Heat-induced compounds development in processed tomato and their influence on corrosion initiation in metal food cans.

Selected ion flow tube mass spectrometry (SIFT-MS) and ion chromatography (IC) were used to investigate the presence of volatile and nonvolatile compounds in canned tomatoes and in the polymeric lining before and after retorting the cans. This allowed us to observe if these compounds contributed to corrosion and the migration of iron and tin compounds from the cans to the tomatoes. Diced Roma tomatoes and other simulant treatment groups were sealed in two-piece tinplated cans (controls in glass jars), retorted at 121℃ for 30 min, then stored at 49℃ for 50 days. Results showed that thermal degradation of amino acids in the tomatoes gave rise to volatile methyl sulfides and nonvolatile nitrogenous compounds which were subsequently sorbed by the can lining. SIFT-MS showed a 20-fold increase in dimethyl sulfide concentration. Inductively coupled plasma (ICP-MS) results showed fourfold and 16-fold increases in iron and tin compounds, respectively, that migrated from the metal to the tomatoes as a result of acid and electrolyte interactions.

Cyanogenesis in Macadamia and Direct Analysis of Hydrogen Cyanide in Macadamia Flowers, Leaves, Husks, and Nuts Using Selected Ion Flow Tube-Mass Spectrometry.

Macadamia has increasing commercial importance in the food, cosmetics, and pharmaceutical industries. However, the toxic compound hydrogen cyanide (HCN) released from the hydrolysis of cyanogenic compounds in Macadamia causes a safety risk. In this study, optimum conditions for the maximum release of HCN from Macadamia were evaluated. Direct headspace analysis of HCN above Macadamia plant parts (flower, leaves, nuts, and husks) was carried out using selected ion flow tube-mass spectrometry (SIFT-MS). The cyanogenic glycoside dhurrin and total cyanide in the extracts were analyzed using HPLC-MS and UV-vis spectrophotometer, respectively. HCN released in the headspace was at a maximum when Macadamia samples were treated with pH 7 buffer solution and heated at 50 °C for 60 min. Correspondingly, treatment of Macadamia samples under these conditions resulted in 93%-100% removal of dhurrin and 81%-91% removal of total cyanide in the sample extracts. Hydrolysis of cyanogenic glucosides followed a first-order reaction with respect to HCN production where cyanogenesis is principally induced by pH changes initiating enzymatic hydrolysis rather than thermally induced reactions. The effective processing of different Macadamia plant parts is important and beneficial for the safe production and utilization of Macadamia-based products.

Swiss Cheese Flavor Variability Based on Correlations of Volatile Flavor Compounds, Descriptive Sensory Attributes, and Consumer Preference.

Minimizing flavor variation in cheeses without perceived flavor defects in order to produce a consistent product is a challenge in the Swiss cheese industry. This study evaluated flavor variability based on correlations of volatile flavor compounds and sensory attributes. The headspace concentrations of volatile compounds were analyzed using selected ion flow tube-mass spectrometry (SIFT-MS), while the sensory attributes were evaluated using descriptive sensory analysis and consumer testing. The important discriminating volatile compounds were classified into five functional groups: sulfur-containing compounds (methyl mercaptan, hydrogen sulfide, dimethyl disulfide, dimethyl trisulfide, and methional), organic acids (propanoic acid, acetic acid, 3-methylbutanoic acid), aldehydes (3-methylbutanal, butanal, and 2-methylpropanal), a ketone (2,3-butanedione), and an ester (ethyl hexanoate). Correlations were identified among volatile compounds and between volatile compounds and sensory attributes. Only a small number of volatile compounds strongly correlated positively or negatively to a specific sensory attribute. Nutty malty, milkfat lactone, salty, umami, and sweet positively correlated to overall liking and nutty flavor liking of Swiss cheese. Evaluation of cheese flavor using correlations between volatile compounds and sensory attributes provided further understanding of the complexity of flavor and flavor variability among Swiss cheeses manufactured from different factories that can be used to improve flavor consistency of Swiss cheeses.

Temperature-dependent Henry's Law constants of 4-alkyl branched-chain fatty acids and 3-methylindole in an oil-air matrix and analysis of volatiles in lamb fat using selected ion flow tube mass spectrometry.

