Magnetic-responsive polysaccharide hydrogels as smart biomaterials: Synthesis, properties, and biomedical applications.

This review reports recent advances in polysaccharide-based magnetic hydrogels as smart platforms for different biomedical applications. These hydrogels have proved to be excellent, viable, eco-friendly alternative materials for the biomedical field due to their biocompatibility, biodegradability, and possibility of controlling delivery processes via modulation of the remote magnetic field. We first present their main synthesis methods and compare their advantages and disadvantages. Next, the synergic properties of hydrogels prepared with polysaccharides and magnetic nanoparticles (MNPs) are discussed. Finally, we describe the main contributions of polysaccharide-based magnetic hydrogels in the targeted drug delivery, tissue regeneration, and hyperthermia therapy fields. Overall, this review aims to motivate the synthesis of novel composite biomaterials, based on the combination of magnetic nanoparticles and natural polysaccharides, to overcome challenges that still exist in the treatment of several diseases.

Montmorillonite with essential oils as antimicrobial agents, packaging, repellents, and insecticides: an overview.

Essential oils (EOs) are complex natural mixtures of secondary plant metabolites that function as biocides and therapeutic agents. They are extensively used in bactericidal, virucidal, fungicidal, antiparasitic, insecticidal, pharmaceutical, and cosmetic products. However, certain characteristics, such as the volatility of EOs, hinder their widespread use. To mitigate this limitation, several studies have investigated combinations of EOs with natural materials, including clay minerals. Clay minerals are abundant in nature, biocompatible, and non-toxic to the environment and humans. Clay minerals such as montmorillonite possess available sites where EO molecules can interact. The combination of EOs with clay minerals produces new materials for various applications including antibacterial, antifungal, insecticidal/repellent, and active packaging materials. Therefore, this review focuses on the immobilization of several types of EOs in raw and modified montmorillonites. The applications of the described systems were evaluated and demonstrated the synergism of the properties of the isolated components as a function of different EOs incorporated in the silicate matrix.

A Brief Photocatalytic Study of ZnO Containing Cerium towards Ibuprofen Degradation.

Ibuprofen (IBU) is one of the most-sold anti-inflammatory drugs in the world, and its residues can reach aquatic systems, causing serious health and environmental problems. Strategies are used to improve the photocatalytic activity of zinc oxide (ZnO), and thosethat involvethe inclusion of metalhave received special attention. The aim of this work was to investigate the influence of the parameters and toxicity of a photoproduct using zinc oxide that contains cerium (ZnO-Ce) for the photodegradation of ibuprofen. The parameters include the influence of the photocatalyst concentration (0.5, 0.5, and 1.5 g L-1) as well as the effects of pH (3, 7, and 10), the effect of H2O2, and radical scavengers. The photocatalyst was characterized by Scanning Electron Microscopy-Energy Dispersive Spectroscopy, Transmission electron microscopy, Raman, X-Ray Diffraction, surface area, and diffuse reflectance. The photocatalytic activity of ibuprofen was evaluated in an aqueous solution under UV light for 120 min. The structural characterization by XRD and SEM elucidated the fact that the nanoparticle ZnO contained cerium. The band gap value was 3.31 eV. The best experimental conditions for the photodegradation of IBU were 60% obtained in an acidic condition using 0.50 g L-1 of ZnO-Ce in a solution of 20 ppm of IBU. The presence of hydrogen peroxide favored the photocatalysis process. ZnO-Ce exhibited good IBU degradation activity even after three photocatalytic cycles under UV light. The hole plays akey role in the degradation process of ibuprofen. The toxicity of photolyzed products was monitored against Artemia salina (bioindicator) and did not generate toxic metabolites. Therefore, this work provides a strategic design to improve ZnO-Ce photocatalysts for environmental remediation.

Thiabendazole/bentonites hybrids as controlled release systems.

Clay minerals are commonly used in pharmaceutical products as excipients and active agents. New drug vehicles based on clay minerals have been developed. In this work, sodium (BentNa), calcium (BentCa) and magnesium (BentMg) exchanged bentonites were used for the sorption of thiabendazole (TBZ), and their potential use as controlled release systems was evaluated. Pristine bentonite and exchanged bentonites were characterized by X-ray diffraction, infrared spectroscopy, thermogravimetry and transmission electron microscopy (TEM), and the influence of the different parameters such as pH, contact time and initial concentration of the drug was investigated. The maximum adsorption reached after 45 min period with 2000 mg L-1 of thiabendazole to BentNa and after 105 min with 1300 mg L-1 to BentCa and BentMg, respectively. The maximum adsorbed quantities of thiabendazole were 164.4; 152.3 and 133.3 mg g-1 for BentNa, BentCa and BentMg, respectively. The emission profiles obtained for the bentonite/drug hybrids were similar when simulated body fluids were used and these emission profiles were fitted according to the Korsmeyer-Peppas kinetic model.

