Odor-active compounds of Iberian hams with different aroma characteristics

The odor-active compounds of different commercial types of Iberian hams (Montanera and Pienso) were researched by gas chromatography-olfactometry based on a detection frequency method. The hams (long- and short-Montanera and Pienso Iberian hams) showed different sensory profiles, differences being significant for Montanera ham typical odor, aroma intensity and persistence, and cured and moldy aroma. Significant differences were also found for some odorants. The largest differences appeared in 2-acetyl-1-pyrroline, hexanal, (Z)-3-hexenal, ethyl 2-methylbutyrate, (E)-2-hexenal, 1-octen-3-one, 1-octen-3-ol, 2-propionyl-1-pyrroline, octanal, and an unknown odorant. Sensory characteristics and olfactometric profiles were significantly different between Montanera and Pienso hams. Significant differences also appeared between long- and short-Montanera hams, which shows great variability in this commercial type. Otherwise, the largest scores for moldy aroma in long-Montanera hams matched with the largest detection frequency of 1-octen-3-one and 1-octen-3-ol in this group.     

Formation of cholesterol oxidation products in marinated foods during heating

The objectives of this study were to develop a gas chromatography-mass spectrometry (GC-MS) method to analyze the contents of cholesterol oxidation products (COPs) in marinated eggs, pork, and juice and to compare the effect of heating time and soy sauce or sugar on the formation of COPs. By using a silica cartridge for purification and GC-MS with selected ion monitoring for detection, seven COPs, including 7alpha-hydroxycholesterol, 7beta-hydroxycholesterol, 5,6alpha-epoxycholesterol, 5,6beta-epoxycholesterol, 5alpha-cholestane-3beta, 5,6beta-triol, 5-cholesten-3beta-25-diol, and 7-ketocholesterol, as well as internal standard 5alpha-cholestane, were resolved within 16 min by using a HP-5MS capillary column. During marinating, the levels of most COPs followed an increasing trend with increasing heating time. However, a higher amount of COPs was generated for ground pork as compared to eggs. The incorporation of soy sauce or sugar (1 and 10%) was effective in inhibiting COPs formation, with the latter being more pronounced than the former in both marinated eggs and pork.     

Formation and inhibition of cholesterol oxidation products during marinating of pig feet

Cholesterol oxidation products (COPs), formed during the heating of cholesterol-rich foods, have been shown to cause cancer and coronary heart disease. The objectives of this study were to develop a GC-MS method for the determination of COPs in pig feet meat, skin, and juice during marinating and to study the formation and inhibition of COPs as affected by the incorporation of soy sauce and sugar. Results showed that an HP-5MS column could provide an adequate separation of cholesterol, 5α-cholestane (internal standard), and seven COPs, including 7α-OH, 7β-OH, 5,6β-OH, 5,6α-OH, triol, 25-OH, and 7-keto, within 15 min with a temperature-programming method. Most COPs in pig feet meat were generated at a larger amount than in pig feet skin and marinating juice over a 24 h heating period at about 100 °C. The Maillard browning index rose with increasing heating time, whereas the pH showed a slight change in marinated juice. Both reducing sugar and free amino acid contributed to the formation of Maillard reaction products. The incorporation of soy sauce and crystal sugar into fresh juice was effective in inhibiting COPs formation in pig feet, skin, and juice over a 30 min preheating period.     