RATIONALE: 4-Alkyl branched-chain fatty acids and 3-methylindole are characteristic flavor compounds associated with sheep meat. Determining their partitioning behavior between the gas and condensed phase and ultimately developing a correlation between the compound's headspace concentration and sensory descriptive grouping are important for high-throughput characterization and grading classification. METHODS: The headspace concentrations of 3-methylindole, 4-methyloctanoic acid, 4-ethyl-octanoic acid, and 4-methylnonanoic acid above corn-oil-based standard solutions and lamb fat samples were measured using selected ion flow tube-mass spectrometry (SIFT-MS). The standard solutions were equilibrated at 80, 100, 110 and 125°C while the fat samples were equilibrated at 125°C. Statistical evaluation, linear and polynomial regression analyses were performed to establish the compound-specific and temperature-dependent Henry's Law constants, enthalpy (ΔH) and entropy (ΔS) of phase changes. RESULTS: The Henry's Law constants (kHcp ) were calculated from the regression analysis with a high degree of confidence (p < 0.05) and linearity (r2  > 0.99). The kHcp increased with increase in equilibrium temperature. The empirical calculation of ΔH and ΔS at different temperatures confirmed the temperature-dependence of the Henry's Law constants. The headspace concentrations of the lamb-flavor compounds were determined above actual lamb fat samples and the corresponding condensed-phase concentrations were successfully derived. CONCLUSIONS: The temperature-dependent Henry's Law constants, ΔH, and ΔS of phase changes for 3-methylindole, 4-methyloctanoic acid, 4-ethyloctanoic acid, and 4-methylnonanoic acid in an air-oil matrix were empirically derived. The effectiveness of SIFT-MS for the direct, real-time, and rapid determination of key flavor compounds in lamb fat samples was established.

Gas-phase chemical ionization of 4-alkyl branched-chain carboxylic acids and 3-methylindole using H3 O+ , NO+ , and O2+ ions.

RATIONALE: 4-Methyloctanoic acid, 4-ethyloctanoic acid, 4-methylnonanoic acid, and 3-methylindole are primary contributors to the distinctive aroma and flavor of lamb meat. The reactions of H3 O+ , NO+ , and O2+ with these compounds, and identification of the product ions and their distribution, are fundamental to their characterization and rapid, real-time trace analysis using selected ion flow tube mass spectrometry (SIFT-MS). METHODS: The chemical ionization of pure standards of 4-ethyloctanoic acid, 4-methyloctanoic acid, 4-ethylnonanoic acid, and 3-methylindole was carried out using the H3 O+ , NO+ , and O2+ reagent ions of a V200™ SIFT mass spectrometer. Kinetic data were calculated using the Langevin collision rate with parameterized trajectory equations. Identification of product ions, distribution, and interferences was performed by further evaluation of the pertinent ion-molecule reaction mechanisms, careful spectral analyses, and molecular mass-molecular structure pairing. RESULTS: The collisional capture rate constants of the reaction of the precursor ions H3 O+ , NO+ , and O2+ , their extended hydrates and the analytes, which were assumed to occur at or near the collisional rate, were all of the order of 10-9  cm3 molecule s-1 - typical for bimolecular ion-molecule reactions. Positive identification of the primary and secondary product ions, fragmented ionic species, and potential ion conflicts and interferences, from each reagent ion channel, was determined for each compound. CONCLUSIONS: We have established the ion chemistry involved in the ionization of the 4-alkyl branched-chain fatty acids and 3-methylindole using the precursor ions, H3 O+ , NO+ , and O2+ in SIFT-MS. The ion-molecular chemistry and the associated kinetics serve as a fundamental basis for the accurate characterization of these compounds by SIFT-MS.

Characterisation and quantification of changes in odorants from litter headspace of meat chickens fed diets varying in protein levels and additives.

