Gas chromatographic method for determination of dimethylamine, trimethylamine, and trimethylamine oxide in fish-meat frankfurters

A method is described for analysis of minced fish-meat and surimi-meat frankfurters for dimethylamine (DMA), trimethylamine (TMA), and trimethylamine oxide (TMAO) using a headspace-gas chromatographic technique. After simple acid extraction and addition of NaOH, the headspace was directly injected into a gas chromatograph by a gas-tight syringe. DMA and TMA were separated on a Chromosorb 103 column and detected by a flame ionization detector. TMAO was measured as TMA after Zn reduction. Repeatability of the method for DMA, TMA, and TMAO was 6.6, 1.0, and 18.8 ppm, respectively. The method was applicable to Alaska pollock-meat and Atlantic menhaden-meat frankfurters, unwashed, and washed mince and surimi.     

Soybean lipoxygenase inactivation by pressure at subzero and elevated temperatures

Soybean lipoxygenase (LOX) inactivation [0.4 mg/mL in Tris-HCl buffer (0.01 M, pH 9)] was studied quantitatively under constant pressure (up to 650 MPa) and temperature (-15 to 68 degrees C) conditions and kinetically characterized by rate constants, activation energies, and activation volumes. The irreversible LOX inactivation followed a first-order reaction at all pressure-temperature combinations tested. In the entire pressure-temperature area studied, LOX inactivation rate constants increased with increasing pressure at constant temperature. On the contrary, at constant pressure, the inactivation rate constants showed a minimum around 30 degrees C and could be increased by either a temperature increase or decrease. On the basis of the calculated rate constants at 102 pressure-temperature combinations, an iso-rate contour diagram was constructed as a function of pressure and temperature. The pressure-temperature dependence of the LOX inactivation rate constants was described successfully using a modified kinetic model of Hawley.     

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).     

Stability of isoflavones in soy milk stored at elevated and ambient temperatures

Soy isoflavones are widely recognized for their potential health benefits. The increased use of traditional and new food products calls for the assessment of their stability during processing and storage. The present study examines the stability of genistein and daidzein derivatives in soy milk. Soy milk was stored at ambient and elevated temperatures, and the change in isoflavone concentration was monitored with time. Genistin loss in time showed typical first-order kinetics, with rate constants ranging from 0.437-3.871 to 61-109 days(-1) in the temperature ranges of 15-37 and 70-90 degrees C, respectively. The temperature dependence of genistin loss followed the Arrhenius relation with activation energies of 7.2 kcal/mol at ambient temperatures and 17.6 kcal/mol at elevated temperatures. At early stages of soy milk storage at 80 and 90 degrees C, the 6' '-O-acetyldaidzin concentration increased, followed by a slow decrease. The results obtained in this study can serve as a basis for estimating the shelf life of soy milk as related to its genistin content.     

Effect of soil solarization on subsequent nitrification activity at elevated temperatures

Soil solarization is a nonchemical method of soil disinfection achieved by covering the soil surface with sheets of vinyl plastic to generate elevated soil temperature, generally over 45°C. Such elevated temperatures may be detrimental to some nitrifying microorganisms and favorable to others. However, little information exists to indicate how nitrification activity in soil is affected after solarization. We performed several experiments to investigate the effects of soil solarization on nitrification activity. We found that: (1) if a soil was subjected to pretreatment of 45 or 50°C for as little as 1 d, nitrification activity in a subsequent incubation at 30°C was less than that of a soil that did not receive any high-temperature pretreatment. However, if a soil received pretreatments of 45 or 50°C for more than 7 d, nitrification activity in a subsequent incubation at 45 or 50°C was greater than that of soil that did not receive high temperature pretreatment. (2) Nitrification activity in three kinds of soil taken from 0–5 cm depth after solarization treatment was greater at 45°C than 30°C. (3) Nitrification activity at 45°C in soil that had received solarization in the preceding year was greater than that in soil that had not been subjected to solarization. This was consistent with the fact that the population densities of ammonia oxidizers were greater in soils that had been subjected to solarization. These results suggest that soil solarization induces nitrifying microorganisms that are more active at 45–50°C than they are at 30°C, and that the effect of solarization on nitrification persists until the next crop season.     

