Ex vivo UV-vis and FTIR photoacoustic spectroscopy of natural nanoemulsions from cellulose nanocrystals and saponins topically applied into the skin: Diffusion rates and physicochemical evaluation.

Nanoemulsions are increasingly gaining importance in the development of topically applied medicine and cosmetic products because their small droplets favor the penetration rates of active compounds into the body. In this scenario, the measurements of their diffusion rates as well as eventual physicochemical changes in the target tissues are of utmost importance. It is also recognized that the use of natural surfactants can avoid allergic reactions as frequently observed for synthetic products. The natural saponins extracted from Sapindus Saponaria have the property of forming foam and are exploited as biocompatible and biodegradable, while cellulose nanocrystals are known to increase the stability of a formulation avoiding the coalescence of drops at the interface. Therefore, nanoemulsions combining natural saponins and cellulose nanocrystals are promising systems that may facilitate greater diffusion rates of molecules into the skin, being candidates to substitute synthetic formulations. This study applied the Photoacoustic Spectroscopy technique to measure the diffusion rates and the physicochemical properties of nanoemulsified formulations containing saponins and cellulose nanocrystals topically applied to the skin. The ex vivo study combined the first-time photoacoustic measurements performed in both ultraviolet-visible and mid-infrared spectral regions. The toxicity of these formulations in L929 cells was also evaluated. The results showed that the formulations were able to propagate throughout the skin to a depth of approximately 756 µm, reaching the dermal side. The non-observation of absorbing band shifting or new bands in the FTIR spectra suggests that there were no structural changes in the skin as well as in the formulations after the nanoemulsions administration. The cytotoxicity results showed that the increase of cellulose nanocrystals concentration decreased cellular toxicity. In conclusion, the results demonstrated the advantage of combining photoacoustic methods in the ultraviolet-visible and mid-infrared spectral regions to analyze drug diffusion and interaction with the skin tissues. Both methods complement each other, allowing the confirmation of the nanoemulsion diffusion through the skin and also suggesting there were no detectable physicochemical changes in the tissues. Formulations stabilized with saponins and cellulose nanocrystals showed great potential for the development of topically administered cosmetics and drugs.

Photoacoustic for thermal diffusivity determination of fish scale: A methodology for environmental integrity monitoring.

In this work the thermal diffusivity (D) of Astyanax lacustris fish scale is investigated aiming to use it for environmental integrity certification. The D values were obtained by a relatively simple procedure by a photoacoustic method. The chosen fish species is from wide occurrence in Brasil's basins. It has short migration, and it has also been used as environmental bioindicator. The results obtained in 195 scales sampled from three different streams in the Midwest region in Brazil gives an average value of D ~ 4 × 10-3 cm2/s. ANCOVA analysis demonstrated that D values are able to differentiate among the three basins and indicates that it is dependent on the scales thickness and water conductivity. This last one is strongly affected by biotic and abiotic actions, so that D values measured by photoacoustic method can be used for interpreting the environmental integrity from where the fishes were sampled.

Glycine Max (L.) Merr isoflavone gel improves vaginal vascularization in postmenopausal women.

Objective: This study aimed to analyze the effects of isoflavones from Glycine max (L.) Merr (soy) used topically as a vaginal gel on the induction of vascularization of the vaginal tissue in postmenopausal women.Study design: A placebo-controlled, randomized, double-blind trial was conducted with 22 postmenopausal women, randomly allocated for treatment with Glycine max (L.) Merr isoflavone 4% vaginal gel daily for 12 weeks or with placebo gel for the same period.Main outcome measure: Vaginal microbiopsies were collected before and after the 12-week treatment. Immunohistochemistry analyses were performed to provide a blood vessel count per field in the vaginal tissue, pre and post intervention.Results: The isoflavone group exhibited a significant increase in blood vessels per field relative to baseline, whereas the placebo group showed no difference compared to baseline. There was a significant difference in the increase of the number of blood vessels between the isoflavone and placebo groups.Conclusion: The results showed that local administration of Glycine max (L.) Merr isoflavone gel promoted a significant improvement in the number of blood vessels in the vaginal tissue of postmenopausal women.

Intraspecific Cuticular Chemical Profile Variation in the Social Wasp Mischocyttarus consimilis (Hymenoptera, Vespidae).

