Strecker degradation of phenylalanine initiated by 2,4-decadienal or methyl 13-oxooctadeca-9,11-dienoate in model systems

The reaction of 2,4-decadienal and methyl 13-oxooctadeca-9,11-dienoate with phenylalanine was studied to determine if alkadienals and ketodienes are able to produce the Strecker-type degradation of amino acids to the corresponding Strecker aldehydes. When reactions were carried out at 180 degrees C, both carbonyl compounds degraded phenylalanine to phenylacetaldehyde, among other compounds. The yield of the phenylacetaldehyde produced depended on the reaction pH and increased linearly with both the amount of the lipid and the reaction time. The yield of this conversion was approximately 8% when starting from decadienal and approximately 6% when starting from methyl 13-oxooctadeca-9,11-dienoate, and the reaction rate was lower for the ketone than for the aldehyde. Simultaneous to these reactions, the lipid was converted into pyrrole, pyridine, or aldehyde derivatives as a result of several competitive reactions. In particular, 9-14% of the decadienal was converted into hexanal under the assayed conditions. All these reactions are suggested to be produced as a consequence of the oxidation of the alkadienal or the ketodiene to the corresponding epoxyalkenal or unsaturated epoxyketone, which were identified in the reaction mixtures by GC-MS. All these results suggest that alkadienals and ketodienes, which are quantitatively important secondary lipid oxidation products, can degrade amino acids to their corresponding Strecker aldehydes. Therefore, under appropriate conditions, these products are not final products of the lipid oxidation and can participate in carbonyl-amine reactions analogously to other lipid oxidation products with two oxygenated functions.     

Quantitative structure-antifungal activity relationships of some benzohydrazides against Botrytis cinerea

Fourteen benzohydrazides have been synthesized and evaluated for their in vitro antifungal activity against the phytopathogenic fungus Botrytis cinerea. The best antifungal activity was observed for the N',N'-dibenzylbenzohydrazides 3b-d and for the N-aminoisoindoline-derived benzohydrazide 5. A quantitative structure-activity relationship (QSAR) study has been developed using a topological substructural molecular design (TOPS-MODE) approach to interpret the antifungal activity of these synthetic compounds. The model described 98.3% of the experimental variance, with a standard deviation of 4.02. The influence of an ortho substituent on the conformation of the benzohydrazides was investigated by X-ray crystallography and supported by QSAR study. Several aspects of the structure-activity relationships are discussed in terms of the contribution of different bonds to the antifungal activity, thereby making the relationships between structure and biological activity more transparent.     

Antioxidative activity of amino phospholipids and phospholipid/amino Acid mixtures in edible oils as determined by the Rancimat method

Phosphatidylethanolamine (PE), phosphatidylcholine (PC), lysine (Lys), and mixtures of them were tested for antioxidative activity in refined olive oil by the Rancimat method to investigate the role of the chemical reactions produced in the Rancimat vessel on the induction periods (IPs) obtained. PE and Lys, but not PC, increased the IPs of the oil when tested alone. In addition, PE/Lys and PC/Lys mixtures, but not PC/PE mixtures, exhibited a synergistic effect. All these results can be understood considering the in situ formation of oxidized lipid/amino compound reaction products with antioxidative activities. Thus, the formation of pyrroles could be detected after derivatization with p-(dimethylamino)benzaldehyde, and some of these compounds could be unambiguously identified by GC-MS after their conversion into volatile derivatives. In addition, the formed products contributed to the color developed, and a correlation was observed between the Rancimat IPs obtained and the yellowness index of the oxidized oils recovered from the Rancimat. Furthermore, the differences observed in the antioxidative activities of PE, PC, Lys, and their mixtures could be explained according to the lipophility and hydrophility of the oxidized lipid/amino compound reaction products formed. All these results suggest that chemical reactions are being produced in the Rancimat vessel and the Rancimat IPs obtained are a consequence of the antioxidative activities of the products formed in these reactions. Furthermore, Rancimat may be a valuable tool for testing antioxidative activities of antioxidants produced during food processing if favorable conditions for antioxidant formation are employed.     

Induction of phase II detoxification enzymes in rats by plant-derived isothiocyanates: comparison of allyl isothiocyanate with sulforaphane and related compounds

Plants of the family Brassicaceae contain high levels of glucosinolates. The latter compounds are degraded to isothiocyanates, some of which have been shown to be potent inducers of phase II detoxification enzymes in vitro. In the present study, the ability of six plant-derived isothiocyanates (allyl isothiocyanate, iberverin, erucin, sulforaphane, iberin, and cheirolin) to increase tissue levels of the phase II detoxification enzymes quinone reductase (QR) and glutathione S-transferase (GST) in a variety of rat tissues has been compared. At the low dose level employed (40 micromol/kg/day), cheirolin was without effect in any tissue. All of the other isothiocyanates, however, increased GST and QR activities in the duodenum, forestomach, and/or the urinary bladder of the animals, with the greatest effects being seen in the urinary bladder. With the exception of cheirolin, little difference was observed in the inductive activity of the various isothiocyanates. Phase II enzymes are known to protect against chemical carcinogenesis, and the selectivity of isothiocyanates in inducing such enzymes in the bladder is of interest in view of recent epidemiological studies showing a decreased incidence of cancer of this organ in individuals with a high dietary intake of Brassica vegetables.     

