatured collagen derived from the extracellular bone matrix, and 6% laponite (Lap), a synthetic phyllosilicate of nanosized particles. Initially, 0.6 g of Lap was added to deionized water, and then a solution of GelMA/Igarcure was added under stirring and UV light for crosslinking. The spectra in the Fourier-transform infrared region showed bands that indicate the interaction between gelatin and methacrylate anhydride. X-ray diffraction patterns confirmed the presence of Lap and GelMA in the hydrogel. The thermogravimetric analysis suggested an increase in the thermal stability of the hydrogel with the presence of clay mineral. Rheological analysis showed that the hydrogel had a viscosity that allowed its injectability. The hydrogel did not show acute toxicity at any of the concentrations tested according to the Artemia salina lethality test. It showed cell viability more significant than 80% in the MTT test, which makes it suitable for in vivo osteogenic induction tests. The cell differentiation test showed the differentiation of stem cells into osteogenic cells. It indicates a material with the potential for osteogenic induction and possible application in bone tissue engineering.

Synthesis and characterization of chitosan/montmorillonite nanocomposites for application as edible coating.

Edible coating can improve fruits shelf life and, consequently, reduce their waste. Chitosan, which presents a potential for chemical modifications and capacity to form films, can be an alternative for coating due to its biocompatibility, biodegradability, and antimicrobial properties. Chitosan film can be obtained through casting method presenting suitable mechanical properties, such as resistance to traction and elongation, ability to adhere to surfaces and selective permeability to gases, such as O2 and CO2. However, it is highly permeable to water vapor, which can limit its potential coating use. The properties of chitosan films can be improved through the formation of composites by inserting nanoclays as montmorillonite in the polymeric matrix. The objective of this study was to develop and characterize chitosan/montmorillonite nanocomposites for fruit coating aiming for future applications in the field of smart packaging. Nanocomposites were characterized by its microstructure, thermal, mechanical, and physicochemical properties. X-ray diffraction analysis indicated changes in crystallinity with the insertion of montmorillonite. Nanocomposites became more transparent and significantly reduced its water permeability rate with 0.5% w/w montmorillonite addition. Elastic rigidity and tensile strength of the films were improved. Chitosan/montmorillonite nanocomposites demonstrated the potential to improve the storage time of Williams pears.

Formulation of Novel Composite (Activated Nanoclay/Hydrocolloid of Nostoc sphaericum) and Its Application in the Removal of Heavy Metals from Wastewater.

The removal of heavy metals from wastewater is an environmental challenge which demands the use of environmentally friendly materials that promote a circular economy. This study aimed to apply a novel composite of an activated nanoclay/hydrocolloid in the removal of heavy metals from wastewater. A composite blended under pressure was prepared with spray-dried hydrocolloid derived from Nostoc sphaericum algae and activated nanoclay in an acid medium and 1M NaCl. The composite and components were analyzed through infrared (IR), X-ray (XR), ζ potential, cation exchange capacity (CEC), particle size, and SEM images. The composite was subjected to the adsorption of heavy metals (Pb, As, Zn, and Cd) at pH 4.5 and the removal percentage, kinetics, and adsorption isotherms were evaluated. It was observed that the activated nanoclay and the composite that presented a particle size of around 400 nm significantly increased (p-value < 0.05) the CEC, ζ potential, the functional groups, and chelating components, removing heavy metals above 99% for Pb, As 33%, Cd 15%, and Zn 10%. Adsorption kinetics was adjusted to the pseudo second-order model (R2 > 0.98), and the Langmuir and Freundlich models better represented the sorption isotherm at 20 °C. The formulated composite presents a good ability to remove heavy metals in wastewater.

A Polypyrrole/Nanoclay Hybrid Film for Ultra-Sensitive Cardiac Troponin T Electrochemical Immunosensor.

