Water distribution in brine salted cod (Gadus morhua) and salmon (Salmo salar): a low-field 1H NMR study

Low-field (LF) (1)H NMR T 2 relaxation measurements were used to study changes in water distribution in lean (Atlantic cod) and fatty (Atlantic salmon) fish during salting in 15% NaCl and 25% NaCl brines. The NMR data were treated by PCA, continuous distribution analysis, and biexponential fitting and compared with physicochemical data. Two main water pools were observed in unsalted fish, T 21, with relaxation times in the range 20-100 ms, and T 22, with relaxation times in the range 100-300 ms. Pronounced changes in T 2 relaxation data were observed during salting, revealing changes in the water properties. Salting in 15% brine lead to a shift toward longer relaxation times, reflecting increased water mobility, whereas, salting in saturated brines had the opposite effect. Water mobility changes were observed earlier in the salting process for cod compared to salmon. Good linear correlations ( F 相似文献   

1H nuclear magnetic resonance relaxometry study of water state in milk protein mixtures

1H NMR signal was used to characterize highly hydrated milk protein dispersions (3-20% dry matter) with various micellar casein concentrations (3-15%), whey protein concentrations (0-3%), lactose concentrations (0-7.5%), CaCl(2) concentrations (0-2 mM), and pH (6.2-6.6). The results showed the predominant effect of micellar casein concentration on water state and were consistent with the three-site relaxation model in the absence of lactose. The relaxation rates observed for these dispersions were explained by the free water relaxation rate, the hydration water relaxation rate, and the exchangeable proton relaxation rate. Hydration water was found to be mainly influenced by casein micelle concentration and structure. The variations in hydration with pH were consistent with those observed for classical measurement of voluminosity observed at this range of pH. The effects of lactose and whey protein content are discussed.     

Water mobility in multicomponent model media as studied by 2H and 17O NMR

Molecular mobility of water was studied in a microbiological media containing complex and heterogeneous mixtures of cellulose, l-sorbose, and orange serum broth (OSB) using (2)H and (17)O high-resolution NMR. All mixtures showed Lorentian (17)O NMR spectra but complex (2)H NMR line shapes. Sorbose, when solubilized, caused line-narrowing where as cellulose-OSB mixtures showed wide peaks with flat plateaus. Presence of liquid or solvent water had a profound effect on a marked increase in T(2) relaxation time observed in sorbose-containing samples. (17)O NMR data were not composition dependent, while (2)H NMR data were highly sorbose dependent.     

Sugar-casein interaction in deuterated solutions of bovine and caprine casein as determined by oxygen-17 and carbon-13 nuclear magnetic resonance: a case of preferential interactions

17O NMR spectroscopy and (13)C NMR spectroscopy have been used to study the mechanism of interaction of sugars with bovine and caprine caseins in D(2)O. The (17)O NMR relaxation results showed in all cases an increase in water of hydration, as a result of added sugar; this was predominantly associated with "trapped" water in the caseins. Analysis of the vir al coefficients, obtained from the (17)O relaxation data, suggested that preferential interactions occur in the sugar-protein solutions. This could be the result of either sugar binding or a solute-solute thermodynamic effect, preferential hydration. The addition of sugars to deuterated solutions of bovine casein and caprine casein high in alpha(s1)-casein had little or no effect on either line width or chemical shifts of the (13)C NMR spectra of these milk proteins. (13)C NMR studies of sucrose, at various concentrations (100-300 mM) in the presence of caprine casein high in alpha(s1)-casein, showed no changes in either chemical shifts or T(1) values. This indicates that the sugar molecules tumble isotropically and therefore neither bind to the protein nor affect viscosity in the protein-sugar studies. All of these data suggest that the preferential exclusion of the sugar from the domain of the caseins results in preferential hydration of the caseins.     

Water properties in cream cheeses with variations in pH, fat, and salt content and correlation to microbial survival

Water mobility and distribution in cream cheeses with variations in fat (4, 15, and 26%), added salt (0, 0.625, and 1.25%), and pH (4.2, 4.7, and 5.2) were studied using (1)H NMR relaxometry. The cheese samples were inoculated with a mixture of Listeria innocua, Escherichia coli O157 and Staphylococcus aureus, and partial least-squares regression revealed that (1)H T(2) relaxation decay data were able to explain a large part of the variation in the survival of E. coli O157 (64-83%). However, the predictions of L. innocua and S. aureus survival were strongly dependent on the fat/water content of the samples. Consequently, the present results indicate that NMR relaxometry is a promising technique for predicting the survival of these bacteria; however, the characteristics of the sample matrix are substantial.     

