Porphyrin deposition induced by UV irradiation

Simple irradiation by UV light of porphyrin TpyP and its zinc(II) and manganese(III) metal derivatives in chlorinated solvents leads to the deposition on silica of mesoscale aggregates. The process is due to the photochemical decomposition of the solvent with generation of HCl, which causes the precipitation of a protonated form. The morphology of the resulting objects is driven by the nature of the inserted metal ion.     

Determination of caffeine and its metabolites in urine by capillary electrophoresis-mass spectrometry

The caffeine content of foods and beverages varies considerably, interfering with our ability to obtain valid interpretations in many human studies with regard to the mechanism of action(s) of caffeine and/or its metabolites. The rate of metabolism of caffeine and other xanthine drugs also varies greatly from one individual to another. Therefore, it is extremely important to develop accurate, reliable analytical methods to quantify caffeine and its metabolites in simple and complex matrixes. A simple method is described for the separation and characterization of caffeine and its major metabolites employing capillary electrophoresis (CE) coupled to ultraviolet-absorption and mass spectrometry (MS) detection. After optimization of the electrophoresis separation conditions, a reliable separation of caffeine and 11 of its major metabolites was achieved in 50 mM ammonium carbonate buffer, pH 11.0. The volatile aqueous electrolyte system used with a normal electroosmotic flow polarity also provided an optimal separation condition for the characterization of the analytes by MS. The CE method achieved baseline resolution for all 12 compounds in less than 30 min. The CE-MS method is suitable for use as a routine procedure for the rapid separation and characterization of caffeine and its metabolites. The usefulness of this method was demonstrated by the extraction, separation, and identification of caffeine and its 11 metabolites from normal urine samples. The urine specimens were first acidified to obtain optimum binding efficiency to the sorbents of the off-line, solid-phase extraction procedure employed here, and an acidified eluent solvent was employed for the desorption step to maximize the recovery of the bound analytes.     

Total assignment of 1H and 13C NMR data for the sesquiterpene lactone 15-deoxygoyazensolide

We describe a complete analysis of the 1H and 13C spectra of the anti-inflamatory, schistossomicidal and trypanosomicidal sesquiterpene lactone 15-deoxygoyazensolide. This lactone, with a structure similar to other important ones, was studied by NMR techniques such as COSY, HMQC, HMBC, Jres and NOE experiments. The comparison of the data with some computational results led to an unequivocal assignment of all hydrogen and carbon chemical shifts, even eliminating some previous ambiguities. We were able to determine all hydrogen coupling constants (J) and signal multiplicities and to confirm the stereochemistry. A new method for the determination of the relative position of the lactonization and the position of the ester group on a medium-sized ring by NMR was developed.     

Synthesis and characterization of two cyclic organosiloxanes by multinuclear NMR spectroscopy and X-ray crystallography

1,3-[2′,6′-Pyridinebis(methyleneoxy)]-1,3-bis(diphenyl)cyclodisiloxane (9) and 2,6-pyridinebis(1,1-diphenylethoxy)diphenylsilane (11) were obtained from 2,6-pyridinediol derivatives with dichlorodiphenylsilane. An N→Si interaction is present in 2,6-pyridinebis(1,1-diphenylethoxy)diphenylsilane, which also shows fluxional behavior. The activation energy of 13.2 kcal mol⁻¹ for 11 was obtained for the intramolecular exchange between the phenyl groups from a variable-temperature ¹H-NMR study. The compounds were characterized by ¹H-, ¹³C- and ²⁹Si-NMR and their structures were established by X-ray crystallographic studies.     

Combination of GC-MS Molecular Networking and Larvicidal Effect against Aedes aegypti for the Discovery of Bioactive Substances in Commercial Essential Oils

Dengue is a neglected disease, present mainly in tropical countries, with more than 5.2 million cases reported in 2019. Vector control remains the most effective protective measure against dengue and other arboviruses. Synthetic insecticides based on organophosphates, pyrethroids, carbamates, neonicotinoids and oxadiazines are unattractive due to their high degree of toxicity to humans, animals and the environment. Conversely, natural-product-based larvicides/insecticides, such as essential oils, present high efficiency, low environmental toxicity and can be easily scaled up for industrial processes. However, essential oils are highly complex and require modern analytical and computational approaches to streamline the identification of bioactive substances. This study combined the GC-MS spectral similarity network approach with larvicidal assays as a new strategy for the discovery of potential bioactive substances in complex biological samples, enabling the systematic and simultaneous annotation of substances in 20 essential oils through LC₅₀ larvicidal assays. This strategy allowed rapid intuitive discovery of distribution patterns between families and metabolic classes in clusters, and the prediction of larvicidal properties of acyclic monoterpene derivatives, including citral, neral, citronellal and citronellol, and their acetate forms (LC₅₀ < 50 µg/mL).     

Self-consistent theory of diagonal and off-diagonal disorder in the screened impurity band of doped semiconductors

We have developed a theory of the impurity band in doped semi-conductors, using a tight-binding basis and a self-consistent treatment to handle the configurational averages. New ingredients in the present calculation are: (1) overlap between different impurity orbitals; (2) simultaneous treatment of diagonal and off-diagonal disorder; (3) inclusion of electron—elctron interactions through the substitution of the bare Coulomb impurity potential by a Yukawa potential. The density of states and the position of the Fermi level (for T=0) are calculated for different impurity concentrations.     

Incorporation of Ce3+ in crystalline Gd-silicate nanoclusters formed in silica

Structural and optical properties of sol–gel silica based glassceramics doped with 0.1 mol% Ce and codoped with Gd at high concentrations, from 5 mol% up to 40 mol%, are investigated and compared to those of analogous samples doped only with Ce. Raman scattering, transmission electron microscopy, and x-ray diffraction reveal the formation of Gd apatite-like silicate (Gd_4.67O(SiO₄)₃) and of Gd pyrosilicate (Gd₂Si₂O₇) nanophases whose morphology and crystallinity depend on the Gd concentration and thermal treatments. Optical absorption measurements demonstrate the role of the densification atmosphere in modifying the charge state of Ce ions. The incorporation of Ce³⁺ ions in the nanophases is put in evidence by photo- and radio-luminescence results.