Avalanche-assisted transient optical phenomenon in aggregated toluidine blue dye.

Pulse-modulated CW laser heat deposition modulates the darkness or the transparency of an aggregated medium in the high signal optical regimen. A recently reported work found that transient optical responses of molecular aggregates can be different depending on whether the sample is excited with a laser wavelength tuned within the absorption band of the monomer or within the absorption band of the aggregates. The different transient responses were attributed to different dynamic processes during the laser-induced disassembling of the molecular aggregates and may have implications in the field of organic electronics and optical devices, such as optical logical gates, optical power limiters and all-optical switching. In this paper laser beams with wavelengths of 663 nm and 532 nm were used to produce sudden changes in the thermodynamic equilibrium of the aggregation states of the ortho-toluidine blue dye, which allowed to observe the occurrence of the avalanche - mediated transient phenomenon in the laser-induced disassembling of ortho-toluidine blue (TBO) aggregates. A double exponential model was adjusted to the registered transient data. The obtained values for the fast components of the transient time responses of ortho-toluidine blue dye, for the studied concentrations, ranged from âˆ¼ 6.5 to 9.5 ms at 532 nm, and from âˆ¼ 43 to 48 ms at 663 nm. A single beam experiment was employed to evaluate the performance of the ortho-toluidine blue dye in a beam power-damping device, driven by the simultaneous and cooperative actions of the laser induced disassembling of aggregated dye units and the thermal lensing effect. It was found that the phenomenon of laser-induced dye disassembling of TBO, acting cooperatively with the thermal lensing effect, damps the laser beam power faster than the thermal lensing phenomenon alone. In addition, the results showed that the speed of the laser beam power-damping is dye dependent.

Taxonomy of Placospongia Gray, 1867 from Northern and Northeastern Brazil, with description of two new species (Porifera: Demospongiae: Clionaida).

The demosponge genus Placospongia includes 13 valid species, of which six occur in the Brazilian Exclusive Economic Zone. In the present study, we describe two new species of Placospongia from Northern (off the Amazon River mouth) and Northeastern Brazilian continental shelf and oceanic islands (i.e., Fernando de Noronha Archipelago), viz., Placospongia beatrizae sp. nov. and Placospongia amphinolastra sp. nov., and redescribe the holotype of Placospongia cristata Boury-Esnault, 1973, a poorly known species. In addition, we revise the Brazilian records of the allegedly cosmopolitan species P. carinata, P. melobesioides and P. intermedia, and provide new records of P. colombiensis and P. ruetzleri from Brazil. We demonstrate that P. carinata sensu Coelho & Mello-Leito and P. intermedia sensu Muricy & Moraes and Jimenez et al. belong in fact to P. ruetzleri, and that P. melobesioides sensu Mothes et al. and Gonzlez-Faras is a new species, described here as Placospongia beatrizae sp. nov. With the description of the two new species and synonymyzation of previous records, six species of Placospongia are currently known in Brazilian waters, two of which are endemic. A key to Placospongia species is also provided.

Voltammetric Sensing of Nifedipine Using a Glassy Carbon Electrode Modified with Carbon Nanofibers and Gold Nanoparticles.

Nifedipine, a widely utilized medication, plays a crucial role in managing blood pressure in humans. Due to its global prevalence and extensive usage, close monitoring is necessary to address this widespread concern effectively. Therefore, the development of an electrochemical sensor based on a glassy carbon electrode modified with carbon nanofibers and gold nanoparticles in a Nafion® film was performed, resulting in an active electrode surface for oxidation of the nifedipine molecule. This was applied, together with a voltammetric methodology, for the analysis of nifedipine in biological and environmental samples, presenting a linear concentration range from 0.020 to 2.5 × 10-6 µmol L-1 with a limit of detection 2.8 nmol L-1. In addition, it presented a good recovery analysis in the complexity of the samples, a low deviation in the presence of interfering potentials, and good repeatability between measurements.