Does oxidation affect the water functionality of myofibrillar proteins?

Water-binding properties of myofibrils extracted from porcine muscle, and added hemoglobin with and without exposure to H2O2, were characterized using low-field proton NMR T2 relaxometry. The effects of pH and ionic strength in the samples were investigated as pH was adjusted to 5.4, 6.2, and 7.0 and ionic strength was adjusted to 0.29, 0.46, and 0.71 M, respectively. The formation of dityrosine as a measure of oxidative protein cross-linking revealed a significant increase in dityrosine concentrations upon H2O2 activation. The formation of dityrosine was strongly pH-dependent and increased with decreasing pH. In addition, increased levels of thiobarbituric acid reactive substances were observed upon addition of H2O2, implying that lipid oxidation was enhanced, however, with a different oxidation pattern as compared to the myofibrillar proteins. Low-field NMR relaxation measurements revealed reduced T2 relaxation times upon H2O2 activation, which corresponds to reduced water-holding capacity upon oxidation. However, a direct relationship between degree of oxidation and T2 relaxation time was not observed with various pH values and ionic strengths, and further studies are needed for a complete understanding of the effect of oxidation on myofibrillar functionality.     

Effects of citric acid on the viscoelasticity of cornstarch pastes

The effects of citric acid on the rheological properties of cornstarch pastes were studied by steady shear and dynamic oscillatory viscoelasticity, intrinsic viscosity measurements and microscopic observation. The pH of cornstarch dispersion was adjusted between 6.0 and 3.0. The viscosity of the pastes was increased by lowering the pH (between 5.5 and 3.6), while the viscosity of samples with pH below 3.5 decreased further than that of the control (pH = 6.3). Citric acid promoted the collapse of starch granules; however, adding excessive citric acid led to the hydrolysis of glucose chains. No decrease in the viscoelasticity was observed for cornstarch pastes by adding acid at 25 degrees C after gelatinization.     

Analysis of the retrogradation of low starch concentration gels using differential scanning calorimetry,rheology, and nuclear magnetic resonance spectroscopy

The retrogradation of 5, 10, 15, and 25% corn starch gels was measured using differential scanning calorimetry (DSC), rheology, and an array of NMR spectroscopy techniques. During the initial (<24 h) stage of retrogradation, an increase in G' corresponding to an increase in the number of solid protons participating in cross-relaxation (M(B)(0) was observed for all four concentrations studied. During the latter (>24 h) stage of retrogradation, amylopectin recrystallization becomes the dominant process as measured by an increase in deltaH(r) for the 25% starch gel, which corresponded to a further increase in. A decrease in the molecular mobility of the liquid component was observed by decreases in (17)O T(2), (1)H D(0), and T(2A). The value for T(2B) (the solid transverse relaxation time) did not change with concentration or time indicating that the mobility of the solid component does not change over time despite the conversion of the highly mobile starch fraction to the less mobile solid state during retrogradation.     

Mobility and distribution of water in cassava and potato starches by 1H and 2H NMR

Mobility and distribution of water in cassava (rainy and drought crops) and potato starches were studied by solid state and NMR relaxometry as a function of H(2)O and D(2)O contents ranging from 0 to 44% (dry basis). Measurements of relative mobility derived from (2)H solid state NMR were based on relative area and line shape analysis. The narrow peak (mobile component) started to show at 5% and increased with increasing D(2)O content. This increase in mobile fraction was accompanied by a line narrowing. The mobile fractions of deuterons reached a >98% level above 15% D(2)O, which is well below the water holding capacity of starch ( approximately 27%) and the previously assigned "glassy-rubbery transition point" (24.3%; Jouppila, K.; Roos, Y. H. The physical state of amorphous corn starch and its impact on crystallization. Carbohydr. Polym. 1997, 32, 95-104). This reconfirms the liquidlike nature of water in the so-called glassy state of starch granules. The plasticization effect of water on starch chains was observed at 14-17% for cassava and potato starches as indicated by the T(1) minimum. This, however, did not seem to relate to the difference observed in swelling among the starches studied.     

