Performance of Thyme Oil@Na-Montmorillonite and Thyme Oil@Organo-Modified Montmorillonite Nanostructures on the Development of Melt-Extruded Poly-L-lactic Acid Antioxidant Active Packaging Films.

Today, the use of natural biodegradable materials in the production processes is more and more adopted by industry to achieve cyclic economy targets and to improve environmental and human health indexes. Active packaging is the latest trend for food preservation. In this work, nanostructures were prepared by incorporation of thyme oil with natural natrium-montmorillonite and organo-montmorillonite with two different techniques, direct impregnation and the green evaporation-adsorption process. Such nanostructures were mixed with poly-L-lactic-acid for the first time via an extrusion molding process to develop a new packaging film. Comparisons of morphological, mechanical, and other basic properties for food packaging were carried out via XRD, FTIR, TG, SEM/EDS, oxygen and water vapor permeation, and antimicrobial and antioxidant activity for the first time. Results showed that poly-L-lactic-acid could be modified with clays and essential oils to produce improved active packaging films. The final product exhibits food odor prevention characteristics and shelf-life extension capabilities, and it could be used for active packaging. The films based on OrgMt clay seems to be more promising, while the thyme oil addition improves their behavior as active packaging. The PLLA/3%TO@OrgMt and PLLA/5%TO@OrgMt films were qualified between the tested samples as the most promising materials for this purpose.

Linear and nonlinear optical parameters of biodegradable chitosan/polyvinyl alcohol/sodium montmorillonite nanocomposite films for potential optoelectronic applications.

Innovations in sophisticated optoelectronic devices have increased interest in high-refractive index polymers. Herein, we report innovative nanocomposite films with high linear and nonlinear refractive indices prepared by casting chitosan (Cs) with polyvinyl alcohol (PVA) (50:50 wt%) along with different concentrations (10-50 wt%) of sodium montmorillonite (NaMMT) nanoclay. The refractive indices in addition to other optical parameters of homopolymers and hybrid materials were investigated by UV-Vis. spectroscopy and optical modeling to assess their potential applications in optics. Besides, the structure, morphology, and thermal stability of the prepared films were investigated by a multitude of experimental techniques including X-ray diffraction (XRD), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), and thermogravimetric analysis (TGA/DTG). The ATR-FTIR, XRD, SEM, and AFM measurements confirmed the complete exfoliation of NaMMT nanolayers in the Cs/PVA matrix. The TGA/DTG revealed an increase in the thermal stability of Cs/PVA film with increasing clay content. The UV-Vis. measurements revealed a decrease in the optical energy gap (Eg) and a substantial increase in the linear (nD) and nonlinear (n2) refractive indices as clay content increased. Additionally, the nanohybrids displayed low UV transmission and reflected about 80 % of UV rays, making them excellent candidates for UV protection. For the first time, the dissipation factor (tanδ) in the UV/Vis. region has been calculated and fitted with the Drude-Lorentz model to predict the plasma frequency (ωp), resonance frequency (ω0), and electron lifetime (τ) of pristine polymers and nanocomposites.

New Methodology for Modifying Sodium Montmorillonite Using DMSO and Ethyl Alcohol.

Modified clays with organic molecules have many applications, such as the adsorption of pollutants, catalysts, and drug delivery systems. Different methodologies for intercalating these structures with organic moieties can be found in the literature with many purposes. In this paper, a new methodology of modifying Sodium Montmorillonite clays (Na-Mt) with a faster drying time was investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), BET, and thermogravimetric analysis (TG and DTG). In the modification process, a mixture of ethyl alcohol, DMSO, and Na-Mt were kept under magnetic stirring for one hour. Statistical analysis was applied to evaluate the effects of the amount of DMSO, temperature, and sonication time on the modified clay (DMSO-SMAT) using a 23-factorial design. XRD and FTIR analyses showed the DMSO intercalation into sodium montmorillonite Argel-T (SMAT). An average increase of 0.57 nm for the interplanar distance was found after swelling with DMSO intercalation. BET analysis revealed a decrease in the surface area (from 41.8933 m2/g to 2.1572 m2/g) of Na-Mt when modified with DMSO. The porosity increased from 1.74 (SMAT) to 1.87 nm (DMSO-SMAT) after the application of the methodology. Thermal analysis showed a thermal stability for the DMSO-SMAT material, and this was used to calculate the DMSO-SMAT formula of Na[Al5Mg]Si12O30(OH)6 · 0.54 DMSO. Statistical analysis showed that only the effect of the amount of DMSO was significant for increasing the interlayer space of DMSO-SMAT. In addition, at room temperature, the drying time of the sample using this methodology was 30 min.

