Nuclear magnetic resonance chiral discrimination of fipronil and malathion agrochemicals: A case study.

The aim of the present study was to optimize a protocol for nuclear magnetic resonance (NMR) chiral discrimination to be used to determine the enantiomers ratio of agrochemicals. For this goal, the commercial agrochemicals fipronil and malathion were employed as active targets due the distinct physicochemical properties. We used the cyclodextrins to evaluate the chiral discrimination in aqueous media and chiral solvent agents to check in organic media. The fipronil chiral discrimination was accessed by ß-CD in aqueous solution, although this procedure was ineffective for malathion due the low solubility. In organic media, the NMR chiral discrimination was successful for both agrochemicals and sensitive to dilution process. The NMR experiments explore very sensitive nuclei, for instance 1 H, 19 F, and 31 P, in a simple, practical and low residue experimental protocol.

Arylseleninic acid as a green, bench-stable selenylating agent: synthesis of selanylanilines and 3-selanylindoles.

Arylseleninic acids were used as an electrophilic selenium source in aromatic substitution reactions, using N,N-substituted anilines and indoles as nucleophiles at 70 °C for 6-15 h. A total of fourteen 4-selanylanilines and five 3-selanylindoles were selectively obtained in good to excellent yields. The starting benzeneseleninic acids are easily prepared from the respective diselenides, are bench stable and easy to handle, affording water as the only waste at the end of the reaction.

Ultrasound-Promoted One-Pot Synthesis of Mono- or Bis-Substituted Organylselanyl Pyrroles.

A simple method for the direct mono- and bis-organylselenylation of N-substituted pyrroles through a multicomponent reaction promoted by ultrasonic radiation was described. These sonochemical promoted reactions were performed between different primary amines, 2,5-hexanedione and dialkyl, diheteroaryl, or diaryl diselenides, using catalytic amounts of copper iodide. Depending on the amount of copper iodide and diorganyl diselenide used in the reactions, mono- or bis-organylselenylation products were efficiently synthesized in high yields.

Synthesis of Isoxazolines by the Electrophilic Chalcogenation of ß,γ-Unsaturated Oximes: Fishing Novel Anti-Inflammatory Agents.

Herein, we describe a new strategy to prepare chalcogen-functionalized isoxazolines. The strategy involves the reaction of ß,γ-unsaturated oximes with electrophilic selenium and tellurium species, affording 19 new selenium- and tellurium-containing isoxazolines in good yields after 1 h at room temperature. The method was efficiently extended to the synthesis of 5 new (bis)isoxazoline ditellurides. One of the prepared compounds, 3-phenyl-5-((phenylselanyl)methyl)-isoxazoline, demonstrated better anti-inflammatory and antiedematogenic effects than the reference drug Celecoxib.

NMR chiral discrimination of chalcogen containing secondary alcohols.

Here, we report the general strategies by which NMR spectroscopy can be used to determine the enantiopurity and absolute configuration of chalcogen containing secondary alcohols, including the evaluation of the use of chiral solvating and chiral derivatizing agents. The BINOL/DMAP ternary complex demonstrated a simple and fast protocol for determining enantiopurity. The drug Naproxen afforded a stable, nonhygroscopic, and readily available chiral derivatizing agent (CDA) for NMR chiral discrimination of chalcogen containing secondary alcohols. The chiral recognition by CDA and chiral solvating agent (CSA) was assessed using 1 H, 77 Se-{1H}, and 125 Te-{1H} NMR spectroscopy. A simple model for the assignment of the absolute configuration from NMR data is presented.

Holocene history of a lake filling and vegetation dynamics of the Serra Sul dos Carajás, southeast Amazonia.

Down-core changes in sedimentary facies, elemental geochemistry, pollen, spore, δ13C, δ15N and radiocarbon records from a filled lake, named R4, of the Serra Sul dos Carajás were used to study the relationship between the paleomorphological and paleoecological processes and their significance for Holocene paleoclimatology of the southeast Amazonia. The sediment deposition of the R4 lake started around 9500 cal yr BP. Increase of detrital components from 9500 to 7000 cal yr BP suggests high weathering of surrounding catchment rocks and soils, and deposition into the lake basin under mudflows. At that time, montane savanna and forest formation were already established suggesting predominance of wet climate. However, from 7000 to 3000 cal yr BP, a decline of detrital input occurred. Also, forest formation and pteridophytes were declined, while palms and macrophytes were remained relatively stable, indicating that water levels of the lake is likely dropped allowing the development of plants adapted to subaerial condition under drier climate conditions. After 3000 cal yr BP, eutrophication and low accommodation space lead to high lake productivity and the final stage of the lake filling respectively, and forest formation may has acquired its current structure, which suggests return of wetter climate conditions.

