Chitosan and chitosan/turmeric-based membranes for wound healing: Production, characterization and application.

In the present study, chitosan and chitosan/turmeric-based membranes were produced, characterized and applied in in vivo experiments showing the applicability for skin wound repair. Chitosan 1 % (w/v), chitosan + glycerol 30 % (w/w) and chitosan + glycerol 30 % + turmeric 1.5 % (w/w) membranes were produced through the casting technique. Self-sustainable, homogeneous, and flexible membranes were obtained from all materials tested. The FTIR spectra showed the main vibrational bands for materials used in the chemical groups. The membranes containing glycerol are more flexible than those formed with pure chitosan. Membranes formed with glycerol and glycerol/turmeric are more hydrophilic compared to the membranes formed by pure chitosan. The in vivo results showed that the group who received the chi/gly/turmeric membrane had a statistically greater reduction in the injured area, as well as a better healing process in the histological analysis compared to the other experimental groups. The material developed here is from a natural source, low cost and easy to apply and can accelerate the process of repairing skin lesions.

Evaluation of How Methacrylate Gelatin Hydrogel Loaded with Ximenia americana L. Extract (Steam Bark) Effects Bone Repair Activity Using Rats as Models.

The use of bioactive materials, such as Ximenia americana L., to stimulate the bone repair process has already been studied; however, the synergistic effects of its association with light emitting diode (LED) have not been reported. The present work aims to evaluate the effect of its stem bark extract incorporated into methacrylate gelatin hydrogel (GelMA) on the bone repair process using pure hydrogel and hydrogel associated with LED therapy. For this purpose, the GelMA hydrogel loaded with Ximenia americana L. extract (steam bark) was produced, characterized and applied in animal experiments. The tests were performed using 50 male Wistar rats (divided into 5 groups) submitted to an induced tibia diaphyseal fracture. The therapy effects were verified for a period of 15 and 30 days of treatment using histological analysis and Raman spectroscopy. After 15 days of induced lesion/treatment, the new bone formation was significantly higher in the GXG (GelMA + X. americana L.) group compared to the control group (p < 0.0001). After 30 days, a statistically significant difference was observed when comparing the GXLEDG (GelMA + X. americana L. + LED) and the control group (p < 0.0001), the GXG and the control group (p < 0.001), and when comparing the GG, GXG (p < 0.005) and GXLEDG (p < 0.001) groups. The results shows that the Ximenia americana L. stem extract incorporated into GelMA hydrogel associated with LED therapy is a potentiator for animal bone repair.

A Review on the Role and Performance of Cellulose Nanomaterials in Sensors.

Sensors and biosensors play a key role as an analytical tool for the rapid, reliable, and early diagnosis of human diseases. Such devices can also be employed for monitoring environmental pollutants in air and water in an expedited way. More recently, nanomaterials have been proposed as an alternative in sensor fabrication to achieve gains in performance in terms of sensitivity, selectivity, and portability. In this direction, the use of cellulose nanomaterials (CNM), such as cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), and bacterial cellulose (BC), has experienced rapid growth in the fabrication of varied types of sensors. The advantageous properties are related to the supramolecular structures that form the distinct CNM, their biocompatibility, and highly reactive functional groups that enable surface functionalization. The CNM can be applied as hydrogels and xerogels, thin films, nanopapers and other structures interesting for sensor design. Besides, CNM can be combined with other materials (e.g., nanoparticles, enzymes, carbon nanomaterials, etc.) and varied substrates to advanced sensors and biosensors fabrication. This review explores recent advances on CNM and composites applied in the fabrication of optical, electrical, electrochemical, and piezoelectric sensors for detecting analytes ranging from environmental pollutants to human physiological parameters. Emphasis is given to how cellulose nanomaterials can contribute to enhance the performance of varied sensors as well as expand novel sensing applications, which could not be easily achieved using standard materials. Finally, challenges and future trends on the use of cellulose-based materials in sensors and biosensors are also discussed.

Acylated Carrageenan Changes the Physicochemical Properties of Mixed Enzyme-Lipid Ultrathin Films and Enhances the Catalytic Properties of Sucrose Phosphorylase Nanostructured as Smart Surfaces.

Control over the catalytic activity of enzymes is important to construct biosensors with a wide range of detectability and higher stability. For this, immobilization of enzymes on solid supports as nanostructured films is a current approach that permits easy control of the molecular architecture as well as tuning of the properties. In this article, we employed acylated carrageenan (AC) mixed with phospholipids at the air-water interface to facilitate the adsorption of the enzyme sucrose phosphorylase (SP). AC stabilized the adsorption of SP at the phospholipid monolayer, as detected by tensiometry, by which thermodynamic parameters could be inferred from the surface pressure-area isotherm. Also, infrared spectroscopy applied in situ over the monolayer showed that the AC-phospholipid system not only permitted the enzyme to be adsorbed but also helped conserve its secondary structure. The mixed monolayers were then transferred onto solid supports as Langmuir-Blodgett (LB) films and investigated with transfer ratio, quartz crystal microbalance, fluorescence spectroscopy, and atomic force microscopy. The enzyme activity of the LB film was then determined, revealing that although there was an expected reduction in activity in relation to the homogeneous environment the activity could be better preserved after 1 month, revealing enhanced stability.

Electrospun polyamide 6/poly(allylamine hydrochloride) nanofibers functionalized with carbon nanotubes for electrochemical detection of dopamine.