Chemical compounds present on the cuticle of social insects are important in communication, as they are used in recognition of nestmates and sexual partners as well as in caste distinction, varying according to several factors, such as genetic and environmental. In this context, some studies have explored the cuticular chemical profile as a tool for assessing intra- and interspecific differences in social insects, although few studies have investigated this in social wasps. This study aimed to assess the differences in cuticular chemical profiles among different geographic samples of the wasp Mischocyttarus consimilis Zikán. Our hypothesis was that environmental factors are decisive to compose the cuticular chemical profiles of colonies of these social wasps and that there are differences regarding the geographic distribution among colonies. We used Fourier Transform Infrared-Photoacoustic Spectroscopy (FTIR-PAS) to assess the chemical profiles of samples. Our results show that despite there are differences between the cuticular chemical composition of the wasps' samples from different populations, there is no significant correlation compared to the spatial distribution of the colonies nor with the environment. Thus, our hypothesis was refuted, and we can infer that in this species neither exogenous nor genetic factors stand out to differentiate the chemical signature of their colonies, but a combination of both.

Comparison of optical spectroscopy techniques for monitoring the stages of thermoxidation of soybean biodiesel.

The thermoxidation of biodiesel was monitored using different spectroscopic techniques: UV-Vis and MIR absorption, Raman spectroscopy, and visible fluorescence. As the oxidation progressed, the UV-Vis absorption spectra showed an increase in the spectral range between 34,000 and 26,000 cm-1, while two main fluorescence bands (under ultraviolet excitation) were observed at around 21,000 and 15,000 cm-1. The UV-Vis absorption and fluorescence intensities presented opposite behavior during the processes, irrespective of the temperature used (90, 140, or 190 °C). These effects could be explained by the consumption of natural antioxidants, followed by the formation of primary oxidation compounds. The Raman and MIR absorption results indicated the existence of a cis-trans isomerization effect, followed by the formation of hydroperoxides during the oxidation, with the behavior being the same as that revealed by the UV-Vis absorption and fluorescence analyses. The comparison, under the same conditions, of different spectroscopy techniques that can be used to monitor the stages of thermoxidation of soybean biofuel provides important information for selection of an appropriate technique for evaluating biodiesel integrity.

DNA barcode sheds light on systematics and evolution of neotropical freshwater trahiras.

We assessed the presence of independent evolving lineages of the trahira, Hoplias malabaricus, one of the few freshwater fish species having wide distribution in the Neotropics which is the region with the highest global diversity of freshwater fish. To achieve that goal, 58 mitochondrial sequences of cytochrome c oxidase subunit I (COI; DNA barcoding) were generated from collected samples and 85 obtained from public databases, which were analyzed in comparison to chromosomal and geological data. The magnitude of genetic diversity found among different sampling sites was greater than 2%. Molecular species delimitation methods indicated the existence of a least four distinct lineages. The recognised cytotypes did not form monophyletic groups, suggesting that the karyotypic macrostructure could be a homoplastic character. The haplotype relationships suggested secondary contacts between the ecoregions of Northern and Northeastern Brazil that were shaped by coastal routes between adjacent watersheds during the Pleistocene epoch and probable exchanges of their ichthyofaunas. Our results indicated that multiple factors have driven the diversification of H. malabaricus, from ancient geological events linked to the reactivation of tectonic faults to more recent occurrences related to eustatic changes in ocean levels. Ultimately, the magnitude of its genetic diversity suggests the necessity of revising its taxonomic status.

Chemical Interaction and Interface Analysis of Self-Etch Adhesives Containing 10-MDP and Methacrylamide With the Dentin in Noncarious Cervical Lesions.

OBJECTIVES: To characterize the chemical interactions and analyze the interface of adhesive systems containing 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP) and N-methacryloyl glycine (methacrylamide) functional monomers with the dentin in noncarious cervical lesions (NCCLs) compared with artificial defects (ADs). METHODS AND MATERIALS: Twenty human teeth with natural NCCLs on the buccal surface were used. Class V cavities, similar to NCCLs, were created on the lingual surface to serve as controls. Teeth were randomly allocated to two groups according to the functional monomer in the adhesive (N=10): G1, 10-MDP; and G2, methacrylamide. NCCLs and ADs were characterized by their mineral composition (MC) and degree of demineralization (DD) using micro-Raman spectroscopy, adhesive/dentin chemical interactions (CIs) were assessed with infrared photoacoustic spectroscopy, and interface morphology was evaluated with scanning electron and light microscopy. MC, CI, and DD data were submitted to Shapiro-Wilk and Student t-tests ( p<0.05). RESULTS: Compared with ADs, dentin in NCCLs was hypermineralized ( p<0.05). In G1, CI, and DD in the first 2 µm, and adhesive projections in NCCLs and ADs interfaces were similar. Additionally, a thin layer of dentin collagen was observed in ADs, while it was hardly present in NCCLs. In G2, although CI could not be identified, changes in the mineral components were observed. The DD in the ADs and NCCLs were statistically similar, while SEM showed a lack of adhesion at NCCLs interface. DD and collagen exposure in the ADs and NCCLs were more pronounced than in G1. CONCLUSIONS: Results suggest that the G1 adhesive could be applied directly on the superficial sclerotic layer in NCCLs. In contrast, previous cavity preparation should be conducted to improve the micromechanical interaction of G2 with the dentin.