Electro-optics of confined systems.

Confinement in microenvironments occurs in many natural systems and technological applications. However, little is known about the behaviour of the immersed nanoparticles. In this work we show that their diffusion, electro-orientation and electric field induced polarization can be determined through electric birefringence experiments. We analyze aqueous dispersions of silver nanowires and clay particles confined inside microdroplets. We have observed that confinement reduces the amount of particles that can be oriented by the external electric field. However, the polarizability of the oriented particles is not affected by the presence of the oil/water boundary, and it is the same as in unbounded media, which agrees with the fact that the electric polarization and related phenomena are short-ranged.

Immobilization of Horseradish Peroxidase onto Montmorillonite/Glucosamine-Chitosan Composite for Electrochemical Biosensing of Polyphenols.

Glucosamine-chitosan synthesized by the Maillard reaction was combined with montmorillonite to obtain a nanohybrid composite to immobilize horseradish peroxidase. The material combines the advantageous properties of clay with those of the chitosan derivative; has improved water solubility and reduced molecular weight and viscosity; involves an eco-friendly synthesis; and exhibits ion exchange capacity, good adhesiveness, and a large specific surface area for enzyme adsorption. The physicochemical characteristics of the composite were analyzed by infrared spectroscopy and X-ray diffraction to determine clay-polycation interactions. The electrochemical response of the different polyphenols to glassy carbon electrodes modified with the composite was evaluated by cyclic voltammetry. The sensitivity and detection limit values obtained with the biosensor toward hydroquinone, chlorogenic acid, catechol, and resorcinol are (1.6 ± 0.2) × 102 µA mM-1 and (74 ± 8) nM; (1.2 ± 0.1) × 102 µA mM-1 and (26 ± 3) nM; (16 ± 2) µA mM-1 and (0.74 ± 0.09) µM; and (3.7± 0.3) µA mM-1 and (3.3 ± 0.2) µM, respectively. The biosensor was applied to quantify polyphenols in pennyroyal and lemon verbena extracts.

Efficient cadmium immobilization by organic loaded Na-montmorillonite in a contaminated soil.

Clay minerals are effective sorbents for toxic metal immobilization in contaminated soils and waters. However, their Cd immobilization efficiency is unclear when they are loaded with organics. In this study, sodium montmorillonite (Na-M) was successfully loaded with potassium humate, chitosan, and glycine to adsorb Cd(II) in solution. Potassium humate loaded Na-M (Na-M-HA), which had the highest specific surface area and cation exchange capacity (CEC), showed the highest Cd(II) adsorption capacity (73.7 mg g-1), 22.5 % and 81.8 % higher than that of chitosan loaded Na-M (Na-M-CTS) and glycine loaded Na-M (Na-M-G), respectively. The pseudo-second-order kinetic model best described (R2 > 0.98) the adsorption kinetics of Cd(II) on the three Na-Ms, indicating that the adsorption processes were of chemisorption nature. The adsorption isotherm of Cd(II) on Na-M-HA was of the Freundlich type, suggesting multilayer adsorption. In contrast, the isothermal adsorption of Cd(II) on Na-M-CTS (R2 = 0.99) and Na-M-G (R2 = 0.89) was better described by the Langmuir model, suggesting the dominance of monolayer adsorption in the adsorption process. High temperature, high pH, low background ionic strength, and low valence competing cations favored Cd(II) adsorption on Na-M-HA. The underlying mechanisms of Cd(II) sorption on Na-M-HA were electrostatic attraction, ion exchange and complexation. Na-M-HA was applied to a Cd polluted soil planted with lettuce (Lactuca sativa L.). in a pot experiment. Compared to the control with no adsorbent application, Na-M-HA application at 2 % effectively reduced the available Cd content in soil and Cd accumulation in plant by 36.0 % and 56.8 %, respectively. This work demonstrated that Na-M-HA is a green, low-cost and excellent adsorbent for Cd stabilization, and that its application in Cd-polluted soils can efficiently reduce Cd bioavailability and thereby Cd transfer along the food chain and eventually reduce the threat of Cd pollution to human health.

Polyaspartate-Ionene/Na+-Montmorillonite Nanocomposites as Novel Adsorbent for Anionic Dye; Effect of Ionene Structure.

