Controlled release of tea tree oil from a chitosan matrix containing gold nanoparticles

Chitosan is a biopolymer that, due to its versatile bioactive properties, has applications in several areas, including food, medicine and pharmaceuticals. In the field of tissue engineering, chitosan can be used, for example, as a dressing to treat wounds or dermal damage, such as burns or abrasions. This work deals with the controlled release of tea tree oil from chitosan-based polymeric films and droplets containing gold nanoparticles (AuNP). AuNPs were successfully incorporated into the chitosan matrix using two different approaches. Both solutions were loaded with tea tree oil, and from these solutions, it was possible to obtain drop-cast films and droplets. The controlled release of oil in water was performed both in the films and in the droplets. The addition of AuNP in the controlled release system of melaleuca oil favored a release time of around 25 h. A series of experiments was carried out to investigate the effects of different reaction temperatures and acetic acid concentrations on the formation of AuNPs in the presence of chitosan. For this purpose, images of the AuNP films and droplets were obtained using transmission electron microscopy. In addition, UV-vis spectra were recorded to investigate the release of tea tree oil from the different samples

Electronic Tongue Based on Nanostructured Hybrid Films of Gold Nanoparticles and Phthalocyanines for Milk Analysis

The use of gold nanoparticles combined with other organic and inorganic materials for designing nanostructured films has demonstrated their versatility for various applications, including optoelectronic devices and chemical sensors. In this study, we reported the synthesis and characterization of gold nanoparticles stabilized with poly(allylamine hydrochloride) (Au@PAH NPs), as well as the capability of this material to form multilayer Layer-by-Layer (LbL) nanostructured films with metal tetrasulfonated phthalocyanines (MTsPc). Film growth was monitored by UV-Vis absorption spectroscopy, atomic force microscopy (AFM), and Fourier transform infrared spectroscopy (FTIR). Once LbL films have been applied as active layers in chemical sensors, Au@PAH/MTsPc and PAH/MTsPc LbL films were used in an electronic tongue system for milk analysis regarding fat content. The capacitance data were treated using Principal Component Analysis (PCA), revealing the role played by the gold nanoparticles on the LbL films electrical properties, enabling this kind of system to be used for analyzing complex matrices such as milk without any prior pretreatment

Effects from the structural characteristics of chitosan on its interaction in Langmuir films as biomembrane models.

As quitosanas são polissacarídeos usados em medicina, farmácia, odontologia e na inibição do crescimento de microrganismos, como agente bactericida. Nessas aplicações sua ação deve depender da interação com membranas celulares, o que é difícil de verificar uma vez que não se isola uma membrana facilmente. Uma alternativa é investigar a interação com modelos de membrana, como um filme de Langmuir de fosfolipídios, a partir do qual é possível obter informações no nível molecular. Nesta dissertação, é avaliada a influência do conteúdo médio de unidades N-acetilglucosamina (GlcNAc) de quitosanas e da massa molecular na interação com filmes de Langmuir do ácido fosfatídico de dipalmitoíla (DMPA). Quitosanas com diferentes graus médios de acetilação e de baixa massa molecular foram produzidas com auxílio de ultrassom de alta intensidade. As quitosanas afetam as isotermas de pressão e potencial de superfície em grandes áreas por molécula, em virtude de interações eletrostáticas e hidrofóbicas com o DMPA. Nos filmes condensados, localizam-se na subsuperfície, com pouco efeito nas isotermas. A quitosana com menos grupos GlcNAc induziu alterações maiores nas isotermas de pressão de superfície e na elasticidade dos filmes, provavelmente devido à maior interação eletrostática com um número maior de grupos amina na quitosana interagindo com as cabeças polares do DMPA. A quitosana com baixa massa molecular foi a mais eficaz para alterar as propriedades dos filmes de DMPA, o que pode ser atribuído à facilidade na adsorção. Um tamanho mínimo de cadeia parece ser essencial, entretanto, pois misturas das unidades repetitivas N-acetilglucosamina (GlcNAc) e glucosamina (GlcN) praticamente não alteraram as isotermas de pressão e a elasticidade dos filmes de DMPA, pela ausência de interações hidrofóbicas. Concluímos que quitosanas com grau de acetilação e massa molecular baixos têm efeitos maiores sobre um modelo de membrana e devem ser mais adequadas em aplicações biológicas que dependam dessa interação.Chitosans are polysaccharides used in medicine, pharmacy, dentistry and in the inhibition of microorganisms growth (eg. as bactericidal agent). In these applications their action should depend on the interaction with cell membranes, which is difficult to verify because isolating a membrane is not easy. An alternative is to investigate the interaction with membrane models, such as a Langmuir film of phospholipids, from which information on the molecular level can be obtained. This dissertation evaluates the influence of the average content of N-acetylglucosamine units (GlcNAc) of chitosan and molecular interaction with Langmuir films of dipalmitoyl phosphatidic acid (DMPA). Chitosans with different average degrees of acetylation and low molecular weight were produced with the high-intensity ultrasound procedure. Chitosans affect the surface pressure and surface potential isotherms at large areas per molecule due to electrostatic and hydrophobic interactions with DMPA. In condensed films, they are located in the subsurface with little effect on the isotherms. The chitosan with fewer GLcNAc groups induced larger changes in the isotherms and in the film elasticity, probably due to stronger electrostatic interaction owing to a larger number of amine groups in chitosan interacting with the polar heads of DMPA. The most effective sample to induce changes in the DMPA monolayers was the low molecular weight chitosan, which can be attributed to the ease of adsorption. A minimum size chain seems essential, however, for mixtures of repeating units N-acetylglucosamine (GlcNAc) and glucosamine (GlcN) did not change the surface pressure isotherms and the elasticity of the DMPA films, owing to the absence of hydrophobic interactions. We conclude that the chitosan with better prospects for biological applications relying on the cell membrane interaction should have a low degree of acetylation and low molecular weight

