Keith R. Cadwallader

Micromachined GC columns for fast separation of organophosphonate and organosulfur compounds.

This article demonstrates how to prepare microfabricated columns (microcolumns) for organophosphonate and organosulfur compound separation that rival the performance of commercial capillary columns. Approximately 16,500 theoretical plates were generated with a 3 m long OV-5-coated microcolumn with a 0.25 microm phase thickness using helium as the carrier gas at 20 cm/s. Key to the advance was the development of deactivation procedures appropriate for silicon microcolumns with Pyrex tops. Active sites in a silicon-Pyrex microcolumn cause peak tailing and unwanted adsorption. Experimentally, we found that organosilicon hydride deactivation lowers adsorption activity in microcolumns more than silazane and silane treatments. But without further treatment, the phosphonate peaks continue to tail after the coating process. We found that heat treatment with pinacolyl methylphosphonic acid (PMP) eliminated the phosphonate peak tailing. In contrast, conventional resilylation employing N, O-bis(trimethylsilyl)acetamide, hexamethyldisilazane, and 1-(trimethylsilyl)imidazole does not eliminate peak tailing. Column activity tests show that the PMP treatment also improves the peaks for 2,6-dimethyl aniline, 1-octanol, and 1-decanol implying a decrease in the columns hydrogen bonding sites with the PMP treatment. FT-IR analysis shows that exposure to PMP forms a bond to the stationary phase that deactivates the active sites responsible for organophosphonate peak tailing.

Effect of enhancement and ageing on flavor and volatile compounds in various beef muscles.

To identify and quantify selected flavor-active volatile compounds and relate them to sensory characteristics, the gluteus medius (round), rectus femoris (round), vastus lateralis (round), vatsus medialis (round), teres major (chuck), infraspinatus (chuck), complexus (chuck), serratus ventralis (chuck), psoas major (loin) and longissimus dorsi (loin) were removed from heifer carcasses, enhanced, vacuum packaged, aged for 7 or 14days, steaks were cut, vacuum packaged and frozen (48h). Flavor-active volatiles affected by enhancement and ageing in the various muscles included nonanal, 2,3-octanedione, pentanal, 3-hydroxy-2-butanone, 2-pentyl furan, 1-octen-3-ol, butanoic acid, pentanal and hexanoic acid, compounds often associated with lipid oxidation. Enhancement decreased hexanal and hexanoic acid. Ageing decreased butanoic acid. Pentanal content varied among muscles depending on enhancement and ageing. Livery off-flavor was positively correlated with pentanal, hexanal, 3-hydroxy-2-butanone and hexanoic acid. Rancid off-flavor was correlated with pentanal and with 2-pentyl furan but not with hexanal.

Investigation of Thermal Decomposition as the Kinetic Process That Causes the Loss of Crystalline Structure in Sucrose Using a Chemical Analysis Approach (Part II)

High performance liquid chromatography (HPLC) on a calcium form cation exchange column with refractive index and photodiode array detection was used to investigate thermal decomposition as the cause of the loss of crystalline structure in sucrose. Crystalline sucrose structure was removed using a standard differential scanning calorimetry (SDSC) method (fast heating method) and a quasi-isothermal modulated differential scanning calorimetry (MDSC) method (slow heating method). In the fast heating method, initial decomposition components, glucose (0.365%) and 5-HMF (0.003%), were found in the sucrose sample coincident with the onset temperature of the first endothermic peak. In the slow heating method, glucose (0.411%) and 5-HMF (0.003%) were found in the sucrose sample coincident with the holding time (50 min) at which the reversing heat capacity began to increase. In both methods, even before the crystalline structure in sucrose was completely removed, unidentified thermal decomposition components were formed. These results prove not only that the loss of crystalline structure in sucrose is caused by thermal decomposition, but also that it is achieved via a time-temperature combination process. This knowledge is important for quality assurance purposes and for developing new sugar based food and pharmaceutical products. In addition, this research provides new insights into the caramelization process, showing that caramelization can occur under low temperature (significantly below the literature reported melting temperature), albeit longer time, conditions.