Analysis of volatiles in porcine liver pâtés with added sage and rosemary essential oils by using SPME-GC-MS

The effect of the addition of two natural antioxidant extracts (sage and rosemary essential oils) and one synthetic (BHT) on the generation of volatile compounds in liver patés from Iberian and white pigs was analyzed using SPME-GC-MS. Lipid-derived volatiles such as aldehydes [hexanal, octanal, nonanal, hept-(Z)-4-enal, oct-(E)-2-enal, non-(Z)-2-enal, dec-(E)-2-enal, deca-(E,Z)-2,4-dienal] and alcohols (pentan-1-ol, hexan-1-ol, oct-1-en-3-ol) were the most abundant compounds in the headspace of porcine liver patés. Patés from different pig breeds presented different volatiles profiles due to their different oxidation susceptibilities as a probable result of their fatty acid profiles and vitamin E content. Regardless of the origin of the patés, the addition of BHT successfully reduced the amount of volatiles derived from PUFA oxidation. Added essential oils showed a different effect on the generation of volatiles whether they were added in patés from Iberian or white pigs because they inhibited lipid oxidation in the former and enhanced oxidative instability in the latter. SPME successfully allowed the isolation and analysis of 41 volatile terpenes from patés with added sage and rosemary essential oils including alpha-pinene, beta-myrcene, 1-limonene, (E)-caryophyllene, linalool, camphor, and 1,8-cineole, which might contribute to the aroma characteristics of liver patés.     

Effect of the type of frying culinary fat on volatile compounds isolated in fried pork loin chops by using SPME-GC-MS

The effect of the type of frying culinary fat (olive oil, sunflower oil, butter, and pig lard) on volatile compounds isolated from fried pork loin chops (m. Longissimus dorsi) was measured by SPME-GC-MS. Frying modified the fatty acid composition of lipids from pork loin chops, which tended to be similar to that of the culinary fat used to fry. Volatile compounds formed from the oxidation of fatty acids increased, such as aldehydes, ketones, alcohols, and hydrocarbons. Besides, each culinary fat used modified the volatile profiles in fried meat differently. Sunflower oil-fried pork loin chops presented the highest aldehyde aliphatic content, probably due to their highest content of polyunsaturated acids. Hexanal, the most abundant aldehyde in fried samples, presented the most elevated content in sunflower oil-fried pork loin chops. In addition, these samples presented more heterocyclic compounds from the Maillard reaction than other fried samples. Volatiles detected in olive oil-fried pork loin chops were mainly lipid-derived compounds such as pentan-1-ol, hexanal, hept-2-enal, nonanal, decanal, benzaldehyde, and nonan-2-one. Butter-fried pork loins were abundant in ketones with a high number of carbons (heptan-2-one, nonan-2-one, undecan-2-one, tridecanone, and heptadecan-2-one). Pig lard-fried pork loin chops presented some Strecker aldehydes isolated in only these samples, such as 2-methylbutanal and 3-(methylthio)propanal, and a sulfur compound (dimethyl disulfide) related to Strecker aldehydes.     

Diurnal and seasonal water variations of temperature,pH, redox potential and conductivity in gnammas (weathering pits): Implications for chemical weathering

A gnamma or weathering pit is a small-sized cavity sculpted into solid rock which refills with rainwater. This study describes the main hydrological processes in gnammas and the underlying chemical interactions with the environment. Four gnammas developed in a granite tor from central Spain were chosen for monitoring and studying the dynamics of the gnamma–water system. Parameters monitored were air and water temperature, pH, ORP (redox potential), and conductivity. These measurements describe the system dynamics, without the need for special sampling or other potential interferences under low water volumes. Additionally, chemical analyses were carried out to contrast the chemical properties with the chemical composition. As a consequence of water volumes less than 100 L, daily fluctuations tended to cause the largest amplitude changes. Photosynthesis and respiration/putrefaction processes in the gnamma are responsible for daily pH fluctuations up to 4 units, with pH values often greater than 9. ORP generally alternates from positive to negative values as the solution oscillates diurnally between basic and acidic conditions. Conductivity values ∼ 10 μS/cm occur most of the year, with only minor daily oscillations. During dry periods, conductivity increases significantly with maximum values > 400 μS/cm. These high conductivity values reflect atmospheric inputs by summer rainstorms after prolonged dry periods. Therefore, conductivity does not relate directly with chemical species dissolved from the host rock. Silica was the main weathering product of granite dissolution during the year, with highest concentrations (> 200 ppm) in the rainy season. Low Si values measured during the dry season are in accordance with observed precipitation of amorphous silica within the gnamma. Seasonal variations in concentration are also present in Al and Fe as a response to ORP variations and evaporative dynamics, causing mineral dissolution and new mineral precipitation during the year. Relations among the measured parameters are influenced by several factors, including biological processes, temperature effects and water level variations. Factors such as large pH oscillations, basic pH values, acids from biological activity, and alkali cations all increase silicate solubility, thus favoring granite dissolution. Overflow of water during the winter, when the water is chemically enriched, is an effective mechanism to remove weathering products.     