Iron oxidation in different types of groundwater of Western Siberia

Background, aim, and scope  The groundwaters of Western Siberia contain high concentrations of iron, manganese, silicon, ammonium, and, in several cases, hydrogen sulfide, carbonic acids, and dissolved organic substances. Generally, the groundwaters of Western Siberia can be divided into two major types: one type with a relatively low concentration of humic substances and high hardness (water of A type) and a second type with a relatively low hardness and high concentration of humic substances (water of B type). For drinking water production, the waters of A type are mostly treated in the classical way by aeration followed by sand bed filtration. The waters of B type often show problems when treated for iron removal. A part of iron practically does not form the flocs or particles suitable for filtration or sedimentation. The aim of this work was to determine the oxidizability of Fe(II), to characterize the iron colloids, and to investigate the complexation of the iron ions with humic substances and the coagulation of the iron colloids in the presence of dissolved organic matter. Materials and methods  Water samples of the A and B types were taken from bore holes in Western Siberia (A type: in Tomsk and Tomsk region, B type: in Beliy Yar and Kargasok). Depth of sampling was about 200 m below surface. The oxidation of the groundwater samples by air oxygen and ozone was done in a bubble reactor consisting of a glass cylinder with a gas-inlet tube. To produce ozone, a compact ozone generator developed by Tomsk Polytechnic University was used. For the characterization of the colloids in the water of B type, the particle size distribution and the zeta potential were measured. To investigate the formation of complexes between iron and humic substances in the water of B type, size exclusion chromatography was used. The coagulation behavior of iron in the presence of dissolved organic substances was investigated at different pH values. The agglomerates were detected by measuring the optical density using a UV-Vis spectrometer. Results  Ozone showed, as expected, a faster oxidation of Fe(II) than air oxygen. The rate constants for Fe(II) oxidation were not much different for the waters of A and B types when the same oxidation process was used. However, the removal of iron after oxidation and filtration was higher in the water of A type than in the water of B type. No evidence for the formation of soluble complexes between iron and humic substances were found. In the water of A type, the coagulation process started at pH = 4.5 and accelerated with increasing pH value. In the water of B type, the coagulation of colloids occurred only at pH = 11 and higher. Discussion  The oxidation experiments indicated no major effect of dissolved organic carbon concentration on the kinetics of Fe(II) oxidation. In contrast to this, the humic substances showed a significant influence on the aggregation behavior of the iron hydroxide colloids. Due to the sorption of humic substances on the iron hydroxide colloids, they were highly stable in the pH range between 4.5 and 10. The particle size measurements confirmed the presence of small colloids in the water of B type. In contrast to this, the iron hydroxide colloids aggregated rapidly at pH = 11. Conclusions  The results showed a great influence of humic substances on the iron removal from groundwaters of Western Siberia with high organic content. The sorption of humic substances on the iron colloids does not obviously allow their coagulation and formation of flocs suitable for filtration or sedimentation. Recommendations and perspectives  By treatment of groundwaters containing high amounts of humic substances, some problems with the removal of iron are likely to occur. To increase the effectiveness of iron removal, the surface coating and pH-dependent charge effects should be taken into account by the selection and optimization of water treatment processes. The iron colloids coated by humic substances should be separated from the water phase by membrane filtration or by flocculation followed by filtration through different solid materials.     

Identification of alpha-tocopherol oxidation products in triolein at elevated temperatures

The effect of high-temperature treatment on the stability of alpha-tocopherol (1) in triolein was assessed under a reduced-pressure atmosphere (4-40 mbar) simulating the deodorization step of the refining of vegetable oils. A marked degradation of 1 was observed, which increased with increasing temperature (180-260 degrees C) and heating time (20-80 min). The degradation of 1 in triolein at 240 degrees C was inhibited by the addition of the synthetic antioxidant TBHQ or when heating was performed under nitrogen atmosphere, indicating oxidative degradation. The oxidation products were isolated and identified as alpha-tocopherolquinone (2), 4a,5-epoxy-alpha-tocopherolquinone (3), and 7,8-epoxy-alpha-tocopherolquinone (4).     

Identification and site-specific relative quantification of beta-lactoglobulin modifications in heated milk and dairy products

During milk processing, proteins can be severely modified by oxidation, condensation, and Maillard reaction, leading to changes in their nutritional and technological properties. In this study, major modifications of beta-lactoglobulin, formed during the heating and processing of milk, were screened by mass spectrometry. For this purpose, beta-lactoglobulin was isolated from the milk samples by gel electrophoresis and analyzed by matrix-assisted laser desorption/ionization mass spectrometry after in-gel digestion with endoproteinase AspN. In heated milk, lactulosyllysine was detected at lysine 47 and 138 or 141 as well as methionine sulfoxide at methionine 7, 24, and 145. All these modifications increased gradually when raw milk was heated for 20, 40, and 60 min at 120 degrees C. The major modifications were also relatively quantified in dairy products, such as raw, high-temperature, ultra-high-temperature, sterilized, and condensed milk as well as infant formulas. The highest contents of lactulosyllysine at Lys47 were detected in powdered infant formulas, whereas lactulosyllysine at Lys138/141 was predominant in condensed milk samples. Methionine sulfoxide at Met7 and Met24 showed a trend toward higher modification rates in more severely processed products.     