Aroma Components of American Country Ham

The aroma-active compounds of American country ham were investigated by using direct solvent extraction-solvent assisted flavor evaporation (DSE-SAFE), dynamic headspace dilution analysis (DHDA), gas chromatography-olfactometry (GCO), aroma extract dilution analysis (AEDA), and gas chromatography-mass spectrometry (GC-MS). The results indicated the involvement of numerous volatile constituents in the aroma of country ham. For DHDA, 38 compounds were identified as major odorants, among them, 1-octen-3-one, 2-acetyl-1-pyrroline, 1-nonen-3-one, decanal, and (E)-2-nonenal were the most predominant, having FD-factors >or= 125 in all 3 hams examined, followed by 3-methylbutanal, 1-hexen-3-one, octanal, acetic acid, phenylacetaldehyde, and Furaneol. For the DSE-SAFE method, the neutral/basic fraction was dominated by 1-octen-3-one, methional, guaiacol, (E)-4,5-epoxy-(E)-decenal, p-cresol as well as 3-methylbutanal, hexanal, 2-acetyl-1-pyrroline, phenylacetaldehyde, and gamma-nonalactone. The acidic fraction contained mainly short-chain volatile acids (3-methylbutanoic acid, butanoic acid, hexanoic acid, and acetic acid) and Maillard reaction products (for example, 4-hydroxy-2,5-dimethyl-3(2H)-furanone). The above compounds identified were derived from lipid oxidation, amino acid degradation, and Maillard/Strecker and associated reactions. Both methods revealed the same nature of the aroma components of American country ham.

Optimization of the Enzymatic Deamidation of Soy Protein by Protein-Glutaminase and Its Effect on the Functional Properties of the Protein

The effects of enzymatic deamidation by protein-glutaminase (PG) on the functional properties of soy protein isolate (SPI) were studied. Conditions for the deamidation were evaluated by means of response surface methodology (RSM). Optimal conditions based on achieving a high degree of deamidation (DD) with a concurrently low degree of hydrolysis (DH) were 44 °C, enzyme:substrate ratio (E/S) of 40 U/g protein and pH 7.0. Under optimal conditions, both DD and DH increased over time. SDS-PAGE results indicated that lower molecular mass subunits were produced with increasing DD. Far-UV circular dichroism spectra revealed that the α-helix structure decreased with higher DD, while the β-sheet structure increased until 15 min of deamidation (32.9% DD), but then decreased at higher DD. The solubility of deamidated SPI was enhanced under both acidic and neutral conditions. SPI with higher DD showed better emulsifying properties and greater foaming capacity than SPI, while foaming stability was decreased. It is possible to modify and potentially improve the functional properties of SPI by enzymatic deamidation using PG.

Sonication in combination with heat and low pressure as an alternative pasteurization treatment – Effect on Escherichia coli K12 inactivation and quality of apple cider

Escherichia coli K12 cells suspended in apple cider were treated by manothermosonication (MTS, 400 kPa/59 °C), thermosonication (TS, 100 kPa/59 °C), and manosonication (MS, 400 kPa/55 °C) for up to 4 min. A 5-log reduction was achieved in 1.4 min by MTS, 3.8 min by TS, and 2.5 min by MS. The inactivation curves of the E. coli exhibited a fast initial reduction followed by a slow inactivation section. The Weibull, log-logistic, and biphasic linear models showed a good fit of the inactivation data. Quality analyses were conducted with raw apple cider (control), thermally-pasteurized (TP), and MTS-, TS-, and MS-treated cider samples over a 3-week period at refrigeration temperature. Titratable acidity and pH did not differ among any of the samples. During storage, the turbidity value of the control was the highest, followed by TP, TS, MTS and MS. All color parameters of the TP sample were significantly different from those receiving the other treatments. The control and sonicated samples showed similar color parameters during storage. In total, 97 aroma compounds were identified in the control, TS-, MS-, and MTS-treated cider samples, while 95 aroma compounds were found in the TP at Week 0. Among all the aroma compounds, 9 key ones were identified in all samples, including ethyl 2-methylbutanoate, butyl acetate, 1-butanol, ethyl hexanoate, 1-hexanol, butanoic acid, β-damascenone, hexanoic acid, and octanoic acid. The profiles of the key aroma compounds in all sonicated samples were more similar to the control than the TP sample at Weeks 0 and 3.

