The impact of methylene blue photosensitizer, aPDT and a calcium hydroxide-based paste on the physicochemical and mechanical characteristics of root canal dentin and the bonding interface of fiberglass posts.

PURPOSE: To investigate the influence of methylene blue (MB)-mediated antimicrobial photodynamic therapy (aPDT) and calcium hydroxide (CH) medication on the mechanical characteristics, degree of conversion (DC), quantification, and volume of gaps at the adhesive interface of glass fiber posts (GFPs) luted to distinct thirds of root canal dentin. Additionally, the microhardness (MH), elastic modulus (Eit), morphology, and chemical structure of the intraradicular dentin were assessed. MATERIALS AND METHODS: 6 experimental groups were formed by sorting 102 bovine incisors. Canals receiving deionized water irrigation as a negative control; canals receiving deionized water irrigation and filled with CH as a positive control; groups treated with CH + MB at 50 and 100 mg/L without irradiation; and groups treated with CH + MB at 50 and 100 mg/L irradiated by red laser for 60 s (660 nm; 100 mW; 6.5 J; 72 J/cm2). MH, Eit, and DC properties were evaluated for both the resin cement layer and root dentin substrate (n = 8). Volume and quantification of gaps at the bonding interface (n = 6), and dentin morphology and chemical content were investigated (n = 3). Data were analyzed using a repeated-measures 2-way ANOVA followed by Tukey post hoc analysis (α = 0.05). RESULTS: The distinct intraradicular thirds and treatment with MB-mediated aPDT, whether activated or not, in combination with CH, had a significant impact on the mechanical characteristics of the root dentin. This effect was also observed in the MH, Eit, DC, quantification, and volume of gaps at the luting interface (P < .05). In general, a higher concentration of MB, whether activated by a red laser or not, led to lower values in the mechanical properties of the root dentin, as well as in MH, Eit, and DC at the adhesive interface (P < .05). Additionally, these groups exhibited higher values for quantification and volume of gaps at the luting substrate (P < .05). Scanning electron micrographs and energy dispersive X-ray spectra showed qualitative similarity among all groups, except for the negative experimental control group. CONCLUSIONS: MB-mediated aPDT at 50 mg/L, in combination with CH, demonstrated favorable physico-chemical and mechanical characteristics in intraradicular dentin, along with satisfactory mechanical features and the adhesive interface integrity for GFPs at all intraradicular depths. CLINICAL SIGNIFICANCE: MB-mediated aPDT at a concentration of 50 mg/L combined to CH medication represents a suitable choice for photosensitization in the context of intracanal disinfection following the biomechanical procedure and prior to luting of intraradicular restorations.

In situ interaction between the hormone 17α-ethynylestradiol and the liquid-ordered phase composed of the lipid rafts sphingomyelin and cholesterol.

Hormone treatments are frequently associated with cardiovascular diseases and cancers in women. Additionally, the detrimental effects of their presence as contaminants in water remain a concern. The transport of hormones through cell membranes is essential for their biological action, but investigating cell permeability is challenging owing to the experimental difficulty in dealing with whole cells. In this paper, we study the interaction of the synthetic hormone 17α-ethynylestradiol (EE2) with membrane models containing the key raft components sphingomyelin (SM) and cholesterol (Chol). The models consisted of Langmuir monolayers and giant unilamellar vesicles (GUVs) that represent bilayers. EE2 induced expansion of SM monolayers upon interacting with the non-hydrated amide group of SM head, but it had practically no effect on SM GUVs because these group are not available for interaction in bilayers. In contrast, EE2 interacted with hydrated phosphate group (PO2-) and amide group of SM/Chol mixture monolayer, which could explain the loss in phase contrast of liquid-ordered GUVs suggesting pore formation. A comparison with reported EE2 effects on GUVs in the fluid phase, for which no loss in phase contrast was observed, indicates that the liquid-ordered phase consisting of lipid rafts is relevant to be associated with the changes on cell permeability caused by the hormones.