Evaluation of lime requirement methods for Delaware soils

Abstract

Rapid, accurate identification of the lime required to attain a desired pH is essential for the coarse‐textured soils of the Atlantic coastal plain to avoid micronutrient deficiencies (Mn, Zn) in sensitive crops and to insure herbicide efficacy. The University of Delaware Soil Testing laboratory is one of only seven of the 25 states in the Northeastern and Southern regions that does not use a buffer solution to make lime requirement determinations. The present method bases lime recommendations on soil pH in water, combined with an estimate of buffering capacity obtained by hand texturing soils. This approach is time‐consuming and includes the potential for considerable operator variability in obtaining the textural estimate. A study was initiated to compare four buffer solutions (Adams‐Evans, Mehlich, SMP‐single buffer, SMP‐double buffer) with the current approach and the actual lime requirement as determined by incubation of 19 Delaware soils with six rates of CaCO₃ for six months. Soil pH effects on Mn and Zn availability were determined by extraction of all samples from the incubation study with the Mehlich I (.05M HCl + .0125M H₂SO4) soil testing solution. Results indicated that organic matter was the primary soil component responsible for pH buffering in Delaware soils, and that the Adams‐Evans or Mehlich buffers were the best predictors of actual lime requirement. The appropriate target pH range for the coarse‐textured soils of Delaware, based on Mn and Zn availability, was determined to be 5.5–6.0. Liming soils to pH values greater than 6.0 is, for most crops, unnecessary and will reduce Mn availability below critical levels for sensitive crops such as soybeans and small grains.     

Evaluation of Four Buffer Solutions for Determining the Lime Requirement for Ohio Soils

Lime is used as a soil amendment to achieve the optimum pH suitable for good crop growth. Buffer pH (BpH) measurements have been calibrated to relate the linear drop in pH of the soil–buffer system to the amount of lime needed to neutralize soil to a certain pH level. The amount of lime required to neutralize soil acidity, called the lime requirement (LR), is obtained from soil–limestone (CaCO₃) incubations. In this study, 13 soils from Ohio were incubated with CaCO₃ for a period of 1 month to determine the LR to achieve different target pHs. This LR was then regressed with the different BpHs of four buffer solutions [(1) Shoemaker, McLean, and Pratt (SMP), (2) Sikora, (3) Mehlich, and (4) modified Mehlich] to obtain calibration equations. The Sikora and modified Mehlich buffers are variations of the SMP and Mehlich buffers, respectively, but they are designed to promote buffering without use of any hazardous constituents [i.e., chromium(VI) in SMP buffer and barium in the Mehlich buffer]. This study was done to verify the applicability of the buffers that do not contain any hazardous constituents and to calibrate these buffers for predicting lime requirement needs for Ohio soils. Comparing the calibrated equations of the SMP and Sikora buffers with CaCO₃‐incubation LR recommendations revealed that the SMP and Sikora buffer solutions were not significantly different, and a single calibrated equation can be used for these two buffers to determine LR predictions in Ohio. The Mehlich and modified Mehlich calibration equations differed significantly from the SMP calibration equations and were not as highly correlated with CaCO₃‐incubation LR recommendations using a linear model (r² < 0.54). Thus, it is possible to use the Mehlich and modified Mehlich for determining lime recommendations, but they require a correction factor such as inclusion of the initial soil pH to improve the precision of the LR prediction. We also found the various buffers tested in this study were better able to predict LR rates for greater LR soils than low LR soils. In conclusion, successful laboratory tests to predict LR for Ohio soils are possible using alternative buffers that do not contain hazardous constituents.     

pH Dependence of the progression in NMR T(2) relaxation times in post-mortem muscle

Continuous NMR T(2) relaxation measurements were carried out on seven rabbit longissimus muscle samples in the period from 25 min to 28 h post-mortem at 200 MHz for (1)H. To display differences in post-mortem pH progress and extent of changes in water characteristics during conversion of muscle to meat, three of the seven animals were pre-slaughter injected with adrenaline (0.5 mg/kg live weight 4 h before sacrifice) to differentiate muscle glycogen stores at the time of slaughter. Distributed analysis of T(2) data displayed clear differences in the characteristics of the various transverse relaxation components dependent on progress in pH, as did the water-holding capacity of samples 24 h post-mortem. This reveals a pronounced effect of the progressive change in pH on the subsequent development in physical/chemical states of water during the conversion of muscle to meat. Finally, the relaxation characteristics are discussed in relation to supposed post-mortem processes of protein denaturation.     

