Tetrachlorocarbonyliridates: water-soluble carbon monoxide releasing molecules rate-modulated by the sixth ligand

A new family of compounds is presented as potential carbon monoxide releasing molecules (CORMs). These compounds, based on tetrachlorocarbonyliridate(III) derivatives, were synthesized and fully characterized by X-ray diffraction, electrospray mass spectrometry, IR, NMR, and density functional theory calculations. The rate of CO release was studied via the myoglobin assay. The results showed that the rate depends on the nature of the sixth ligand, trans to CO, and that a significant modulation on the release rate can be produced by changing the ligand. The reported compounds are soluble in aqueous media, and the rates of CO release are comparable with those for known CORMs, releasing CO at a rate of 0.03-0.58 μM min(-1) in a 10 μM solution of myoglobin and 10 μM of the complexes.     

Photophysical study of naphthalenophanes: evidence of adduct formation with molecular oxygen

The photophysical properties of two atropisomeric naphthalenophanes (1 and 2) have been studied. Their structure only differs in the relative arrangement, syn (1) or anti (2), of the two aromatic units. The compounds emission is mainly excimeric and is strongly quenched in the presence of oxygen. Comparison of emission intensities obtained from steady state and from decay times provides clear evidence of the formation of ground state charge transfer complexes between oxygen and the naphthalenophanes 1 and 2. The calculated values for the association constants are on the order of 10(3) M(-1) (ethanol, room temperature) for both naphthalenophanes.     

Characterization of the singlet and triplet excited states of 3-chloro-4-methylumbelliferone

An extensive photophysical characterization of 3-chloro-4-methylumbelliferone (3Cl4MU) in the ground-state, S(0), first excited singlet state, S(1), and lowest triplet state, T(1), was undertaken in water, neutral ethanol, acidified ethanol, and basified ethanol. Quantitative measurements of quantum yields (fluorescence, phosphorescence, intersystem crossing, internal conversion, and singlet oxygen formation) together with lifetimes were obtained at room and low temperature in water, dioxane/water mixtures, and alcohols. The different transient species were assigned and a general kinetic scheme is presented, summarizing the excited-state multiequilibria of 3Cl4MU. In water, the equilibrium is restricted to neutral (N*) and anionic (A*) species, both in the ground (pK(a) = 7.2) and first excited singlet states (pK(a)* = 0.5). In dioxane/water mixtures (pH ca. 6), substantial changes of the kinetics of the S(1) state were observed with the appearance of an additional tautomeric T* species. In low water content mixtures (mixture 9:1 v:v), only the neutral (N*) and tautomeric (T*) forms of 3Cl4MU are observed, whereas at higher water content mixtures (water mole fraction superior to 0.45), all three species N*, T*, and A* coexist in the excited state. In the triplet state, in the nonprotic and nonpolar solvent dioxane, the observed transient signals were assigned as the triplet-triplet transition of the neutral form, N*(T(1)) → N*(T(n)). In water, two transient species were observed and are assigned as the triplets of the neutral N*(T(1)) and the anionic form, A*(T(1)) (also obtained in basified ethanol). The phosphorescence spectra and decays of 3Cl4MU, in neutral, acidified, and basified solutions, demonstrate that only these two species N*(T(1)) and A*(T(1)) exist in the lowest lying triplet state, T(1). The radiative channel was found dominant for the deactivation of the anionic species, whereas with the neutral the S(1) ? S(0) internal conversion competes with fluorescence. For both N* and A* the intersystem crossing yield represents a minor deactivation channel for S(1).     

Yeast cell wall particles: a promising class of nature-inspired microcarriers for multimodal imaging

This communication demonstrates that yeast cell wall particles (YCWPs) are a promising class of nature-inspired biocompatible microcarriers for the delivery of amphipathic/lipophilic imaging reporters. When a paramagnetic MRI agent is loaded, the longitudinal relaxivity per particle at 0.5 T is the highest ever reported for Gd-based systems.     

A simple and green analytical method for determination of glyphosate in commercial formulations and water by diffuse reflectance spectroscopy

This article describes a simple, inexpensive, and environmentally friendly method for the monitoring of glyphosate using diffuse reflectance spectroscopy. The proposed method is based on reflectance measurements of the colored compound produced from the spot test reaction between glyphosate and p-dimethylaminocinnamaldehyde (p-DAC) in acid medium, using a filter paper as solid support. Experimental designs were used to optimize the analytical conditions. All reflectance measurements were carried out at 495 nm. Under optimal conditions, the glyphosate calibration graphs obtained by plotting the optical density of the reflectance signal (AR) against the concentration were linear in the range 50-500 μg mL(-1), with a correlation coefficient of 0.9987. The limit of detection (LOD) for glyphosate was 7.28 μg mL(-1). The technique was successfully applied to the direct determination of glyphosate in commercial formulations, as well as in water samples (river water, pure water and mineral drinking water) after a previous clean-up or pre-concentration step. Recoveries were in the ranges 93.2-102.6% and 91.3-102.9% for the commercial formulations and water samples, respectively.     

