Electrochemical Doping Effect on the Conductivity of Melanin-Inspired Materials.

Eumelanin is a natural pigment that can be particularly valuable for sustainable bioelectronic devices due to its inherent biocompatibility and hydration-dependent conductivity. However, the low conductivity of eumelanin limits its technological development. In this research, electrochemical doping was proposed as an alternative route to increase the electronic conductivity of synthetic eumelanin derivatives. Thin films of sulfonated eumelanin were deposited on platinum interdigitated electrodes and electrochemically treated by using cyclic voltammetry and chronoamperometry treatments. X-ray photoelectron spectroscopy analysis confirmed ion doping in sulfonated melanin. Current-voltage, current-time, and electrochemical impedance measurements were used to investigate the effect of different aqueous electrolytes (including KCl and LiClO4) treatments on the charge transport of sulfonated eumelanin. We show that the conductivity depends on the type and size of the anion used and can reach 10-3 S·cm-1. Additionally, depending on the electrolyte, there is a change in charge transport from mixed ionic/electronic to a predominantly electronic-only conduction. Our results show that the chemical nature of the ion plays an important role in the electrochemical doping and, consequently, in the charge transport of eumelanin. These insights serve as inspiration to explore the use of alternative electrolytes with different compositions further and develop eumelanin-based devices with tunable conductivities.

Pro-angiogenic approach for skeletal muscle regeneration.

The angiogenesis process is a phenomenon in which numerous molecules participate in the stimulation of the new vessels' formation from pre-existing vessels. Angiogenesis is a crucial step in tissue regeneration and recovery of organ and tissue function. Muscle diseases affect millions of people worldwide overcome the ability of skeletal muscle to self-repair. Pro-angiogenic therapies are key in skeletal muscle regeneration where both myogenesis and angiogenesis occur. These therapies have been based on mesenchymal stem cells (MSCs), exosomes, microRNAs (miRs) and delivery of biological factors. The use of different calls of biomaterials is another approach, including ceramics, composites, and polymers. Natural polymers are use due its bioactivity and biocompatibility in addition to its use as scaffolds and in drug delivery systems. One of these polymers is the natural rubber latex (NRL) which is biocompatible, bioactive, versatile, low-costing, and capable of promoting tissue regeneration and angiogenesis. In this review, the advances in the field of pro-angiogenic therapies are discussed.

Longevity of bonded composite restorations after dentin biomodification with neolignans obtained from Nectandra leucantha / Longevidade de restaurações de resina composta após biomodificação de dentina com neolignanas obtidas de Nectandra leucantha

Objective: This in vitro study evaluated the effect of neolignan-containing solutions on dentin biomodification previously applied to the bonding procedure in adhesive restorations. Material and Methods: Neolignans, dehydrodieugenol B­CP1 and dehydrodieugenol B methyl ether­CP2, were isolated from Nectandra leucanthaand two aqueous solutions containing 0.13% neolignans, 0.2% propylene glycol and 3.0% ethanol were prepared. Bovine teeth were ground flat to obtain 2-mm thick specimens which received resin composite restorations (N=10). The neolignan solutions were applied before the bonding procedure (60 s). Experimental groups were: control, untreated group, 0.12% chlorhexidine gel, 0.13% CP1 solution, and 0.13% CP2 solution. A push-out bond strength test was conducted (0.5 mm/min). Bovine tooth sections (0.5×1.7×7.0 mm) were also obtained to assess the modulus of elasticity and mass change after treatment (N=15). A three-point bending test evaluated the elastic modulus of fully demineralized dentine beams after immersion in the solutions. The data were statistically analyzed (α = 0.05). Results: The bond strength of the restorations to dentin was significantly improved by the treatment with neolignan-containing solutions, irrespective of the evaluation time (p<0.05). After 6 months, a significant reduction in the bond strength was observed in the groups treated with the solutions (p>0.05), but the means were significantly higher than the control groups (p<0.05). The elastic modulus of demineralized dentin was significantly improved after the treatment with the solutions (p<0.05). All groups lost mass weight. Conclusion: The solutions improved the in vitro longevity of bonded restorations, possibly due to the dentin biomodification effect of the neolignans.(AU)