Spectral refractive index technique for monitoring the beer mashing process.

During beer production, the mashing process is fundamental for extraction of the main sugars from the starch. The quantification of these fermentable sugars during the process provides a measure of the alcoholic content of the final beer. Therefore, monitoring of the sugar composition during beer production is very important for obtaining a quality product. This paper demonstrates the potential of white light interferometry (WLI) for monitoring the extraction of sugars in different mashing processes, by observing the refractive index of the mixture. All the mashings presented linear increases of the refractive index during the temperature steps, which were influenced by the concentrations of sugars produced in each step. Cauchy parameters obtained by refractive index interpretation showed the influence of carbohydrates on absorption in the infrared region, and amino acids on absorption in the ultraviolet region. Strong correlation was obtained between the refractive index and °Bx values, indicating that the WLI technique is a potential analytical method for monitoring the mashing process during beer production.

Near-near-infrared thermal lens spectroscopy to assess overtones and combination bands of sulfentrazone pesticide.

Thermal lens spectroscopy (TLS) in the near-near-infrared region was used to explore the absorptions of overtones and combination bands of sulfentrazone (SFZ) herbicide diluted in methanol. This spectroscopic region was chosen in order to guarantee that only thermal lens effect is noted during the experimental procedure. The results showed that it was possible to detect very low concentrations (~2ng/µL) of SFZ in methanol by determining its thermal diffusivity or the absorption coefficient due to the 3ν(NH)+1δ(CH) combination band. This minimum SFZ concentration is the limit observed by chromatography method. The findings demonstrated that the TLS can be used for precise and accurate assessment of pesticides in ecosystems. Besides, the 3ν(NH)+1δ(CH) combination band at 960nm can be used as a marker for SFZ in methanol.

Integrated Analyses of Cuticular Hydrocarbons, Chromosome and mtDNA in the Neotropical Social Wasp Mischocyttarus consimilis Zikán (Hymenoptera, Vespidae).

In the present work, we explored multiple data from different biological levels such as cuticular hydrocarbons, chromosomal features, and mtDNA sequences in the Neotropical social wasp Mischocyttarus consimilis (J.F. Zikán). Particularly, we explored the genetic and chemical differentiation level within and between populations of this insect. Our dataset revealed shallow intraspecific differentiation in M. consimilis. The similarity among the analyzed samples can probably be due to the geographical proximity where the colonies were sampled, and we argue that Paraná River did not contribute effectively as a historical barrier to this wasp.

Chemical Interaction Analysis of an Adhesive Containing 10-Methacryloyloxydecyl Dihydrogen Phosphate (10-MDP) With the Dentin in Noncarious Cervical Lesions.

The purpose of this study was to evaluate the chemical bonds of a self-etch 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP) adhesive to natural noncarious cervical lesions (NCCLs) and compare them with those occurring in sclerotic dentin in artificially prepared defects (APDs). Four human teeth with natural NCCLs on the buccal surface were selected. Artificial defects matching the natural lesions were prepared on the lingual surface of the same teeth serving as control. Micro-Raman (MR) spectroscopy was used to quantify mineral content in natural NCCLs and in APDs. Fourier transform infrared-photoacoustic spectroscopy (FTIR-PAS) readouts were taken before and after adhesive application to analyze the protein matrix/mineral (M:M) ratio and chemical interactions between 10-MDP adhesive and dentin. The MR and FTIR-PAS spectra collected from natural NCCLs demonstrated a larger area of the band (961 cm-1, PO4) and lower M:M ratio, respectively, characterizing a hypermineralized dentin, compared with APDs. FTIR-PAS demonstrated emergence of a peak (1179 cm-1, P=O) in spectra after adhesive treatment, demonstrating a more intense chemical interaction in natural NCCLs. The results demonstrated that chemical bonding of 10-MDP adhesive to natural NCCLs is more intense, due to the hypermineralized surface, and suggest that it is unnecessary to remove the hypermineralized layer with burs, as this may decrease the chemical bonding potential of 10-MDP.