Use of stable tracer studies to evaluate pesticide photolysis at elevated temperatures

New methods were developed to determine photolysis rates of medium-weight pesticides in the gas phase using elevated air temperatures and solid-phase microextraction (SPME). A 57-L glass chamber was constructed that utilized collimated xenon arc irradiation that could heat chamber air to increase the amount of pesticide in the gas phase. Gas-phase photolysis rates were determined at various air temperatures by comparing the rate of loss of each of the tested pesticides to a photochemically stable tracer, hexachlorobenzene. Interval sampling of gas-phase constituents was performed using SPME immediately followed by GC-ECD or GC-MSD analysis. The two pesticides under examination were the dinitroaniline herbicide trifluralin and the organophosphorus insecticide chlorpyrifos. The gas-phase photolysis for trifluralin was found to be rapid with half-lives of 22-24 min corrected for sunlight. These results were comparable to photochemical lifetime estimates from other investigators under sunlight conditions. Elevating temperatures from 60 to 80 degrees C did not affect photolysis rates, and these rates could be extrapolated to environmental temperatures. From 60 to 80 degrees C, gas-phase chlorpyrifos photolysis lifetimes were observed to range from 1.4 to 2.2 h corrected for sunlight and will thus be important together with hydroxyl radical reactions for removing this substance from the atmosphere. At these elevated temperatures, pesticides and tracer compounds were found to be substantially in the gas phase, and possible effects on reaction rates from wall interactions were minimized.     

Reactivity of certain organophosphorus insecticides toward hydroxyl radicals at elevated air temperatures

Methods were developed to determine OH reaction rates for medium-weight organophosphorus pesticides in the gas phase. A 57-L chamber was constructed that utilized xenon arc irradiation (>290 nm) to photolyze the OH precursor, methyl nitrite. Experiments were performed at elevated temperatures ranging from 60 to 80 degrees C to minimize wall sorption. Solid-phase microextraction (SPME) sampling of the gas phase was employed to assess the simultaneous rate of loss of the pesticides in relation to the rate of loss of two reference substances with known OH rate constants. An internal gas-phase standard (hexachlorobenzene), relatively stable to hydroxyl radicals, was used to assess other processes, which included dilution and wall sorption. The relative reaction rates of the organophosphorus insecticides, diazinon and chlorpyrifos, when compared to reference compounds, were unaffected by various air temperatures between 60 and 80 degrees C. Although both insecticides were expected to react at similar rates on the basis of structural activity model predictions, diazinon reacted 3 times more rapidly than chlorpyrifos and gave estimated environmental OH half-lives of 0.5 and 1.4 h, respectively. The degree of sorption onto the chamber walls was minimal and similar for each of the compounds examined. Experimental gas-phase determinations at elevated temperatures may provide important information that can be used when in the assessment of the potential of airborne pesticide risks to nontarget and ecologically sensitive areas.     

Vegetable oil stability at elevated temperatures in the presence of ferric stearate and ferrous octanoate

The thermoxidative stability of partially hydrogenated soybean oil (PHSBO) was examined after addition of ferric stearate and ferrous octanoate, and then heating the samples at 120, 160, 180, and 200 degrees C. In a second experiment, the effect of iron concentration (ferric stearate) on PHSBO stability was examined at 180 degrees C, and at concentrations of approximately 0.5 and 1.2 mg of added iron/kg PHSBO. Oil samples were heated continuously for 72 h and sampled every 12 h. The acid value, p-anisidine value, color, dielectric constant and the triacylglycerol polymer content of oil samples were compared to oil samples containing no added iron. Generally, the value of each oxidative index increased with (1) an increase in temperature, (2) an increase in heating time, and/or (3) an increase in iron. The results demonstrate that low concentrations of iron will substantially increase the rate of oxidation for vegetable oil samples heated to temperatures of 120 degrees C to 200 degrees C.     

