Chemical properties of pyrimidoquinoxaline 6‐oxides

The reactivity of some representative 5‐arylpyrimidoquinoxaline 6‐oxides 1 was investigated. Reduction with sodium borohydride afforded the corresponding N‐deoxy compounds 2. Reaction with methyl iodide in excess led selectively to N‐methyl derivatives 3 . The preference for N vs. O‐alkylation is analyzed considering electronic effects. Alkaline hydrolysis of compounds 1 involved initial nucleophilic attack to the amidine carbon (C4a), and subsequent regioselective ring opening leading to 4‐(3‐aminopropyl)‐2‐aryl‐quinoxaline‐3‐one 1‐oxides 4. The regioselectivity observed in alkaline hydrolysis is also discussed.     

Extraction and analysis of ochratoxin A in bread using pressurised liquid extraction and liquid chromatography

A pressurised liquid extraction (PLE) method for the analysis of ochratoxin A (OTA) in bread samples is given. Parameters such as solvent, temperature, pressure and time were investigated thoroughly. The optimized PLE conditions were: methanol as extraction solvent, 80 degrees C, 2000 psi and a 5-min cycle. OTA was determined by liquid chromatography coupled with fluorescence detection and confirmed by methyl ester derivatization. Under these conditions OTA recovery is 92.3% with a RSD of 5%. Limits of detection and quantification were 0.02 and 0.06 microg/kg, respectively. The proposed method was applied to 20 bread samples, finding two positive samples with OTA levels below the maximum permitted levels by the European Union.     

Permeability of a seemingly nonporous crystal formed by a discrete metallocyclic complex

We describe the structure and permeability of a crystalline material that appears to be nonporous in a conventional sense. The material is initially formed as a solvate, and removal of the solvent molecules under relatively mild conditions proceeds via a single-crystal to single-crystal transformation, leaving the host structure intact. Although discrete unoccupied voids of 108 A3 are present in the structure, it is not possible to map open channels that represent an intuitive pathway for guest diffusion. Despite the apparent absence of pores, the material is permeable to a variety of gases including H2, O2, N2, CO, CH4, CO2, and I2. These findings show that porosity in crystalline systems cannot always be rationalized by considering the static structures and that as-yet unknown dynamic and cooperative mechanisms prevail by which porosity can be induced.     

Infrared spectroscopy and multivariate calibration to monitor stability quality parameters of biodiesel

This paper evaluates analytical methods based on near infrared (NIR) and middle infrared (MIR) spectroscopy and multivariate calibration to monitor the stability of biodiesel. There was a focus on three parameters: oxidative stability index, acid number and water content. Ethylic and methylic biodiesel from different feedstocks were used in experiments of accelerated aging, in order to take into account the wide variety of oilseeds and feedstocks available in Brazil. Partial least squares (PLS) and multiple linear regression (MLR) models were developed. Different pre-processing techniques and spectral variable/regions selection algorithms were evaluated. For MLR models, the successive projection algorithm (SPA) was employed. Interval PLS (iPLS) and selection of variables taking into account the significant regression coefficients were used for PLS models. Results showed that both near and middle infrared regions, and all variable selection methods tested were efficient for predicting these three important quality parameters of B100, the root mean squares error of prediction (RMSEP) values being comparable to the reproducibility of the corresponding standard method for each property investigated.     

Diterpenes from teucrium capitatum L. X-ray crystal and molecular structure of capitatin

Two diterpenes, capitatin 4 and teucapitatin 5 have been isolated from Teucrium capitatum. The X-ray structure of 4, including absolute stereochemistry, is given. Diterpene 4 has been chemically related to picropolin 1 and picropolinone 2, thereby establishing the absolute stereochemistry of these two neoclerodane-type diterpenes.     

Analysis of protein phosphorylation by mass spectrometry

Phosphorylation is one of the most frequently occurring post-translational modifications in proteins. In eukaryotic cells, protein phosphorylation on serine, threonine and tyrosine residues plays a crucial role as a modulator of protein function. A comprehensive analysis of protein phosphorylation involves the identification of the phosphoproteins, the exact localization of the residues that are phosphorylated and the quantitation of phosphorylation. In this short review we will summarize and discuss the methodologies currently available for the analysis and full characterization of phosphoproteins with special attention at mass spectrometry-based techniques. In particular, we will discuss affinity-based purification of phosphopeptides coupled to MALDI-TOF analysis, their detection using mass mapping and precursor ion scan, identification of modified sites by MS/MS and quantitation analysis     

Calorimetric determination of activated carbons in aqueous solutions

The interactions among five samples of activated carbons, obtained from different lignocellulosic materials with different degrees of activation of approximately 20% and aqueous solutions of phenol and 4-nitro phenol are studied by means of the determination of immersion enthalpies. It is established that the obtained activated carbons are of a basic character and show values for the pH at the point of zero charge, pH_PZC, that range from 7.4 to 9.7 and, in all cases, higher total basicity contents than the values obtained for total acidity. The immersion heat of the activated carbons in CCl₄ and water is determined obtaining values which are higher for CCl₄ immersion and vary from 31.4 to 48.6 J g⁻¹. The hydrophobic factor, hf, it is calculated from the relation between of the immersion heat of the activated carbons in CCl₄ and the immersion heat in water, the obtained values were 2.98 and 6.75, which are greater than 1 due to the greater values obtained in CCl₄ when compared to the values obtained in water. Immersion enthalpies in phenol solution range from 7.6 to 13.9 J g⁻¹ and for the case of 4-nitro phenol such enthalpies range from 12.7 to 20.5 J g⁻¹; all the 5 samples studied showed a higher value for the heat of immersion in aqueous solutions of 4-nitro phenol.     

Simultaneous Determination of Vitamins D3 (Calcitriol,Cholecalciferol) and K2 (Menaquinone-4 and Menaquinone-7) in Dietary Supplements by UHPLC

The content and composition of dietary supplements is of great interest due to their increasing consumption and variety of available brand offered in the market. Accurate determination of vitamins is important for the improvement of dietary supplement quality and nutrition assessments. In this regard, the simultaneous determination of vitamin D3 (calcitriol—CT and cholecalciferol—CHL) and K2 (menaquinone-4—MK-4 and menaquinone-7—MK-7) in dietary supplements was developed by using ultra-high-pressure liquid chromatography (UHPLC). The overall runtime per sample was above 35 min, with the retention times of 2.40, 6.59, 7.06, and 32.6 min for vitamin D3 (CT and CHL) and vitamin K2 (MK-4 and MK-7), respectively. The limits of detection and limits of quantification for the target nutritional compounds ranged between 0.04–0.05 µg/mL, respectively. The validation results indicated that the method had reasonable linearity (R² ≥ 0.9990), good recovery (>82%), satisfactory intra-day precision (≤1.9%) and inter-day precision (≤3.5%), and high selectivity and specificity. The validated UHPLC method was demonstrated to be precise, accurate, and robust for the simultaneous determination of vitamins D3 (CT and CHL) and K2 (MK-4 and MK-7) in dietary supplements.