Simultaneous determination of aflatoxins B2 and G2 in peanuts using spectrofluorescence coupled with parallel factor analysis

In the present study a method for the simultaneous determination of aflatoxins B₂ and G₂ in peanuts has been developed. The method uses second order standard addition method and excitation–emission fluorescence data together with parallel factor analysis (PARAFAC). The aflatoxin analysis was based on extraction with methanol–water and carried out using immunoaffinity clean-up. The results of PARAFAC on a set of spiked and naturally contaminated peanuts indicated that the two aflatoxins could be successfully determined. The method was validated and analytical figures of merit were obtained for both analytes. The limits of detection (LOD) were 0.05 and 0.04 μg kg⁻¹ for aflatoxins B₂ and G₂, respectively. The limits of quantification (LOQ) were 0.16 and 0.12 μg kg⁻¹ for aflatoxins B₂ and G₂, respectively. Coupling of spectrofluorimetry with PARAFAC can be considered as an alternative method for quantification of aflatoxins in the presence of unknown interferences obtained through analysis of highly complex matrix of peanuts samples at a reduced cost per analysis.     

Influence of the magnetic transition on the optical properties of CrBr3

Reflectance and thermoreflectance spectra of the magnetic insulator CrBr₃ have been measured in the para- and ferromagnetic phases. Below the Curie temperature the structure at ? 7.30 eV splits into two components separated by ? 0.27 eV. This doublet is ascribed to an optical excitation involving the exchange split conduction band.     

Supramolecular self-assembled arrangements of maltose glyconanoparticles

Our group previously reported the preparation of water-soluble Au-Fe(x)O(y) nanoparticles functionalized with a maltose neoglycoconjugate. A fraction soluble in methanol was also separated and originated a new supramolecular polymeric aggregate. We report here the full characterization of this novel material by transmission electron microscopy (TEM), fluorescence emission, and atomic force microscopy. By means of noncontact dynamic atomic force microscopy, we have been able to obtain information about the organization of the organic components of the polymers, which eluded TEM analysis. We have observed that polymers packed in units about 65 nm in length and 40 nm in width on Au surfaces. The nanoparticles seem to be encapsulated by the organic material. We propose interactions between the sugar residues and the amphiphilic character of the maltose neoglycoconjugate (with a lipophilic undecane spacer) as responsible for the origin of these amazing supramolecular arrangements.     

Fluorescence of zirconium-naphthalene complexes: effect of ortho-naphthalene substitution

The effect of the position of substituents on the formation of metal-naphthalene complexes has been investigated. Two positional isomers, 1-hydroxy-2-naphthoic acid (1H2NA) and 3-hydroxy-2-naphthoic acid (3H2NA), have been chosen. A comparative study of the luminescence behaviour of the two isomers in the presence of Zr(IV) has been performed. Interesting results were obtained. While 1-hydroxy-2-naphthoic acid is quenched in the presence of Zr(IV), 3-hydroxy-2-naphthoic acid produced high-fluorescence enhancement. Several pH studies were performed between pH 2.5 and 5.0 and the stoichiometries of the complexes were also established at the different pH values tested, by use of the Benesi-Hildebrand method. In addition, the formation constants have been calculated. Finally, quenching and lifetime studies were performed in an attempt to establish the type of quenching (static or dynamic) that is produced when a complex is formed between 1-hydroxy-2-naphthoic acid and zirconium metal ion.     

Synthesis of novel enantiopure 4-hydroxypipecolic acid derivatives with a bicyclic beta-lactam structure from a common 3-azido-4-oxoazetidine-2-carbaldehyde precursor

Two different stereocontrolled accesses to new 4-hydroxypipecolic acid analogues with a bicyclic beta-lactam structure have been developed by using intramolecular reductive amination or allenic hydroamination reactions in 2-azetidinone-tethered azides. The access to the cyclization precursors was achieved from 3-azido-4-oxoazetidine-2-carbaldehyde via metal-mediated carbonyl-allenylation in aqueous environment or by organocatalytic direct aldol reaction. The tin hydride-promoted cyclization of the 2-azetidinone-tethered azidoallene is totally regioselective for the central allenic carbon providing a fused piperidine.     