Simultaneous Determination of Uric Acid and Caffeine by Flow Injection Using Multiple-Pulse Amperometry.

The present study reports the development and application of a flow injection analysis (FIA) system for the simultaneous determination of uric acid (UA) and caffeine (CAF) using cathodically pretreated boron-doped diamond electrode (CPT-BDD) and multiple-pulse amperometry (MPA). The electrochemical profiles of UA and CAF were analyzed via cyclic voltammetry in the potential range of 0.20-1.7 V using 0.10 mol L-1 H2SO4 solution as supporting electrolyte. Under optimized conditions, two oxidation peaks at potentials of 0.80 V (UA) and 1.4 V (CAF) were observed; the application of these potentials using multiple-pulse amperometry yielded concentration linear ranges of 5.0 × 10-8-2.2 × 10-5 mol L-1 (UA) and 5.0 × 10-8-1.9 × 10-5 mol L-1 (CAF) and limits of detection of 1.1 × 10-8 and 1.3 × 10-8 mol L-1 for UA and CAF, respectively. The proposed method exhibited good repeatability and stability, and no interference was detected in the electrochemical signals of UA and CAF in the presence of glucose, NaCl, KH2PO4, CaCl2, urea, Pb, Ni, and Cd. The application of the FIA-MPA method for the analysis of environmental samples resulted in recovery rates ranging between 98 and 104%. The results obtained showed that the BDD sensor exhibited a good analytical performance when applied for CAF and UA determination, especially when compared to other sensors reported in the literature.

Voltammetric Determination of 3-Methylmorphine Using Glassy Carbon Electrode Modified with rGO and Bismuth Film.

This work reports the development and application of a simple, rapid and low-cost voltammetric method for the determination of 3-methylmorphine at nanomolar levels in clinical and environmental samples. The proposed method involves the combined application of a glassy carbon electrode modified with reduced graphene oxide, chitosan and bismuth film (Bi-rGO-CTS/GCE) via square-wave voltammetry using 0.04 mol L-1 Britton-Robinson buffer solution (pH 4.0). The application of the technique yielded low limit of detection of 24 × 10-9 mol L-1 and linear concentration range of 2.5 × 10-7 to 8.2 × 10-6 mol L-1. The Bi-rGO-CTS/GCE sensor was successfully applied for the detection of 3-methylmorphine in the presence of other compounds, including paracetamol and caffeine. The results obtained also showed that the application of the sensor for 3-methylmorphine detection did not experience any significant interference in the presence of silicon dioxide, povidone, cellulose, magnesium stearate, urea, ascorbic acid, humic acid and croscarmellose. The applicability of the Bi-rGO-CTS/GCE sensor for the detection of 3-methylmorphine was evaluated using synthetic urine, serum, and river water samples through addition and recovery tests, and the results obtained were found to be similar to those obtained for the high-performance liquid chromatography method (HPLC)-used as a reference method. The findings of this study show that the proposed voltammetric method is a simple, fast and highly efficient alternative technique for the detection of 3-methylmorphine in both biological and environmental samples.

Biosynthesis of silver nanoparticles from Syzygium cumini leaves and their potential effects on odontogenic pathogens and biofilms.