Morphology and morphometry of upland lakes over lateritic crust, Serra dos Carajás, southeastern Amazon region.

High-resolution satellite images, digital elevation models, bathymetric and sedimentological surveys coupled with statistical analysis were used to understand the physical environment and discuss their influence on water quality of the five upland lakes of Serra Sul dos Carajás, southeast Amazonia. The lakes have mid-altitude ranges (elevation), very small (catchment) and shallow to very shallow (central basins). Based on the length, area and volume, Violão and TI (Três Irmãs)-3 lakes may present large vertical movements of the water due to wind action and weakly stratified waters. Trophic conditions based on depth and shore development (Ld) parameters must be used with caution, since Amendoim Lake is relatively deep, but it is oligotrophic to ultra-oligotrophic. Ld values suggest that the lakes are circular to subcircular and are likely formed by solution process, as also suggested by volume development. TI-2 Lake is only presenting convex central basin and has highest dynamic ratio (DR), thus it may have high sedimentation and erosion rates. Based on the relationship between studied parameters, morphometric index and DR likely influence temperature and dissolved oxygen of waters of TI-2 Lake due to its depth profile and wind-induced surface mixing. Nevertheless, water quality parameters are controlled by catchment characteristics of the lakes.

Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds.

Nuclear magnetic resonance (NMR) is a powerful tool for the elucidation of chemical structure and chiral recognition. In the last decade, the number of probes, media, and experiments to analyze chiral environments has rapidly increased. The evaluation of chiral molecules and systems has become a routine task in almost all NMR laboratories, allowing for the determination of molecular connectivities and the construction of spatial relationships. Among the features that improve the chiral recognition abilities by NMR is the application of different nuclei. The simplicity of the multinuclear NMR spectra relative to ¹H, the minimal influence of the experimental conditions, and the larger shift dispersion make these nuclei especially suitable for NMR analysis. Herein, the recent advances in multinuclear (19F, 31P, 13C, and 77Se) NMR spectroscopy for chiral recognition of organic compounds are presented. The review describes new chiral derivatizing agents and chiral solvating agents used for stereodiscrimination and the assignment of the absolute configuration of small organic compounds.

Influence of seasonal variation on the hydro-biogeochemical characteristics of two upland lakes in the Southeastern Amazon, Brazil.

Limnological characteristics of the Violão and Amendoim lakes, in the Serra dos Carajás, Amazon, were studied interannually (2013-2014). Climate data indicate anomalous conditions during the 2013 rainy period with higher rainfall and lower temperature in the beginning (November). Lake levels were influenced after the first and second hour of each rainfall, which showed a strong synchronization between seasonal fluctuation of lake levels and local weather patterns. Based on the water quality, both lakes are classified as classes "1" and "2" in the CONAMA (Conselho Nacional do Meio Ambiente) scheme and as "excellent" to "good" in the WQI (Water Quality Index) categories. However, the limnology is distinctly different between the lakes and seasons. Higher trophic state and phytoplankton productivity were observed mainly during the rainy period in Violão Lake compared to Amendoim Lake. This may be due to deposition of leached nutrients in the former, mainly total phosphorus (TP), which was probably derived from mafic soils and guano. This is consistent with the significant positive correlation between Chlorophyll-a and TP at the end of the rainy period (March-April), whereas this was not observed in the beginning (November). This could possibly be a consequence of the more intense cloud cover, and unusual high rainfall that limits nutrient availability.

(77)Se and (125)Te NMR spectroscopy on a selectivity study of organochalcogenanes with L-amino acids.

The hypervalent selenium- and tellurium-containing compounds (halo-organoselenuranes and halo-organotelluranes) were treated with amino acids to evaluate their reactivity and chemoselectivity by (1)H, (13)C, (77)Se and (125)Te NMR spectroscopy. The study of forced thermal stability was performed and analyzed by NMR. The organotelluranes remained stable at temperatures around 60 °C but in the case of organoselenuranes, there was formation of new products at 37 °C as a result of halogen loss. (77)Se and (125)Te NMR spectroscopy has proved to be a very efficient and fast technique to evidence the high selectivity of organochalcogenanes against l-amino acids, specific to l-cysteine.