Objetivo: Este estudo in vitro avaliou o efeito de soluções contendo neolignanas na biomodificação da dentina aplicadas previamente à restaurações adesivas. Material e Métodos: Neolignanas, desidrodieugenol B­CP1 e éter metílico de desidrodieugenol B-CP2, foram isolados da espécie Nectandra leucantha e duas soluções aquosas contendo 0,13% de neolignanos, 0,2% de propilenoglicol e 3,0% de etanol foram preparadas. Dentes bovinos foram lixados para obter espécimes de 2 mm de espessura e preparos cavitários restaurados com resina composta (N=10). As soluções foram aplicadas em dentina antes do procedimento adesivo (60 s). Os grupos experimentais foram: controle, grupo não tratado, gel de clorexidina 0,12%, solução de CP1 a 0,13% e solução de CP2 a 0,13%. Foi realizado o teste de resistência de união push-out (0,5 mm/min). O módulo de elasticidade e a alteração de massa após tratamento da dentina (0,5×1,7×7,0 mm) foram também avaliados em teste de flexão de três pontos (N=15). Os dados foram analisados estatisticamente (α=0,05). Resultados: A resistência de união das restaurações à dentina melhorou significativamente com o tratamento com as soluções, independentemente do tempo de avaliação (p<0,05). Após 6 meses, foi observada redução significativa da resistência de união nos grupos tratados com as soluções (p>0,05), com médias significativamente maiores do que nos grupos controle (p<0,05). O módulo de elasticidade da dentina desmineralizada aumentou significativamente após tratamento com as soluções (p<0,05). Todos os grupos perderam massa, independentemente do tratamento. Conclusão: As soluções melhoraram in vitroa longevidade das restaurações adesivas, possivelmente devido ao efeito biomodificador da dentina das neolignanas(AU)

Modified Synthesis and Physicochemical Characterization of a Bioglass-Based Composite for Guided Bone Regeneration.

OBJECTIVES: Bioglass composites and polymers are materials of great interest for the medical and dental areas due to their properties, combining the bioactivity of ceramic materials and the mechanical properties of polymers. The purpose of the present study was to develop and to characterize the physicochemical and morphological properties an experimental bioglass-based ternary composite composed associated with sodium carboxymethylcellulose (Na-CMC) and polyvinyl alcohol (PVA). The compatibility of functional groups with bioglass was previously evaluated. The composite was then synthesized and evaluated in terms of morphology, elemental composition, compressive strength, porosity, and bioactivity. MATERIALS AND METHODS: The bioglass was previously synthesized using a sol-gel route and characterized using FTIR analysis to identify the functional groups. The bone graft composite was then synthesized associating the bioglass with PVA, surfactant Triton X, and Na-CMC. The composite was then morphologically characterized using SEM/EDS. The porosity of the composite was analyzed using µCT, which also provided the composite compression strength. The composite was then evaluated in terms of its bioactivity using SEM/EDS analyses after immersion in SBF for 12, 24, 48, and 72 h. RESULTS: FTIR analysis confirmed, among other components, the presence of Si-O-Ca and Si-O-Si bonds, compatible with bioglass. SEM analysis exhibited a composite with a porous structure without spikes. The elemental mapping confirmed the presence of Si, Ca, and P in the composite. µCT analysis demonstrated a porous structure with 42.67% of open pores and an average compression strength of 124.7 MPa. It has also demonstrated ionic changes in the composite surface after immersion in SBF, with increasing detection of Ca and P as a function of time, highlighting its chemical bioactivity. CONCLUSIONS: It can be concluded that the proposed bioglass-based composite presents a three-dimensional, well-structured, chemically bioactive porous structure, mechanically resistant for being reinforced with polymeric phases, with promising results as a synthetic bone graft, which makes it suitable for guided bone regeneration.

Bonding Reactions of Dental Self-Adhesive Cements with Synthetic Hydroxyapatite as a Function of the Polymerization Protocol.