This study analyzed the antimicrobial and antibiofilm action and cytotoxicity of extract (HEScL) and silver nanoparticles (AgNPs-HEScL) from Syzygium cumini leaves. GC-MS, UV-Vis, EDX, FEG/SEM, DLS and zeta potential assays were used to characterize the extract or nanoparticles. Antimicrobial, antibiofilm and cytotoxicity analyses were carried out by in vitro methods: agar diffusion, microdilution and normal oral keratinocytes spontaneously immortalized (NOK-SI) cell culture. MICs of planktonic cells ranged from 31.2-250 (AgNPs-HEScL) to 1,296.8-10,375 µg/ml (HEScL) for Actinomyces naeslundii, Fusobacterium nucleatum, Staphylococcus aureus, Staphylococcus epidermidis, Streptococcus mutans, Streptococcus oralis, Veillonella dispar, and Candida albicans. AgNPs-HEScL showed antibiofilm effects (125-8,000 µg/ml) toward Candida albicans, Streptococcus mutans and Streptococcus oralis, and Staphylococcus aureus and Staphylococcus epidermidis. The NOK-SI exhibited no cytotoxicity when treated with 32.8 and 680.3 µg/ml of AgNPs-HEScL and HEScL, respectively, for 5 min. The data suggest potential antimicrobial and antibiofilm action of HEScL, and more specifically, AgNPs-HEScL, involving pathogens of medical and dental interest (dose-, time- and species-dependent). The cytotoxicity of HEScL and AgNPs-HEScL detected in NOK-SI was dose- and time-dependent. This study presents toxicological information about the lyophilized ethanolic extract of S. cumini leaves, including their metallic nanoparticles, and adds scientific values to incipient studies found in the literature.

Circumflex Coronary Artery Fistula Draining into Coronary Sinus

ABSTRACT Coronary artery fistula draining into the coronary sinus is a rare vascular malformation, and its diagnosis and clinical manifestations usually occur late. We describe the case of a 72-year-old female patient with dyspnea on exertion (New York Heart Association Class III) associated with palpitations. The transthoracic echocardiogram showed significant tricuspid insufficiency. Cardiac catheterization showed aneurysm of the circumflex coronary artery and fistula of this artery draining into the coronary sinus. The patient underwent fistula ligation and tricuspid valve repair, with excellent surgical results.

Determination of ofloxacin in the presence of dopamine, paracetamol, and caffeine using a glassy carbon electrode based on carbon nanomaterials and gold nanoparticles.

A new electrode was prepared based on functionalized graphene and gold nanoparticles dispersed in a chitosan film. Such an electrochemical sensor determines ofloxacin in the presence of dopamine, paracetamol, and caffeine. Characterization (morphological and electrochemical) was done using scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. The sensor design improved the analytical signal, the electrochemical activity, and the electron transfer rate. Ofloxacin was determined by square-wave voltammetry, with a linear concentration range of 0.10-4.9 µmol L-1 (r = 0.999, LOD = 12 nmol L-1). The proposed sensor showed good repeatability and selectivity and was applied successfully to the determination of ofloxacin in pharmaceutical formulations, synthetic urine, and water river samples. The proposed method proved to be excellent; therefore, it is an alternative method for the determination of ofloxacin.

Enhancing the electrochemical sensitivity of hydroquinone using a hydrophobic deep eutectic solvent-based carbon paste electrode.

The present study reports the synthesis and characterization of hydrophobic deep eutectic solvents (HDES) based on fatty acids and tetrabutylammonium bromide (TBAB) or 1-octanol using Fourier transform infrared spectroscopy, and the analysis of the physicochemical properties (viscosity, density, electrical conductivity, and water content) of these solvents. A carbon paste electrode modified with 6.0% (m/m) decanoic acid and TBAB-based HDES was characterized by cyclic voltammetry, electrochemical impedance spectroscopy, and scanning electron microscopy. The oxidation peak currents of the proposed electrode were enhanced by its high electrochemical activity, fast electron transfer rate, and high surface area, while a remarkable decrease was observed in the peak potential separation. The electrochemical determination of hydroquinone (H2Q) was carried out using square-wave adsorptive anodic stripping voltammetry (SWAdASV). The electrode response was found to be linear in the H2Q concentration range of 2.5 × 10-6-3.0 × 10-3 mol L-1, with the limit of detection (LOD) of 7.7 × 10-7 mol L-1. The method was successfully applied for H2Q determination in dermatological creams.

Circumflex Coronary Artery Fistula Draining into Coronary Sinus.