The effect of dietary crude protein (CP) and additives on odor flux from meat chicken litter was investigated using 180 day-old Ross 308 male chicks randomly allocated to five dietary treatments with three replicates of 12 birds each. A 5 × 3 factorial arrangement of treatments was employed. Factors were: diet (low CP, high CP, high CP+antibiotic, high CP+probiotic, high CP+saponin) and age (15, 29, 35 days). The antibiotic used was Zn bacitracin, the probiotic was a blend of three Bacillus subtilis strains and the saponin came from a blend of Yucca and Quillaja. Odorants were collected from litter headspace with a flux hood and measured using selective ion flow tube mass spectrometry (SIFT-MS). Litter moisture, water activity (Aw), and litter headspace odorant concentrations were correlated. The results showed that low CP group produced lower flux of dimethyl amine, trimethyl amine, H2S, NH3, and phenol in litter compared to high CP group (P < 0.05). Similarly, high CP+probiotic group produced lower flux of H2S (P < 0.05) and high CP+saponin group produced lower flux of trimethylamine and phenol in litter compared to high CP group (P < 0.05). The dietary treatments tended (P = 0.065) to have higher flux of methanethiol in high CP group compared to others. There was a diet × age interaction for litter flux of diacetyl, 3-hydroxy-2-butanone (acetoin), 3-methyl-1-butanol, 3-methylbutanal, ethanethiol, propionic acid, and hexane (P < 0.05). Concentrations of diacetyl, acetoin, propionic acid, and hexane in litter were higher from low CP group compared to all other treatments on d 35 (P < 0.05) but not on d 15 and 29. A high litter moisture increased water activity (P < 0.01) and favored the emissions of methyl mercaptan, hydrogen sulfide, dimethyl sulfide, ammonia, trimethyl amine, phenol, indole, and 3-methylindole over others. Thus, the low CP diet, Bacillus subtilis based probiotic and the blend of Yucca/Quillaja  saponin were effective in reducing the emissions of some key odorants from meat chicken litter.

Headspace quantification of pure and aqueous solutions of binary mixtures of key volatile organic compounds in Swiss cheeses using selected ion flow tube mass spectrometry.

RATIONALE: Twelve volatile organic compounds (VOCs) have recently been identified as key compounds in Swiss cheese with split defects. It is important to know how these VOCs interact in binary mixtures and if their behavior changes with concentration in binary mixtures. METHODS: Selected ion flow tube mass spectrometry (SIFT-MS) was used for the headspace analysis of VOCs commonly found in Swiss cheeses. Headspace (H/S) sampling and quantification checks using SIFT-MS and further linear regression analyses were carried out on twelve selected aqueous solutions of VOCs. Five binary mixtures of standard solutions of VOCs were also prepared and the H/S profile of each mixture was analyzed. RESULTS: A very good fit of linearity for the twelve VOCs (95% confidence level) confirms direct proportionality between the H/S and the aqueous concentration of the standard solutions. Henry's Law coefficients were calculated with a high degree of confidence. SIFT-MS analysis of five binary mixtures showed that the more polar compounds reduced the H/S concentration of the less polar compounds, while the addition of a less polar compound increased the H/S concentration of the more polar compound. CONCLUSIONS: In the binary experiment, it was shown that the behavior of a compound in the headspace can be significantly affected by the presence of another compound. Thus, the matrix effect plays a significant role in the behavior of molecules in a mixed solution.

Analysis of selected volatile organic compounds in split and nonsplit swiss cheese samples using selected-ion flow tube mass spectrometry (SIFT-MS).

Splits/cracks are recurring product defects that negatively affect the Swiss cheese industry. Investigations to understand the biophysicochemical aspects of these defects, and thus determine preventive measures against their occurrence, are underway. In this study, selected-ion, flow tube mass spectrometry was employed to determine the volatile organic compound (VOC) profiles present in the headspace of split compared with nonsplit cheeses. Two sampling methodologies were employed: split compared with nonsplit cheese vat pair blocks; and comparison of blind, eye, and split segments within cheese blocks. The variability in VOC profiles was examined to evaluate the potential biochemical pathway chemistry differences within and between cheese samples. VOC profile inhomogeneity was most evident in cheeses between factories. Evaluation of biochemical pathways leading to the formation of key VOCs differentiating the split from the blind and eye segments within factories indicated release of additional carbon dioxide by-product. These results suggest a factory-dependent cause of split formation that could develop from varied fermentation pathways in the blind, eye, and split areas within a cheese block. The variability of VOC profiles within and between factories exhibit varied biochemical fermentation pathways that could conceivably be traced back in the making process to identify parameters responsible for split defect.