Prenyl Ethers: Novel Fungal Volatiles Formed by Penicillium digitatum.

Prenyl ethyl ether (PEE) was previously described as the cause for a solvent-like off-note in ground hazelnuts, but its origin remained unclear. Investigations were carried out by analytical groups of Coop and Givaudan over four years to elucidate this phenomenon. From mouldy citrus fruits a strain of Penicillium digitatum was isolated and found to form PEE. Formation on citrus and other fruits was prominent and contributed to the particular smell of decayed fruits. Several strains of P. digitatum formed PEE, while other fungal species did not. In contrast to citrus fruit, prenyl methyl ether (PME) was formed as dominant prenyl ether on hazelnuts while only small amounts of PEE were found. PME has not been previously described as volatile metabolite of fungi or as a food-taint. Spiking experiments with deuterated ethanol showed that the ethyl group is likely incorporated into PEE via the aldehyde form. On hazelnuts strongly decayed by P. digitatum yet another prenyl ether was tentatively identified: Prenyl isopropyl ether. Prenyl ethers present a novel group of volatile metabolites of P. digitatum. They are likely typical for this species and have not been described before. Prenyl ethers seem to play a significant role in the smell of food decayed by P. digitatum and should be considered in cases of off-notes and taints.

Determination of phosphine in plant materials: method optimization and validation in interlaboratory comparison tests.

The optimization and validation of a method for the determination of phosphine in plant materials are described. The method is based on headspace sampling over the sample heated in 5% sulfuric acid. Critical factors such as sample amount, equilibration conditions, method of quantitation, and matrix effects are discussed, and validation data are presented. Grinding of coarse samples does not lead to lower results and is a prerequisite for standard addition experiments, which present the most reliable approach for quantitation because of notable matrix effects. Two interlaboratory comparisons showed that results varied considerably and that an uncertainty of measurement of about 50% has to be assessed. Flame photometric and mass spectrometric detection gave similar results. The proposed method is well reproducible within one laboratory, and results from the authors' laboratories using different injection and detection techniques are very close to each other. The considerable variation in the interlaboratory comparison shows that this analysis is still challenging in practice and further proficiency testing is needed.

Identification of prenyl ethyl ether as a source of metallic, solvent-like off-flavor in hazelnut.

In a large batch of ground hazelnuts, a metallic, solvent-like off-note was detected. In this investigation, the volatiles from the batch showing off-notes were compared to a batch without off-notes. On the basis of gas chromatography (GC) sniffing and instrumental analysis, a terpenoid compound, prenyl ethyl ether, was identified as a key contributor to the off-note. The compound was quantified, and its contribution to the metallic, solvent-like off-flavor was confirmed by spiking experiments and sensory evaluation. Analytical and sensory experiments found that the off-note was still present in hazelnut cakes. Fat oxidation did not contribute to the off-flavor. Analysis of market products demonstrated the correlation between the identified terpenoid and the off-flavor. It is assumed that fungi are involved in off-flavor formation.

Influence of roasting conditions on the acrylamide content and the color of roasted almonds.

The influence of roasting conditions on the acrylamide content and on the color of roasted almonds of 3 cultivars was investigated. The temperature inside the almond kernel, the water content, the color, and the acrylamide content were determined at different roasting temperatures and times. The formation of acrylamide started only when the kernel temperature had exceeded approximately 130 degrees C. The activation energy for the acrylamide formation during the roasting of almonds was 123 kJ x mol(-1). The color as measured by the degree of brightness correlated well with the acrylamide content as acrylamide content increased with increasing darkness. Therefore, control of roasting temperature presents the critical factor for limiting the acrylamide concentration in the final product. At constant roasting conditions, almonds with higher initial moisture content contained less acrylamide after roasting, which is probably due to the influence of moisture on the development product temperature during roasting.

Occurrence of acrylamide in selected foods and mitigation options.

Acrylamide reduction in certain food products is an important issue for both the food industry and academic research institutions. The present paper summarises past and current research on the occurrence and reduction of acrylamide in potatoes, bakery products, almonds, olives and dried fruit. In potatoes, the control of reducing sugars, process temperature and moisture is imperative to limit acrylamide formation. In bakery products, free asparagine and the type of baking agent largely determine acrylamide formation and present the starting points for reduction. The application of asparaginase is promising in this respect because it acts only on the key precursor, asparagine, whereby the product character remains unchanged. The baking agent NH4HCO3 promotes acrylamide formation in sweet bakery but its replacement by NaHCO3 effectively decreases acrylamide concentrations. Temperature and free asparagine are the key factors for acrylamide formation in roasted almonds. Olives and dried fruit may contain acrylamide and large amounts of acrylamide can be formed upon heating these products, a phenomenon which needs further investigation.

Investigations on the promoting effect of ammonium hydrogencarbonate on the formation of acrylamide in model systems.