Dual nanocarrier of chlorhexidine and fluconazole: Physicochemical characterization and effects on microcosm biofilms and oral keratinocytes.

OBJECTIVES: This study assembled and characterized a dual nanocarrier of chlorhexidine (CHX) and fluconazole (FLZ), and evaluated its antibiofilm and cytotoxic effects. METHODS: CHX and FLZ were added to iron oxide nanoparticles (IONPs) previously coated by chitosan (CS) and characterized by physical-chemical analyses. Biofilms from human saliva supplemented with Candida species were grown (72 h) on glass discs and treated (24 h) with IONPs-CS carrying CHX (at 39, 78, or 156 µg/mL) and FLZ (at 156, 312, or 624 µg/mL) in three growing associations. IONPs and CS alone, and 156 µg/mL CHX + 624 µg/mL FLZ (CHX156-FLZ624) were tested as controls. Next, microbiological analyses were performed. The viability of human oral keratinocytes (NOKsi lineage) was also determined (MTT reduction assay). Data were submitted to ANOVA or Kruskal-Wallis, followed by Fisher's LSD or Tukey's tests (α=0.05). RESULTS: Nanocarriers with spherical-like shape and diameter around 6 nm were assembled, without compromising the crystalline property and stability of IONPs. Nanocarrier at the highest concentrations was the most effective in reducing colony-forming units of Streptococcus mutans, Lactobacillus spp., Candida albicans, and Candida glabrata. The other carriers and CHX156-FLZ624 showed similar antibiofilm effects, and significantly reduced lactic acid production (p<0.001). Also, a dose-dependent cytotoxic effect against oral keratinocytes was observed for the dual nanocarrier. IONPs-CS-CHX-FLZ and CHX-FLZ significantly reduced keratinocyte viability at CHX and FLZ concentrations ≥7.8 and 31.25 µg/mL, respectively (p<0.05). CONCLUSION: The nanotherapy developed outperformed the effect of the combination CHX-FLZ on microcosm biofilms, without increasing the cytotoxic effect of the antimicrobials administered. CLINICAL SIGNIFICANCE: The dual nanocarrier is a promising topically-applied therapy for the management of oral candidiasis considering that its higher antibiofilm effects allow the use of lower concentrations of antimicrobials than those found in commercial products.

Analysis of the effects of curcumin and symbiotic consumption on bones of rats submitted to the use of dexamethasone.

AIMS: Glucocorticoids have adverse side effects that can compromise bone tissue. There is evidence to show that symbiotics and curcumin can prevent bone loss. The aim of this study was to analyze the effects of curcumin and symbiotic to prevent and/or minimize a possible bone impairment in rats submitted to the use of dexamethasone. METHODS: Fifty Wistar female rats were divided into five groups: control group (CT), dexamethasone control group (D), dexamethasone and symbiotic group (DS), dexamethasone and curcumin group (DC), and dexamethasone and symbiotic/curcumin group (DSC). Dexamethasone was applied three times a week, while the symbiotic and curcumin were administered daily. Alkaline phosphatase and calcium dosages, analysis of structural and material properties, and Raman analysis of femurs were performed. KEY FINDINGS: Alkaline phosphatase was higher in the DC group. Maximum load and structural stiffness were higher in the CT group. Maximum stress was lower and similar between dexamethasone groups. The CT group had a lower percentage of strain, the D group had greater deformation compared to the DC group and the DS group presented more deformation than the DC group. The D, DS, and DSC groups had a lower elastic modulus compared to the CT group. The 960/1660 ratios of the D, DS, and DSC groups were different from the CT group. The 1070/1660 ratio was higher in the DC group. SIGNIFICANCE: It was possible to verify that curcumin showed promising effects related to the increase in bone strength and mineralization, mitigating the deleterious effects caused by dexamethasone, when used simultaneously with this drug.

Chemical and morphological effects of the contraceptive hormone 17 α-ethynylestradiol on fluid lipid membranes.

