NMR Spectroscopy Applied to the Metabolic Analysis of Natural Extracts of Cannabis sativa.

Cannabis sativa is a herbaceous multiple-use species commonly employed to produce fiber, oil, and medicine. It is now becoming popular for the high nutritional properties of its seed oil and for the pharmacological activity of its cannabinoid fraction in inflorescences. The present study aims to apply nuclear magnetic resonance (NMR) spectroscopy to provide useful qualitative and quantitative information on the chemical composition of seed and flower Cannabis extracts obtained by ultra-sound-assisted extraction, and to evaluate NMR as an alternative to the official procedure for the quantification of cannabinoids. The estimation of the optimal ω-6/ω-3 ratio from the 1H NMR spectrum for the seed extracts of the Futura 75 variety and the quantitative results from the 1H and 13C NMR spectra for the inflorescence extracts of the Tiborszallasi and Kompolti varieties demonstrate that NMR technology represents a good alternative to classical chromatography, supplying sufficiently precise, sensitive, rapid, and informative data without any sample pre-treatment. In addition, different extraction procedures were tested and evaluated to compare the elaboration of spectral data with the principal component analysis (PCA) statistical method and the quantitative NMR results: the extracts obtained with higher polarity solvents (acetone or ethanol) were poor in psychotropic agents (THC < LOD) but had an appreciable percentage of both cannabinoids and triacylgliceroles (TAGs). These bioactive-rich extracts could be used in the food and pharmaceutical industries, opening new pathways for the production of functional foods and supplements.

Pyrolysis and Gasification of a Real Refuse-Derived Fuel (RDF): The Potential Use of the Products under a Circular Economy Vision.

Refuse-Derived Fuels (RDFs) are segregated forms of wastes obtained by a combined mechanical-biological processing of municipal solid wastes (MSWs). The narrower characteristics, e.g., high calorific value (18-24 MJ/kg), low moisture content (3-6%) and high volatile (77-84%) and carbon (47-56%) contents, make RDFs more suitable than MSWs for thermochemical valorization purposes. As a matter of fact, EU regulations encourage the use of RDF as a source of energy in the frameworks of sustainability and the circular economy. Pyrolysis and gasification are promising thermochemical processes for RDF treatment, since, compared to incineration, they ensure an increase in energy recovery efficiency, a reduction of pollutant emissions and the production of value-added products as chemical platforms or fuels. Despite the growing interest towards RDFs as feedstock, the literature on the thermochemical treatment of RDFs under pyrolysis and gasification conditions still appears to be limited. In this work, results on pyrolysis and gasification tests on a real RDF are reported and coupled with a detailed characterization of the gaseous, condensable and solid products. Pyrolysis tests have been performed in a tubular reactor up to three different final temperatures (550, 650 and 750 °C) while an air gasification test at 850 °C has been performed in a fluidized bed reactor using sand as the bed material. The results of the two thermochemical processes are analyzed in terms of yield, characteristics and quality of the products to highlight how the two thermochemical conversion processes can be used to accomplish waste-to-materials and waste-to-energy targets. The RDF gasification process leads to the production of a syngas with a H2/CO ratio of 0.51 and a tar concentration of 3.15 g/m3.

Environmental and economic impacts of improper materials in the recycling of separated collected food waste through anaerobic digestion and composting.

Separately collected food waste (SC-FW) is effectively recycled through industrial anaerobic digestion (AD) and composting. However, the presence of improper materials in SC-FW not only generates technical problems to AD and composting, but also lowers the quality of the outputs of the processes. As a consequence, improper materials found in SC-FW cause not negligible environmental and economic burdens. In this study, the environmental and economic impacts due to the presence of unsuitable materials in the SC-FW, determined through compositional analysis, were estimated through life cycle assessment and environmental life cycle costing approaches. Three different scenarios were analysed for both AD and composting processes: (i) the current situation (CS); (ii) the improved scenario (AS) with an amount of improper materials in SC-FW reduced to 3 % (w/w); (iii) the ideal scenario (IS) with the total absence of foreign materials. Environmental benefits were determined for the AS and IS scenarios in 17 of the 19 analysed impact categories. Considering the GHG emissions, higher savings were measured for AD in AS and IS scenarios (47 % and 79 %, respectively) than in CS scenario. Similarly, savings of -10.4 kg fossil oil eq/tonSC-FW (AS) and - 17.1 kg fossil oil eq/tonSC-FW (IS) for AD could be obtained with respect to the CS scenario. Greater economic benefits were calculated for AD (-76.4 €/tonSC-FW) and composting (-52.2 €/tonSC-FW) in the IS scenario. Savings up to € 2,249,780 and € 3,888,760 could have been obtained in 2022 by reducing to 3 % (w/w) and eliminating, respectively, the amount of improper materials in the SC-FW. The results of the compositional analyses of SC-FW allowed to identify the incorrect behaviours in FW source-sorting activity and to plan interventions to improve the current FW management system. The quantified environmental and economic benefits could further motivate citizens to correctly differentiate FW.

