Effects of thermal processing and storage on available lysine and furfural compounds contents of infant formulas

The Maillard reaction-related effects that thermal treatments during the manufacturing process and storage (at 20 and 37 degrees C) have on powdered adapted and follow-up milk-based infant formulas were estimated by measuring the available lysine and furfural compounds contents of raw cow milk used in manufacturing, intermediate products and formulas. A fluorimetric method was used to measure the available lysine contents, and free and total furfural compounds were determined by HPLC. Statistically significant losses in available lysine (about 20%) in the infant formulas with respect to raw milk were found. The storage period did not affect the available lysine contents of adapted formulas but reduced (16%) the contents of the follow-up ones (from 6.61 to 5.33 g/100 g of protein). No furfural compounds were detected in raw milk, and free and total furyl methyl ketone (FMC) and methylfurfural (MF) were not observed in the analyzed samples. After 6 months of storage, an increase in free hydroxymethylfurfural (HMF) (from 0.34 to 0.77 mg/100 g of protein) and furfural (F) (from nondetectable to 0.1 mg/100 g of protein) in adapted formulas and free HMF (from 1.84 to 2.62 mg/100 g of protein) in follow-up formulas was observed.     

Rheological properties of concentrated skim milk: influence of heat treatment and genetic variants on the changes in viscosity during storage

Heat treatment during manufacturing of milk powder is one of the most important tools for manipulation of its functional properties, and it is the basis of the classification of these proteins into low-, medium-, and high-heat types. Slight differences in the sequences of the major proteins in milk (genetic variants) seem to have also a significant effect in milk powder processing (U.S. patent). Therefore, the effects of high-temperature storage and heat treatment on skim milk of defined genetic variants of beta-lactoglobulin (beta-LG) were measured. The samples had 45% total solids, the temperature of aging was 50 degrees C, and the heat treatment was 90 degrees C for 10 min prior to evaporation. Measurements on shear rate and on apparent viscosity were determined for each sample. During storage of the concentrated milk, the apparent viscosity and yield values increased markedly, and the age-dependent increase in viscosity in heat-treated concentrated skim milks was much more pronounced than in those prepared from unheated skim milks. The increase in apparent viscosity and yield value with storage time was notably different for milks containing different genetic variants. Unheated concentrated milks containing the B variant of beta-LG showed the most rapid increase in apparent viscosity with storage time, whereas the viscosity increase was slowest in the concentrate containing the A variant. In contrast, heat-treated concentrated milks containing the A variant of beta-LG showed the most rapid increase in viscosity with storage time, whereas the viscosity increase was slowest in the concentrate containing the AB variant. The changes in apparent viscosity of concentrated milk were largely reversible under high shear during the early stages of storage, but samples stored for a long time showed irreversible changes in apparent viscosity. Particle size analysis confirmed irreversible aggregation and fusion of casein particles during storage.     

Chemical indicators of heat treatment in fortified and special milks

Carbohydrate and furosine contents in 12 commercial fortified and special milk samples (pasteurized goat's and ewe's milks; ultrahigh-temperature (UHT) goat's milk, UHT milks fortified with calcium, magnesium, fiber, or royal jelly and honey; and lactose-hydrolyzed milks) were analyzed. Except for lactose-hydrolyzed milks, furosine, lactose, lactulose, galactose, glucose, N-acetylgalactosamine, N-acetylglucosamine, and myo-inositol contents were similar to the previously reported values for UHT or pasteurized milk samples. In lactose-hydrolyzed milks, lactulose was not detectable and lactose was present in low amount; high levels of glucose, galactose, fructose, tagatose, and furosine were also detected in this type of milk. Results found in commercial milks were compared to those obtained in laboratory-prepared UHT milks with lactose hydrolyzed prior to heating. Hydrolysis of lactose before thermal treatments promoted elevated accumulation of reducing sugars (galactose and glucose) that could be partially converted to the corresponding isomers (tagatose and fructose) during heating. In addition, the reducing sugars could also react with the amino groups of proteins, giving rise to the corresponding Amadori compound. According to the obtained results, heating prior to hydrolysis of lactose is suggested to avoid a considerable loss of available lysine.     