OBJECTIVES: This study evaluated the influence of the cement composition and different polymerization protocols on the bonding chemical interaction of self-adhesive cements with synthetic hydroxyapatite. MATERIALS AND METHODS: Two commercial self-adhesive resin cements (RelyX U200 and Maxcem Elite) were selected, manipulated, mixed with hydroxyapatite dry powder (HAp), dispensed into molds, and distributed into three groups according to polymerization protocols: immediate photoactivation (IP); delayed photoactivation, 10 min self-curing and light-curing (DP); and chemical activation (CA, no light exposure). The detailed chemical information, at atomic scale, on the surface and deeper into the bulk of self-adhesive cement/hydroxyapatite mixtures was evaluated with X-ray photoelectron spectroscopy (XPS). RESULTS: Chemical elements were detected in both cements, such as Na, O, Ca, C, P, and Si. Other elements were detected in minor concentrations. RelyX U200 exhibited the most intense formation of calcium salts products when the cement/HAp mixtures were photoactivated (immediate or delayed). RelyX U200/HAp mixture under delayed photoactivation (DP) also exhibited higher binding energy between calcium moieties of the HAp and methacrylates in the cement. A higher energy difference in the interaction of HAp with the cement comparing the bulk and surface areas was observed when RelyX U200 underwent the delayed photoactivation protocol. Maxcem Elite exhibited an increased chemical reactivity when either chemically activated or immediately photoactivated and a higher binding energy of the carboxyl groups bonded to the calcium of HAp when chemically activated. CONCLUSIONS: The interaction of cements with hydroxyapatite is chemical in nature and leads to the formation of calcium salts, which may favor better integrity and longevity of adhesive restorations. The polymerization protocol affects the chemical interaction in mixtures of self-adhesive cements and hydroxyapatite, influencing the formation of these salts and the establishment of intermolecular interactions between the HAp and the cements.

Influence of Dentin Priming with Tannin-Rich Plant Extracts on the Longevity of Bonded Composite Restorations.

OBJECTIVE: This in vitro study evaluated the influence of bioactive plant extracts as dentin biomodifying agents to improve the longevity of bonded restorations. For that, plant extracts were applied to the dentin surface prior to the adhesive system. MATERIALS AND METHODS: Bovine incisors were ground flat to obtain 2 mm thick slices in which conical preparations were made (N = 10). Tannin-containing plant extracts were applied to dentin before the application of the restorative system, as follows: control group (untreated, CTL), chlorhexidine 0.12% (CHX), mastruz (Dysphania ambrosioides, MTZ), cat's claw (Uncaria tomentosa, CTC), guarana (Paullinia cupana, GUA), galla chinensis (Rhus chinensis, GCH), and tannic acid (extracted from Acacia decurrens, TNA). The push-out bond strength test was conducted (0.5 mm/min). Dentin biomodification was assessed by the modulus of elasticity and mass change in bovine tooth sections (0.5 × 1.7 × 7.0 mm). The dentin staining after extract treatments of dentin slices was compared. The dentin surface wettability was also evaluated by means of the contact angles of the adhesive system with the dentin surface and compared with the untreated control group. Data were subjected to ANOVA/Tukey's test (α = 0.05). RESULTS: The bond strength of the restoratives to dentin was not significantly improved by the plant extracts, irrespective of the evaluation time (p > 0.05). Except for TNA, the elastic modulus of demineralized dentin significantly reduced after treatment with the plant extracts (p < 0.05). The dentin staining correlated with the tannin content of the extracts. The contact angle was significantly reduced when treated with CTC, GCH, and TNA. CONCLUSIONS: The tannin-containing extracts had a questionable effect on the longevity of bonded restorations. The dentin modulus was negatively affected by the extract treatments. Although some of the extracts changed the contact angle, which seems to improve the adhesive monomer permeation, the tannin-rich plant extract application prior to adhesive application was proven to be clinically unfeasible due to dentin staining.

Exploring the Properties of Niobium Oxide Films for Electron Transport Layers in Perovskite Solar Cells.

In this work, niobium oxide films were deposited by reactive magnetron sputtering under different oxygen flow rate and applied as electron transport layer in perovskite solar cells. It was found that the deposition made using 3.5 sccm of oxygen flow resulted in films with better electrical properties which helped the extraction of the photogenerated electrons to the external circuit, improving the Jsc and consequently the device efficiency. In addition, by photoluminescence measurements, we found a better charge transfer from perovskite to TiO2/niobium oxide film deposited at 3.5 sccm of oxygen flow.

NbCl5 -Promoted Synthesis of Fluorescein Dye Derivatives: Spectroscopic and Spectrometric Characterization and Their Application in Dye-Sensitized Solar Cells.