Surface modification of sodium montmorillonite (Na+-Mt) was performed using antimicrobial agents to produce an ecofriendly nanocomposite. The adsorption performance of the nanocomposite has been evaluated for the removal of Acid Blue 25 dye (AB25) as a model organic pollutant from wastewater. Sodium montmorillonite (Na+-Mt) was modified with three different ionene compounds through ion exchange, and further modified through reaction with polyaspartate to provide three ecofriendly nanocomposites (denoted ICP-1-3). The nanocomposites were characterized using FTIR, PXRD, TEM, SEM, and BET surface area. The adsorption isotherm of AB25 onto ICP-1, ICP-2 and ICP-3 was analyzed using the Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) models. The adsorption isotherm was found to be best fitted by a Freundlich model. The thermodynamic parameters were calculated. The kinetics of the adsorption data were analyzed and the adsorption behavior was found to obey pseudo-second-order kinetics, and the intraparticle diffusion model. The adsorption mechanism was studied by FTIR.

Improving Thermal, Mechanical, and Barrier Properties of Feather Keratin/Polyvinyl Alcohol/Tris(hydroxymethyl)aminomethane Nanocomposite Films by Incorporating Sodium Montmorillonite and TiO2.

In this study, feather keratin/polyvinyl alcohol/tris(hydroxymethyl)aminomethane (FK/PVA/Tris) bionanocomposite films containing two types of nanoparticles, namely one-dimensional sodium montmorillonite (MMT) clay platelets (0.5, 1, 3, and 5 wt%) and three-dimensional TiO2 nanospheres (0.5, 1, 3, and 5 wt%), are prepared using solvent casting method. X-ray diffraction studies confirm the completely exfoliated structure of FK/PVA/Tris/MMT nanocomposites. The successful formation of new hydrogen bonds between the hydroxyl groups of the film matrix and the nanofillers is confirmed by Fourier transform infrared spectroscopy. The tensile strength, elongation at break, and initial degradation temperature of the films are enhanced after MMT and TiO2 incorporation. The water vapor permeability, oxygen permeability, and light transmittance decrease with increase in TiO2 and MMT contents. In summary, nanoblending is an effective method to promote the application of FK/PVA/Tris blend films in the packaging field.

Fabrication and characterization of CMC-based nanocomposites reinforced with sodium montmorillonite and TiO2 nanomaterials.

In this study, a novel carboxymethyl cellulose (CMC)-based ternary nanocomposite films containing sodium montmorillonite (Na-MMT) (1, 3 and 5% wt) and titanium dioxide (TiO2) (1, 3 and 5% wt) nanoparticles (NPs) were made via casting method. The results showed that addition of NPs decremented water vapor permeability of the films up to 39% and 50% by adding Na-MMT, and Na-MMT + TiO2, respectively, while moisture content, density and glass transition temperature incremented slightly. The nanoclays amplified resistance of the nanocomposites against tensile stress and Young's modulus (YM) of the films at the expense of elongation at break. A synergistic effect of NPs on moisture uptake reduction (≈ 40%) of films was observed. Nano-TiO2 was strongly effective in UV-light blocking (The films containing 5% TiO2 removed more than 99% of UV and more than 98% of visible lights). The interactions, crystallinity and morphology of the nanocomposites were investigated by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM). Development of hydrogen bonds between the hydroxyl groups of CMC and nanoparticles was indicated by FT-IR spectroscopy. Conforming to the XRD analysis, clay nanolayers organized an intercalated structure in the nanocomposites, whereas a limited agglomeration of TiO2 nanoparticles led to increment of films crystallinity. SEM micrographs showed well-dispersed Na-MMT and TiO2 NPs through the films surface especially at low concentrations. In conclusion, although the films loaded with nanoclays exhibited better properties than the control film, inclusion of TiO2 more improved the functional characteristics of them and extended the potential as a biodegradable packaging.

Controlling the melt dripping of polyester fabrics by tuning the ionic strength of polyhedral oligomeric silsesquioxane and sodium montmorillonite coatings assembled through Layer by Layer.

This work deals with the Layer by Layer (LbL) assembly of hybrid organic/inorganic flame retardant coatings made of Octa-ammonium POSS (polyhedral oligomeric silsesquioxane) and sodium montmorillonite clay on polyester (PET) fabrics. The effects of ionic strength on the achieved flame retardancy properties were investigated. The coating growth asa function of different ionic strengths was evaluated by infrared spectroscopy. 0.10M NaCl was found able to promote the highest adsorption of each coating species at each deposition step strongly affecting clay stacking as evaluated by X-ray diffraction measurements. The coatings on PET assembled at high ionic strength turned out to be more homogeneous and thicker than the reference one. Thanks to the increased thickness and better surface coverage, the same coatings efficiently suppressed the melt dripping phenomenon and significantly slowed down flame spread rate in horizontal flammability tests with only 2wt% of coating mass added. Furthermore, the same performances were maintained after 1h washing at 70°C. By cone calorimetry, coated fabrics showed a strong reduction in the combustion kinetics by nearly halving the peak of heat release rate. This paper provides an important insight on the viability of tuning deposition of LbL coatings on fabrics employing industrial-like processes by simple modification of ionic strength.