Identification and quantification of aminophospholipid-linked Maillard compounds in model systems and egg yolk products

While the Maillard reaction of free amino acids and proteins is a well-established process, no defined structures from the nonenzymatic browning of aminophospholipids in foodstuffs have been described so far. Phosphatidylethanolamine (PE)-linked glucosylamines (Schiff-PE), Amadori products (Amadori-PE), 5-hydroxymethylpyrrole-2-carbaldehydes (Pyrrole-PE), and carboxymethyl (CM-PE) as well as carboxyethyl (CE-PE) derivatives were detected and quantified by liquid chromatography- electrospray mass spectrometry (LC-(ESI)MS). Model incubations of soy-PE and D-glucose were employed to firmly establish the LC-(ESI)MS procedure. Analyses of spray-dried egg yolk powders and lecithin products derived therefrom show one-fourth of the native D-glucose content of egg yolk to be transformed to Amadori-PE, corresponding to a PE derivatization quota of 11-15.5 mol %. Schiff-PE and Pyrrole-PE were present only in low amounts, no CM-PE and CE-PE could be identified in any of the investigated samples. The high glycation rate of egg yolk PE will influence the emulsifying properties and perhaps even the oxidation resistance of the respective products.     

Volatile profiles of dry-cured meat products from three different Iberian x Duroc genotypes

Volatile profiles of two Iberian dry-cured products, dry-cured loin and ham, from three different Iberian x Duroc genotypes, was assessed. Three groups of 10 pigs, each (5 males and 5 females) from different genotypes, were studied: GEN1 = male Iberian x female Duroc1; GEN2 = male Duroc1 x female Iberian; and GEN3 = male Duroc2 x female Iberian. The genotype Duroc1 (DU1) corresponded to pigs selected for the production of dry-cured meat products (hams, loins, and shoulders), with a high level of fattening, while the genotype Duroc2 (DU2) corresponded to animals selected for meat production. Genotype slightly affected the volatile profiles of both dry-cured meat products, although dry-cured loin from GEN3 showed higher hexanal content. Dry-cured loin showed a volatile profile very different to that found in dry-cured ham. Volatile compounds of dry-cured meat products were mainly originated by lipid and protein degradation. Most of the volatile detected in both meat products came from lipid oxidation such as acids, aldehydes, ketones, alcohols, and hydrocarbons. In addition, a high proportion of volatile compounds from the Maillard reaction was found. Branched aldehydes and some sulfur and nitrogen compounds have their origin in the amino acids degradation by the Strecker reaction, while branched alcohols and acids come from the lipid oxidation of branched aldehydes. Dry-cured ham showed a higher number and a higher level of compounds with origin in protein and lipid degradation than dry-cured loin, which agrees with the longer ripening of the hams (24 months) with respect to the loins (4 months). In dry-cured loins, apart from these compounds, seasoning mixture provides high amount of volatiles, such as terpenes (from paprika and oregano) and sulfur compounds (from garlic), which have great importance in the overall aroma of this product.     

Identification and formation pathway of laccase-mediated oxidation products formed from hydroxyphenylureas

Hydroxyphenylureas are the first main metabolites formed in the environment from pesticide and biocide urea compounds. Because fungi release potent exocellular oxidases, we studied the ability of laccases produced by the white rot fungus, T. versicolor, to catalyze in vitro the transformation of five hydroxyphenylureas, to identify transformation pathways and mechanisms. Our results establish that the pH of the reaction has a strong influence on both the kinetics of the reaction and the nature of the transformation products. Structural characterization by spectroscopic methods (NMR, mass spectrometry) of eleven transformation products shows that laccase oxidizes the substrates to quinones or to polyaromatic oligomers. Slightly acidic conditions favor the formation of quinones as final transformation products. In contrast, at pH 5-6, the quinones further react with the remaining substrate in solution to give hetero-oligomers via carbon-carbon or carbon-oxygen bond formation. A reaction pathway is proposed for each of the identified products. These results demonstrate that fungal laccases could assist the transformation of hydroxyphenylureas.     