Fluorescein has several applications owing to its properties, such as high molar absorptivity, high fluorescence quantum yield, high photostability, and wavelengths of absorption and emission in the visible region. The syntheses of fluorescein derivatives between phenol and anhydride derivatives by using NbCl5 as a Lewis acid is described. The products have high yields and short reaction times are observed. The study of the UV/Vis and fluorescence spectra of these derivatives and their application in dye-sensitized solar cells is also described.

Effects of age condition on the distribution and integrity of inorganic fillers in dental resin composites.

OBJECTIVES: The aim of this study is to evaluate the distribution of the filler size along with the zeta potential, and the integrity of silane-bonded filler surface in different types of restorative dental composites as a function of the material age condition. MATERIALS AND METHODS: Filtek P60 (hybrid composite), Filtek Z250 (small-particle filled composite), Filtek Z350XT (nanofilled composite), and Filtek Silorane (silorane composite) (3M ESPE) were tested at different stage condition (i.e., fresh/new, aged, and expired). Composites were submitted to an accelerated aging protocol (Arrhenius model). Specimens were obtained by first diluting each composite specimen in ethanol and then dispersed in potassium chloride solution (0.001 mol%). Composite fillers were characterized for their zeta potential, mean particle size, size distribution, via poly-dispersion dynamic light scattering. The integrity of the silane-bonded surface of the fillers was characterized by FTIR. RESULTS: The material age influenced significantly the outcomes; Zeta potential, filler characteristics, and silane integrity varied both after aging and expiration. Silorane presented the broadest filler distribution and lowest zeta potential. Nanofilled and silorane composites exhibited decreased peak intensities in the FTIR analysis, indicating a deficiency of the silane integrity after aging or expiry time. CONCLUSION: Regardless to the material condition, the hybrid and the small-particle-filled composites were more stable overtime as no significant alteration in filler size distribution, diameter, and zeta potential occurred. A deficiency in the silane integrity in the nanofilled and silorane composites seems to be affected by the material stage condition. CLINICAL SIGNIFICANCE: The materials conditions tested in this study influenced the filler size distribution, the zeta potential, and integrity of the silane adsorbed on fillers in the nanofilled and silorane composites. Thus, this may result in a decrease of the clinical performance of aforementioned composites, in particular, if these are used after inappropriate storage conditions.

Polymerization kinetics and polymerization stress in resin composites after accelerated aging as a function of the expiration date.

OBJECTIVES: To determine the effect of material condition (new, aged, and expired) on the polymerization kinetics and polymerization stress of different classifications of dental composites. MATERIALS AND METHODS: Specimens were obtained according to the following factors: Composites: (3M ESPE) Filtek P60, Filtek Z250, Filtek Z350XT, and Filtek Silorane; and Material conditions: new, aged, and expired. The syringe composites underwent an accelerated aging protocol (Arrhenius model) representing approximately 9 months of aging. Infrared (IR) spectra were obtained kinetically and were analyzed for: maximum conversion rate (%/s), time into exposure when maximum rate occurred (s), conversion at maximum rate (%), and total conversion (%) at 90 s by comparison of absorption IR peak ratios before and after polymerization. Polymerization was evaluated at the bottom surface of 2.0 mm-thick specimens. Polymerization stress was determined in a tensilometer, inserting the composite between acrylic rods fixed to clamps in a universal test machine and dividing the maximum load recorded by the rods cross-sectional area. Polymerization stress (MPa) was calculated at 300 s. Data were statistically analyzed by two-way ANOVA and Tukey's post hoc test (α=0.05). RESULTS: The majority of the polymerization kinetic parameters were not influenced by the material condition. Silorane composite presented significantly lower conversion rate and lower conversion at the maximum rate when expired (p<0.05). The nanofilled composite (Filtek Z350XT) presented a significantly higher total conversion when aged and expired compared to the new one (p>0.05). In all conditions, Filtek Z350XT and Filtek Silorane presented significantly lower conversion rates (p < 0.05). Filtek Silorane also exhibited the lowest stress, irrespective of the material condition (p<0.05). The polymerization stress was not influenced by the material condition (p>0.05). CONCLUSIONS: Most of the kinetic parameters are not influenced by the material condition. Filtek P60 and Filtek Z250 are more stable as both composites present similar polymerization kinetic results, irrespective of the material condition. Silorane composite presents lower stress values among the tested materials in all conditions. Aging does not affect stress development in restorative composites.