An electrochemical immunosensor based on a nanohybrid film of carboxylated polypyrrole and amine nanoclay was developed for label-free detection of the human cardiac troponin T (cTnT). The nanohybrid film was formed in situ on the surface of the glassy carbon electrode, followed by the covalent immobilization of anti-troponin T antibodies by glutaraldehyde. Morphological and chemical characterizations of the nanohybrid film were performed by scanning electron microscopy and Fourier-transform infrared spectroscopy. Under the optimized conditions, a calibration curve for cTnT in spiked serum was obtained by square wave voltammetry, and a low limit of detection and quantification was achieved (0.35 and 1.05 pg mL-1, respectively). This was the first time that this type of nanohybrid film was used in the development of an immunosensor for cTnT that proved to be a simple and efficient strategy for the manufacture of a label-free electrochemical device that could be applied in the diagnosis of acute myocardial infarction.

Nanocomposite PLA/C20A Nanoclay by Ultrasound-Assisted Melt Extrusion for Adsorption of Uremic Toxins and Methylene Blue Dye.

Design of functional materials it is of great importance to address important problems in the areas of health and environment. In the present work, the synthesis and application of poly-meric nanocomposite materials with poly (lactic acid) (PLA) and modified nanoclay (cloisite 20A) with 1,4-diaminobutane dihydrochloride at different reaction times were studied. The concentra-tions of the nanoclays in the PLA matrix were 0.5, 1 and, 5% by weight (wt%). TGA showed that sample C20AM 120 (120 min of treatment) obtained the highest degree of modification considering the weight losses of the analyzed samples. An FT-IR signal at 1443 cm-1 suggests that the organic modifier is intercalated between the galleries of the clay. XRD, SEM and XPS suggest good disper-sion at low concentrations of the nanoclay. Adsorption tests revealed that the highest percentage of removal of uremic toxins and methylene blue was the sample with 5% wt/wt chemically modified nanoclay, suggesting good affinity between the modified nanoclays in the PLA matrix with the nitrogenous compounds.

Toxicological effects of leachate extracts from asphalt mixtures nanomodified under Daphnia magna and Landoltia punctata test organisms.

The incorporation of nanomaterials in binders in the paving area has been studied to improve the mechanical behavior of asphalt mixtures. However, asphalt mixture compounds are susceptible to leaching and deposition in the environment. In this context, this research aimed to investigate the toxic effect of two leachate extracts from asphalt mixtures nanomodified with 2% carbon nanotube and 3% organophilic nanoclay, compared to conventional mixture, using Daphnia magna and Landoltia punctata as test organisms. The nanomaterials were characterized to confirm morphology, stability and effective diameter. Extracts were chemically characterized using the Fourier-Transform Infrared Spectroscopy (FTIR) technique, which indicated presence of functional groups of the asphalt binder in greater intensity in the leachate from conventional mixture. Acute toxicity with D. magna indicated EC50,48h of 83.5 ± 6.2 mL/L for leachate extract from conventional mixture, 306.0 ± 87.6 mL/L for leachate extract from mixture with nanoclay and 464.8 ± 32.1 mL/L for leachate extract from mixture with carbon nanotube. No leachate caused significant chronic toxicity. As for L.punctata, concentrations that caused 50% growth inhibition were 127.5 mL/L for the leachate extract from mixture with carbon nanotube, 196.9 mL/L for the leachate extract from mixture with nanoclay and 205 mL/L for the leachate extract from conventional mixture. For these test organisms, there is no evidence of negative impacts directly associated with the use of the present nanomaterials in asphalt mixtures. The incorporation of these nanos may also reduce the acute toxicity of the mixtures.

Hyperstabilization of a thermophile bacterial laccase and its application for industrial dyes degradation.

In the present study, a novel extracellular laccase isolated from Geobacillus stearothermophilus ATCC 10149 was entrapped in a bionanocomposite matrix consisting of copper alginate (Cu-alginate) supplemented with the nanoclay bentonite. After optimization, this nanobiocatalyst was able to degrade up to 90% of Remazol Brilliant Blue R (RBBR) without the addition of redox mediators and retained 70% of its initial activity for at least 1440 h, equivalent to more than 288 uses. The incorporation of nanoclay allowed alginate beads to be used in alkaline pH and strengthened its mechanical properties. Besides, this thermophilic laccase was able to decolorize other structurally different synthetic dyes such as Methyl Orange, Malachite Green and Indigo Carmine. These preliminary results suggested that the nanobiocatalyst could be a suitable option for dye decolorization and be further developed for large scale bioremediation of toxic dyes.