Reduction of stale flavor development in low-heat skim milk powder via epicatechin addition

The influence of epicatechin (EC) on off-flavor development in low-heat skim milk powder samples during processing and storage was investigated. Milk powder samples were prepared from a concentrated skim milk (control) plus a concentrated skim milk with EC (treatment). Volatile extracts of the powders were analyzed by aroma extract dilution analysis (AEDA) at 0 days and after 17 months of storage in conjunction with sensory analysis of the flavor attributes. The treatment milk powders with EC added prior to drying reported a reduction in the formation of three main compounds, 4-hydroxy-2,5-dimethyl-3-(2H)-furanone, o-aminoacetophenone, and furfural, by 8-, 4-, and 4-fold for the 0 day old samples, while for the 17 month aged samples o-aminoacetophenone was the major compound reduced in formation by 8-fold, respectively, based on the flavor dilution factors reported. The sensory evaluations indicated that the treatment milk powders for 0 day old and 17 month aged samples were statistically lower (alpha = 0.05) in stale flavor intensity in comparison to the respective control samples, while no differences were noted in bitterness intensity.     

Comparison of nosespace,headspace, and sensory intensity ratings for the evaluation of flavor absorption by fat

The goal of this study was to better understand the correspondence between sensory perception and in-nose compound concentration. Five aroma compounds at three different concentrations increasing by factors of 4 were added to four matrixes (water, skim milk, 2.7% fat milk, and 3.8% fat milk). These were evaluated by nosespace analysis with detection by proton transfer reaction mass spectrometry (PTR-MS), using five panelists. These same panelists evaluated the perceived intensity of each compound in the matrixes at the three concentrations. PTR-MS quantification found that the percent released from an aqueous solution swallowed immediately was between 0.1 and 0.6%, depending on the compound. The nosespace and sensory results showed the expected effect of fat on release, where lipophilic compounds showed reductions in release as fat content increases. The effect is less than that observed in headspace studies. A general correlation between nosespace concentration and sensory intensity ratings was found. However, examples of perceptual masking were found where higher fat milks showed reductions in aroma compound intensity ratings, even if the nosespace concentrations were the same.     

Rapid fingerprinting of milk thermal processing history by intact protein mass spectrometry with nondenaturing chromatography

Thermal processing of foods results in proteins undergoing conformational changes, aggregation, and chemical modification notably with sugars via the Maillard reaction. This can impact their functional, nutritional, and allergenic properties. Native size-exclusion chromatography with online electrospray mass spectrometry (SEC-ESI-MS) was used to characterize processing-induced changes in milk proteins in a range of milk products. Milk products could be readily grouped into either pasteurized liquid milks, heavily processed milks, or milk powders by SEC behavior, particularly by aggregation of whey proteins by thermal processing. Maillard modification of all major milk proteins by lactose was observed by MS and was primarily present in milk powders. The method developed is a rapid tool for fingerprinting the processing history of milk and has potential as a quality control method for food ingredient manufacture. The method described here can profile milk protein oligomeric state, aggregation, and Maillard modification in a single shot, rapid analysis.     

New methodology for the determination of phthalate esters, bisphenol A, bisphenol A diglycidyl ether, and nonylphenol in commercial whole milk samples

This paper reports a new methodology aimed at determining dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, butylbenzyl phthalate, bis(2-ethylhexyl) phthalate, nonylphenol, bisphenol A, and bisphenol A diglycidyl ether in commercial whole milk. These compounds are used as plastic additives, lacquers, resins, or surfactants and can be found in milk due to contact with plastic materials during food processing and storage. They are all suspected endocrine disrupters or mutagens. A multiresidue method based in solid-phase extraction with C-18 cartridges followed by a cleanup step using disposable cartridges was developed. Detection and quantification were performed by gas chromatography coupled to mass spectrometric (GC-MS) detection using an appropriate surrogate (4-n-nonylphenol) and internal standard [deuterated bis(2-ethylhexyl) phthalate]. Limits of detection were from 0.06 to 0.36 microg/kg and intraday variation from 3 and 27%, with recoveries between 73 and 119%. Five brands of commercial whole milk processed and packed in different ways were analyzed. All samples contained target compounds at concentrations between 0.28 and 85.3 microg/kg, and the total concentration ranged between 79.3 and 187.4 microg/kg, the levels being higher in sterilized milks. Nonylphenol, diethyl phthalate, dibutyl phthalate, and bis(2-ethylhexyl) phthalate were the major contributors.     