Resistant starch/pectin free-standing films reinforced with nanocellulose intended for colonic methotrexate release.

Although resistant starch/pectin (RS/P) films have previously displayed suitable properties for colon-specific drug delivery, nanocomposite films were developed aiming to enhance physicochemical, thermal, mechanical and barrier properties, as well as the low oral bioavailability of methotrexate (MTX). FEG-SEM micrographs of nanocomposite films showed different interaction patterns occurring among nanocellulose and RS/P. The nanofiller addition led to an increase in the thermal stability, probably due to its interaction with RS crystalline double helices. Results also displayed an improvement of the puncture strength, while barrier properties revealed a low water vapor permeability. Ex vivo bioadhesion test displayed the nanocomposites films to interact strongly with porcine gastrointestinal mucosa. In vitro drug release studies showed that the films developed enhanced the drug dissolution rates with approximately 80% of MTX release in 150min, suggesting the potential of these materials as a poor solubility drugs carrier, which constitutes an important tool for enhancing oral bioavailability.

Exploring the favorable ion-exchange ability of phthalylated cellulose biopolymer using thermodynamic data.

A phthalylated ion-exchange biopolymer was obtained by adding cellulose to molten phthalic anhydride in a quasi solvent-free procedure. Through this route 2.99+/-0.07 mmolg(-1) of pendant groups containing ester and carboxylic acid moieties were incorporated into the polymeric structure that was characterized by elemental analysis, solid-state carbon nuclear magnetic resonance (CP/MAS), infrared spectroscopy, X-ray diffraction, and thermogravimetry. The chemically modified polysaccharide is able to exchange cations from aqueous solution as demonstrated by batchwise methodology. The data were adjusted to a modified Langmuir equation to give 2.43+/-0.12 and 2.26+/-0.11 mmolg(-1) for divalent cobalt and nickel cations, respectively. The net thermal effects obtained from calorimetric titration measurements were also adjusted to a modified Langmuir equation, and the enthalpy of the interaction was calculated to give endothermic values of 2.11+/-0.28 and 2.50+/-0.31kJmol(-1) for these cations, respectively. The spontaneity of this ion-exchange process is reflected in negative Gibbs energy and with a contribution of positive entropic values. This set of thermodynamic data at the solid-liquid interface suggests a favorable ion-exchange process for this anchored biopolymer for cation exchange from the environment.

Immobilization of ethylenesulfide on babassu coconut epicarp and mesocarp for divalent cation sorption.

A new synthetic methodology route consisted in reacting the natural babassu coconut mesocarp (BCM) and babassu coconut epicarp (BCE) with ethylenesufide, for adding basic sulfur centers in pendant chains that possess high potential activity for coordinating divalent cations from aqueous solution. All biomaterials were characterized by elemental analysis, infrared (IR), (13)C NMR and thermogravimetry. The sulfur elemental analysis gave 2.00+/-0.05 and 8.67+/-0.01% for BCES and BCMS, which correspond to 0.60+/-0.01 and 2.71+/-0.01 mmol of this element per each gram of BCE and BCM, to confer a degree of functionalization of 20.2+/-0.07 and 86.7+/-0.01 mg g(-1). This synthesis enabled from IR weak SH band at 2544 cm(-1) due to the incorporation of the reagent into the structure. The basic centers favor copper sorption with increasing pH from 2 to 6 observed by a batchwise methodology and the data obtained from the chosen pH 6 were adjusted to Freundlich and Langmuir models, favoring fit for the latter equation. The kinetics of sorption was established at 30 min for both biopolymers with a pseudo-second-order model.

Cation removal using cellulose chemically modified by a Schiff base procedure applying green principles.

Pentane-2,4-dione (acetylacetone) molecules were covalently incorporated under several different conditions to ethylene-1,2-diamine (en)-modified cellulose, using polar solvents or without solvents. The quantitative amount of en incorporated was given from 0.37+/-0.01 to 3.03+/-0.01 mmol of nitrogen per gram of cellulose, depending on the synthetic routes and after Schiff base formation this percentage was reduced by 1.38-6.12%. The synthetic routes indicated that lower solvent volumes produced higher amounts of en incorporation. However, the highest degree of pendant groups on the polymeric cellulose structure was obtained from a solvent-free reaction route. This procedure was applied for synthesizing all Schiff bases, causing a decrease in the amount of nitrogen. The available basic centers on the best covalently bonded biopolymer were investigated for adsorption of divalent copper, cobalt, nickel, and zinc from aqueous solution, with a capacity order of Cu2+ > Co2+ > Ni2+ > Zn2+.

