Measurement of long-range 1H-19F scalar coupling constants and their glycosidic torsion dependence in 5-fluoropyrimidine-substituted RNA

Long-range scalar 5J(H1',F) couplings were observed in 5-fluoropyrimidine-substituted RNA. We developed a novel S3E-19F-alpha,beta-edited NOESY experiment for quantitation of these long-range scalar 5J(H1',F) couplings, where the J-couplings can be extracted from inspection of intraresidual (H1',H6) NOE cross-peaks. Quantum chemical calculations were exploited to investigate the relation between scalar couplings and conformations around the glycosidic bond in oligonucleotides. The theoretical dependence of the observed 5J(H1',F) couplings on the torsion angle chi can be described by a generalized Karplus relationship. The corresponding density functional theory (DFT) analysis is outlined. Additional NMR experiments facilitating the resonance assignments of 5-fluoropyrimidine-substituted RNAs are described, and chemical shift changes due to altered shielding in the presence of fluorine-19 (19F) are presented.     

Chiral seleno-amines from indium selenolates. A straightforward synthesis of selenocysteine derivatives

A simple and efficient procedure for the synthesis of chiral beta-seleno-amines derivatives from a one-pot indium(I) iodide-mediated aziridine ring opening with diorganoyl diselenides has been developed. As an application, the synthesis of selenocysteine and selenotreonine derivatives has been accomplished.     

Automated software-guided identification of new buspirone metabolites using capillary LC coupled to ion trap and TOF mass spectrometry

The identification and structure elucidation of drug metabolites is one of the main objectives in in vitro ADME studies. Typical modern methodologies involve incubation of the drug with subcellular fractions to simulate metabolism followed by LC-MS/MS or LC-MS(n) analysis and chemometric approaches for the extraction of the metabolites. The objective of this work was the software-guided identification and structure elucidation of major and minor buspirone metabolites using capillary LC as a separation technique and ion trap MS(n) as well as electrospray ionization orthogonal acceleration time-of-flight (ESI oaTOF) mass spectrometry as detection techniques.Buspirone mainly underwent hydroxylation, dihydroxylation and N-oxidation in S9 fractions in the presence of phase I co-factors and the corresponding glucuronides were detected in the presence of phase II co-factors. The use of automated ion trap MS/MS data-dependent acquisition combined with a chemometric tool allowed the detection of five small chromatographic peaks of unexpected metabolites that co-eluted with the larger chromatographic peaks of expected metabolites. Using automatic assignment of ion trap MS/MS fragments as well as accurate mass measurements from an ESI oaTOF mass spectrometer, possible structures were postulated for these metabolites that were previously not reported in the literature.     

Thermal decomposition study of sewage sludge and of organicwaste used in the sorption of metals

The conventional treatments of effluents containing heavy metals produce significant quantities of byproducts with recalcitrant characteristics, making necessary looking after alternative techniques in order to avoid the production of new contaminated residues. Sorption process of chromium and zinc in vertical columns loaded with sewage sludge and organic solid waste has been studied in this work. The data from the TG curves of the two sorbents presented significant differences when they were submitted to the metal uptake, being noticed the displacement of the thermal events towards lower temperatures for both types of sorbents studied. As it was expected, for both sorbents, an increase in the mass of samples has been observed at the completion of the thermal tests upon metal uptake. Therefore, these facts demonstrate that during the biosorption process a physico-chemical interaction took place between sorbents and metals, as it was evidenced by the more than 100 K increase in the decomposition temperatures as well as the variation of the ΔH values of the samples.     

Hazard in reaction of titanium raw materials with sulphuric acid

The reaction of ilmenite titanium raw material with sulphuric acid was investigated in ‘hazard’ type calorimetric system. The investigations show the essential influence of initial temperature, particle size distribution and concentration of sulphuric acid on rate and heat power of reaction and determine the limits of safety of the process and also its efficiency.     

Composition dependence of the structural chemistry and magnetism of Ca2.5Sr0.5(Ga,Co)1+xMn2−xO8

Polycrystalline samples of bilayered brownmillerite-like Ca_2.5Sr_0.5GaCo_0.15Mn_1.85O₈ and Ca_2.5Sr_0.5Ga_1.2Mn_1.8O₈ have been prepared and characterised by magnetometry and neutron diffraction over a wide temperature range. The structural chemistry and magnetic properties are compared to those of Ca_2.5Sr_0.5GaMn₂O₈. Ga enrichment has a significant effect on the former but not on the latter, whereas changes in both occur when paramagnetic Co³⁺ cations enter the parent phase on the 4-coordinate sites. The coupling between the environment around the 4-coordinate cations and the transition to an antiferromagnetic ordered state that was observed in Ca_2.5Sr_0.5GaMn₂O₈ is not apparent in the cation-substituted compositions, although both show long-range antiferromagnetic order at low temperatures.     

Indium(I) bromide-mediated coupling of dibromoacetonitrile with aldehydes followed by Boord elimination of bromine and oxygen of β-bromo alkoxides for preparation of 3-organyl-2-alkenenitriles

The organoindium compound derived from indium monobromide and dibromoacetonitrile reacts with carbonyl compounds to afford the corresponding 2-bromo-2-cyano-indium(III) alkoxide. The action of a second equivalent of indium monobromide onto the alkoxides derived from aldehydes promotes the Boord elimination of the β-related oxygen and bromine atoms leading to 2-alkenenitriles.     

Synthesis of 2,4,6-tri-substituted-1,3,5-triazines

Several specific synthetic protocols were developed for the preparation from cyanuric chloride of a range of symmetric and non-symmetric di- and tri-substituted 1,3,5-triazines containing alkyl, aromatic, hindered, chiral and achiral hydroxyalkyl, ester and imidazole groups via sequential nucleophilic substitution of the C-Cl bond by C-O, C-N and C-S bonds.     

Kinetic study of template removal of Al-MCM-41 synthesized at room temperature

The Al-MCM-41 molecular sieve with Si/Al = 20 molar ratio was synthesized at room temperature and characterized by X-ray diffractometry, surface area, thermogravimetry, and infrared spectroscopy. The kinetic study was conducted by Vyazovkin and Ozawa method, in order to verify the activation energy during the Hofmann degradation between 130 and 370 °C, in which most of surfactant removal occurs. The results suggest that the activation energy for template removal is close to 80 kJ mol^?1 lower in Al-MCM-41 synthesized at room temperature, when compared to results obtained for mesopores Al-MCM-41 and MCM-41 synthesized by hydrothermal method. This lower activation energy may be understood as consequence of textural properties, such as higher pore size.     

Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification

A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH₂ groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m² g^?1. The material also possesses good CO₂ (8 wt %) and H₂ (1.87 wt %) adsorption capabilities.