Properties of tofus and soy milks prepared from soybeans having different subunits of glycinin

The contribution of soybean protein to the physical properties of tofu, a product manufactured by curdling soy milk with coagulants such as calcium or magnesium chloride, was studied by comparing the properties of soy milk prepared from soybeans with different subunits (I, IIa, and IIb) of glycinin with amino acid residues deleted. The breaking stress value of the tofu curds prepared from soybeans having group I was higher than those without group I. The soy milks having group I contained more protein particles and showed more sensitivity to calcium and magnesium ions than those without group I. The amounts of glycinin and protein particles were higher in the soy milks having group I than those in the soy milks without group I. To elucidate the influence of each group on the breaking stress, the glycinin content was adjusted to an identical level in soy milks having each group. Among the tofu curds from three groups, their order of hardness according to their breaking stress was IIa, IIb, and I. The order of particle content among these soy milks was also IIa, IIb, and I. Therefore, the results suggested that the breaking stress value of the tofu curd is dependent upon the number of protein particles in the soy milk and that the number of the particles is determined by the proportion and structure of glycinin in the soybean.     

Flavor threshold for acetaldehyde in milk, chocolate milk, and spring water using solid phase microextraction gas chromatography for quantification

The detection threshold of acetaldehyde was determined on whole, lowfat, and nonfat milks, chocolate-flavored milk, and spring water. Knowledge of the acetaldehyde threshold is important because acetaldehyde forms in milk during storage as a result of light oxidation. It is also a degradation product of poly(ethylene terephthalate) during melt processing, a relatively new packaging choice for milk and water. There was no significant difference in the acetaldehyde threshold in milk of various fat contents, with thresholds ranging from 3939 to 4040 ppb. Chocolate-flavored milk and spring water showed thresholds of 10048 and 167 ppb, respectively, which compares favorably with previous studies. Solid phase microextraction (SPME) was verified as an effective method for the recovery of acetaldehyde in all media with detection levels as low as 200 and 20 ppb in milk and water, respectively, when using a polydimethyl siloxane/Carboxen SPME fiber in static headspace at 45 degrees C for 15 min.     

Chemometric studies of several minerals in milks

A statistical study of correlation, factorial, and discriminant analysis on the metal composition (Se, Fe, Cu, Zn, Na, K, Ca, Mg) of different types of milks (human, cow, goat, pasteurized, and powdered infant formula) was carried out to establish the relationships between the metal concentrations and, therefore, differentiate the samples according to the type of milk. A large number of significant intermetallic correlations were found in all samples, which could be due to biological relationships between the metals studied. After the factorial analysis, the dimension space was reduced from eight variables to two factors, accounting for approximately 71.4% of the total variance. After an orthogonal rotation, the first factor was positively correlated with Ca and the second factor with Fe. The representation of the scores makes it possible to separate not only human milk from powdered infant formula but also to separate both of these from the other milks. In the discriminant analysis, four discriminant functions were obtained, which are linear combinations of the quantitative variables that best explain the differences among the different milks analyzed. These functions make it possible to classify 98% of the samples analyzed within each type of milk correctly. Therefore, discriminant functions obtained here can be used to identify the origin of any milk sample.     