Kinetics and thermodynamics of textile dye adsorption from aqueous solutions using babassu coconut mesocarp.

Extracted babassu coconut (Orbignya speciosa) mesocarp (BCM) was applied as a biosorbent for aqueous Blue Remazol R160 (BR 160), Rubi S2G (R S2G), Red Remazol 5R (RR 5), Violet Remazol 5R (VR 5) and Indanthrene Olive Green (IOG) dye solutions. The natural sorbent was processed batchwise while varying several system parameters such as stirring time, pH and temperature. The interactions were assayed with respect to both pseudo-first-order and second-order reaction kinetics, with the latter the more suitable kinetic model. The maximum adsorption was obtained at pH 1.0 for all dyes due to available anionic groups attached to the structures, which can be justified by pH(pzc) 6.7 for the biosorbent BCM. The ability of babassu coconut mesocarp to adsorb dyes gave the order R S2G>VR 5>BR 160>IOG>RR 5, which data were best fit to Freundlich model, but did not well-adjusted for all dyes. The dye/biopolymer interactions at the solid/liquid interface are all spontaneous as given by free Gibbs energy, with exothermic enthalpic values of -26.1, -15.8, -17.8, -15.8 and -23.7 kJ mol(-1) for BR 160, R S2G, RR 5, IOG and VR 5, respectively. In spite of the negative entropic values contribution, the set of thermodynamic data is favorable for all dyes removal. However, the results pointed to the effectiveness of the mesocarp of babassu coconut as a biosorbent for removing textile dyes from aqueous solutions.

Preparation of ethylenediamine-anchored cellulose and determination of thermochemical data for the interaction between cations and basic centers at the solid/liquid interface.

Cellulose was first modified with thionyl chloride, giving 99% substitution at C6, and then reacted with ethylene-1,2-diamine to produce 6-(2'-aminoethylamino)-6-deoxy-cellulose. From the 8.5% of nitrogen incorporated in the polysaccharide backbone, the amount of ethylene-1,2-diamine anchored per gram of modified cellulose was determined to be 3.03+/-0.01mmol. This chemically immobilized surface was characterized by FTIR, TG, (13)C NMR, and SEM techniques. The available basic nitrogen centers covalently bonded to the biopolymer skeleton were studied for copper, cobalt, nickel, and zinc adsorption from aqueous solutions and the respective thermal adsorption effects were determined by calorimetric titration. The ability to adsorb cations gave a capacity order of Co(2+)>Cu(2+)>Zn(2+)>Ni(2+) with affinities of 1.91+/-0.07, 1.32+/-0.07, 1.31+/-0.02, and 1.08+/-0.04mmol/g, respectively. The net thermal effects obtained from calorimetric titration measurements were adjusted to a modified Langmuir equation and the enthalpy of the interaction was calculated to give the following exothermic values: -20.8+/-0.05, -11.72+/-0.03, -7.32+/-0.01, and -6.27+/-0.02kJ/mol for Co(2+), Cu(2+), Zn(2+), and Ni(2+), respectively. With the exception of the entropic value for copper, the other thermodynamic data for these systems are favorable for cation adsorption from aqueous solutions at the solid/liquid interface, suggesting the use of this anchored biopolymer for cation removal from the environment.

Hydroxyapatite organofunctionalized with silylating agents to heavy cation removal.

Hydroxyapatite surface silylation with organosilane derivatives (H3CO)3SiR, R being the corresponding organic moieties CH2CH2CH2NH2, CH2CH2CH2NHCH2CH2NH2, and CH2CH2CH2NHCH2CH2NHCH2CH2NH2, was carried out to yield organofunctionalized nanomaterials, named HApR1, HApR2, and HApR3, respectively. The products were characterized by elemental analysis, infrared spectroscopy, X-ray diffraction, thermogravimetry, and (1P and 13C NMR in the solid state. The amounts of groups grafted onto surfaces were 0.75+/-0.05, 2.35+/-0.14, and 2.48+/-0.18 mmolg(-1) for HApRx (x=1,2,3) surfaces, respectively. Linear correlations between elemental analysis, mass loss, (31)P chemical shift data, and the characteristics of the chain of each alkoxysilane were observed. The organic basic centers distributed onto the external surface have the ability to adsorb divalent copper and cobalt cations from aqueous solution. The degree of adsorption obtained from batchwise processes showed the best performance of these synthesized nanomaterials when compared with the pristine hydroxyapatite.