The lack of studies involving the effects in human health associated with the chronic ingestion of pollutants lead to the path of investigating the action of these compounds in cell membrane models. We demonstrated the interaction (causes and consequences) of the hormone 17 α-ethinylestradiol (EE2) with lipid monolayers (prepared as Langmuir films) and bilayers prepared as small unilamellar vesicles (SUVs) and giant unilamellar vesicles (GUVs). Both fluidity and majority chemical composition of real plasma cell membrane were guaranteed using the phospholipid 1-palmitoil-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC). Surface pressure-mean molecular area (π-A) isotherms and PM-IRRAS measurements highlighted the strong interaction of EE2 with POPC monolayers, leading the hormone to remain at the air/water interface and promoting its penetration into the phospholipid hydrophobic chains. In the case of bilayers, the entrance of the hormone inside the SUV is likely facilitated by their high curvature. In GUVs, EE2 was responsible for changes in the spherical shape, forming structures like buds and lipid protrusions. The set of results indicates the strong effects of EE2 on fluid membranes, which is an important feature to predict its damage in human cells.

Langmuir-Schaefer Perylene Derivative Films: Influence of the Molecular Chemical Structure on the Supramolecular Arrangement.

Since the optical and electrical properties of organic thin films devices depend on their supramolecular arrangement and the molecular chemical structure, the understanding of such characteristics is essential for the optimization of these devices. In this study, we determine the supramolecular arrangement of thin films produced using the Langmuir-Schaefer (LS) technique and explain how its supramolecular arrangement is affected by the molecular chemical structure using two perylene derivatives: bis-butylimide (BuPTCD) and bis-phenethylimide (PhPTCD). The optical absorption measurements reveal that both films grow homogeneously and indicate that the presence of H aggregates (forbidden emission) is higher for BuPTCD LS film than for PhPTCD LS film. Atomic force microscopic analysis shows that the PhPTCD LS film is rougher than the BuPTCD film. In addition, FTIR analyses indicate that both films have head-on molecular organization. XRD patterns reveal that both the BuPTCD LS film and the PhPTCD LS film are crystalline, but that crystallinity is more prevalent in the BuPTCD LS film. Thus, the results show that the difference presented in the chemical structures leads the films to have different supramolecular arrangements, with consequences for their optical properties.

Unravelling the effects of the food components ascorbic acid and capsaicin as a novel anti-biofilm agent against Escherichia coli.

This study aimed to evaluate the influence of capsaicin and ascorbic acid on the physiology of biofilm formation and dispersion. The influence of the E. coli ATCC 25922 biofilm and five E. coli isolates were observed in the presence of sodium hypochlorite 2.5 mM and subinhibitory concentrations of capsaicin (7 mM) and ascorbic acid (100 mM). The cells counts were performed through standard plaque count and the architecture visualized by confocal microscopy. The proteins, carbohydrates, and DNA present in the biofilm matrix were also quantified. There was a reduction in adhered cells in the presence of capsaicin (7 mM) and ascorbic acid (100 mM) in the biofilm formation kinetics, however, regarding the dispersion, only capsaicin altered the biofilm, data confirmed by confocal fluorescence microscopy (p < 0.05). It was noted that the matrix composition is dynamic and may be affected by changes in growth conditions such as the presence of antimicrobial substances.

Effects of consumption of contaminated feed with 2,4-dichlorophenoxyacetic acid (2,4-D) on the rat tibia: analysis by Raman spectroscopy and mechanical properties.