Inhibition of key aroma compound generated during ultrahigh-temperature processing of bovine milk via epicatechin addition

The ability of epicatechin (EC) to inhibit the thermal development of aroma compounds (i.e., Maillard reaction products) formed during ultrahigh-temperature (UHT) processing of bovine milk was evaluated. Volatile extracts were prepared for two UHT-processed milk samples made from (1) raw milk and (2) raw milk containing 0.1% EC by solvent-assisted flavor evaporation (SAFE) and subsequently analyzed by aroma extract dilution analysis (AEDA). Sensory evaluation was also conducted by a trained panel on the intensity of cooked flavor and bitterness in four UHT-processed milk samples (0.00, 0.01, 0.10, and 0.20% EC added prior to processing), as well as a commercial pasteurized milk sample for comparison. AEDA indicated that addition of EC to raw fluid milk prior to UHT processing reduced the overall thermal formation of key aroma-active compounds in comparison to the traditional UHT milk sample. The largest changes in FD values were reported for methional, furfural, 2-isopropyl-3-methoxypyrazine, 2-acetyl-1-pyrroline, and 2-acetyl-2-thiazoline (Maillard-type aroma compounds) with 32-, 8-, 8-, 4-, and 4-fold reductions in formation, respectively. Sensory evaluation also revealed that all EC-containing UHT milk samples had statistically (P < 0.05) lower cooked flavor intensity in comparison to the control, whereas the 0.2% EC sample was statistically similar to a pasteurized milk sample. Furthermore, addition of EC at or below 0.1% in UHT fluid milk did not significantly increase the bitterness intensity.     

ELISA to detect proteolysis of ultrahigh-temperature milk upon storage

Casein proteolysis can occur in milk during storage leading to its gelation. The two main proteolytic systems suspected to be involved are the plasmin and the proteases produced by psychrotrophic bacteria. The latter have been shown to cleave kappa-casein at the Phe105-Met106 bond. Although several techniques allow the determination of plasmin in milk, few rapid and easy-to-perform analytical techniques are available to check for bacterial proteolytic activity. This study presents the development of an inhibition ELISA allowing for the quantification of the kappa-casein intact at the Phe105-Met106 bond. It uses a monoclonal antibody specifically directed against this peptide bond that binds to the protein as long as the molecule's cleavage site is intact but not when it is cleaved. This simple technique allows for the rapid analysis of more than 20 samples within 3 h. Applied to commercial milks, this assay allowed for the detection of unstable milk.     

Physicochemical properties of acidified skim milk gels containing cocoa flavanols

The physicochemical properties of acidified milk gels after the addition of cocoa flavanols were studied. As the flavanol level increased (from 0 to 2.5 mg/g), syneresis and gel elasticity (tan δ) were found to significantly increase and decrease, respectively. Flavanol addition reduced the stress at fracture, with no changes in fracture strain, suggesting that the bond type (i.e., covalent vs noncovalent) was the underlying factor explaining the ease of fracture. Gels made from recombined milks containing the casein fraction of heated milk and the serum of heated flavanol/milk mixtures showed the lowest values of G' and fracture stress. It was concluded that whey proteins/flavanol interactions were responsible for the poor mechanical properties of flavanol-added acidified milk gels. High-performance liquid chromatography analysis of milk sera showed that 60% of the total available monomeric flavanols was found in the serum phase from which 75% was non-associated to whey proteins. Concomitantly, >70% of flavanols with degree of polymerization >3 were found to be associated with the casein fraction.     

Relevance of isotopic and molecular biomarkers for the authentication of milk according to production zone and type of feeding of the cow