The use of nanomaterials as an electroactive medium has improved the performance of bio/chemical sensors, particularly when synergy is reached upon combining distinct materials. In this paper, we report on a novel architecture comprising electrospun polyamide 6/poly(allylamine hydrochloride) (PA6/PAH) nanofibers functionalized with multiwalled carbon nanotubes, used to detect the neurotransmitter dopamine (DA). Miscibility of PA6 and PAH was sufficient to form a single phase material, as indicated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), leading to nanofibers with no beads onto which the nanotubes could adsorb strongly. Differential pulse voltammetry was employed with indium tin oxide (ITO) electrodes coated with the functionalized nanofibers for the selective electrochemical detection of dopamine (DA), with no interference from uric acid (UA) and ascorbic acid (AA) that are normally present in biological fluids. The response was linear for a DA concentration range from 1 to 70 µmol L(-1), with detection limit of 0.15 µmol L(-1) (S/N = 3). The concepts behind the novel architecture to modify electrodes can be potentially harnessed in other electrochemical sensors and biosensors.

Low molecular-weight chitosans are stronger biomembrane model perturbants.

The influence from the chitosan molecular weight on its interaction with cell membrane models has been studied. A low molecular weight chitosan (LMWChi) adsorbed from the subphase expanded the surface pressure-area and surface potential-area isotherms of dimyristoyl phosphatidic acid (DMPA) monolayers and decreased the compressional modulus. The expansion in the monolayers and the decrease in the compressional modulus were larger for LMWChi than for a high molecular weight chitosan (Chi). The polymeric nature is still essential for the interaction though, which was demonstrated by measuring negligible changes in the mechanical properties of the DMPA monolayer when the subphase contained glucosamine and acetyl-glucosamine. The results were rationalized in a model through which chitosan interacted with the membrane via electrostatic and hydrophobic interactions, with the smaller chains of LMWChi having less steric hindrance to be accommodated in the membrane. In summary, the activity based on membrane interactions depends on the distribution of molar mass, with lower molecular weight chitosan more likely to have stronger effects.

Electrostatic interactions are not sufficient to account for chitosan bioactivity.

Recent studies involving chitosan interacting with phospholipid monolayers that mimic cell membranes have brought molecular-level evidence for some of the physiological actions of chitosan, as in removing a protein from the membrane. This interaction has been proven to be primarily of electrostatic origin because of the positive charge of chitosan in low pH solutions, but indirect evidence has also appeared of the presence of hydrophobic interactions. In this study, we provide definitive proof that model membranes are not affected merely by the charges in the amine groups of chitosan. Such a proof was obtained by comparing surface pressure and surface potential isotherms of dipalmitoyl phosphatidyl choline (DPPC) and dipalmitoyl phosphatidyl glycerol (DPPG) monolayers incorporating either chitosan or poly(allylamine hydrochloride) (PAH). As the latter is also positively charged and with the same charged functional group as chitosan, similar effects should be observed in case the electrical charge was the only relevant parameter. Instead, we observed a large expansion in the surface pressure isotherms upon interaction with chitosan, whereas PAH had much smaller effects. Of particular relevance for biological implications, chitosan considerably reduced the monolayer elasticity, whereas PAH had almost no effect. It is clear therefore that chitosan action depends strongly either on its functional uncharged groups and/or on its specific conformation in solution.

Probing chitosan and phospholipid interactions using Langmuir and Langmuir-Blodgett films as cell membrane models.

The interaction between chitosan and Langmuir and Langmuir-Blodgett (LB) films of dimyristoyl phosphatidic acid (DMPA) is investigated, with the films serving as simplified cell membrane models. At the air-water interface, chitosan modulates the structural properties of DMPA monolayers, causing expansion and decreasing the monolayer elasticity. As the surface pressure increased, some chitosan molecules remained at the interface, but others were expelled. Chitosan could be transferred onto solid supports alongside DMPA using the LB technique, as confirmed by infrared spectroscopy and quartz crystal microbalance measurements. The analysis of sum-frequency vibration spectroscopy data for the LB films combined with surface potential measurements for the monolayers pointed to chitosan inducing the ordering of the DMPA alkyl chains. Furthermore, the morphology of DMPA LB films, studied with atomic force microscopy, was affected significantly by the incorporation of chitosan, with the mixed chitosan-DMPA films displaying considerably higher thickness and roughness, in addition to chitosan aggregates. Because chitosan affected DMPA films even at pressures characteristic of cell membranes, we believe this study may help elucidate the role of chitosan in biological systems.

Interaction of chitosan with cell membrane models at the air-water interface.

In this paper we employed phospholipid Langmuir monolayers as membrane models to probe interactions with chitosan. Using a combination of surface pressure--area and surface potential--area isotherms and rheological measurements with the pendent drop technique, we observed that chitosan interacts with phospholipid molecules at the air-water interface. We propose a model in which chitosan interacts with the phospholipids mainly through electrostatic interactions, but also including H-bonding and hydrophobic forces, depending on the phospholipid packing density. At large areas per molecule, chitosan in the subphase adsorbs onto the monolayer, expanding it. At small areas per molecule, chitosan is located in the subsurface. Indeed, a mixed chitosan-phospholipid monolayer can be transferred onto solid supports, even at high surface pressures. The effects of chitosan on the viscoelastic properties of phospholipid monolayers may be taken as evidence for the ability of chitosan to disrupt cell membranes.