Studies reported the harmful effects of 2,4-D on body tissues, provoking changes in the anatomy and physiology of the kidneys, liver, and testicles. Thus, the objective was to evaluate if there were alterations in the bone quality of the tibia of rats submitted to feed consumption that were exposed to three different 2,4-D doses. Male Wistar rats were divided into four groups: oral control group (C: feed consumption without 2,4-D contamination); low oral concentration group (G3: contaminated feed with low concentration of 2,4-D); medium concentration group (G6: contaminated feed with medium concentration of 2,4-D); and high concentration group (G9: contaminated feed with high concentration of 2,4-D). The results demonstrated alterations of the mechanical properties and Raman ratios of the tibias of the contaminated groups. The maximum load, maximum stress, elastic modulus, and the cortical area were lower in the G6 and G9 compared to C group. The mineral-to-matrix ratio (relative mineral to organic content) was lower in the G6 and G9 groups compared to C group, but carbonate-to-matrix ratio (indicator of bone turnover) was higher in both groups. Thus, it is possible to suggest that the 2,4-D herbicide performed deleterious effects on the bone quality of male Wistar rats.

Effects of muscular strength training and growth hormone (GH) supplementation on femoral bone tissue: analysis by Raman spectroscopy, dual-energy X-ray absorptiometry, and mechanical resistance.

The aim of the present study was to verify the effects of muscular strength training and growth hormone (GH) supplementation on femoral bone tissue by Raman spectroscopy (Raman), dual-energy X-ray absorptiometry (DXA), and mechanical resistance (F-max) analysis. A total of 40 male Wistar animals, 60 days old, were used. The animals were distributed into four groups: control (C), control with GH (GHC), muscular strength training (T), and muscular strength training with GH (GHT). Blood samples were collected for the quantification of creatine kinase (CK-MB) and the femurs were removed for analysis by Raman, DXA, and F-max. A more pronounced increase in the bone mineral components was verified in the T group, for all the variables obtained by the Raman (calcium, phosphate, amide, and collagen). In addition, for animals submitted to GH supplementation, there was a reduction in the variable bone mineral density (BMD) obtained by the DXA (p < 0.05). Finally, the animals that received GH supplementation presented a higher F-max, but without statistical significance (p > 0.05). It was concluded that animals that received GH supplementation demonstrated a decrease in BMD. In addition, T alone was able to promote increased calcium, phosphate, amide, and collagen compounds in bone tissue.

Designing Silver Nanoparticles for Detecting Levodopa (3,4-Dihydroxyphenylalanine, L-Dopa) Using Surface-Enhanced Raman Scattering (SERS).

Detection of the drug Levodopa (3,4-dihydroxyphenylalanine, L-Dopa) is essential for the medical treatment of several neural disorders, including Parkinson's disease. In this paper, we employed surface-enhanced Raman scattering (SERS) with three shapes of silver nanoparticles (nanostars, AgNS; nanospheres, AgNP; and nanoplates, AgNPL) to detect L-Dopa in the nanoparticle dispersions. The sensitivity of the L-Dopa SERS signal depended on both nanoparticle shape and L-Dopa concentration. The adsorption mechanisms of L-Dopa on the nanoparticles inferred from a detailed analysis of the Raman spectra allowed us to determine the chemical groups involved. For instance, at concentrations below/equivalent to the limit found in human plasma (between 10-7-10-8 mol/L), L-Dopa adsorbs on AgNP through its ring, while at 10-5-10-6 mol/L adsorption is driven by the amino group. At even higher concentrations, above 10-4 mol/L, L-Dopa polymerization predominates. Therefore, our results show that adsorption depends on both the type of Ag nanoparticles (shape and chemical groups surrounding the Ag surface) and the L-Dopa concentration. The overall strategy based on SERS is a step forward to the design of nanostructures to detect analytes of clinical interest with high specificity and at varied concentration ranges.

Sperm quality of rats exposed to difenoconazole using classical parameters and surface-enhanced Raman scattering: classification performance by machine learning methods.