Telescoping Synthesis of 4-Organyl-5-(organylselanyl)thiazol-2-amines Promoted by Ultrasound.

In this work, we describe the synthesis of new 4-organyl-5-(organylselanyl)thiazol-2-amine hybrids through a one-pot two-step protocol. The transition metal-free method involves the use of ultrasound as an alternative energy source and Oxone® as oxidant. To obtain the products, a telescoping approach was used, in which 4-organylthiazol-2-amines were firstly prepared under ultrasonic irradiation, followed by the addition of diorganyl diselenides and Oxone®. Thus, 16 compounds were prepared, with yields ranging from 61 % to 98 %, using 2-bromoacetophenone derivatives and diorganyl diselenides as easily available starting materials.

A greener protocol for the synthesis of phosphorochalcogenoates: Antioxidant and free radical scavenging activities.

In this contribution, a metal- and base-free protocol has been developed for the synthesis of phosphorochalcogenoates (Se and Te) by using DMSO as solvent at 50 °C. A variety of phosphorochalcogenoates were prepared from diorganyl dichalcogenides and H-phosphonates, leading to the formation of a Chal-P(O) bond, in a rapid procedure with good to excellent yields. A full structural elucidation of products was accessed by 1D and 2D NMR, IR, CGMS, and HRMS analyses, and a stability evaluation of the phosphorochalcogenoates was performed for an effective operational description of this simple and feasible method. Typical 77Se{1H} (δSe = 866.0 ppm), 125Te{1H} (δTe = 422.0 ppm) and 31P{1H} (δP = -1.0, -13.0 and -15.0 ppm) NMR chemical shifts were imperative to confirm the byproducts, in which this stability study was also important to select some products for pharmacological screening. The phosphorochalcogenoates were screened in vitro and ex vivo tests for the antioxidant potential and free radical scavenging activity, as well as to investigation toxicity in mice through of the plasma levels of markers of renal and hepatic damage. The pharmacological screening of phosphorochalcogenoates indicated that compounds have antioxidant propriety in different assays and not changes plasma levels of markers of renal and hepatic damage, with excision of 3g compound that increased plasma creatinine levels and decreased plasma urea levels when compared to control group in the blood mice. Thus, these compounds can be promising synthetic antioxidants that provide protection against oxidative diseases.

20S proteasome as novel biological target for organochalcogenanes.

A series of hypervalent selenium- and tellurium-containing compounds (organoselenuranes and organotelluranes) was evaluated aiming novel inhibitors of a threonine protease, namely the 20S proteasome (20S PT). In vitro assays demonstrated high inhibitory potency and specificity of these compounds toward the ß2 catalytic site of the 20S PT. Organotelluranes were identified as more potent inhibitors than organoselenuranes since their IC50 ranged from 3.5 to 16 µM while for organoselenuranes the IC50 ranged from 16 to 35 µM indicating great potential to be explored in 20S proteasome inhibition. Cellular assays with those compounds were employed to verify the cytotoxicity and ability to inhibit 20S proteasome in cell. These assays demonstrated that organoselenuranes are capable of maintaining their selectivity in cell while the organotelluranes became inactive under cellular conditions. Stability studies of the organochalcogenanes were performed by (77)Se and (125)Te NMR analysis. It was observed that organotelluranes are stable under enzymatic assay conditions and, organoselenuranes, the structures responsible for inhibitory activity are cyclized organoselenuranes.

Avaliaçäo de assistência médica baseada na opiniäo dos pacientes / Evaluation of medical assistance based in patient's opinion

Estuda-se a assistência médica de 3 clínicas de um Hospital Universitário segundo a opiniäo dos pacientes. Säo considerados, na opiniäo dos pacientes, a oportunidade de fazer perguntas, as explicaçöes médicas recebidas e o conhecimento acerca do diagnóstico e terapêutica que säo capazes de referir. Praticamente a totalidade dos pacientes declarou-se satisfeita com a assistência recebida embora 20 a 30% deles näo soubesse referir adequadamente seu problema de saúde ou a terapêutica que deveria seguir. Em torno de 20% dos pacientes disseram näo ter recebido explicaçöes do médico, porcentagem que variou em relaçäo inversa ao nível de instruçäo dos mesmos (entre 38% e 0%). As equipes de saúde devem ser alertadas para estes fatos