Variation in Venoms of Polybia Paulista Von Ihering and Polybia Occidentalis Olivier (Hymenoptera: Vespidae), Assessed by the FTIR-PAS Technique.

Wasps are able to synthesize toxic compounds known as venoms, which form a part of a mechanism to overcome prey and also to defend their colonies. Study of the compounds that constitute these substances is essential in order to understand how this defense mechanism evolved, since there is evidence that the venoms can vary both intra- and interspecifically. Some studies have used liquid and gas chromatography as a reliable technique to analyze these compounds. However, the use of Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS) to analyze the variations in venom's chemical profile has been proposed recently. This study evaluated whether the FTIR-PAS technique is effective for assessing the role of environmental factors on intra- and interspecific differences in the venom of the wasps Polybia paulista Von Ihering and Polybia occidentalis Olivier by FTIR-PAS. The colonies were collected in three municipalities of Mato Grosso do Sul, Brazil, in different types of environments. The results showed that the venoms of P. paulista and P. occidentalis differed significantly in profile. In addition, the intraspecific differences in the venom's chemical profile of P. paulista are related to the type of environment where they nested, regardless of the geographical distance between the nests. The FTIR-PAS technique proved to be reliable and effective to evaluate the variations in the venom's chemical profile in social wasps.

Measurements of refractive indices and thermo-optical coefficients using a white-light Michelson interferometer.

A dispersive white-light Michelson interferometer was used to determine the wavelength dependence of the refractive index (n) in the visible range from 425 to 775 nm and the thermo-optical coefficient (dn/dT) of fused silica (FS) and borosilicate glass (BK7). For FS, the values obtained for n and dn/dT at 546 nm were 1.46079 and 11.3×10-6 K-1, respectively, while the values for BK7 glass were 1.51825 and 2.2×10-6 K-1, respectively, which is in good agreement with the literature. The accuracy of the methodology used for n was almost 10-6, enabling precise spectroscopic characterization of materials across a wide spectral range.

In situ structural analysis of calcium aluminosilicate glasses under high pressure.

In situ micro-Raman spectroscopy was used to investigate the structural evolution of OH(-)-free calcium aluminosilicate glasses, under high pressure and at room temperature. Evaluation was made of the role of the SiO2 concentration in percalcic join systems, for Al/(Al + Si) in the approximate range from 0.9 to 0.2. Under high pressure, the intensity of the main band related to the bending mode of bridging oxygen ([Formula: see text][T-O-T], where T = Si or Al) decreased gradually, suggesting that the bonds were severely altered or even destroyed. In Si-rich glasses, compression induced a transformation of Q (n) species to Q (n-1). In the case of Al-rich glass, the Al in the smallest Q (n) units evolved from tetrahedral to higher-coordinated Al (([5])Al and ([6])Al). Permanent structural changes were observed in samples recovered from the highest pressure of around 15 GPa and, particularly for Si-rich samples, the recovered structure showed an increase of three-membered rings in the Si/Al tetrahedral network.

Impact of GGCX, STX1B and FPGS Polymorphisms on Warfarin Dose Requirements in European-Americans and Egyptians.

Genotype-based algorithms that include VKORC1 and CYP2C9 genotypes are less predictive of warfarin dose variability in Africans as opposed to Europeans. Polymorphisms in GGCX, FPGS, or STX1B are associated with warfarin dose requirements in African-Americans. We sought to determine if they influenced warfarin dose in European-Americans, and another African population, specifically Egyptians. We genotyped 529 adults (n = 325 European-Americans, 204 Egyptians) on a stable warfarin dose for GGCX rs12714145 and rs10654848, FPGS rs7856096, and STX1B rs4889606. Rs12714145, rs10654848, and rs7856096 were not associated with warfarin dose, whereas STX1B rs4889606 was a significant determinant in univariate analysis (P < 0.0001) in both cohorts. However, STX1B rs4889606 was in high linkage disequilibrium with VKORC1-1639 G>A, and was no longer significant after including VKORC1-1639 G>A in the regression model. Based on these data, the polymorphisms do not appear to influence, in a clinically important way, warfarin dose requirements in European-Americans and Egyptians.

Morphological and Chemical Characterization of the Invasive Ants in Hives of Apis mellifera scutellata Lepeletier (Hymenoptera: Apidae).