Chemical conversion of phenylethylamine into phenylacetaldehyde by carbonyl-amine reactions in model systems

The chemical conversion of phenylethylamine into phenylacetaldehyde in the presence of lipid oxidation products (LOPs) was studied to investigate the possibility that biogenic amines can be converted into Strecker aldehydes upon processing. Model systems of phenylethylamine and methyl 13-hydroperoxyoctadeca-9,11-dienoate (HP), 2,4-decadienal (DD), 4,5-epoxy-2-heptenal (EH), 4,5-epoxy-2-decenal (ED), 4-oxo-2-hexenal (OH), 4-oxo-2-nonenal (ON), or 4-hydroxy-2-nonenal (HN) were heated for 1 h at 180 °C and pH 3. Although HN and EH did not produce more phenylacetaldehyde than when phenylethylamine was heated alone, all other lipid oxidation products assayed increased the amount of phenylacetaldehyde produced by 300-900%, with ON being the most reactive compound for this reaction. The reaction was mainly produced at acidic pH values (<6) and was dependent upon the concentration of the LOPs involved, and the phenylacetaldehyde produced increased linearly as a function of the time and temperature. The E(a) values for the reactions between phenylethylamine and DD and ON were 54.8 and 53.8 kJ/mol, respectively. The reaction is proposed to take place by the formation of an imine between the phenylethylamine and the LOPs, which is later converted into another imine by an electronic rearrangement. This new imine is the origin of phenylacetaldehyde by hydrolysis. These results show a new pathway for Strecker aldehyde formation. This route provides a potential way to reduce biogenic amine content in foods when they can be thermally processed before consumption.     

Food-derived peptides stimulate mucin secretion and gene expression in intestinal cells

In this study, the hypothesis that food-derived opioid peptides besides β-casomorphin 7 might modulate the production of mucin via a direct action on epithelial goblet cells was investigated in HT29-MTX cells used as a model of human colonic epithelium. Seven milk whey or casein peptides, a human milk peptide, and a wheat gluten-derived peptide with proved or probable ability to bind μ- or δ-opioid receptors were tested on the cell culture. Significantly increased secretion of mucins was found after exposure to six of the assayed peptides, besides the previously described β-casomorphin 7, as measured by an enzyme-linked lectin assay (ELLA). Human β-casomorphin 5 and α-lactorphin were selected to study the expression of mucin 5AC gene (MUC5AC), the HT29-MTX major secreted mucin gene. α-Lactorphin showed increased expression of MUC5AC from 4 to 24 h (up to 1.6-fold over basal level expression), although differences were statistically different only after 24 h of exposure. However, this increased expression of MUC5AC did not reach significance after cell treatment with human β-casomorphin 5. In conclusion, six food-derived peptides have been identifed with described or probable opioid activity that induce mucin secretion in HT29-MTX cells. Concretely, α-lactorphin is able to up-regulate the expression of the major secreted mucin gene encoded by these cells.     

Methyl linoleate oxidation in the presence of bovine serum albumin

The oxidation of methyl linoleate (LMe) in the presence of bovine serum albumin (BSA) was studied to analyze both the processes involved when lipid oxidation occurs in the presence of proteins and the relative progression of the several reactions implicated. The disappearance of LMe, the formation of primary and secondary lipid oxidation products, the loss of essential amino acids, and the production of oxidized lipid/amino acid reaction products (OLAARPs) were studied as a function of incubation time. During the first steps of lipid oxidation, LMe was converted quantitatively to methyl linoleate hydroperoxides, which were very rapidly degraded to either secondary products of lipid oxidation or OLAARPs. No significant differences were identified in the major lipid oxidation products formed in incubations with or without proteins, indicating that mechanisms for formation of these compounds are similar in both cases. In addition, no significant differences were observed between the time-courses of formation of secondary oxidation products and OLAARPs, suggesting that hydroperoxide decomposition and OLAARP formation occur simultaneously when the lipid oxidation process takes place in the presence of proteins. Furthermore, OLAARP formation seems to be an unavoidable process that should be considered as a last step in the lipid peroxidation process.