Innovative bionanocomposite films of edible proteins containing liposome-encapsulated nisin and halloysite nanoclay.

Films and coatings based on natural polymers have gained increased interest for food packaging applications. In this work, halloysite and phosphatidylcholine liposomes encapsulating nisin were used to develop nanocomposite films of gelatin and casein. Liposomes prepared with either soybean lecithin or Phospholipon(®) showed particle size ranging from 124 to 178nm and high entrapment efficiency (94-100%). Considering their stability, Phospholipon(®) liposomes with 1.0mg/ml nisin were selected for incorporation into nanocomposite films containing 0.5g/l halloysite. The films presented antimicrobial activity against Listeria monocytogenes, Clostridium perfringens and Bacillus cereus. Scanning electron microscopy revealed that the films had a smooth surface, but showed increased roughness with addition of liposomes and halloysite. Casein films were thinner and slightly yellowish, less rigid and very elastic as compared with gelatin films. Thermogravimetric analysis showed a decrease of the degradation temperature for casein films added with liposomes. The glass transition temperature decreased with addition of liposomes and halloysite. Gelatin and casein films containing nisin-loaded liposomes and halloysite represent an interesting alternative for development of active food packaging.

Macro- and Micronutrient Simultaneous Slow Release from Highly Swellable Nanocomposite Hydrogels.

Clay-loaded hydrogels have been arousing great interest from researchers and academics due to their unique properties and broad applicability range. Here we developed hydrogel-based nanocomposites intended for slow/controlled release of macro- and micronutrients into independent or concurrent systems. The produced nanocomposites underwent a hydrolysis treatment that improved their physicochemical properties. We obtained materials capable of absorbing water contents 5000 times greater than their weights, an outcome that makes them promising, particularly if compared with commercially available materials. Though swelling degree was affected by the presence of calcium montmorillonite (MMt), MMt has increased nutrient (urea and boron) loading capacity and, as a consequence of its interaction with the studied nutrients, has led to a slower release behavior. By evaluating the simultaneous release behavior, we observed that both the ionic (sodium octaborate) and the nonionic (urea) sources competed for the same active sites within the nanocomposites as suggested by the decreased loading and release values of both nutrients when administrated simultaneously. Because of its great swelling degree, higher than 2000 times in water, the nanocomposites formulated with high MMt contents (approximately 50.0% wt) as well as featuring high loading capacity and individual (approximately 74.2 g of urea g(-1) of nanocomposite and 7.29 g of boron g(-1) of nanocomposite) and simultaneous release denote interesting materials for agricultural applications (e.g., carriers for nutrient release).

Adsorption of nisin and pediocin on nanoclays.

Three different nanoclays (bentonite, octadecylamine-modified montmorillonite and halloysite) were studied as potential carriers for the antimicrobial peptides nisin and pediocin. Adsorption occurred from peptide solutions in contact with nanoclays at room temperature. Higher adsorption of nisin and pediocin was obtained on bentonite. The antimicrobial activity of the resultant bacteriocin-nanoclay systems was analyzed using skimmed milk agar as food simulant and the largest inhibition zones were observed against Gram-positive bacteria for halloysite samples. Bacteriocins were intercalated into the interlayer space of montmorillonites as deduced from the increase of the basal spacing measured by X-ray diffraction (XRD) assay. Infrared spectroscopy suggested non-electrostatic interactions, such as hydrogen bonding between siloxane groups from clays and peptide molecules. Transmission electron microscopy did not show any alteration in morphologies after adsorption of antimicrobial peptides on bentonite and halloysite. These results indicate that nanoclays, especially halloysite, are suitable nanocarriers for nisin and pediocin adsorption.