Flavours and Off-Flavours in Milk and Dairy Products

Milk and milk products are an important part of daily nutrition in many regions of the world. Besides fulfilling nutritional requirements, the flavour of milk and milk products is a key parameter for consumer acceptance and marketing (Drake et al., 2007a). The market for dairy products in more traditional dairying countries has been growing steadily; most of this growth can be attributed directly to the introduction of novel product options and increasing application of milk constituents in other food formulations. Due to the importance of dairy products in daily life, especially for consumers in traditional dairying countries, they are being used increasingly as delivery systems for biologically active/nutraceutical preparations. Even higher growth in the consumption of milk and milk products is now coming from countries which did not have any tradition of dairying; such countries offer tremendous opportunity for further enhanced sales. At the same time this increased consumption also challenges researchers and manufacturers to create new product solutions to better suit the palette of consumers recently introduced to dairy products.

Effect of Enzymatic Deamidation of Soy Protein by Protein–Glutaminase on the Flavor-Binding Properties of the Protein under Aqueous Conditions

The effect of the enzymatic deamidation by protein-glutaminase (PG) on flavor-binding properties of soy protein isolate (SPI) under aqueous conditions was evaluated by a modified equilibrium dialysis (ultrafiltration) technique. Binding parameters, such as number of binding sites (n) and binding constants (K), were derived from Klotz plots. The partial deamidation of SPI by PG (43.7% degree of deamidation) decreased overall flavor-binding affinity (nK) at 25 °C for both vanillin and maltol by approximately 9- and 4-fold, respectively. The thermodynamic parameters of binding indicated that the flavor-protein interactions were spontaneous (negative ΔG°) and that the driving force of the interactions shifted from entropy to enthalpy driven as a result of deamidation. Deamidation of soy protein caused a change in the mechanism of binding from hydrophobic interactions or covalent bonding (Schiff base formation) to weaker van der Waals forces or hydrogen bonding.

Effect of addition of commercial rosemary extracts on potent odorants in cooked beef.

Solid-phase microextraction-gas chromatography-olfactometry (SPME-GCO) and aroma extract dilution analysis (AEDA) were applied to measure the effects of the addition of two commercial rosemary extracts (RE) on the potent odorants in cooked beef extracts (BE). On the basis of the results of SPME-GCO and AEDA, the addition of RE imparted sweet and floral notes to BE as a result of the addition of esters and terpenes of RE. In addition, RE suppressed the formation of odorants derived via lipid oxidation and Maillard reactions. The most potent lipid oxidation volatiles consisted of 1-octen-3-one (mushroom-like), (E)-2,4-epoxy-(E)-2-decenal (metallic), and eight different aldehydes (fatty). The Maillard reaction volatiles, necessary for typical cooked beef flavor, included compounds with meaty [2-methyl-3-furanthiol, 2-methyl-3-(methylthio)furan, 2-methyl-3-(methyldithio)furan], roasty (2-furanmethanethiol), caramel-like [4-hydroxy-2,5-dimethyl-3(2H)-furanone], baked potato-like [3-(methylthio)propanal], and spicy [3-hydroxy-4,5-dimethyl-2(5H)-furanone] attributes. The suppressive effects of RE may be caused by the action of antioxidative substances in RE alone or in combination with the pH increase in BE induced by the matrix components of RE.

Characterization of protein hydrolysis and odor-active compounds of fish sauce inoculated with Virgibacillus sp. SK37 under reduced salt content.

The effect of Virgibacillus sp. SK37, together with reduced salt content, on fish sauce quality, particularly free amino acids and odor-active compounds, was investigated. Virgibacillus sp. SK37 was inoculated with an approximate viable count of 5 log CFU/mL in samples with varied amounts of solar salt, for example, 10, 15, and 20% of total weight. Eighteen selected odorants were quantitated by stable isotope dilution assays (SIDA), and their odor activity values (OAVs) were calculated. Samples prepared using 10% salt underwent spoilage after 7 days of fermentation. The viable count of Virgibacillus sp. SK37 was found over 3 months in the samples containing 15 and 20% salt. However, acceleration of protein hydrolysis was not pronounced in inoculated samples at both 15 and 20% salt. Virgibacillus sp. SK37, together with salt contents reduced to 15-20%, appeared to increase the content of 2-methylpropanal, 2-methylbutanal, 3-methylbutanal, acetic acid, and 2-methylpropanoic acid. However, only aldehydes were found to have an effect on the overall aroma of fish sauce based on high OAVs, suggesting that the inoculation of samples with Virgibacillus sp. SK37 under reduced salt contents of 15-20% likely contributed to stronger malty or dark chocolate notes.