Thermal behavior of residues (sludge) originating from the sugarcane industry

The Brazilian sugarcane industry shows a great amount of generated sludge which should be utilized adequately. Two sludge samples, aerobic and anaerobic, were collected. Both were evaluated by thermogravimetry and differential thermal analysis (DTA) as well as X-ray power diffraction. These compounds show variations of mass between 30 and 140 °C due to the dehydration stage. The DTA curves show that the compounds have an exothermic reaction between 450 and 550 °C, which indicates that this can be used as an energy source. Details concerning the kinetic parameters of the dehydration and thermal decomposition have also been described here. The kinetic study of these stages was evaluated in open crucibles under nitrogen atmosphere. The obtained data were evaluated with the isoconversional kinetic method. The results show that different activation energies were obtained for thermal decomposition.     

Thermal analysis characterization of PAAm-<Emphasis Type="Italic">co</Emphasis>-MC hydrogels

This paper reports the thermal characterization of polyacrylamide-co-methylcellulose hydrogels and the constituent monomers (acrylamide and methylcellulose). Polymeric materials can be used to produce hydrogels, which can be natural, synthetic, or a mixture. The hydrogels described here were obtained by free radical polymerization, in the presence of N,N′-methylene-bis-acrylamide as a cross-linker agent. Four acrylamide concentrations were used for the synthesis of hydrogels: 3.6, 7.2, 14.7, and 21.7% (w/v). The materials so obtained were analyzed by TG, DTG, DSC, and FT-IR. The TG curves of acrylamide and methylcellulose showed three mass loss events. In DSC curves, the acrylamide exhibited one melting peak at 84.5 °C, and methylcellulose indicated one exothermic event. Nevertheless, acrylamide was considered more stable than methylcellulose. The TG curves of the hydrogels exhibited three mass loss events, and on the DSC curves, three endothermic events were observed. It was verified that the different acrylamide proportions influenced the thermic behavior of hydrogels, and that the authors considered the 7.2% hydrogel a promising drug carrier system. The absorption bands were well defined, confirming the presence of the functional groups in the samples.     

Trypanocidal activity of oxoaporphine and pyrimidine-β-carboline alkaloids from the branches of Annona foetida Mart. (Annonaceae)

Phytochemical investigation of the branches of Annona foetida Mart. led to isolation from the CH(2)Cl(2) extract of four alkaloids: Atherospermidine (1), described for the first time in this species, liriodenine (2), O-methylmoschatoline (3), and annomontine (4). Their chemical structures were established on the basis of spectroscopic data from IR, MS, NMR (1D and 2D), and comparison with the literature. Compounds 2-4 showed potent trypanocidal effect when evaluated against epimastigote and trypomastigote forms of Trypanosoma cruzi.     

Drug resistance modulation in Staphylococcus aureus, a new biological activity for mesoionic hydrochloride compounds

Two salts of the mesoionic compounds 1,4-diphenyl-5-(5-nitro-2-furanyl)-1,3,4-thiadiazolium-2-thiol chloride (MC-1) and 4-phenyl-5-(5-nitro-2-furanyl)-1,3,4-thiadiazolium-2-phenylamine chloride (MC-2) were synthesized utilizing 1,4-diphenyl-thiosemicarbazide and 5-nitro-2-furoyl chloride as starting materials. Their structures were characterized by IR, 1H-NMR, 13C-NMR and elemental analysis. These compounds were analyzed for their influence on the effectiveness of norfloxacin, tetracycline, and erythromycin (standard antibiotics) against resistant strains of Staphylococcus aureus. MC-1 and MC-2, at sub-inhibitory concentrations of 16 μg/mL, favourably modulated the antibiotic activity of tetracycline by 16- and 32-fold, respectively (MIC), and that of erythromycin by 4-fold.     

Biomolecule profiles in inedible wild mushrooms with antioxidant value

The use of natural products isolated from mushrooms, included inedible species, against infection, cancer diseases and other oxidative-stress related diseases is one of the cornerstones of modern medicine. In the present work, the antioxidant molecule profiles of inedible mushroom species were evaluated and compared with those of edible species. The order of antioxidant abundance found in inedible wild mushrooms was: phenolics > flavonoids > ascorbic acid > tocopherols > carotenoids, similar to that of edible species. Furthermore the same energetic biomolecules were found including the disaccharide trehalose, the monosaccharide alcohol derivative mannitol and the fatty acids palmitic, oleic and linoleic acids. Fomitopsis pinicola revealed a very high phenolics concentration (388 mg GAE/g extract) and powerful antioxidant properties, mainly reducing power (EC??) value 60 μg/mL similar to the standard Trolox?). It could find applications in the prevention of free radical-related diseases as a source of bioactive compounds.