Electronic structure calculations of ESR parameters of melanin units.

Melanins represent an important class of natural pigments present in plants and animals that are currently considered to be promising materials for applications in optic and electronic devices. Despite their interesting properties, some of the basic features of melanins are not satisfactorily understood, including the origin of their intrinsic paramagnetism. A number of experiments have been performed to investigate the electron spin resonance (ESR) response of melanin derivatives, but until now, there has been no consensus regarding the real structure of the paramagnetic centers involved. In this work, we have employed electronic structure calculations to evaluate the ESR parameters of distinct melanin monomers and dimers in order to identify the possible structures associated with unpaired spins in this biopolymer. The g-factors and hyperfine constants of the cationic, anionic and radicalar structures were investigated. The results confirm the existence of at least two distinct paramagnetic centers in melanin structure, identifying the chemical species associated with them and their roles in electrical conductivity.

Hancornia speciosa latex for biomedical applications: physical and chemical properties, biocompatibility assessment and angiogenic activity.

The latex obtained from Hancornia speciosa is used in folk medicine for treatment of several diseases, such as acne, warts, diabetes, gastritis and inflammation. In this work, we describe the biocompatibility assessment and angiogenic properties of H. speciosa latex and its potential application in medicine. The physical-chemical characterization was carried out following different methodologies (CHN elemental analyses; thermogravimetric analyses and Fourier transform infrared spectroscopy). The biocompatibility was evaluated through cytotoxicity and genotoxicity tests in fibroblast mouse cells and the angiogenic properties were evaluated using the chick chorioallantoic membrane (CAM) assay model. The physical-chemical results showed that the structure of Hancornia speciosa latex biomembrane is very similar to that of Hevea brasiliensis (commercially available product). Moreover, the cytotoxicity and genotoxicity assays showed that H. speciosa latex is biocompatible with life systems and can be a good biomaterial for medical applications. The CAM test showed the efficient ability of H. speciosa latex in neovascularization of tissues. The histological analysis was in accordance with the results obtained in the CAM assay. Our data indicate that the latex obtained from H. speciosa and eluted in water showed significant angiogenic activity without any cytotoxic or genotoxic effects on life systems. The same did not occur with H. speciosa latex stabilized with ammonia. Addition of ammonia does not have significant effects on the structure of biomembranes, but showed a smaller cell survival and a significant genotoxicity effect. This study contributes to the understanding of the potentialities of H. speciosa latex as a source of new phytomedicines.

Free radical entrapment and crystallinity of resin composites after accelerated aging as a function of the expiration date.

This study evaluated the spin concentration and the crystallinity in different classifications of dental composites as a function of the material condition (new, aged and expired). Specimens were obtained according to the factors: composites: Filtek P60, Filtek Z250, Filtek Z350XT, and Filtek Silorane; and material conditions: new, aged, and expired. The syringe composites underwent an accelerated aging protocol (Arrhenius model). The magnetic properties of the composites were characterized using Electron Paramagnetic Resonance (EPR) and the concentration of spins (number of spins/mass) was calculated. The crystallinity of the composites tested was characterized with X-ray diffraction (XRD). Filtek P60 and Filtek Z250 presented similarities in terms of spin concentration and crystallinity, irrespective of the material condition. The aging protocol influenced the composite Filtek Z350XT that exhibited a significant increase in the spin concentration. Besides, lower intensity peaks of the organic matrix and amorphous silica were also observed for both aged and expired Filtek Z350XT. Although a significant lower spin concentration was observed for the silorane composite in comparison to that of the methacrylates, a decrease in the relative intensity of peaks of the amorphous region related to the organic components in the diffractograms was observed. The material conditions tested influence the crystallinity and the magnetic properties of the composites evaluated.

Resin composite characterizations following a simplified protocol of accelerated aging as a function of the expiration date.