Interactions between short-term and long-term cardiovascular control mechanisms

The cardiovascular system incorporates several controlling mechanisms acting as feedback loops over different time horizons. Because of their complex interrelationships, information-based methods such as autonomic information flow (AIF) functions promise to be useful in identifying normal and pathological behavior. Optimal adjustment between those controllers is necessary for healthy global behavior of the organism. We investigated the question as to whether there are typical relationships between short-term and long-term AIF by means of a meta-analysis of several of our own clinical studies of the mortality of patients with multiple organ dysfunction syndrome, heart failure, idiopathic dilated cardiomyopathy, and the length of stay in hospital after abdominal aorta surgery. We found a fundamental association of increased short-term randomness (decreased AIF) and decreased long-term randomness (increased AIF) due to pathology. A systems theoretic validation of this fundamental type of association was done by an appropriate mathematical model using a dissipative system with two feedback loops over different time horizons. The systematic simulation of an increasing collapse of the short feedback loop confirmed the inverse association between short-term and long-term information flow as a fundamental, system inherent type of readjustment that occurs under pathological conditions.     

Splitting of core-level lines in photoemission spectra of transition metal compounds

The multiplet structure of core-electron binding energies in Cr 3s, Cr 3p and Cr 2p levels of CrCl₃ and CrBr₃ compounds has been investigated by X-ray photoelectron spectroscopy. The Cr 3s levels show a doublet splitting (about 4.3?eV) for the main emission in both halides. Satellites features are observed in Cr 3s, 3p and 2p levels at higher binding energies. In the Cr 3s spectrum, the main emission is assigned to unscreened intra-atomic multiplet splittings with correlation-induced satellites. The Cr 3p and 2p spectra can be better explained by the multiplet splitting arising from the interaction between valence band 3d electrons and core p holes in the crystal field. Final state screening (charge-transfer) effects do not play a major role in Cr 3s main emission nor do they affect the satellite structures in a relevant way. This explains why the Cr 3s exchange splitting in chromium halides is proportional to the local magnetic moment.     

Antinociceptive and anti-inflammatory effects of a lectin-like substance from Clitoria fairchildiana R. Howard seeds

Lectins are proteins that have the ability to bind specifically and reversibly to carbohydrates and glycoconjugates, without altering the structure of the glycosyl ligand. They are found in organisms such as viruses, plants and humans, and they have been shown to possess important biological activities. The objective of this study was to purify and characterize lectins in the seeds of Clitoria fairchildiana, as well as to verify their biological activities. The results indicated the presence of a lectin (CFAL) in the glutelin acid protein fraction, which agglutinated native rabbit erythrocytes. CFAL was purified by column chromatography ion-exchange, DEAE-Sephacel, which was obtained from a peak of protein retained in the matrix by applying 0.5 M NaCl using the step-wise method. Electrophoretic analysis of this lectin in SDS-PAGE indicated a two band pattern protein molecular mass of approximately 100 and 116 kDa. CFAL proved to be unspecific to all carbohydrates/glycoconjugates in common use for the sugar inhibition test. This lectin showed no significant cytotoxicity to human red blood cells. It was observed that CFAL has anti-inflammatory activity in the paw edema induced by carrageenan model, in which a 64% diminution in edema was observed. Antinociceptive effects were observed for CFAL in the abdominal writhing test (induced by acetic acid), in which increasing doses of the lectin caused reduction in the number of contortions by up to 72%. It was concluded that the purified and characterized lectin from the seeds of Clitoria fairchildiana has anti-inflammatory and antinociceptive activity, and is not cytotoxic to human erythrocytes.     

New thiourea and urea derivatives containing trifluoromethyl- and bis-triflouromethyl-4H-chromen-3-yl substituents

Two new thiourea (1) and urea (2) derivatives, substituted with 2-trifluoromethyl-4H-chromen-3-yl moieties at defined positions, were obtained by convenient synthetic methodologies. The pure compounds were studied in solid state by vibrational spectroscopy (FT-IR and Raman) and in solution by NMR and UV–Vis spectroscopy. The crystal structure of the urea derivative (compound 2) was also determined by X-ray diffraction. The crystal packing is governed by N–H···O intramolecular interactions of moderate strength in a self-assembled dimer of the terminal amide fragment (C(=O)–NH₂). Hirshfeld surface and 2D-fingerprint plots were also performed to characterise the role in the packing stabilisation of all contacts, including weak C–H···F hydrogen bonds and π–π stacking interactions. For both compounds, the tentative assignment of vibrational and electronic spectra was assisted by theoretical calculations. Besides, to evaluate the influence on the pharmacokinetic and pharmacodynamic properties of molecules with –CF₃ groups, the anti-microbial activity of the title compounds was tested against the standard strains of various Gram-positive and Gram-negative organisms with noteworthy antimicrobial effect over Staphylococcus aureus, Klebsiella pneumoniae and Salmonella typhi.