Structural, conformational and orientational effects on the chitosan interaction with cell membrane models

Muitas aplicações biológicas da quitosana dependem de sua interação com membranas celulares, cujo mecanismo não é conhecido em nível molecular. Nesta tese, empregam-se filmes de Langmuir dos fosfolipídios dipalmitoil fosfatidil colina (DPPC), dipalmitoil fosfatidil glicerol (DPPG) e ácido dimiristoil fosfatídico (DMPA) para mimetizar a membrana, e é avaliada a influência dos grupos hidroxila e amino de quitosana nas propriedades dos filmes. Para tanto, O-acilquitosanas foram produzidas por meio de reação de acilação, gerando os derivados 3,6 - O,O\'- dietanoilquitosana (DEQUI) e 3,6 - O,O\'- dipropanoilquitosana (DPPQUI) solúveis em solução aquosa ácida, e 3,6 - O,O\'- dimiristoilquitosana (DMQUI) e 3,6 - O,O\'- dipalmitoilquitosana (DPQUI), solúveis em clorofórmio. DEQUI e DPPQUI afetam mais fortemente as isotermas de pressão de superfície e elasticidade dos filmes do que quitosana, sendo os efeitos de DPPQUI (mais hidrofóbico) maiores do que para DEQUI. Isso indica que ligações hidrogênio envolvendo as hidroxilas da quitosana não são essenciais na interação. Espectros no infravermelho com modulação de polarização (PM-IRRAS) confirmaram interações hidrofóbicas, com penetração dos derivados entre as moléculas de fosfolipídio. DEQUI causa mais ordenamento das cadeias do fosfolipídio, enquanto o efeito de DPPQUI é oposto. DMQUI e DPQUI formam filmes de Langmuir altamente compactados com agregação de moléculas, inferida das isotermas de pressão e potencial de superfície. Os resultados sobre a influência dos grupos amino foram inconclusivos, pois o comportamento atrativo entre os materiais pode ser devido tanto à existência de grupos com cargas opostas, quanto interações hidrofóbicas. Quitosanas com diferentes massas moleculares (alta - QAMM e baixa - QBMM) foram utilizadas para obter informações sobre a orientação dos grupos químicos da quitosana e fosfolipídios e conformação do polímero em solução. Espectros PM-IRRAS indicam maior efeito de QBMM em monocamadas de DPPG, provocando diminuição na intensidade e deslocamento para maiores números de onda das bandas de CH, inversão na orientação do grupo P=O do DPPG e maior intensidade da banda amida II, sugerindo maior densidade desses grupos na interface. Os espectros de geração de soma de frequência (SFG) mostraram diminuição na ordenação/compactação das caudas de DPPG, aumento do espaçamento entre as moléculas e de defeitos gauche. Conclui-se que derivados O-acilados de quitosana têm maior efeito sobre modelos de membrana, principalmente devido às forças hidrofóbicas, sendo mais adequados em aplicações biológicas que dependam dessa interação. Também favorece a interação com a membrana a atração eletrostática, com efeitos mais relevantes para quitosanas de menores massas moleculares.Many biological applications of chitosan depend on its interaction with cell membranes, whose mechanism at the molecular level is not known. In this thesis, Langmuir films from the phospholipids dipalmitoyl phosphatidyl choline (DPPC), dipalmitoyl phosphatidyl glycerol (DPPG) and dimyristoyl phosphatidic acid (DMPA) were used to mimic the cell membrane, and effects from the hydroxyl and amine groups in chitosan on the film properties were evaluated. For this, O-acylchitosans were produced by acylation reaction, resulting in the derivatives 3,6 - O,O\' - diacetylchitosan (DECT) and 3,6 - O,O\'- dipropionylchitosan (DPPCT), which are soluble in acidic aqueous solution, and 3,6 - O,O\'- dimyristoylchitosan (DMCT) and 3,6 - O,O\'- dipalmitoylchitosan (DPCT), soluble in chloroform. DECT and DPPCT affect the surface pressure and elasticity of the films more strongly than chitosan, especially DPPCT that is more hydrophobic. This indicates that hydrogen bonds involving the hydroxyl groups from chitosan are not essential for the interaction. Polarization-modulated infrared reflection absorption (PM-IRRAS) spectra confirmed hydrophobic interactions with penetration of derivatives between the phospholipid molecules. DECT induces ordering in the chains, while the opposite occurs for DPPCT. DMCT and DPCT form highly compressed films with aggregation, as shown by surface pressure and surface potential isotherms. The results on the importance of amino groups were inconclusive because the attractive behavior between materials may be due to either the oppositely charged groups or hydrophobic interactions. Chitosans with different molecular weights (high - CHMW and low - CLMW) were used to obtain information about the chitosan and phospholipids chemical groups orientation and polymer conformation in solution. PM-IRRAS spectra indicate greater effect from QBMM on DPPG monolayers, causing a decrease in intensity and shift to higher wavenumbers of the CH bands, inversion in the orientation of the P=O group from DPPG and greater intensity of the amide II band, suggesting greater density of these groups at the interface. The sum-frequency generation (SFG) spectra showed a decrease in ordering/packing of the DPPG chains, increased spacing between molecules and gauche defects. Overall, the O-acyl derivatives of chitosan have greater effect on cell membrane models, owing to hydrophobic forces, being therefore more suitable for biological applications that depend on this interaction. Also important for the interaction is the electrostatic attraction, with more relevant effects observed with low-molecular weight chitosans