Environmental sustainability of an integrate anaerobic digestion-composting treatment of food waste: Analysis of an Italian plant in the circular bioeconomy strategy.

In light of the adoption of recent global policies and strategies for a more sustainable food waste management system and a greater control of environmental impacts, this study describes a circular bioeconomy plant model, currently operating in South Italy, for treatment and enhancement of organic fraction of municipal solid waste. The key basis for plant activity is dry anaerobic digestion of separately collected organic fraction of municipal solid waste (SC-OFMSW) followed by digestate composting process. Biomethane for use in the transport sector is obtained by biogas cleaning and upgrading, while high-quality compost for organic farming is produced by digestate composting. Plant activities are completed by the transformation of part of the produced waste into refuse derived fuel (RDF) to be allocated to waste-to-energy plants and the treatment of odour emissions which allows the recovery of ammonium sulphate as a fertilizer. A rooftop photovoltaic system supplies most of electric energy needed by the plant. For plant activities relative to 2020, carbon footprint was equal to -112 kg CO2eq. for Mg of organic waste, while depletion of fossil resources was estimated at -89.6 kg oil eq. Mg-1 of waste. Primary energy demand of food waste treatment system was -2.66 GJ Mg-1 of input waste. Replacement of natural gas with biomethane for transport sector provided the greatest improvement contribution for all the examined categories.

Determination by gas chromatography/mass spectrometry of p-phenylenediamine in hair dyes after conversion to an imine derivative.

In this paper we describe an analytical method for the determination of p-phenylenediamine (PPDA) in hair dyes. In the adopted methodology the analyte is transformed into the corresponding imine derivative by treatment with benzaldehyde, and then analyzed by gas chromatography (GC) combined to mass spectrometry (MS), operating in SIM conditions. The direct and simultaneous chemical derivatization of the two amino functions of the analyte with benzaldehyde enhances the instrumental responses enabling the use of a sensitive and accurate method. Concentrations of PPDA in a set of commercial hair coloring creams are determined making use of N-benzylidene-4-methylbenzene-amine as a very stable internal standard which is easily prepared by condensation of 4-methylbenzene-amine with benzaldehyde. The regression calibration curves for PPDA in hair dyes are linear within 0.1 +/- 25 mg/ml with 0.99 as a typical correlation coefficient.

A straightforward chemical synthesis of 17-ketosteroids by cleavage of the C-17-dihydroxy acetone side chain in corticosteroids.

A facile and convenient approach to 17-ketosteroids is described. Treatment of steroids containing the C-17-dihydroxy acetone side chain with an excess of sodium methoxide in dry 1,4-dioxane under reflux, affords high yields of the corresponding 17-ketosteroids that are recovered as pure products, without the need of further purification.

Quantitative analysis of human salivary glucose by gas chromatography-mass spectrometry.

A reference analytic methodology was developed for the determination of human salivary glucose concentration. The technique involves the glucose derivatization with acetic anhydride and subsequent analysis of glucose penta-acetylated by gas chromatography combined with mass spectrometry. Glucose concentration in the biological fluid depends on the physiological status of the donor.

Optically pure N-hydroxy-O-triisopropylsilyl-alpha-L-amino acid methyl esters from AlCl3-assisted ring opening of chiral oxaziridines by nitrogen containing nucleophiles.

[reaction: see text] This article reports a straightforward and unprecedented process of AlCl3-assisted oxaziridine ring opening by nitrogen containing nucleophiles, in a totally anhydrous milieu. Under these conditions, nucleophiles exclusively attack the carbon atom of the three-membered heterocycles, obtained from methyl esters of natural alpha-amino acids, generating N-hydroxy-alpha-L-amino acid methyl esters. No nitrones, amides, or other side products, either from unwanted rearrangements or due to the attack of the nucleophile on the N atom of the oxaziridine systems, are formed. The hydroxylamine compounds are recovered in excellent yields, after their site-specific conversion into the corresponding O-triisopropylsilyl derivatives, by exposure to triisopropylsilyl triflate in the presence of 1H-imidazole. Derivatization, performed immediately after the recovery of the N-hydroxylated precursors, allows the chiral integrity of the asymmetric alpha-carbon atoms in the amino acid methyl esters to be retained. It also protects the obtained compounds from frame degradation by disproportionation. N-Hydroxy-O-triisopropylsilyl-alpha-L-amino acid methyl esters are important intermediates in the study of natural alpha-L-amino acid metabolic pathways and are ideal candidates as starting materials in the synthesis of biologically, pharmacologically, and nutritionally important N-hydroxy peptides.

"One-pot" methylation of N-Nosyl-alpha-amino acid methyl esters with diazomethane and their coupling to prepare N-methyl dipeptides.

N-Nosyl-alpha-amino acid methyl esters are methylated quantitatively with diazomethane. After proper deprotection of the amino function by treatment with the reagent system mercaptoacetic acid/sodium methoxide, the obtained N-methyl amino acid methyl esters are coupled with N-Fmoc amino acid chlorides to afford the corresponding dipeptides. The obtained products do not show any detectable extent of racemization by (1)H NMR and HPLC.