This study evaluated the mechanical, thermal, and morphological characteristics of different classifications of dental composites as a function of the material condition (new, aged and expired). Specimens were obtained according to these factors: Composites: Filtek P60, Filtek Z250, Filtek Z350XT, and Filtek Silorane; and Material conditions: new, aged, and expired. The syringe composites underwent an accelerated aging protocol (Arrhenius model). The flexural strength (FS) and flexural modulus (E) were obtained. The thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were also performed and the glass transition temperature (Tg) and the weight loss calculated. Topographic analysis of the composites was performed under SEM. The material conditions influenced the mechanical properties of the composites. The silorane composite exhibited a characteristic thermal behavior different from that of the methacrylates. In general, the Tg increased after the accelerated aging protocol and decreased for expired ones, compared to the new composites. A significant increase in FS of Filtek Z350XT after aging was accompanied by an increase in the Tg. The filler packings were in accordance with the manufacture׳s information. The topographic aspects of the composites were modified as a function of the material condition. The mechanical properties of the composites following a simplified protocol of accelerated aging varied as a function of the expiration date. The silorane composite presented a characteristic thermal behavior. Although the dental manufacturers may not be able to control variables as storage temperature and transportation conditions, these effects on the composite clinical performance can be minimized if properly considered.

Estudo comparativo do desempenho de diferentes membranas oclusivas de látex em natural no reparo ósseo / A comparative study on the performance of different occlusive natural latex membranes in bone repair

Introdução: Na odontologia, a reabsorção óssea alveolar é fator limitante no bem estar dos indivíduos interferindo diretamente no sistema estomatognático, acarretando problemas no âmbito de saúde em geral. Com o objetivo de promover modalidades biológicas que possam estimular a regeneração óssea, várias estratégias biomiméticas têm sido desenvolvidas recorrendo à utilização dos mais diversos materiais possíveis à matriz óssea, culminando com o desenvolvimento de técnicas que promovam tal reparo. Objetivo: Este trabalho consiste no estudo comparativo do desempenho de filmes confeccionados com látex como membrana oclusiva em procedimento de Regeneração Óssea Guiada (ROG) em 3 preparações: Látex preservado em amônia, Látex produzidos por seringueiras dos clones IAN873 e PR255 polimerizados logo após a coleta e sem uso de amônia como conservante. Métodos: Foram utilizados 60 ratos Wistar, divididos randomicamente em 4 grupos de 15 animais, nos quais defeitos ósseos de tamanho crítico (8mm de diâmetro) foram confeccionados cirurgicamente na calvária. O grupo A foi tratado por ROG através da membrana de látex preservada em amônia, o grupo B recebeu a membrana do clone IAN873, o grupo C, a membrana do clone PR255 e o grupo D, não foi tratado por ROG. Após o período de 7, 15 e 50 dias, 5 animais de cada grupo foram eutanasiados, e as peças contendo o defeito ósseo coletadas para análise microscópica (histológica descritiva e histomorfometria). Resultados: Os resultados demonstraram que após 50 dias, houve formação óssea em maiores proporções no grupo D (p<0.05, ANOVA seguido de Tukey), sugerindo que novos experimentos devem ser realizados para se concluir a respeito da presença da amônia e a influência da espécie de seringueira.

Introduction: In dentistry, alveolar bone resorption is a limiting factor in the well being of individuals directly interfering in the stomatognathic system, causing problems in the context of overall health. Aiming to promote biological methods that can stimulate bone regeneration, several biomimetic strategies have been developed by the use of diverse materials possible to the bone matrix, culminating in the development of techniques that promote such repair. Objective: This work is a comparative study of the performance of films made with latex as occlusive membrane for Guided Bone Regeneration (GBR) procedure in three preparations: Latex preserved in ammonia, produced by Latex rubber clones IAN873 and PR255 polymerized immediately after collection and without use ammonia as a preservative. Methods: Sixty Wistar rats were randomly divided into 4 groups of 15 animals in which bone defects of critical size (8mm diameter) were made surgically in the skull. Group A was treated by GBR through the membrane látex preserved with ammonia, Group B received the membrane made of latex from IAN873, Group C, the membrane clone PR255 and group D was not treated by GBR. After a period of 7, 15 and 50 days, 5 animals from each group were euthanized, and specimens containing bone defect collected for microscopic examination (descriptive histology and histomorphometry). Results: The results showed that after 50 days there was bone formation in higher proportions in group D (p <0.05, ANOVA followed by Tukey), suggesting that further experiments should be conducted to conclude about the presence of ammonia and the influence of kind of rubber.