Difenoconazole is a fungicide extensively used in agriculture. The aim of this study was to evaluate the effects of difenoconazole fungicide on the sperm quality of rats. Wistar rats were divided into four groups: control and exposed to 5 (D5), 10 (D10), or 50 mg-1 kg bw-1day (D50) of difenoconazole for 30 days, by gavage. Classical sperm parameters and surface-enhanced Raman scattering (SERS) were performed. Progressive motility, acrosomal integrity, and percentage of morphologically normal spermatozoa were reduced in the D10 and D50 groups in comparison with the control group. Sperm viability was reduced only in the D50 group. Sperm number in the testis and caput/corpus epididymis and daily sperm production were reduced in the three exposed groups. SERS measurements showed changes in the spectra of spermatozoa from D50 group, suggesting DNA damage. In addition, machine learning (ML) methods were used to evaluate the performance of three classification algorithms (artificial neural network-ANN, K-nearest neighbors-K-NN, and support vector machine-SVM) in the identification task of the groups exposed to difenoconazole. The results obtained by ML algorithms were very promising with accuracy ≥ 90% and validated the hypothesis of the exposure to difenoconazole reduces sperm quality. In conclusion, exposure of rats to different doses of the fungicide difenoconazole may impair sperm quality, with a recognizable classification pattern of exposure groups.

Interaction of Artepillin C with model membranes: Effects of pH and ionic strength.

Artepillin C is the major constituent of green propolis, one of the most consumed products in popular medicine owing to its therapeutic effects, including antitumor activity. Artepillin C differs from other cinnamic acid derivatives due to the presence of two prenylated groups in its structure, believed to enhance access to the cell membrane and resulting in pharmacological activity. The membrane outer leaflet of tumor cells is exposed to an acidic extracellular environment, which could modulate the protonation state of antitumor drugs and hence their interaction with the cell membrane. Herein, we investigated the interaction of Artepillin C with Langmuir monolayers and giant unilamellar vesicles (GUVs) of 1,2­dipalmitoyl­sn­glycerol­3­phosphocholine (DPPC) used as model membranes, in physiological and acidic environments. We observed that protonation of the carboxyl group of Artepillin C is essential for the interaction, with larger shifts induced in the surface pressure isotherms of DPPC monolayers in comparison with deprotonated Artepillin C. Also observed was a decrease in lipid packing inferred from the compressibility modulus and Brewster angle microscopy (BAM) images for monolayers on acidic subphases. Results with microscopy techniques on GUVs confirmed that. Artepillin C causes a curvature stress of the lipid bilayer only in its neutral state, causing the GUVs to burst. The stronger effects of neutral Artepillin C on both monolayers and GUVs were maintained when the ionic strength was increased. Taken together, the results indicate that Artepillin C may have preferential attachment to a more acidic environment which might be an important feature for its antitumor activity.

Photoluminescent properties in perylene PVD films: Influence of molecular aggregates and supramolecular arrangement.

Organic thin films are at the forefront of basic studies and applications in the field of physics, chemistry, biochemistry and materials science. For example, the intrinsic supramolecular arrangement, or simply the formation of aggregates may alter the optical and electrical properties, which would impact the potential applications of the material. Here, an attempt is made to correlate the molecular structures of two perylene derivatives, bis butylimido perylene (BuPTCD) and bis phenethylimido perylene (PhPTCD), with their film formation, in particular, the supramolecular arrangement and the photoluminescent properties. Emission spectra show that the PhPTCD has a radiative efficiency (RE) higher than that for BuPTCD when both are in solutions (monomers). Complementary, regarding PVD films, UV-Vis absorption measurements reveal that PhPTCD forms, predominantly, J aggregates, which are responsible for perylene derivative emission. However, BuPTCD PVD films are found to provide higher RE than PhPTCD PVD film. This apparent controversy could be explained considering other features such as crystallinity and molecular organization. The PVD film of BuPTCD is crystalline while PhPTCD PVD film is amorphous; BuPTCD has an edge-on while PhPTCD has a face-on molecular organization in PVD films.