Stretchable Biofuel Cells as Wearable Textile-based Self-Powered Sensors.

Highly stretchable textile-based biofuel cells (BFCs), acting as effective self-powered sensors, have been fabricated using screen-printing of customized stress-enduring inks. Due to synergistic effects of nanomaterial-based engineered inks and the serpentine designs, these printable bioelectronic devices endure severe mechanical deformations, e.g., stretching, indentation, or torsional twisting. Glucose and lactate BFCs with the single enzyme and membrane-free configurations generated the maximum power density of 160 and 250 µW cm-2 with the open circuit voltages of 0.44 and 0.46 V, respectively. The textile-BFCs were able to withstand repeated severe mechanical deformations with minimal impact on its structural integrity, as was indicated from their stable power output after 100 cycles of 100% stretching. By providing power signals proportional to the sweat fuel concentration, these stretchable devices act as highly selective and stable self-powered textile sensors. Applicability to sock-based BFC and self-powered biosensor and mechanically compliant operations was demonstrated on human subjects. These stretchable skin-worn "scavenge-sense-display" devices are expected to contribute to the development of skin-worn energy harvesting systems, advanced non-invasive self-powered sensors and wearable electronics on a stretchable garment

Stretchable Biofuel Cells as Wearable Textile-based Self-Powered Sensors.

Highly stretchable textile-based biofuel cells (BFCs), acting as effective self-powered sensors, have been fabricated using screen-printing of customized stress-enduring inks. Due to synergistic effects of nanomaterial-based engineered inks and the serpentine designs, these printable bioelectronic devices endure severe mechanical deformations, e.g., stretching, indentation, or torsional twisting. Glucose and lactate BFCs with the single enzyme and membrane-free configurations generated the maximum power density of 160 and 250 µW cm-2 with the open circuit voltages of 0.44 and 0.46 V, respectively. The textile-BFCs were able to withstand repeated severe mechanical deformations with minimal impact on its structural integrity, as was indicated from their stable power output after 100 cycles of 100% stretching. By providing power signals proportional to the sweat fuel concentration, these stretchable devices act as highly selective and stable self-powered textile sensors. Applicability to sock-based BFC and self-powered biosensor and mechanically compliant operations was demonstrated on human subjects. These stretchable skin-worn "scavenge-sense-display" devices are expected to contribute to the development of skin-worn energy harvesting systems, advanced non-invasive self-powered sensors and wearable electronics on a stretchable garment

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.FAPESPCNPqCAPESRede Capes de NanoBiotecnologia (nBionet

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