Coronary artery fistula draining into the coronary sinus is a rare vascular malformation, and its diagnosis and clinical manifestations usually occur late. We describe the case of a 72-year-old female patient with dyspnea on exertion (New York Heart Association Class III) associated with palpitations. The transthoracic echocardiogram showed significant tricuspid insufficiency. Cardiac catheterization showed aneurysm of the circumflex coronary artery and fistula of this artery draining into the coronary sinus. The patient underwent fistula ligation and tricuspid valve repair, with excellent surgical results.

Manned submersible dives reveal a singular assemblage of Hexactinellida (Porifera) off the Amazon River mouth, Northern Brazil.

The outer shelf and upper slope region under the influence of the Amazon River mouth harbors an extensive reef system with a rich sponge fauna, but no hexactinellids were recorded in the area so far. In this work, manned submersibles were used to describe for the first time three species of Hexactinellida off the Amazon River mouth: Hyalonema (Cyliconemaoida) alucia sp. nov., Dactylocalyx pumiceus and Claviscopulia facunda. We found two morphotypes of Dactylocalyx pumiceus, suggesting that it may be a complex of cryptic species. The populations of the three species off Par State were sparse, but a large aggregation of D. pumiceus was found off Maranho State from 145 to 230 m depth. These findings indicate that hexactinellid grounds may be more common along the Northern Brazilian continental outer shelf and slope than previously thought.

A sutureless valve with sutures.

The use of sutureless valves in infective endocarditis has been previously reported. Singh et al. have reported a single-center successful surgical treated pulmonary endocarditis in two cases with a sutureless bioprosthesis.

Taxonomy of Petrosiidae Van Soest, 1980 (Haplosclerida, Porifera) from Brazil.

Petrosiidae (Haplosclerida, Demospongiae) is characterized by the hard and friable consistency, and an isotropic reticulated skeleton of oxeas/ strongyles. The Brazilian coast and oceanic islands harbor three out of four known genera of Petrosiidae: Neopetrosia de Laubenfels, 1949; Petrosia (Petrosia) Vosmaer, 1885 and Xestospongia de Laubenfels, 1932. A taxonomic survey of samples from several expeditions housed at the Porifera Collection of Museu Nacional, Universidade Federal do Rio de Janeiro, with additional comparative materials obtained from the Museu de Cincias Naturais, Fundao Zoobotnica do Rio Grande do Sul, and Universidade Federal de Pernambuco enabled the description of two new species: P. (P.) revizee sp. nov. and X. dorigo sp. nov. We also recorded a range extention for Neopetrosia proxima and Xestospongia muta, and Xestospongia grayi was synonymized with X. muta. Other species reported from the country are diagnosed, and an identification key for Petrosiidae from Brazil is provided.

Calcium carbonate production in the southernmost subtropical Atlantic coral reef.

Emerging evidence have been supporting the idea that the better known South Atlantic coral reefs (located between 18°S and 24°S) are now essentially senescent structures that have experienced little or no additional vertical reef growth over the past millennia. This has often coincided with a shift to a dominance of non-coral calcifying organisms becoming the main CaCO3 producers in these high latitude and marginal marine settings. Here, we used Calcification Accretion Units (CAUs) and census-based methods to measure non-coral rates of CaCO3 production on the geologically senescent reef and adjacent rhodolith beds within the southernmost subtropical Atlantic reef (i.e., Queimada Grande Reef, QGR). The reef habitat is currently producing CaCO3 at rates of ∼126 g m-2 yr-1. In contrast, fragments of dead corals skeletons deposited adjacent to the reef over the last ∼2000 years are now colonized by crustose coralline red algae. These form a rhodolith bed that produces CaCO3 at rates of 858 g m-2 yr-1. Our results indicate that, whilst not sufficient to promote active net framework accumulation, CaCO3 production by coralline algae and bryozoans on the QGR appears to be sufficient to at least limit net large-scale erosion of the underlying reef structure, allowing the reef structure to persist in a state close to budgetary stasis. Finally, our results are also of relevance for providing insights regarding the balance of CaCO3 production/dissolution/erosion processes in coral reefs, especially in these less understood marginal reefs.