Identification and quantification of polybrominated hexahydroxanthene derivatives and other halogenated natural products in commercial fish and other marine samples

During routine analysis of commercial fish on halogenated pollutants, an unknown tribromo component (TriBHD) was initially detected as an abundant peak in sample extracts from the Mediterranean Sea. The molecular formula was established to be C16H19Br3O by gas chromatography with electron ionization high-resolution mass spectrometry (GC/EI-HRMS). GC/EI-MS data were virtually identical with a polybrominated hexahydroxanthene derivative (PBHD) previously isolated from an Australian sponge species known to occur in the Mediterranean Sea as well. A tetrabromo isomer (TetraBHD) was also found in the fish samples. The concentrations of TriBHD and other halogenated compounds in commercial fish (sea bass, gilt head bream, anchovy, sardine, and salmon) were estimated with GC/electron capture detection (ECD). Using the ECD response of trans-nonachlor, the concentration of TriBHD reached up to 90 ng/g lipid weight and accounted for up to >90% of the concentration of p,p'-DDE, which was the most abundant peak in the most samples investigated. On the basis of the GC/ECD response, TetraBHD amounted for approximately 1/7 of TriBHD in all fish samples investigated. The sample with the highest content was a green-lipped mussel from New Zealand (236 ng/g lipid weight). The halogenated natural products TBA, Q1, and MHC-1 were also present in most of the samples. We assume that the bulk of the residues in fish from aquaculture may originate from algae and sponges living in proximity of the fish farms. Detection of TriBHD and TetraBHD in blubber of a monk seal (Monachus monachus) suggests that both HNPs may reach the top predators of food webs and thus also humans.     

Identification of TLC markers and quantification by HPLC-MS of various constituents in noni fruit powder and commercial noni-derived products

The composition of noni (Morinda citrifolia) products has been investigated. TLC profiles of several commercial juices and capsules were compared. 3-Methyl-1,3-butanediol was identified as a typical marker in noni juices. The presence of sorbic acid (E200) was detected in one juice declared as additive free. Quantitative data have been obtained by HPLC-MS. A method for the quantification of characteristic noni constituents, such as iridoid glucosides, scopoletin, rutin, fatty acid glucosides, and anthraquinones, was developed and validated. The separation was performed on a C18 column with a gradient of acetonitrile in water containing 0.1% formic acid. Detection was carried out with ESI-MS in the negative ion mode. Significant differences were observed between the products. Asperulosidic acid, deacetylasperulosidic acid, and rutin were present in all samples analyzed, but their concentrations differed considerably between the products. Fatty acid glucosides, noniosides B and C, were present in capsules and most juices. Scopoletin was mainly found in juices. The anthraquinone alizarin, which has been reported from roots and leaves, was not detected in the samples investigated.     

Identification and quantification of polyphenols in carob fruits (Ceratonia siliqua L.) and derived products by HPLC-UV-ESI/MSn

The polyphenolic patterns of carob pods (Ceratonia siliqua L.) and derived products were identified and quantified using high-performance liquid chromatography-UV absorption-electrospray ion trap mass spectrometry after pressurized liquid extraction and solid-phase extraction. In carob fiber, 41 individual phenolic compounds could be identified. In addition, spectrophotometric quantification using the Folin-Ciocalteu and vanillin assays was performed, and the antioxidative activity was determined as the 1,1-diphenyl-2-picrylhydrazyl radical scavenging activity. Carob pods contain 448 mg/kg extractable polyphenols comprising gallic acid, hydrolyzable and condensed tannins, flavonol-glycosides, and traces of isoflavonoids. Among the products investigated, carob fiber, a carob pod preparation rich in insoluble dietary fiber (total polyphenol content = 4142 mg/kg), shows the highest concentrations in flavonol-glycosides and hydrolyzable tannins, whereas roasted carob products contain the highest levels of gallic acid. The production process seems to have an important influence on the polyphenolic patterns and quantities in carob products.     