Muscle strength training is better than the use of growth hormone (GH) in bone health of Wistar rats / Entrenamiento de la fuerza muscular es mejor que el uso de la hormona del crecimiento (GH) en salud ósea del ratas Wistar

SUMMARY: The objective of this study was to evaluate the effects of growth hormone (GH) and muscle strength training (ST) on the composition of bone tissue of Wistar rats through Raman spectroscopy. In total, 40 male rats were randomly distributed into four groups: (N = 10) control (C), control with the application of GH (GHC), strength training (T), and strength training with the application of GH (GHT). The training consisted of four series of 10 water jumps, performed three times a week, with an overload corresponding to 50 % of body weight and duration of four weeks. GH was applied at a dose of 0.2 IU / kg in each animal three times a week and every other day. After four weeks, the animals were euthanized and the right femurs collected for analysis of the bone structure. Raman spectroscopy (ER) was used to observe the following compounds from their respective bands: Calcium Carbonate-Triglycerides (fatty acids) 1073 cm-1, Collagen type I 509 cm-1, Bone-DNA Phosphate (Protein) 589 cm-1, Phosphate Phospholipids 1078 cm-1. For the statistical analysis, the Shapiro-Wilk and ANOVA One-Way variance analysis normality tests were performed, followed by the Tukey post-test. The results showed an increase in the concentrations of calcium carbonate-triglycerides (fatty acids), type I collagen, bone phosphate-DNA (protein), and phosphate phospholipids in all experimental groups, with or without ST and/or GH , But only the isolated training group differed significantly from the control group (P <0.05). It was concluded that all treatments could promote bone tissue gain, however, only the T group demonstrated a significant difference in the mineral compounds analyzed.

RESUMEN: El objetivo del estudio fue avaluar el efecto de la aplicación de la hormona del crecimiento (GH) y entrenamiento de la fuerza muscular (EF) en la composición del tejido óseo de ratas Wistar a partir de la espectroscopía Raman. Fueron utilizadas 40 ratas machos distribuidas de forma aleatoria en cuatro grupos (n=10): control (C), control y aplicación de GH (GHC), entrenamiento de la fuerza muscular (EF) y entrenamiento de la fuerza muscular y aplicación del GH (GHE). El entrenamiento fue consistió en cuatro series de 10 saltos acuáticos, realizados tres veces en la semana, con sobrecarga correspondiente a 50 % de la masa corporal y durante cuatro semanas. El GH fue aplicado en la dosificación de 0,2 UI/kg en cada animal, tres veces en la semana y en días alternados. Después de cuatro semanas, los animales fueran eutanasiados y retirados los fémures derechos para un análisis de la estructura ósea. La espectroscopía Raman fue utilizada para observar los siguientes compuestos a partir de las respectivas bandas: Carbonato de Calcio-Triglicéridos (ácidos grasos) 1073 cm-1, Colágeno Tipo I 509 cm-1, Fosfato Óseo-DNA (Proteína) 589 cm1, Fosfato Fosfolípidos 1078 cm-1. Para el análisis estadístico, fueron realizadas las pruebas Shapiro-Wilk y el análisis de variancia ANOVA One-Way, seguida de test post hoc de Tukey. Los resultados revelaran aumento de la concentración de Carbonato de Calcio-Triglicéridos (ácidos grasos), Colágeno Tipo I, Fosfato Óseo- DNA (Proteína), Fosfato Fosfolípidos en todos los grupos experimentales, asociados o no a la realización del EF y/o aplicación del GH. Además, solamente el grupo EF mostró diferencia significativa del grupo C (p<0,05). Es posible concluir que todos los tratamientos mostraran aumentos en el tejido óseo, sin embargo, solamente el grupo T demostró una diferencia significativa en los compuestos minerales analizados.

Analysis of photobiomodulation associated or not with platelet-rich plasma on repair of muscle tissue by Raman spectroscopy.