Effect of high-pressure processing at elevated temperatures on thiamin and riboflavin in pork and model systems

High-pressure/high-temperature properties of vitamins in food are important with respect to the new pressure-assisted thermal sterilization method utilizing pressure-induced adiabatic temperature changes. Riboflavin, thiamin, and thiamin monophosphate (TMP) stabilities were assayed in the temperature range from 25 to 100 degrees C under normal pressure (0.1 MPa) and high pressure (600 MPa) in acetate-buffered (pH 5.5) model solutions, some with added fructose, hemoglobin, or ascorbic acid. Thiamin and riboflavin stabilities were also assayed in minced fresh pork fillet and in rehydrated pork reference material with and without pressure treatment at 600 MPa in the temperature range from 20 to 100 degrees C. In pork, the vitamins proved to be sufficiently stabile for high-pressure/high-temperature processing. Under similar conditions, vitamin decay in model solutions was up to 30 times faster, especially that of TMP. Thus, it appears that it may not be possible to draw conclusions for the pressure behavior of real food matrices from the results of investigations in food models. A further consequence is that caution is necessary when supplementing foods with synthetic B vitamins preceding high-pressure/high-temperature processing.     

Nutrient leaching from dormant trees at an elevated site

Observations are presented on ion concentration in winter deposits to coniferous and deciduous trees at an elevated site (860 m). Such sites, with persistent snow and ice cover and considerable deposition of atmospheric pollutants, are common in Eastern Canada and the North-Eastern U.S. Spot samples at a given sampling date and samples of total deposits accumulated over extended periods of time were taken during the winters of 1986–87 and 1987–88. Samples were analyzed for pH and the major anion and cations. Results of spot samples were similar between different sampling times (and years) for deposits on balsam fir but variable for those on branches and twigs of deciduous trees (birch, choke cherry). The chemistries of snow on the ground and snow on trees not in contact with foliage or branches were found not to be significantly different statistically (p<0.05). However, significant differences exist between concentrations of nutrient ions in snow and ice with and without contact with biological elements of coniferous and deciduous trees. This indicates occurrence of nutrient leaching during winter conditions, leading to possibly non-negligent nutrient stress for K? and Mg?. Based on spot and cumulative samples for balsam fir, and correcting for possible contributions from dry deposition, the contribution from leaching in winter deposits on balsam fir foliage has been estimated at 26, 14 and 9 μeq L^?1, for K⁺, Ca⁺⁺ and Mg⁺⁺, respectively. With approximate estimates of stand characteristics and precipitation loading at the sampling sites, these figures represent 90/c, 1% and 8%, respectively, of the estimated annual growth component of the stand for K⁺, Ca⁺⁺ and Mg⁺⁺ This indicates the possibility of non-negligible nutrient stress for K⁺ and Mg⁺ during winter conditions at the given site.     

Aroma volatility from aqueous sucrose solutions at low and subzero temperatures

The gas-liquid partition coefficients of ethyl acetate and ethyl hexanoate have been measured in water and aqueous sucrose solutions from 25 to -10 degrees C by dynamic headspace. Experiments were carried out on sucrose solutions at temperatures where no ice formation was possible. Results showed that when sucrose concentration increased, aroma volatility increased except for ethyl hexanoate and in the highest sucrose concentration solution (57.5%). A quasi-linear temperature decrease on aroma volatility was observed in sucrose solutions from 25 to around 4 and 0 degrees C. Then, from 0 to -10 degrees C, aroma volatility did not decrease: ethyl acetate volatility remained constant but that of ethyl hexanoate increased. Enthalpy of vaporization and activity coefficients of the aroma compounds were calculated.     