HPLC separation and determination of 12 cholesterol oxidation products in fish: comparative study of RI, UV, and APCI-MS detectors

A simple, fast, and sensitive method for the extraction through direct saponification, separation, quantification, and identification of 12 cholesterol oxidation products (COPs) and cholesterol in a single isocratic, normal-phase, high-performance liquid chromatography (HPLC) was developed. Three detectors were compared for determination of COPs and cholesterol in fish samples: refractive index (RI), ultraviolet (UV), and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). The results did not show significant differences (p > 0.05) between the concentration of the cholesterol oxides and cholesterol obtained with these detectors. The present study demonstrated the presence of 19-hydroxycholesterol, 22"R"-hydroxycholesterol, 22"S"-hydroxycholesterol, 24"S"-hydroxycholesterol, and 25"R"-hydroxycholesterol for the first time in fish samples.     

Gas chromatographic determination of cholesterol in egg products

A method has been developed for quantification of cholesterol in fresh egg yolks, spray-dried egg yolks, fresh whole eggs, and spray-dried whole eggs. The method uses saponification followed by petroleum ether extraction of cholesterol. Separation of organic and aqueous layers is enhanced by sodium chloride. Petroleum ether extracts are dried under nitrogen and redissolved in chloroform-methanol (2 + 1) for injection into a gas chromatograph. Cholesterol is separated and quantitated on a high temperature capillary column coated with 5% diphenyl and 95% dimethyl polysilicone crosslinked gum. The method was compared with the current AOAC method 17.017-17.022, and results indicated no significant difference (alpha = 0.05). However, the proposed method allowed separation and analysis of 16 samples in 7 h while the current AOAC method allowed separation and analysis of only 4 samples in 9 h.     

Identification and quantification of cyclolinopeptides in five flaxseed cultivars

Cyclolinopeptides are a group of naturally occurring hydrophobic cyclic peptides found in flaxseed and flax oil that have immunosuppressive activity. This study describes the measurement of flaxseed cyclolinopeptide concentrations using an internal standard HPLC method. In addition, the concentration of cyclolinopeptides in the seed of Canadian flax cultivars grown at two locations over two years is reported. The data are consistent with the formation of flaxseed cyclolinopeptides from two ribosome-derived precursors. Each precursor protein includes the sequences corresponding to three cyclolinopeptides from which those cyclolinopeptides are presumably derived by precursor processing. The concentrations of cyclolinopeptides C and E, which are encoded by the same gene sequence, are highly correlated, and the concentrations of cyclolinopeptides D, F, and G, which are encoded by a second gene sequence, are also highly correlated. The strong correlation between the cyclolinopeptides arising from the same gene may prove to be important in understanding how peptide concentration is controlled. Additional research may lead to approaches to improve flax either as a platform for peptide production or as a source of oil with improved drying properties and flavor.     

Identification and quantification of seed carotenoids in selected wheat species

Selected primitive and modern wheat species were evaluated on the basis of their carotenoid composition and effects of the genotype and environment on lutein using spectrometry and liquid chromatography. Carotenoids in the wheat extracts were identified and confirmed on the basis of their UV/vis and mass spectra compared with those of authentic standards. The protonated molecule (M + 1)+ at m/z 569 was the predominant ion for zeaxanthin compared to the fragment ion at m/z 551 for lutein. A similar carotenoid profile was obtained for the wheat species investigated, but significant differences were observed in the concentration of carotenoids. Einkorn (Triticum monococcum) exhibited the highest level of all-trans-lutein, averaging 7.41 microg/g with small amounts of all-trans-zeaxanthin, cis-lutein isomers, and beta-carotene. Durum, Kamut, and Khorasan (Triticum turgidum) had intermediate levels of lutein (5.41-5.77 microg/g), while common bread or pastry wheat (Triticum aestivum) had the lowest content (2.01-2.11 microg/g). Lutein in einkorn appeared to be influenced significantly by environmental growing conditions.     