Treatment of muscle injuries usually results in the interruption of sports practice; thus, studies aimed at accelerating the return to activity, with proper tissue repair, are important. Therefore, this study aimed to evaluate the effects of photobiomodulation (PBM), associated or not with platelet-rich plasma (PRP), on the treatment of muscle injury. Thirty-five animals were used and divided into five groups (n = 7): control (C), control lesion (CL), lesion treated with low-level laser therapy (LLLT) (LLt), lesion treated with PRP (LP), and lesion treated with both techniques, LLLT and PRP (LLtP). Muscle injury was induced by stretching the gastrocnemius muscle, and the animals in the LLtP and LP groups received the application of PRP immediately following the injury. The LLLT was applied daily for 7 days. The animals were euthanized 7 days after the injury. Analysis of the NADH/NAD ratio and collagen was performed by Raman spectroscopy; in addition to which, histological analysis of the gastrocnemius muscle was performed. The LLtP group demonstrated a reduction in the area of injury, regenerating cells and a healthy appearance of muscle fibers. The Raman analyses showed a reduction in the NADH/NAD ratio in the CL group, demonstrating oxidative stress, and the collagen presented a reduction in the CL and LLt groups, when compared with the C group. It is concluded that either PBM or PRP, and the association of both, was able to reduce the oxidative stress promoted by injury and modulate collagen production at the site of the injury. Furthermore, although both treatments individually were effective for repairing the damage caused by muscle injury, the association of both demonstrated a better histological aspect.

Synergy between polyaniline and OMt clay mineral in Langmuir-Blodgett films for the simultaneous detection of traces of metal ions.

We report on Langmuir-Blodgett (LB) films made with emeraldine salt polyaniline (PAni-ES) and organophilic montmorillonite clay mineral (OMt), where synergy between the components was reached to yield an enhanced performance in detecting trace levels of cadmium (Cd(2+)), lead (Pb(2+)) and copper (Cu(2+)). Detection was carried out using square wave anodic stripping (SWAS) voltammetry with indium tin oxide (ITO) electrodes modified with LB films of PAni-ES/OMt nanocomposite, whose data were compared to those obtained with electrodes coated with neat PAni-ES and neat OMt LB films. The enhanced performance in the nanocomposite may be attributed to the stabilizing and ordering effect promoted by OMt in PAni-ES Langmuir films, which then led to more homogeneous LB films. According to X-ray diffraction data, the stacking of OMt layers was preserved in the LB films and therefore the PAni-ES chains did not cause clay mineral exfoliation. Instead, OMt affected the polaronic state of PAni-ES as indicated in UV-vis, Raman and FTIR spectra, also consistent with the changes observed for the Langmuir films. Taken together these results do indicate that semiconducting polymers and clay minerals may be combined for enhancing the electrical properties of nanostructures for sensing and related applications.

Raman spectroscopy and scanning electron microscopy characterizations of fission track method datable zircon grains.

Spectroscopic and morphological studies, designed to improve our understanding of the physicochemical phenomena that occur during zircon crystallization, are presented. The zircon fission track method (ZFTM) is used routinely in various laboratories around the world; however, there are some methodological difficulties needing attention. Depending on the surface fission track density observed under an optical microscope, the zircon grain surfaces are classified as homogeneous, heterogeneous, hybrid, or anomalous. In this study, zircon grain surfaces are characterized using complementary techniques such as optical microscopy (OM), micro-Raman spectroscopy, and scanning electron microscopy (SEM), both before and after chemical etching. Our results suggest that anomalous grains have subfamilies and that etching anisotropy related to heterogeneous grains is due to different crystallographic faces within the same polished surface that cannot be observed under an optical microscope. The improved methodology was used to determine the zircon fission track ages of samples collected from the Bauru Group located in the north of Paraná Basin, Brazil. A total of 514 zircon grains were analyzed, consisting of 10% homogeneous, about 10% heterogeneous, about 20% hybrid, and 60% anomalous grains. These results show that the age distributions obtained for homogeneous, heterogeneous, and hybrid grains are both statistically and geologically compatible.

Micro-Raman spectroscopic characterization of a CR-39 detector.