Kinetic modeling of malonylgenistin and malonyldaidzin conversions under alkaline conditions and elevated temperatures

The conversion and degradation of malonylglucosides were kinetically characterized under elevated pH/heat conditions. Malonylgenistin and malonyldaidzin were heated at 60, 80, and 100 degrees C and pH values of 8.5, 9, and 9.5. A simple kinetic model was developed, which adequately predicted the conversion and degradation reactions. The conversion and degradation rates increased as temperature and pH increased. The rates of conversion of both malonylglucosides into their respective beta-glucosides were comparable under all pH/heat treatments. However, at 100 degrees C, the rates of degradation of malonyldaidzin were approximately double those of malonylgenistin, under all pH treatments. When malonlydaidzin was heated at 100 degrees C and pH 9.5, degradation of the produced daidzin occurred. Therefore, an alternative kinetic model was developed to better predict the conversion and degradation of malonyldaidzin occurring at 100 degrees C and pH 9.5. The models developed provide soy food manufacturers with guidelines for better control of the profile and level of isoflavones..     

Model studies on the influence of high hydrostatic pressure on the formation of glycated arginine modifications at elevated temperatures

Aqueous solutions of Nalpha-acetylarginine and glucose were reacted for 2 h with pressure application from 0 to 600 MPa and varying temperatures between 90 and 120 degrees C. After enzymatic deacetylation of the reaction products, the glycated amino acids were separated by means of a self-assembled preparative ion exchange chromatography system using ninhydrin detection. On the basis of the use of eight synthesized reference compounds known in the literature as posttranslational arginine modifications, first, the presence of several glycated amino acids could be excluded. On the other hand, N5-[[(1-carboxyethyl)amino]iminomethyl]ornithine [N7-(1-carboxyethyl)arginine; N7-CEA; 12] was identified as a previously unknown arginine modification based on LC-MS, NMR measurements, and synthesis. In addition, N5-(5-hydro-5-methyl-4-imidazolon-2-yl)-L-ornithine (1) was identified as a further major reaction product. In further experiments, the formation of 1 and 12 was quantitatively followed at different pressures and/or temperatures. The results indicated that high hydrostatic pressure at elevated temperatures significantly increased the amounts of both arginine modifications. 2-Oxopropanal, known to form 1 in a reaction with arginine, was also quantified to explain the different yields observed after pressure application. A new formation mechanism leading to 12 by a reaction of the guanidine group or arginine with 2-oxopropanal is discussed.     

Lipoxygenase inactivation in green beans (Phaseolus vulgaris L.) due to high pressure treatment at subzero and elevated temperatures

The kinetics of lipoxygenase (LOX) inactivation in green beans due to high-pressure treatment were studied in the pressure-temperature area of 0.1 up to 650 MPa and -10 up to 70 degrees C for systems with different levels of food complexity, i.e., in green bean juice and intact green beans (in situ study). For both systems, LOX was irreversibly inactivated by high-pressure treatment combined with subzero and elevated temperatures and the inactivation could be described as a first-order reaction. At ambient pressure, in situ LOX was less thermostable than in the juice at temperatures below 68 degrees C whereas the stability ranking was reverse at temperatures above 68 degrees C. At temperatures below 63 degrees C, sensitivity of the inactivation rate constants to temperature changes was on the same order of magnitude in the juice and in situ, while at higher temperature it was lower in situ. The pressure needed to obtain the same rate of LOX inactivation at a given temperature was lower in situ than in the juice. Application of high-pressure treatment at low/subzero temperature resulted in an antagonistic effect on LOX inactivation for both systems, whereas no such effect was found above room temperature. The pressure-temperature dependence of the LOX inactivation rate constants in green beans was successfully modeled.     

不同温度下水稻秸秆多孔生物炭结构与电化学性能

针对一步热解活化技术制备的秸秆多孔生物炭的表面活性位点偏少、孔隙结构不发达和电化学性能欠佳的问题,该研究以水稻秸秆微波磷酸水热炭为前驱体,开展500～900 ℃下多孔生物炭的制备试验,探讨不同温度下多孔生物炭的结构及电化学性能。结果表明,随着活化温度的升高,水稻秸秆多孔生物炭产率由50.31%降低到33.47%,800 ℃多孔生物炭的C含量最高,为74.09%。多孔生物炭表面上含有的-OH、C-O-C等含O基团和吡啶氮、吡咯氮、石墨氮和氮的氧化物等含N基团,有利于其在电解质中的润湿性,降低离子转移电阻。随着活化温度的升高,多孔生物炭的碳的无序度和缺陷程度先增加后降低。800 ℃多孔生物炭的表面缺陷较多,其比表面积为1 002.20 m2/g,总孔体积最大为0.79 cm3/g,中孔体积率为45.57%。在三电极的KOH电解质体系下,800 ℃多孔生物炭电极的比电容最大,倍率性能较好,电阻较小,且其在1 A/g电流密度下的比电容为312.81 F/g。800 ℃多孔生物炭制备的对称电容器在228 W/kg功率密度下的能量密度达到10.73 W·h/kg,且在10 A/g电流密度和5 000次循环充放电后,其比电容保持率为95.82%。     