A voltammetric sensor based on a carbon black and chitosan-stabilized gold nanoparticle nanocomposite for ketoconazole determination.

A modified glassy carbon electrode with carbon black (CB) and gold nanoparticles (AuNPs) within a crosslinked chitosan (CTS) film is proposed in this work. The electroanalytical performance of the modified CB-CTS-AuNPs/GCE has been evaluated towards the voltammetric sensing of ketoconazole (KTO), a widespread antifungal drug. The nanocomposite was characterized by scanning electron microscopy, X-ray diffraction spectroscopy, and electrochemistry experiments. The evaluation of the electrochemical behaviour of KTO on the proposed modified electrode shows an irreversible oxidation process at a potential of +0.65 V (vs. Ag/AgCl (3.0 mol L-1 KCl)). This redox process was explored to carry out KTO sensing using square-wave voltammetry. The analytical curve was linear in the KTO concentration range from 0.10 to 2.9 µmol L-1, with a limit of detection (LOD) of 4.4 nmol L-1 and a sensitivity of 3.6 µA L µmol-1. This modified electrode was successfully applied to the determination of KTO in pharmaceutical formulations and biological fluid samples.

Bryozoa from the reefs off the Amazon River mouth: checklist, thirteen new species, and notes on their ecology and distribution.

The reef system off the Amazon River mouth extends from Amapá state to Maranhão state along the Brazilian Equatorial Margin, encompassing more than 10,000 km2 of rhodolith beds and high-relief hard structures on the outer shelf and upper slope. This unique hard bottom mosaic is remarkable for being influenced by the turbid and hyposaline plume from the world's largest river, and also for representing a connectivity corridor between the Caribbean and Brazil. Bryozoans were recently recognized as major reef builders in the Southwestern Atlantic, but their diversity off the Amazon River mouth remained unknown. Here, we report on recent collections obtained from 23 to 120 m depth in Northern Brazil. Sixty-five bryozoan taxa were characterized using scanning electron microscopy, including 57, five and three taxa of Cheilostomatida, Cyclostomatida and Ctenostomatida, respectively. Cribrilaria smitti and three genera (Cranosina, Glabrilaria and Thornelya) are new records for Brazil, and 13 new species are herein described: Antropora cruzeiro n. sp., Cranosina gilbertoi n. sp., Cribrilaria lateralis n. sp., Crisia brasiliensis n. sp., Glabrilaria antoniettae n. sp., Micropora amapaensis n. sp., Parasmittina amazonensis n. sp., Plesiocleidochasma arcuatum n. sp., Poricella bifurcata n. sp., Pourtalesella duoavicularia n. sp., Stephanollona domuspusilla n. sp., Therenia dianae n. sp., and Thornelya atlanticoensis n. sp. Our results highlight the biodiversity significance of the Amazon reefs and the need for more comprehensive sampling to clarify the role of bryozoans in modern turbid-zone reefs and rhodolith beds.

Decadal (2006-2018) dynamics of Southwestern Atlantic's largest turbid zone reefs.

