Antinociceptive profile of 2,3,6-trisubstituted piperidine alkaloids: 3-O-acetyl-spectaline and semi-synthetic derivatives of (-)-spectaline

In early studies, we have reported the antinociceptive profile of (-)-spectaline, a piperidine alkaloid from Cassia spectabilis. The present study describes the synthesis, the antinociceptive and anti-inflammatory activities of a series of 2,3,6-trialkyl-piperidine alkaloids: the natural (-)-3-O-acetyl-spectaline (LASSBio-755) and ten semi-synthetic spectaline derivatives. Structure-activity relationship (SARs) studies were performed. The structures of all synthesized derivatives were confirmed by means of nuclear magnetic resonance. Compounds were evaluated for their analgesic (acetic acid-induced mouse abdominal constrictions, hot-plate test, formalin-induced pain test) and some of them for the anti-inflammatory activities (carrageenan-induced rat paw edema test). The pharmacological results showed that several of the new compounds given orally at a dose of 100 micromol/kg significantly inhibited the acetic acid-induced abdominal constrictions, but they were less active than (-)-spectaline. LASSBio-755 and LASSBio-776 were the most actives with 37% and 31.7% of inhibition. In the formalin-induced pain only LASSBio-776 was able to inhibit by 34.4% the paw licking response of the inflammatory phase, (-)-spectaline and LASSBio-755 did show any activity. In the carrageenan-induced rat paw edema, only (-)-spectaline exhibited an anti-inflammatory profile, showing an ED(50) value of 56.6 micromol/kg. Our results suggest different mechanisms of action for the analgesic activity observed for LASSBio-776 (3-O-Boc-spectaline), LASSBio-755 (3-O-acetyl-spectaline) and (-)-spectaline (LASSBio-754). The antinociceptive profile of some of the semi-synthetic spectaline derivatives extends our research concerning the chemical and pharmacological optimization of isolated natural products in the search of new drug candidates from Brazilian biodiversity.     

Micellar Effects on the Reaction between an Arenediazonium Ion and the Antioxidants Gallic Acid and Octyl Gallate

The effect of sodium dodecyl sulfate (SDS) micelles on the reaction between the 3‐methylbenzenediazonium (3MBD) ion and either the hydrophilic antioxidant gallic acid (GA) or the hydrophobic analogue octyl gallate (OG) have been investigated as a function of pH. Titration of GA in the absence and presence of SDS micelles showed that the micelles do not alter the first ionization equilibrium of GA. Analysis of the dependence of the observed rate constant (k_obs) with pH shows that the reactive species are GA^2? and OG^?. Kinetics results in the absence and presence of SDS micelles suggest that SDS aggregates do not alter the expected reaction pathway. SDS Micelles inhibit the spontaneous decomposition of 3MBD as well as the reaction between 3MBD and either GA or OG, and upon increasing the SDS concentration, with k_obs approaching the value for the thermal decomposition of 3MBD in the presence of SDS. Our results are consistent with the prediction of the pseudophase model and show that the origin of the inhibition for the reaction with GA is different to that for the reaction with OG; in the former case, the observed inhibition can be rationalized in terms of the micelle‐induced electrostatic separation of reactants in the micellar Stern layer, whereas the observed inhibition in the reaction with OG is a consequence of the dilution effect caused by increasing SDS concentration, decreasing the local OG^? concentration in the Stern layer.     

Remote state preparation: arbitrary remote control of photon polarization

We experimentally demonstrate the first remote state preparation of arbitrary single-qubit states, encoded in the polarization of photons generated by spontaneous parametric down-conversion. Utilizing degenerate and nondegenerate wavelength entangled sources, we remotely prepare arbitrary states at two wavelengths. Further, we derive theoretical bounds on the states that may be remotely prepared for given two-qubit resources.     

Inspection of a magneto-optical trap via electromagnetically induced absorption

Electromagnetically induced absorption (EIA) was observed for the first time on a sample of ⁸⁵Rb in a magneto-optical trap using low intensity cw copropagating pump and probe optical fields. Narrow resonances revealing the dependence of the ground-state Zeeman sublevels energy structure on the quadrupolar magnetic field and the trapping optical field intensity at different trap positions, were observed. Coherence resonances as narrow as 30 kHz were obtained under low trapping field intensities. The use of EIA spectroscopy for the magnetic field mapping of cold atomic samples is illustrated.     