Characterization by micro-Raman spectroscopy of polymeric materials used as nuclear track detectors reveals physico-chemical and morphological information on the material's molecular structure. In this work, the nuclear track detector poly(allyl diglycol carbonate), or Columbia Resin 39 (CR-39), was characterized according to the fluence of alpha particles produced by a (226)Ra source and chemical etching time. Therefore, damage of the CR-39 chemical structure due to the alpha-particle interaction with the detector was analyzed at the molecular level. It was observed that the ionization and molecular excitation of the CR-39 after the irradiation process entail cleavage of chemical bonds and formation of latent track. In addition, after the chemical etching, there is also loss of polymer structure, leading to the decrease of the group density C-O-C (∼888 cm(-1)), CH=CH (∼960 cm(-1)), C-O (∼1110 cm(-1)), C-O-C (∼1240 cm(-1)), C-O (∼1290 cm(-1)), C=O (∼1741 cm(-1)), -CH2- (∼2910 cm(-1)), and the main band -CH2- (∼2950 cm(-1)). The analyses performed after irradiation and chemical etching led to a better understanding of the CR-39 molecular structure and better comprehension of the process of the formation of the track, which is related to chemical etching kinetics.

Effects of etching on zircon grains and its implications for the fission track method.

Studies of zircon grains using optical microscopy, micro-Raman spectroscopy, and scanning electron microscopy (SEM) have been carried out to characterize the surface of natural zircon as a function of etching time. According to the surface characteristics observed using an optical microscope after etching, the zircon grains were classified as: (i) homogeneous; (ii) anomalous, and (iii) hybrid. Micro-Raman results showed that, as etching time increases, the crystal lattice is slightly altered for homogeneous grains, it is completely damaged for anomalous grains, and it is altered in some areas for hybrid grains. The SEM (energy dispersive X-ray spectroscopy, EDS) results indicated that, independent of the grain types, where the crystallinity remains after etching, the chemical composition of zircon is approximately 33% SiO(2):65% ZrO(2) (standard natural zircon), and for areas where the grain does not have a crystalline structure, there are variations of ZrO(2) and, mainly, SiO(2). In addition, it is possible to observe a uniform surface density of fission tracks in grain areas where the determined crystal lattice and chemical composition are those of zircon. Regarding hybrid grains, we discuss whether the areas slightly altered by the chemical etching can be analyzed by the fission track method (FTM) or not. Results of zircon fission track and U-Pb dating show that hybrid and homogeneous grains can be used for dating, and not only homogeneous grains. More than 50 sedimentary samples from the Bauru Basin (southeast Brazil) were analyzed and show that only a small amount of grains are homogeneous (10%), questioning the validity of the rest of the grains for thermo-chronological evolution studies using zircon FTM dating.

Iron phthalocyanine in non-aqueous medium forming layer-by-layer films: growth mechanism, molecular architecture and applications.

The application of organic thin films as transducer elements in electronic devices has been widely exploited, with the electrostatic layer-by-layer (LbL) technique being one of the most powerful tools to produce such films. The conventional LbL method, however, is restricted in many cases to water soluble compounds. Here, an alternative way to produce LbL films containing iron phthalocyanine (FePc) in non-aqueous media (chloroform) is presented. This film fabrication was made possible by exploiting the specific interactions between Fe and NH(2) groups from PAH, poly(allylamine hydrochloride) used as the supporting layer, leading to the formation of bilayers structured as (PAH/FePc)(n). We have also incorporated silver nanoparticles (AgNPs) in LbL films with (PAH/FePc/AgNP)(n) trilayers, making it possible to achieve the surface-enhanced Raman scattering (SERS) phenomenon. The molecular architecture of the LbL films was determined through different techniques. The growth was monitored with UV-Vis absorption spectroscopy, their morphology characterized by optical and scanning electron (SEM) microscopes, and their molecular organization determined using FTIR. The electrochemical properties of the LbL films were successfully applied in detecting dopamine in KCl aqueous solutions at different concentrations using cyclic voltammetry. The results confirmed that the LbL films from FePc in non-aqueous media keep their electroactivity, while showing an interesting electrocatalytic effect. The SERS phenomenon suggested that FePc aggregates might be directly involved in the maintenance of the electroactivity of the LbL films.