The first objective of the present paper was to assess the potential of both isotopic ( (18)O/ (16)O in milk water) and molecular biomarkers (terpenes, fatty acids, carotenoids, and vitamins) and milk color to discriminate the production zone (lowland or upland areas) from which 49 tanker bulk milks were collected over one year from a total of 204 farms. The milk water (18)O enrichment was higher in lowland (<500 m altitude) than in upland (>700 m altitude), but the delta (18)O values failed to discriminate systematically the production zone at the scale of the year because of its high variability related to the sampling period. In contrast with vitamins A and E, carotenoids, and milk color measurements, terpenes and fatty acids were confirmed to be relevant tracers of the production zone. The milk compounds with the strongest discriminative potential were fatty acids, which were determined by high-resolution gas chromatography. The calculation of fatty acid ratios, which permits the limitation of using fatty acid relative quantity expressed in percentage of total fatty acids to be overcome, was shown to be particularly relevant in discriminating upland from lowland milk ratios. The selection of two pairs of ratios, namely, iso-C17:0/C18:3 n-3 and iso-C15:0/iso-C14:0, enabled the authentication of 100% of the highland versus lowland milks whatever the season. The second objective was to evaluate the relevance of fatty acid composition to discriminate milks according to the proportion of corn silage in the diets of dairy cows. The selection of two fatty acids ratios, namely, trans11 cis15-C18:2/trans11-C18:1 and cis9-C16:1/iso-C16:0, enabled the correct classification of 100% of the milk samples according to the proportion of corn silage in the basic fodder rations (<25% vs >30%). The relationship between the milk production zone and the type of forage fed to the cows is discussed.     

Instrumental and sensory characterization of heat-induced odorants in aseptically packaged soy milk

Predominant heat-induced odorants generated in soy milk by ultrahigh-temperature (UHT) processing were evaluated by sensory and instrumental techniques. Soy milks processed by UHT (143 degrees C/14 s, 143 degrees C/59 s, 154 degrees C/29 s) were compared to a control soy milk (90 degrees C/10 min) after 0, 1, and 7 days of storage (4.4 +/- 1 degrees C). Dynamic headspace dilution analysis (DHDA) and solvent-assisted flavor evaporation (SAFE) in conjunction with GC-olfactometry (GCO)/aroma extract dilution techniques and GC-MS were used to identify and quantify major aroma-active compounds. Sensory results revealed that intensities of overall aroma and sulfur and sweet aromatic flavors were affected by the processing conditions. Odorants mainly responsible for the changes in sulfur perception were methional, methanethiol, and dimethyl sulfide. Increases in 2-acetyl-1-pyrroline, 2-acetyl-thiazole, and 2-acetyl-2-thiazoline intensities were associated with roasted aromas. A marginal increase in intensity of sweet aromatic flavor could be explained by increases in 2,3-butanedione, 3-hydroxy-2-butanone, beta-damascenone, and 2- and 3-methylbutanal. Predominant lipid-derived odorants, including (E,E)-2,4-nonadienal, (E,E)-2,4-decadienal, (E,Z)-2,4-decadienal, (E)-2-nonenal, (E)-2-octenal, 1-octen-3-one, 1-octen-3-ol, and (E,Z)-2,6-nonadienal, were affected by processing conditions. Intensities of overall aroma and sulfur notes in soy milk decreased during storage, whereas other sensory attributes did not change. Color changes, evaluated by using a Chroma-meter, indicated all UHT heating conditions used in this study generated a more yellow and saturated color in soy milk in comparison to the control soy milk.     

Evolution of chemical and sensory properties during aging of top-fermented beer

The aging and consequent changes in flavor molecules of a top-fermented beer were studied. Different aging conditions were imposed on freshly bottled beer. After 6 months of aging, the concentration changes were recorded for acetate esters, ethyl esters, carbonyls, Maillard compounds, dioxolanes, and furanic ethers. For some flavor compounds, the changes with time of storage were monitored at different temperatures, either with CO(2) or with air in the headspace of the bottles. For some molecules a relationship was determined between concentration changes and sensory evaluation results. A decrease in volatile esters was responsible for a reduced fruity flavor during aging. On the contrary, various carbonyl compounds, some ethyl esters, Maillard compounds, dioxolanes, and furanic ethers showed a marked increase, due to oxidative and nonoxidative reactions. A very high increase was found for furfural, 2-furanmethanol, and especially the furanic ether, 2-furfuryl ethyl ether (FEE). For FEE a flavor threshold in beer of 6 mug/L was determined. In the aged top-fermented beer, FEE concentrations multiple times the flavor threshold were observed. This was associated with the appearance of a typical solvent-like flavor. As the FEE concentration increased with time at an almost constant rate, with or without air in the headspace, FEE (and probably other furanic ethers) is proposed as a good candidate to evaluate the thermal stress imposed on beer.     