Hydration properties and the role of water in taste modalities of sucrose, caffeine, and sucrose-caffeine mixtures

Solution properties of sapid molecules are informative on their type of hydration (hydrophobic or hydrophilic) and on the extent of the hydration layer. Physicochemical properties (intrinsic viscosity and apparent specific volume) and nuclear magnetic resonance (NMR) relaxation rates R(1) and R(2) for pure sucrose, bitter molecule caffeine, and their mixture were found to be relevant in the interpretation of the effects of these solutes on water mobility. Likewise, surface tension, contact angles with a hydrophobic surface, and the adhesion forces to this type of surface of the aqueous solutions of sapid molecules were found to discriminate between their effects on water cohesion and also between their taste qualities. The interpretation of the two sets of independent experimental results, namely physicochemical and spectroscopic data, helps in the elucidation of the role of water in sweet and bitter taste chemoreception.     

FOLIAR SPRAY OF POTASSIUM SILICATE ON THE CONTROL OF ANGULAR LEAF SPOT ON BEANS

This study aimed to determine if potassium silicate (KSi) sprays could reduce the intensity of angular leaf spot. In field experiment 1, bean plants were sprayed with KSi (pH 10.5) at rates of 8, 20, 40, and 60 g L^?1. In field experiment 2, with the same treatments, the pH of the KSi solutions was 5.5. In experiment 3, the treatments were KSi (40 g L^?1, pH 5.5), potassium hydroxide (KOH) (6.5 g L^?1, pH 5.5), tebuconazole (0.5 L ha^?1), and control. In experiment 4, the treatments were the same as in experiment 3, but the pH of the KSi and KOH solutions was 10.5. Plants sprayed with water served as a control treatment for all field experiments. Plants were artificially inoculated with Pseudocercopora griseola before products application. For experiments 3 and 4, the treatment with KOH was included to equalize the amount of potassium (K) with the treatment corresponding to the application of KSi. Disease severity was evaluated using a scale with values ranging from 0.2 to 30.4% at 85 days after seedling emergence. Plant defoliation, Si, and K concentration in the plant tissues, and yield were also determined. There was no relationship between KSi rates and Si concentration in leaf tissues, but Si concentration increased by 58 and 57%, respectively, as the KSi rates increased from 0 to 60 g L^?1 regardless of the pH. The K concentration in leaf tissues did not change among the treatments. Disease severity decreased by 42 and 30%, respectively, at the highest KSi rate with pH 5.5 and pH 10.5 over the control. Disease severity levels were similar between the KSi and KOH treatments, but they were significantly higher compared to the tebuconazole. Plant defoliation at the highest KSi rate with pH 5.5 and 10.5 was 17 and 33%, respectively, less than the control. Plant defoliation decreased with the application of KSi with pH 5.5 and 10.5 in 29 and 34%, respectively, compared to the control. Yield increased by 30 and 43%, respectively, as the KSi rates increased from 0 to 60 g L^?1with pH 5.5 and 10.5. No statistical difference in yield was detected between the KSi and KOH treatments regardless of the pH used, but both were different from tebuconazole. Significant differences in yield were found only between tebuconazole and the control. Results from this study suggest that foliar application of KSi and KOH has the potential to reduce angular leaf spot severity. The KSi did not offer any advantage over the KOH spray, suggesting a lack of a direct effect of Si accumulated in the leaf tissue on disease control.     