Tropical reefs are declining rapidly due to climate changes and local stressors such as water quality deterioration and overfishing. The so-called marginal reefs sustain significant coral cover and growth but are dominated by fewer species adapted to suboptimal conditions to most coral species. However, the dynamics of marginal systems may diverge from that of the archetypical oligotrophic tropical reefs, and it is unclear whether they are more or less susceptible to anthropogenic stress. Here, we present the largest (100 fixed quadrats at five reefs) and longest time series (13 years) of benthic cover data for Southwestern Atlantic turbid zone reefs, covering sites under contrasting anthropogenic and oceanographic forcing. Specifically, we addressed how benthic cover changed among habitats and sites, and possible dominance-shift trends. We found less temporal variation in offshore pinnacles' tops than on nearshore ones and, conversely, higher temporal fluctuation on offshore pinnacles' walls than on nearshore ones. In general, the Abrolhos reefs sustained a stable coral cover and we did not record regional-level dominance shifts favoring other organisms. However, coral decline was evidenced in one reef near a dredging disposal site. Relative abundances of longer-lived reef builders showed a high level of synchrony, which indicates that their dynamics fluctuate under similar drivers. Therefore, changes on those drivers could threaten the stability of these reefs. With the intensification of thermal anomalies and land-based stressors, it is unclear whether the Abrolhos reefs will keep providing key ecosystem services. It is paramount to restrain local stressors that contributed to coral reef deterioration in the last decades, once reversal and restoration tend to become increasingly difficult as coral reefs degrade further and climate changes escalate.

Voltammetric determination of ethinylestradiol using screen-printed electrode modified with functionalized graphene, graphene quantum dots and magnetic nanoparticles coated with molecularly imprinted polymers.

The present work reports the development of a sensitive and selective method for ethinylestradiol detection using screen-printed electrode (SPE) modified with functionalized graphene (FG), graphene quantum dots (GQDs) and magnetic nanoparticles coated with molecularly imprinted polymers (mag@MIP). The performance of the mag@MIP sensor was compared with that of a non-molecularly imprinted sensor (mag@NIP). Chemical and physical characterizations of the mag@NIP and mag@MIP sensors were performed using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and Brunauer-Emmett-Teller (BET) techniques. The electrochemical behavior of the electrodes investigated, which included (mag@MIP)-GQDs-FG-NF/SPE, (mag@NIP)-GQDs-FG-NF/SPE, GQDs-FG-NF/SPE and FG-NF/SPE, was evaluated by cyclic voltammetry. The results obtained show a significant increase in peak current magnitude for (mag@MIP)-GQDs-FG-NF/SPE. Using square wave voltammetry experiments, the efficiency of the (mag@MIP)-GQDs-FG-NF/SPE sensor was also tested under optimized conditions. The linear response range obtained for ethinylestradiol concentration was 10 nmol L-1 to 2.5 µmol L-1, with limit of detection of 2.6 nmol L-1. The analytical signal of the (mag@MIP)-GQDs-FG-NF/SPE sensor suffered no interference from different compounds and the sensor exhibited good repeatability. The proposed sensor was successfully applied for ethynilestradiol detection in river water, serum and urine samples, where recovery rates between 96 to 105% and 97-104% were obtained for environmental and biological samples, respectively.

Using BiVO4/CuO-Based Photoelectrocatalyzer for 4-Nitrophenol Degradation.

The present work reports the degradation of 4-nitrophenol using BiVO4/CuO hybrid material synthesized by the precipitation of BiVO4 in the presence of CuO. Morphological and structural characterizations were performed using X-ray diffraction and scanning electronic microscopy coupled to energy dispersive X-ray spectroscopy. Through the calculation of the Kubelka-Munk function applied to diffuse reflectance spectrophotometry data, the hybrid material presented absorption edge of 1.85 eV. The formation of p-n heterojunction between BiVO4 and CuO renders the hybrid material suitable for the construction of a photoanode employed in hydroxyl radical generation. UV-vis spectrophotometry and high-performance liquid chromatography experiments were performed in order to monitor the degradation of 4-nitrophenol and the formation of secondary products. Additional information regarding the hybrid material was obtained through ion chromatography and total organic carbon analyses. The application of BiVO4/CuO-based photocatalyzer led to a 50.2% decrease in total organic carbon after the degradation of 4-nitrophenol. Based on the results obtained in the study, BiVO4/CuO has proved to be a promising material suitable for the removal of recalcitrant compounds in water treatment plants.