NH4HCO3 is known to promote acrylamide formation in sweet bakery products. This effect was investigated with respect to sugar fragmentation and formation of acrylamide from asparagine and sugar fragments in model systems under mild conditions. The presence of NH4HCO3 led to increases in acrylamide and alpha-dicarbonyls from glucose and fructose, respectively. As compared to glucose or fructose, sugar fragments such as glyoxal, hydroxyethanal, and glyceraldehyde formed much higher amounts of acrylamide in reaction with asparagine. The enhancing effect of NH4HCO3 is explained by (1) the action of NH3 as base in the retro-aldol reactions leading to sugar fragments, (2) facilitated retro-aldol-type reactions of imines in their protonated forms leading to sugar fragments, and (3) oxidation of the enaminols whereby glyoxal and other reactive sugar fragments are formed. These alpha-dicarbonyl and alpha-hydroxy carbonyl compounds may play a key role in acrylamide formation, especially under mild conditions.

Influence of thermal processing conditions on acrylamide generation and browning in a potato model system.

Fried potato products such as French fries and chips may contain substantial amounts of acrylamide. Numerous efforts are undertaken to minimize the acrylamide content of these products while sensory properties such as color and flavor have to be respected as well. An optimization of the frying process can be achieved if the basic kinetic data of the browning and acrylamide formation are known. Therefore, heating experiments with potato powder were performed under controlled conditions (moisture, temperature, and time). Browning and acrylamide content both increased with heating time at all temperatures and moisture contents tested. The moisture content had a strong influence on the activation energy of browning and acrylamide formation. The activation energy strongly increased at moisture contents below 20%. At higher moisture contents, it was very similar for both parameters. At low moisture contents, the activation energy of acrylamide formation was larger as compared to the one for browning. This explains why the end of the frying process is very critical. Therefore, a lower temperature toward the end of frying reduces the acrylamide content of the product while color development is still good.

Acrylamide in roasted almonds and hazelnuts.

The influences of composition and roasting conditions on acrylamide formation in almonds and hazelnuts were investigated. Eighteen samples of almonds originating from the U.S. and Europe were analyzed for sugars and free amino acids, and acrylamide formed during roasting was determined. Asparagine was the main free amino acid in raw almonds and correlated with the acrylamide content of dark roasted almonds. Roasting temperature was another key factor and had a very strong influence on acrylamide formation. Almonds of European origin contained significantly less free asparagine and formed significantly less acrylamide during roasting as compared to the almonds from the U.S. Roasted hazelnuts contained very little acrylamide because of the low content of free asparagine in the raw nut. Reducing sugars, although being consumed much faster than free amino acids in both types of nuts, were not decisive for the extent of acrylamide formation during roasting.

Factors influencing acrylamide formation in gingerbread.

The influence of ingredients, additives, and process conditions on the acrylamide formation in gingerbread was investigated. The sources for reducing sugars and free asparagine were identified and the effect of different baking agents on the acrylamide formation was evaluated. Ammonium hydrogencarbonate strongly enhanced the acrylamide formation, but its N-atom was not incorporated into acrylamide, nor did acrylic acid form acrylamide in gingerbread. Acrylamide concentration and browning intensity increased both with baking time and correlated with each other. The use of sodium hydrogencarbonate as baking agent reduced the acrylamide concentration by more than 60%. Free asparagine was a limiting factor for acrylamide formation, but the acrylamide content could also be lowered by replacing reducing sugars with sucrose or by adding moderate amounts of organic acids. A significant reduction of the acrylamide content in gingerbread can be achieved by using sodium hydrogencarbonate as baking agent, minimizing free asparagine, and avoiding prolonged baking.

Acrylamide in gingerbread: critical factors for formation and possible ways for reduction.

The influence of ingredients, additives, and process conditions on acrylamide formation in gingerbread was investigated. The sources for reducing sugars and free asparagine were identified, and the effect of different baking agents on acrylamide formation was evaluated. Ammonium hydrogencarbonate strongly enhanced acrylamide formation, but its N atom was not incorporated into acrylamide, nor did acrylic acid form acrylamide in gingerbread. Acrylamide concentration and browning intensity both increased with baking time and correlated with each other. The use of sodium hydrogencarbonate as baking agent reduced the acrylamide concentration by >60%. Free asparagine was a limiting factor for acrylamide formation, but the acrylamide content could also be lowered by replacing reducing sugars with sucrose or by adding organic acids. It is concluded that a significant reduction of acrylamide in gingerbread can be achieved by using sodium hydrogencarbonate as baking agent, minimizing free asparagine, and avoiding prolonged baking.

Potential of acrylamide formation, sugars, and free asparagine in potatoes: a comparison of cultivars and farming systems.

Glucose, fructose, sucrose, free asparagine, and free glutamine were analyzed in 74 potato samples from 17 potato cultivars grown in 2002 at various locations in Switzerland and different farming systems. The potential of these potatoes for acrylamide formation was measured with a standardized heat treatment. These potentials correlated well with the product of the concentrations of reducing sugars and asparagine. Glucose and fructose were found to determine acrylamide formation. The cultivars showed large differences in their potential of acrylamide formation which was primarily related to their sugar contents. Agricultural practice neither influenced sugars and free asparagine nor the potential of acrylamide formation. It is concluded that acrylamide contents in potato products can be substantially reduced primarily by selecting cultivars with low concentrations of reducing sugars.