Mineral dialyzability in milk and fermented dairy products fortified with FeNaEDTA

Iron, zinc, and calcium dialyzability and ascorbic acid (AA) concentrations were evaluated in milk and yogurt fortified with FeNaEDTA (FE) or ferrous sulfate (FS) as a control, with or without AA addition. The values obtained for FE iron dialyzability in milk were much higher than those obtained for FS. The addition of AA to milk improved Fe dialyzability when using FS and slightly decreased Fe dialyzability in the FE-fortified nonfermented samples. Milk fermentation increased iron availability from both iron sources. Zinc and calcium dialyzability in products containing any of the two iron sources was increased in fermented milks. EDTA improved Zn dialyzability from intrinsic zinc in every manufactured dairy product. Whereas for milks fortified with FS and stored at 4 degrees C for 24 h, the AA content remained close to the original concentration, a higher AA degradation was observed when milks were fortified with FE.     

Casein micelles: size distribution in milks from individual cows

The size distribution and protein composition of casein micelles in the milk of Holstein-Friesian cows was determined as a function of stage and number of lactations. Protein composition did not vary significantly between the milks of different cows or as a function of lactation stage. Differences in the size and polydispersity of the casein micelles were observed between the milks of different cows, but not as a function of stage of milking or stage of lactation and not even over successive lactations periods. Modal radii varied from 55 to 70 nm, whereas hydrodynamic radii at a scattering angle of 73° (Q2 = 350 μm?2) varied from 77 to 115 nm and polydispersity varied from 0.27 to 0.41, in a log-normal distribution. Casein micelle size in the milks of individual cows was not correlated with age, milk production, or lactation stage of the cows or fat or protein content of the milk.     

Retention of essential amino acids during extrusion of protein and reducing sugars

This research investigates the retention of essential amino acid profiles of products during the extrusion of proteins and reducing sugars. Animal proteins (egg and milk protein at 10 and 30% levels) and reducing sugars (fructose and galactose at 0, 2, and 8% levels), with pregelatinized wheat flour, were extruded at 110 and 125 degrees C product temperatures and feed moistures of 19 and 23.5% for egg protein and 13.75 and 16% for milk protein. The nutritional property analyzed was essential amino acid retention, and sugar retention was also considered to understand the relationship of sugars with retention of amino acids. Lysine showed the lowest retention (up to 40%) of all the essential amino acids. Retention of other essential amino acids varied from 80 to 100% in most situations. Apart from lysine, tryptophan, threonine, and methionine were found to be significantly changed ( P < 0.05) with processing conditions. Increased protein and sugar levels resulted in a significant degradation of lysine. Greater lysine retention was found at a lower temperature and higher feed moisture. Results of sugar retention also showed similar patterns. The products made from fructose had greater lysine retention than products made from galactose with any type of protein. The outcomes of this research suggested that the combination of milk protein and fructose at a lower temperature and higher feed moisture is most favorable for developing high-protein extruded products.     

Fortification of milk with calcium: effect on calcium bioavailability and interactions with iron and zinc

Calcium solubility, dialysability, and transport and uptake (retention + transport) by Caco-2 cells as indicators of calcium bioavailability have been estimated in the in vitro gastrointestinal digests of milk and calcium fortified milk. A significant linear correlation (p < 0.05) was obtained between calcium uptake and the amount of soluble calcium added to the cells, and also between percentage calcium uptake and the calcium measured in the analyzed samples. The solubility, dialysis, transport, and uptake values are higher (p < 0.05) for calcium fortified milks than for nonfortified milks; that is, calcium fortification increases not only calcium content but also its bioavailability. An inhibitory effect of calcium from fortified milks upon iron absorption was found. The observed effect of calcium from fortified milks upon zinc bioavailability depends on the in vitro method used, zinc solubility and dialysis decrease in calcium fortified milks, and percentage zinc uptake remains unchanged.