Effects of different cooking procedures on lipid quality and cholesterol oxidation of farmed salmon fish (Salmo salar)

Salmon fillets were steamed, or pan-fried without oil, with olive oil, with corn oil, or with partially hydrogenated plant oil. The exchange between the salmon and the pan-frying oils was marginal, but it was detectable as slight modifications in the fatty acid pattern and the tocopherol contents according to the oil used. Primary and secondary oxidation products were only slightly increased or remained unchanged, which indicated a slight lipid oxidation effect due to the heating procedures applied. The same was observed for tocopherol levels, which remained almost stable and were not affected by the oxidation process. The sum of cholesterol oxidation products (COPs) increased after the heating processes from 0.9 microg/g in the raw sample to 6.0, 4.0, 4.4, 3.3, and 9.9 microg/g extracted fat in pan-fried without oil, with olive oil, corn oil, partially hydrogenated plant oil, and steamed, respectively. A highly significant correlation was found between the fatty acid pattern and the total amount of COPs (r2 = 0.973, p < 0.001). No change has been determined in the n-3 fatty acids content and in the polyunsaturated/saturated-ratio of the cooked salmon fillets. Moderate pan-frying (6 min total) and steaming (12 min) of salmon did not accelerate lipid oxidation but significantly increased the content of COPs. The highest increase of COPs was found through steaming, mainly due to the longer heat exposure. The used frying oils did not influence the outcome; no significant difference between heat treatment with or without oil has been determined.     

Purification of ethoxyquin and its two oxidation products

2,6-Dihydro-2,2,4-trimethyl-6-quinolone (QI) and 1,8'-bis(1, 2-dihydro-6-ethoxy-2,2,4-trimethylquinoline) (DM) are two oxidation products of 1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline (ethoxyquin, EQ). This paper describes several methods for the purification of technical grade EQ and for the production of pure QI and DM as standards with the purity required (>99%) for calibration of quantitative determination methods. EQ of high purity was obtained through vacuum distillation followed by a quick column chromatographic purification on silica gel. Preparative scale purity DM could be obtained through recrystallization from methanol, but QI could be purified only by a high-pressure liquid chromatographic method.     

Inhibition of cholesterol oxidation products (COPs) formation in emulsified porcine patties by phenolic-rich avocado (Persea americana Mill.) extracts

The effect of phenolic-rich extracts from avocado peel on the formation of cholesterol oxidation products (COPs) in porcine patties subjected to cooking and chill storage was studied. Eight COPs (7α-hydroxycholesterol, 7β-hydroxycholesterol, 7-ketocholesterol, 20α-hydroxycholesterol, 25-hydroxycholesterol, cholestanetriol, 5,6β-epoxycholesterol, and 5,6α-epoxycholesterol) were identified and quantified by GC-MS. The addition of avocado extracts (～600 GAE/kg patty) to patties significantly inhibited the formation of COPs during cooking. Cooked control (C) patties contained a larger variety and greater amounts of COPs than the avocado-treated (T) counterparts. COPs sharply increased in cooked patties during the subsequent chilled storage. This increase was significantly higher in C patties than in the T patties. Interestingly, the amount of COPs in cooked and chilled T patties was similar to those found in cooked C patties. The mechanisms implicated in cholesterol oxidation in a processed meat product, the protective effect of avocado phenolics, and the potential implication of lipid and protein oxidation are thoroughly described in the present paper.     

不同包装对山核桃脂肪氧化的影响（简报）

为了选择合适的包装措施以减缓山核桃仁中油脂在贮藏期间的氧化酸败,延长其贮藏期,研究了用聚乙烯塑料膜（Polyethylene,PE）和聚乙烯塑料铝箔膜（Polyethylene/Al,PE/Al）的普通包装与PE、PE/Al的真空包装,4种不同包装措施对山核桃贮藏过程中油脂氧化的影响。通过不同包装对山核桃油脂的酸价、碘价、过氧化值、p-茴香胺值和脂肪氧合酶活性在贮藏过程中的变化情况的影响,确定适合山核桃的包装形式。试验结果表明PE/Al真空包装能有效减缓山核桃油脂的氧化进程,从而延缓山核桃的品质的下降,延长其货架期。