Adsorption and intercalation of low and medium molar mass chitosans on/in the sodium montmorillonite.

Chitosan-montmorillonite composites can provide hydrophobicity and amino groups to enhance the performances of montmorillonite in wastewater treatment. In this paper, low molar mass chitosan (LC) and medium molar mass chitosan (MC) were selected to intercalate a sodium montmorillonite (Mt). The adsorption isotherm of LC and MC on the Mt and the pH dependency were measured. Thermo X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the chitosan-Mt composites. Results showed that with hydrochloric acid as the solvent of chitosans, increasing pH from 3 to 5.5 enhanced the adsorption of both LC and MC on the Mt, and when the equilibrium concentration of chitosans approached 300mg/L at pH 5.5, the amount of adsorbed chitosan reached the highest level of 0.203mg/mg for LC and 0.190mg/mg for MC, respectively. When the Mt was saturated with the chitosan, the amino groups on the chitosan were bonded with the Mt through electrostatic interaction and there was monolayer of the chitosan in the interlayer space of Mt, which were confirmed by FTIR spectra and XRD patterns, respectively.

Carboxymethyl starch/montmorillonite composite microparticles: Properties and controlled release of isoproturon.

Preparation of novel high substituted carboxymethyl starch-based microparticles containing sodium montmorillonite (MMT) by crosslinking with Al(3+) was described. For preparing nanocomposite granules carboxymethyl starch (CMS) from native potato starch as well as CMS from amylopectin has been used. The hydrophilic CMS/MMT composite systems were used for herbicide, i.e. isoproturon encapsulation (ca. 75% encapsulation efficiency). The herbicide release rate from CMS/MMT composites in water was significantly reduced when compared to commercial isoproturon: 95% released after ca. 700 h and ca. 24h, respectively. Leaching in soil from composite systems was relatively slower than release in water. After a series of eight irrigations leached about 10% of isoproturon loaded. The CMS/MMT carriers could reduce the potential leaching of herbicide and beneficially reduce pollution of the environment.

Ibuprofen analysis in blood samples by palladium particles-impregnated sodium montmorillonite electrodes: Validation using high performance liquid chromatography.

The electrochemical detection of ibuprofen has been studied on Palladium-Montmorillonite (Mt) modified carbon paste electrode using differential pulse voltammetry. The optimization of the modifier preparation and the instrumental parameters was investigated. The results indicate that ibuprofen oxidation was favored in the presence of Pd-PdO particles. The quantitative determination of ibuprofen was statistically analyzed and validated using HPLC method. The detection and quantification limits, specificity and precision were found to be acceptable. Finally, the developed method was successfully applied for ibuprofen determination in human blood samples.

Preparation and evaluation of antimicrobial activity of nanosystems for the control of oral pathogens Streptococcus mutans and Candida albicans.

BACKGROUND: Diseases that affect the buccal cavity are a public health concern nowadays. Chlorhexidine and nystatin are the most commonly used drugs for the control of buccal affections. In the search for more effective antimicrobials, nanotechnology can be successfully used to improve the physical chemical properties of drugs whilst avoiding the undesirable side effects associated with its use. Herein described are studies using nystatin and chlorhexidine with sodium montmorillonite (MMTNa), and chlorhexidine with ß-cyclodextrin and two derivatives methyl-ß-cyclodextrin and hydroxypropyl-ß-cyclodextrin in the development of antimicrobial nanosystems. METHODS: The nanosystems were prepared by kneading and solubilization followed by freeze-drying technique. The nanosystems were characterized by X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). Nanosystem antimicrobial activity against Streptococcus mutans and Candida albicans strains was evaluated with inhibition halo analysis. RESULTS: The nanocarriers MMTNa and cyclodextrins showed good yields. XRPD, FTIR, and DSC analysis confirmed the proposed nanosystems formation and the suitability of the production methods. The nanosystems that showed best antimicrobial effect were chlorhexidine gluconate (CHX) and cyclodextrin inclusion complexes and CHX:MMTNa 60% cation exchange capacity - 24 hours. CONCLUSION: The nanosystem formulations present higher stability for all chlorhexidine inclusion complexes compared with pure chlorhexidine. The nystatin nanosystems have the potential to mask the bitter taste, justifying subsequent in-vivo studies. For these reasons, further studies are being carried out to evaluate their application in professional formulations.