Influence of pH and soil copper on adsorption of metalaxyl and penconazole by the surface layer of vineyard soils

The upper horizons of old vineyard soils have substantial copper contents due to the traditional use of copper-based fungicides. Total copper levels in eight vineyard soils in the Rías Baixas area of Galicia (northwestern Spain) ranged from 60 to 560 mg kg(-1) (mean +/- SD = 206 +/- 170 mg kg(-1)). The adsorption of the fungicides metalaxyl (pK(a) = 1.41) and penconazole (pK(a) = 2.83) by these soils was determined using fungicide solutions of pH 2.5 and 5.5, and desorption of fungicide adsorbed at pH 5.5 was also determined. In all cases, Freundlich equations were fitted to the data with R (2) > 0.96. Penconazole was adsorbed and retained more strongly than metalaxyl, with K(F) values more than an order of magnitude greater. In the desorption experiments, both fungicides exhibited hysteresis. Soil copper content hardly affected the adsorption of metalaxyl, but K(F) values for adsorption of penconazole increased at a rate of about 0.1 mL(n) (microg of penconazole)(1-n) (microg of Cu)(-1), which is attributed to the formation of Cu(2+)-penconazole complexes with greater affinity for soil colloids than penconazole itself. Because the dependence of K(F) for penconazole adsorption on copper content was the same at both pH values, complex formation appears not to have been affected by the solubilization of 6-17% of soil copper at pH 2.5. A similar copper dependence, or lack of dependence, was observed when 100-1000 mg kg(-1) of copper was added as Cu(NO(3))(2).2H(2)O to the solutions from which the fungicides were adsorbed.     

Effect of Extraction Conditions on Yield,Composition, and Viscosity Stability of Barley β-Glucan Gum

Cereal β-glucan can function as a thickener, but endogenous β-glucanase enzymes of the grain cleave β-glucan, reducing its viscosity. Although different extraction techniques have been developed, the viscosity stability of β-glucan gum has not been reported. The objective of this study was to investigate the effect of extraction treatments on the yield, purity, and viscosity stability of barley β-glucan (BBG) gum. A regular barley cultivar, Condor, and a waxy cultivar blend were extracted at pH 7–10 and 55°C for 0.5 hr. Four extraction conditions were evaluated: 1) extraction at high pH with no additional heat treatment; 2) boiling of extract; 3) prior refluxing of flour with 70% ethanol; and 4) treatment of extract with thermostable α-amylase for purification. Viscosity of extracts was monitored for ≥24 hr at 25°C. The highest β-glucan purities were achieved with a boiled Condor extract at pH 7 (81.3% db, 4.1% yield) and with refluxed waxy barley extracted at pH 8 and treated with α-amylase and (79.3% db, 5.1% yield). Gums extracted without subsequent heat treatment or prior refluxing of flour had high protein (>17%) and starch (>24%) impurities, respectively. The viscosity of gums obtained without heating was unstable. Prior refluxing treatment was not sufficient to stabilize final extracts. Boiling extracts resulted in stable but low viscosity. Reflux followed by purification treatment produced the highest stable viscosity for 0.5% solutions of both Condor (64 mPa sec^-1, pH 7) and waxy (48.8 mPa sec^-1, pH 8) extracts. Stable BBG gum with high viscosity can be obtained using thermal treatments in combination with high pH. The potential use of such gums as thickeners in food systems needs to be assessed.     

Sugar fragmentation in the maillard reaction cascade: formation of short-chain carboxylic acids by a new oxidative alpha-dicarbonyl cleavage pathway

The formation of short-chain carboxylic acids was studied in Maillard model systems (90 degrees C, pH 6-10) with emphasis on the role of oxygen and water. The total amount of acetic acid formed did not depend on the reaction atmosphere. In the presence of labeled dioxygen or water (18O2, H2 17O), labeled oxygen was partially incorporated into acetic acid. Thermal treatment of 1-deoxy-d-erythro-2,3-hexodiulose (1) and 3-deoxy-d-erythro-hexos-2-ulose in the presence of 17O-enriched water under alkaline conditions led to acetic and formic acid, respectively, as indicated by 17O NMR spectroscopy. The suggested mechanism involves an oxidative alpha-dicarbonyl cleavage leading to an intermediary mixed acid anhydride that releases the acids, e.g., acetic and erythronic acid, from 1. Similarly, glyceric and lactic acids were formed from 1-deoxy-3,4-hexodiuloses, corroborated by complementary analytical techniques. This paper provides for the first time evidence for the direct formation of acids from C6-alpha-dicarbonyls by an oxidative mechanism and incorporation of a 17OH group into the carboxylic moiety. The experimental data obtained support the coexistence of at least two newly described reaction mechanisms leading to carboxylic acids, i.e., (i) a hydrolytic beta-dicarbonyl cleavage as a major pathway and (ii) an alternative minor pathway via oxidative alpha-dicarbonyl cleavage induced by oxidizing species.     