A column-switching method for quantification of the enantiomers of omeprazole in native matrices of waste and estuarine water samples

This work reports the use of a two-dimensional liquid chromatography (2D-LC) system for quantification of the enantiomers of omeprazole in distinct native aqueous matrices. An octyl restricted-access media bovine serum albumin column (RAM-BSA C₈) was used in the first dimension, while a polysaccharide-based chiral column was used in the second dimension with either ultraviolet (UV-vis) or ion-trap tandem mass spectrometry (IT-MS/MS) detection. An in-line configuration was employed to assess the exclusion capacity of the RAM-BSA columns to humic substances. The excluded macromolecules had a molecular mass in the order of 18 kDa. Good selectivity, extraction efficiency, accuracy, and precision were achieved employing a very small amount (500 μL or 1.00 mL) of native water sample per injection, with detection limits of 5.00 μg L⁻¹, using UV-vis, and 0.0250 μg L⁻¹, using IT-MS/MS. The total analysis time was only 35 min, with no time spent on sample preparation. The methods were successfully applied to analyze a series of waste and estuarine water samples. The enantiomers were detected in an estuarine water sample collected from the Douro River estuary (Portugal) and in an influent sample from the wastewater treatment plant (WWTP) of São Carlos (Brazil). As far as we are concerned, this is the first report of the occurrence of (+)-omeprazole and (−)-omeprazole in native aqueous matrices.     

Synthesis and antimicrobial activities of silver(I) sulfanylcarboxylates. Structural isomers with identically or unequally coordinated Ag centers in an Ag4S4 ring

We have investigated the reactions of silver nitrate and 3-(aryl)-2-sulfanylpropenoic acids [H(2)xspa, x: p = 3-phenyl-, f = 3-(2-furyl)-, t = 3-(2-thienyl)-, py = 3-(2-pyridyl)-] and 2-cyclopentylidene-2-sulfanylacetic acid (H(2)L) in 1 : 1 and 2 : 1 molar ratios. The 1 : 1 molar ratio gave compounds of type [Ag(HL)]; reaction of these compounds with diisopropylamine and NaOH gave [HQ][Ag(L)] (HQ = diisopropylammonium) and Na[Ag(L)] x H(2)O, respectively. These compounds, as well as those of type [Ag(2)(L)] obtained with the 1 : 2 molar ratio, were isolated and characterized by IR and NMR ((1)H and (13)C) spectroscopy. (109)Ag NMR spectroscopy and ESI-MS spectrometry were also used in some cases. The crystal structures of [HQ][Ag(pspa)] (11), in which the presence of structural isomers was detected, and [HQ][Ag(cpa)] (15) were determined by X-ray diffractometry. The antimicrobial activity of the complexes against E. coli, S. aureus, B. subtilis, P. aeruginosa/Resistant P. aeruginosa, and C. albicans was tested.     

Detection of freeze injury in oranges by magnetic resonance imaging of moving samples

Magnetic resonance imaging (MRI) is applied for on-line inspection of fruits. The aim of this work is to address the applicability of MRI for freeze injury detection in oranges directly on a distribution chain. Undamaged and damaged oranges are conveyed at 50 and 100 mm/s by a specially designed conveyor within a 4.7 T spectrometer obtaining fast low-angle shot images. An automatic segmentation algorithm is proposed that allows the discrimination between undamaged and damaged oranges.     

Inferring interdependencies in climate networks constructed at inter-annual, intra-season and longer time scales

We study global climate networks constructed by means of ordinal time series analysis. Climate interdependencies among the nodes are quantified by the mutual information, computed from time series of monthly-averaged surface air temperature anomalies, and from their symbolic ordinal representation (OP). This analysis allows identifying topological changes in the network when varying the time-interval of the ordinal pattern. We consider intra-season time-intervals (e.g., the patterns are formed by anomalies in consecutive months) and inter-annual time-intervals (e.g., the patterns are formed by anomalies in consecutive years). We discuss how the network density and topology change with these time scales, and provide evidence of correlations between geographically distant regions that occur at specific time scales. In particular, we find that an increase in the ordinal pattern spacing (i.e., an increase in the timescale of the ordinal analysis), results in climate networks with increased connectivity on the equatorial Pacific area. On the contrary, the number of significant links decreases when the ordinal analysis is done with a shorter timescale (by comparing consecutive months), and interpret this effect as due to more stochasticity in the time-series in the short timescale. As the equatorial Pacific is known to be dominated by El Niño-Southern Oscillation (ENSO) on scales longer than several months, our methodology allows constructing climate networks where the effect of ENSO goes from mild (monthly OP) to intense (yearly OP), independently of the length of the ordinal pattern and of the thresholding method employed.