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A nano-HPLC electrospray ionization multi-stage tandem mass spectrometry (nLC-ESI-MS/ MS) approach was applied to a complex crude triterpene saponin extract of Chenopodium quinoa seed coats. In ESI-MS/MS spectra of triterpene saponins, characteristic fragmentation reactions are observed and allow the determination of aglycones, saccharide sequences, compositions, and branching. Fragmentation of aglycones provided further structural information. The chemical complexity of the mixture was resolved by a complete profiling. Eighty-seven triterpene saponins comprising 19 reported and 68 novel components were identified and studied by MS. In addition to four reported, five novel triterpene aglycones were detected and characterized according to their fragmentation reactions in ESI-MS/MS and electron ionization mass spectrometry (EI-MS). As a novelty fragmentation pathways were proposed and analyzed based upon quantum chemical calculations using a hybrid HartreeFock density functional method. Accuracy of the assignment procedure was proven by isolation and structure determination of a novel compound. As the relative distribution and composition of saponins varies between different cultivars and soils, the presented strategy allows a rapid and complete analysis of Chenopodium quinoa saponin distribution and composition, and is particularly suitable for quality control and screening of extracts designated for pharmaceutical, agricultural, and industrial applications. (J Am Soc Mass Spectrom 2006, 17, 795-806)

Oxidation stability of biodiesel is an important issue because FA derivatives are more sensitive to oxidative degradation than mineral fuel. Therefore, in the most recent European Specifications for biodiesel, a minimum value of 6 h for the induction period at 110°C, measured with a Rancimat instrument, is specified. To guarantee this value at the filling station, the use of additional antioxidants will be necessary. In this paper we show the influence of different synthetic and natural antioxidants on the oxidation stability, using the specified test method. Biodiesel produced from rapeseed oil, sunflower oil, used frying oil, and beef tallow, both undistilled and distilled, was investigated. The four synthetic antioxidants pyrogallol (PY), propylgallate (PG), TBHQ, and BHA produced the greatest enhancement of the induction period. These four compounds and the widely used BHT were selected for further studies at concentrations from 100 to 1000 mg/kg. The induction periods of methyl esters from rapeseed oil, used frying oil, and tallow could be improved significantly with PY, PG, and TBHQ, whereas BHT was not very effective. A good correlation was found between the improvement of the oxidation stability and the FA composition.

Environmental concerns are driving industry to develop viable alternative fuels from renewable resources. On the other hand, to reduce food surplus, the Agricultural Policy of the European Union (EU) obliges the European farmers to leave a percentage of the arable land as set-aside, where can be grown, as an exception, vegetables for nonfood purposes, i.e., energetic ones. Currently, fossil fuels are used in diesel engines and are essential in industrialized places. In addition, petroleum-based diesel increases environmental pollution. To solve these problems, transesterified vegetable oil that has been grown in set-aside lands can be considered to be a renewable energy resource. In this sense, this work describes the optimization of the parameters involved in the transesterification process of Brassica carinata oil. Gas chromatography was used to determine the fatty acid composition of Brassica carinata oil and its esters. Results revealed that the free fatty acid content is a notorious parameter to determine the viability of the vegetable oil transesterification process. In this sense, it was not possible to perform a basic transesterification using Brassica carinata oil with a high erucic acid content. The transesterification process of Brassica carinata without erucic acid required 1.4% KOH and 16% methanol, in the range of 20-45°C, after 30 min of stirring. Our results suggest that the greater the presence of KOH, the lesser the methanol requirements. However, this is valid only under certain limits. Also, if the presence of KOH or methanol is lower or higher than the optimal values, the reaction either does not fully occur or leads to soap production, respectively. Based on this field trial, biodiesel from Brassica carinata oil could be recommended as a diesel fuel candidate if long-term engine performance tests provide satisfactory results.