Origin of the high-frequency resonances in 1H NMR spectra of muscle tissue: an in vitro slow magic-angle spinning study

High-resolution slow magic-angle spinning (150 Hz) 1H PASS NMR spectroscopy is performed on intact excised rat m. tibialis anterior. Untreated muscles and muscles in vitro incubated in Krebs-Ringers buffer based on deuterium oxide are investigated. In the high-frequency region of the 1H NMR spectra, resonances from H4 (approximately 7.1-7.2 ppm) and H2 (approximately 8.2-8.5 ppm) in histidine are observed. In addition, a resonance appears at 6.7 ppm for the untreated muscles. However, this resonance is absent in muscles following incubation in deuterium oxide. On the basis of its behavior in deuterium oxide combined with supplementary measurements for creatine solutions, the 6.7 ppm resonance is ascribed to the amino protons in creatine. Moreover, the present study demonstrates that the observation of the 6.7 ppm resonance depends on pH, which explains earlier reports stating its occasional appearance. Finally, measurements on solutions of ATP/AMP and histidine indicate that both ATP/AMP and histidine contribute to the resonances at approximately 8.2-8.5 ppm in the 1H NMR spectra of muscle tissue.     

Influence of Added Starch on Mixing of Dough Made with Three Wheat Flours Differing in High Molecular Weight Subunit Composition: Rheological Behavior

The effect of mixing time (6 and 20 min) and starch content were studied on doughs prepared with three wheat flours differing in high molecular weight subunit composition. Rheological measurements were performed in dynamic oscillation: frequency and strain sweeps, stress relaxation, and in large deformation viscosity measurements. The flours were diluted with starch to cover flour protein contents of 10–15%. Water was added to keep the starch‐water ratio constant when doughs were prepared with different protein contents. By increasing the starch content of the doughs, the rheological properties approached those of a starch‐water mixture prepared with the same starch‐water ratio as in the dough. The effect of the starch granules was reinforced by prolonged mixing. This may explain the higher values of the storage modulus and relaxation times observed after 20 min of mixing. Qualities related to gluten properties, appeared more clearly in large deformation viscosity measurements.     

The effect of water content on solid-state 13C NMR quantitation and relaxation rates of soil organic matter

Two hydrofluoric acid‐treated soils were prepared with water contents ranging up to 22% by exposing them to a range of atmospheric humidities. There was no effect of water content on the chemical shift distribution of nuclear magnetic resonance (NMR) signal in ¹³C cross‐polarization (CP) NMR spectra. The sensitivity of the ¹³C CP NMR spectra decreased slightly with increasing water content. Much of this decrease could be attributed to decreases in T_1ρH relaxation rates, caused by enhanced molecular mobility of the organic matter in the presence of absorbed water. Rates of T_1H relaxation were very sensitive to water content, and average T_1H relaxation rates decreased four‐ to five‐fold from the smallest to the largest water content. Rates of T_1H relaxation were non‐uniform, and were better modelled by two‐T_1H component fits than one‐T_1H component fits. The ratio of rapidly to slowly relaxing components increased with increasing water content. Proton spin relaxation editing (PSRE) subspectra revealed substantial changes in the nature of these two components with increasing water content. These results indicate the presence of an organic matter component that is very sensitive to water content, transforming from slowly relaxing at a small water content to rapidly relaxing at a greater water content. This component was shown to be rich in O–alkyl and carbonyl C, and may be hemicellulosic root exudates and microbial mucilages. The slowly relaxing PSRE component was a mixture of ligno‐cellulose and alkyl biopolymers, whereas the rapidly relaxing component was primarily charcoal for one of the soils, and was reminiscent of dissolved organic carbon for the other soil. These findings show that care must be taken in controlling water contents when using PSRE to study organic matter.