Apiculture in Brazil is quite profitable and has great potential for expansion because of the favorable climate and abundancy of plant diversity. However, the occurrence of pests, diseases, and parasites hinders the growth and profitability of beekeeping. In the interior of the state of São Paulo, apiaries are attacked by ants, especially the species Camponotus atriceps (Smith) (Hymenoptera: Formicidae), which use the substances produced by Apis mellifera scutellata (Lepeletier) (Hymenoptera: Apidae), like honey, wax, pollen, and offspring as a source of nourishment for the adult and immature ants, and kill or expel the adult bees during the invasion. This study aimed to understand the invasion of C. atriceps in hives of A. m. scutellata. The individuals were classified into castes and subcastes according to morphometric analyses, and their cuticular chemical compounds were identified using Photoacoustic Fourier transform infrared spectroscopy (FTIR-PAS). The morphometric analyses were able to classify the individuals into reproductive castes (queen and gynes), workers (minor and small ants), and the soldier subcaste (medium and major ants). Identification of cuticular hydrocarbons of these individuals revealed that the eight beehives were invaded by only three colonies of C. atriceps; one of the colonies invaded only one beehive, and the other two colonies underwent a process called sociotomy and were responsible for the invasion of the other seven beehives. The lack of preventive measures and the nocturnal behavior of the ants favored the invasion and attack on the bees.

Fluorescence analysis of iodinated acetophenone derivatives.

In the present paper the synthesis and optical characterization of iodinated acetophenone, 4-hydroxy-3-iodoacetophenone and 4-hydroxy-3,5-diiodoacetophenone obtained from 4-hydroxyacetophenone, were carried out. The optical features of iodinated molecules were determined by performing the UV-Vis absorption, fluorescence and thermal lens spectroscopies. The results showed that the optical properties of the 4-hydroxyacetophenone is altered when the iodine atom is inserted, as substituent, in the aromatic ring. Although it was determined that the optical feature was changed when one iodine atom was inserted in the aromatic ring (4-hydroxy-3-iodoacetophenone), the results revealed that emission behavior was strongly altered when two iodine atoms (4-hydroxy-3,5-diiodoacetophenone) were acting as substituents: the fluorescence quantum efficiency increases approximately 60%.

Fourier transform infrared photoacoustic spectroscopy as a potential tool in assessing the role of diet in cuticular chemical composition of Ectatomma brunneum.

The cuticular chemical composition plays a significant role in the recognition of nest mates in social insects, thus functioning as a chemical signature of the colony. The structure of cuticular chemicals is subject to interference from genetic and exogenous factors, including diet. In this study, various colonies of the Ectatomma brunneum ant were removed from their natural environment and housed in a laboratory to monitor the response of the cuticular chemical composition to dietary changes. Analyses were performed using gas chromatography and Fourier transform infrared photoacoustic spectroscopy, which has not been previously used for this type of analysis. The results indicate that this method is useful for analyzing biological and natural systems. We observed changes in the chemical signature with food traces in the first 30 days under feed control. Therefore, genetic information may not be the only criterion that can be used to describe the chemical signature of a species; environmental variations also influence recognition signals. Furthermore, these results reinforce the reliability of the Fourier transform infrared photoacoustic spectroscopy method.

Resonant excited state absorption and relaxation mechanisms in Tb3+-doped calcium aluminosilicate glasses: an investigation by thermal mirror spectroscopy.

Resonant excited state absorption (ESA) and relaxation processes in Tb(3+)-doped aluminosilicate glasses are quantitatively evaluated. A model describing the excitation steps and upconversion emission is developed and applied to interpret the results from laser-induced surface deformation using thermal mirror spectroscopy. The fluorescence quantum efficiency of level (5)D(4) was found to be close to unity and concentration independent while, for the level (5)D(3), it decreases with Tb(3+) concentration. Emission spectroscopy measurements supported these results. ESA cross sections are found to be more than three orders of magnitude higher than the ground state absorption cross section.

Modeling the population lens effect in thermal lens spectrometry.

We report a theoretical model and experimental results for laser-induced lensing in solids. The model distinguishes and quantifies the contributions from population and thermal effects. Laser-induced lensing in ytterbium-doped fluorozirconate glass ZBLAN:Yb(3+) is measured, and the thermal and optical properties obtained from analyzing the data with the proposed model agree well with published values. Photothermal techniques are used extensively for the investigation of laser and laser-cooling materials, and the model developed here enables the interpretation of convoluted laser-induced lensing signals that have contributions from different sources.