Síntese e análise de compósitos experimentais para uso odontológico reforçados com nanoargila / Synthesis and analysis of experimental composites for dentistry use reinforced with nanoclay

O objetivo do presente estudo foi de avaliar os efeitos de diferentes frações de partículas de nanoargila modificadas do tipo montmorilonita Cloisite® 20A em propriedades físicas, mecânicas e biológicas de resinas experimentais do tipo nanohíbrida. Compósitos dentais foram preparados através da mistura de 30% de matriz resinosa (BisGMA/TEGDMA) em 70% de partículas de carga (vidro de bário silicato silanizado ­VB, dióxido de silício ­ SD, partículas de nanoargila MMT). Quatro grupos de compósitos experimentais foram formados, variando o percentual de nanoargila empregada (0%, 5%, 7,5%, 10%). O processamento foi realizado em uma máquina de dupla mistura (SpeedMixer DAC, Germany, 3500 rpm). A citotoxicidade in vitro do material foi avaliada baseada nas normas ISO 10993- 5-2009 e comparado com compósito comercial. Ensaios mecânicos para cálculo de Resistência à Flexão e Módulo de Elasticidade foram realizados em máquina de ensaios universal EMIC. O aparelho Acuvol® foi utilizado para o ensaio de contração de polimerização. A sorção e solubilidade dos compósitos foram calculadas baseadas nas normas ISO 4049. Os dados foram analisados estatisticamente, utilizando-se a tabela ANOVA e o Teste de Tukey para comparação dos grupos de dois em dois. O nível de significância utilizado foi de 95% (p< 0,05). Por meio do exame dos resultados, concluiu-se que foi possível esfoliar 5 e 7,5% de partículas de MMT satisfatoriamente na matriz BisGMA/TEGDMA, porém, o inserção de 10% de MMT na matriz orgânica não trouxe vantagens ao compósito, certamente por não permitir a total exfoliação de suas partículas. A inserção de 5 e 7,5% de nanoargila ao compósito dental experimental possibilitou uma diminuição da contração de polimerização do material em 22,13 e 17,4%, respectivamente. Além disso, esses dois grupos permaneceram com suas propriedades mecânicas e de absorção e solubilidade satisfatórias, além de apresentar ausência de citotoxicidade para as células fibroblasticas L929 testadas

The aim of the present study was to evaluate the effect of different weight fractions of modified montmorillonite nanoclay fillers Cloisite ® 20A on mechanical, physical and biological properties of nanohybrid experimental resins. Dental composites were prepared by mixing 30% of resin matrix (BisGMA / TEGDMA) to 70% of particulate fillers (Silanized barium silicate particles - BS, silicone dioxide - SD, montmorillonite nanoclay cloisite 20AMMT). Four groups of experimental composite were formed with various fractions of the nanoclay fillers (0%; 5%; 7,5%; 10% ). Processing was performed using a dual high speed mixing machine (SpeedMixer DAC, Germany, 3500 rpm). In vitro citotoxicity of the material was calculated based on standards ISO 10993-5-2009 and compared to a comercial composite. Tensile strenght and elastic modulus were performed using an universal test machine EMIC. The volumetric shrinkage was calculated by Acuvol® machine. Water sorption and solubility were measured based on International Standard ISO 4049. Data were statistically analyzed by ANOVA and Tukey Test for multiple comparisons. The significance level utilized was 95% (p < 0,05). By the results, it was concluded that it is possible to exfoliate nicely 5 and 7.5% of MMT particles inside Bis-GMA/TEGDMA matrix. However, insertion of 10% of MMT did not improve composite, certainly, because the total exfoliation of particles did not occured. Insertion of 5 and 7.5% of nanoclay in dental composite diminished polymerization shrinkage in 22,13% and 17,4% , respectively. Furthermore, these two groups maintained their mechanical properties, satisfactory sorption and solubility and also presented no citotoxicity for L929 fibroblastic cells

Nanocomposites of rice and banana flours blend with montmorillonite: partial characterization.

Rice and banana flours are inexpensive starchy materials that can form films with more improved properties than those made with their starch because flour and starch present different hydrophobicity. Montmorillonite (MMT) can be used to further improve the properties of starch-based films, which has not received much research attention for starchy flours. The aim of this work was to evaluate the mechanical and barrier properties of nanocomposite films of banana and rice flours as matrix material with addition of MMT as a nanofiller. MMT was modified using citric acid to produce intercalated structures, as verified by the X-ray diffraction pattern. The intercalated MMT was blended with flour slurries, and films were prepared by casting. Nanocomposite films of banana and rice flours presented an increase in the tensile at break and elongation percentage, respectively, more than their respective control films without MMT. This study showed that banana and rice flours could be alternative raw materials to use in making nanocomposite films.