Reactions of benzotriazoles with diethyl ethoxymethylenemalonate; ethylation and michael addition. Comparison with other esters and N-heterocycles

Benzotriazole and its 5-methyl-and 5-nitro derivatives react with diethyl ethoxymethylenemalonate by ethylation at each of the ring N-atoms and through Michael addition, to give the isomeric esters ethyl (E/Z) 3-[5(6)-R-benzotriazol-1-yl]propenoates. Benzotriazole and its 5-nitro derivative react similarly with ethyl acetoacetate but N-ethyl derivatives are obtained in lower yields. Other 1,2,3-triazoles derivatives and indole were ineffective in this reaction while benzimidazole produced similar results but accompanied with a small amount of a benzimidazoline addition product, whose structure has been determined by crystallo-graphic analysis.     

Colour fading in textiles: A model study on the decomposition of natural dyes

This paper describes an analytical procedure based on GC-MS to identify in textiles the most common flavonoid yellow dyes used in Europe since ancient times, extracted from weld, young fustic, dyer's broom, sawwort and the berries of some species of Rhamnus. Later on, old fustic and quercitron bark were introduced as sources of yellow colours.The method is based on the solvent extraction of flavonoids from raw plant materials (weld, dyer's broom and old fustic), aged and not aged alum-mordanted wool dyed specimens; subsequently, flavonoids are derivatised with N,O-bis(trimethylsilyl)trifluoroacetamide and analysed by GC-MS. The method easily allows the identification of a dyestuff by the detection of the molecular markers apigenin, luteolin, genistein, morin, maclurin, together with 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4,6- trihydroxybenzoic acid, which survive in aged textiles. Two photo-oxidative degradation pathways for colour fading, one involving the mordant metallic ion and the other the light as a catalyst, are suggested.     

A dilute-and-inject low-pressure gas chromatography-tandem mass spectrometry method for phthalate determination in extra virgin olive oil

The goal of this study was to develop a method for the determination of nine phthalic acid esters in extra virgin olive oils using low-pressure gas chromatography-triple-quadrupole mass spectrometry. Sample preparation was simple, environmental friendly, and rapid inasmuch that it involved only dilution (< 1 mL of hexane). The low-pressure gas chromatography analyses were performed by using a 5 m wide-bore column. The limit of quantification for the phthalates ranged from 0.06 to 1.14 mg kg⁻¹. Both intra- and interday precisions were measured, with coefficient of variation values ranging from 0.2% to 11.7%. The trueness of the method was measured by evaluating accuracy at the initial stage of the work and after 2 months, with values ranging between −8.7% and 12.1%. Moreover, blind accuracy was comprised between −11.6% and 14.2%. The method involves the use of simplified instrumentation and reduced analysis times (nearly two times faster) compared to a previously published comprehensive two-dimensional gas chromatography-triple-quadrupole mass spectrometry method, leading to a reduction of energy and helium consumption. The approaches were compared in analytical terms and for the environmental impact. In total, 23 olive oil samples were analyzed, with at least one phthalate detected in all but one sample.     

Calcium Phosphate Particles Coated with Humic Substances: A Potential Plant Biostimulant from Circular Economy

Nowadays, the use of biostimulants to reduce agrochemical input is a major trend in agriculture. In this work, we report on calcium phosphate particles (CaP) recovered from the circular economy, combined with natural humic substances (HSs), to produce a plant biostimulant. CaPs were obtained by the thermal treatment of Salmo salar bones and were subsequently functionalized with HSs by soaking in a HS water solution. The obtained materials were characterized, showing that the functionalization with HS did not sort any effect on the bulk physicochemical properties of CaP, with the exception of the surface charge that was found to get more negative. Finally, the effect of the materials on nutrient uptake and translocation in the early stages of development (up to 20 days) of two model species of interest for horticulture, Valerianella locusta and Diplotaxis tenuifolia, was assessed. Both species exhibited a similar tendency to accumulate Ca and P in hypogeal tissues, but showed different reactions to the treatments in terms of translocation to the leaves. CaP and CaP–HS treatments lead to an increase of P accumulation in the leaves of D. tenuifolia, while the treatment with HS was found to increase only the concentration of Ca in V. locusta leaves. A low biostimulating effect on both plants’ growth was observed, and was mainly scribed to the low concentration of HS in the tested materials. In the end, the obtained material showed promising results in virtue of its potential to elicit phosphorous uptake and foliar translocation by plants.     

Isotope dilution method for the assay of rotenone in olive oil and river waters by liquid chromatography/multiple reaction monitoring tandem mass spectrometry

A new approach for the assay of rotenone (1) by isotope dilution mass spectrometry is presented. The extreme toxicity of rotenone, a natural phytodrug with insecticidal and piscicidal activity, recently banned by national and international environmental protection agencies, calls for the development of sensitive and accurate methods of analyses. Accordingly, the proposed protocol is based on the availability of the labeled internal standard rotenone‐d₃ (3) which can be conveniently prepared by consecutive and specific mono‐O‐demethylation, and remethylation with methyl iodide‐d₃. The sensitivity of the method is confirmed by the very low limit of detection (LOD) and quantitation (LOQ) values achieved in the assay of 1 in two distinct fortified matrices, and is further supported by the observed accuracy values. Copyright © 2009 John Wiley & Sons, Ltd.     

A Novel LC–MS/MS-Based Method for the Diagnosis of ADA2 Deficiency from Dried Plasma Spot

Adenosine Deaminase 2 Deficiency (DADA2) (OMIM: 607575) is a monogenic, autoinflammatory disease caused by the loss of functional homozygous or heterozygous mutations in the ADA 2 gene (previously CECR1, Cat Eye Syndrome Chromosome Region 1). A timely diagnosis is crucial to start Anti-TNF therapies that are efficacious in controlling the disease. The confirmation of DADA2 is based on DNA sequencing and enzymatic assay. It is, thus, very important to have robust and reliable assays that can be rapidly utilized in specialized laboratories that can centralize samples from other centers. In this paper, we show a novel enzymatic assay based on liquid chromatography-tandem mass spectrometry that allows the accurate determination of the ADA2 enzyme activity starting from very small amounts of plasma spotted on filter paper (dried plasma spot). The method allows significantly distinguishing healthy controls from affected patients and carriers and could be of help in implementing the diagnostic workflow of DADA2.