Labile,recalcitrant, microbial carbon and nitrogen and the microbial community composition at two Abies faxoniana forest elevations under elevated temperatures

We investigated the interactions of altitude and artificial warming on the soil microbial community structure in a subalpine Abies faxoniana forest in southwestern China after four years of warming. Open top chambers (OTCs) at two elevations (3000 m and 3500 m) were established, and their soil microbial characteristics, organic carbon (C) and nitrogen (N) were measured. The microbial community structure was quantified by phospholipid fatty acid (PLFA) analysis. A two-step sulfuric acid hydrolysis was used to quantify the labile and recalcitrant C fractions in the soil organic matter. The results showed that bacterial PLFAs and gram-negative bacterial PLFAs increased and the fungal PLFAs and the fungi/bacteria ratio decreased with warming at the high altitude. By contrast, the warming effects on those parameters at low altitude were small. The higher proportion of labile easily decomposable soil C may explain the different responses of the microbial community composition at the two altitudes. An RDA analysis confirmed that the variations in the soil community structure were significantly associated with soil organic matter properties such as the sizes of the soil labile N pool (LP-N), the recalcitrant N pool (RP-N), and the labile C pool as well as dissolved organic C (DOC) and dissolved organic N concentrations (DON). Our results also showed that labile C and N pools increased with the altitude, but the microbial biomass C as measured with chloroform fumigation techniques decreased. Warming increased only the recalcitrant C pools at the high altitude. Given the longer mean residence time for recalcitrant C and the much greater size of this soil organic carbon pool, the results indicated that a rise in temperature in our case increased soil C pools at higher altitudes, at least during the early stages of experimental soil warming. Warming could also cause changes in the composition of the microbial community and enzyme activities, consequently leading to functional changes in soil ecosystem processes at the high altitude.     

Modeling bleaching of tomato derivatives at subzero temperatures

This work was addressed to obtain a predictive model of the rate of bleaching in tomato derivatives at subzero temperatures. To this aim, a tomato puree was freeze-dried and equilibrated at increasing solid fractions. The bleaching rate was assessed by measuring tomato color during storage for up to 18 months at temperatures from -30 to 0 degrees C. The temperature dependence of the tomato-bleaching rate was neither predictable using the Arrhenius equation nor simply related to tomato physical state. The lack of a clear Arrhenius relation was attributed to the occurrence of temperature-dependent phenomena, such as ice crystallization and oxygen solubility modifications, which strongly changed the local concentration of reactants. A modified Arrhenius equation predicting the tomato-bleaching rate in the entire temperature range was proposed. Tomato concentration, and hence its physical state, affected the temperature dependence of bleaching, modifying apparent activation energy and frequency factor of the modified Arrhenius equation. In light of these considerations, a mathematical model was set up and validated to accurately predict the tomato-bleaching rate on the basis of only its concentration and storage temperature.     

不同温度下葡甘聚糖的分子模拟

用计算机模拟技术确定了不同温度条件下魔芋葡甘聚糖大分子糖单元的几何构型,并用分子力学方法计算了单元结构的最低能量构象,为葡甘聚糖的几何构型和稳定构象研究搭建了桥梁.还探讨氢键的形成和对结构稳定的影响,以及计算机模拟技术在多糖研究中的发展趋势.实验结果表明T=368K时,葡甘聚糖单元结构氢键形成数量最多,体系能量最低,结构最稳定.