NMR转折点温度对食品储存过程中Maillard反应速率影响

采用核磁共振(NMR)技术对以葡萄糖、海藻糖、蔗糖、赖氨酸构成的模型食品进行磁共振实验,绘制体系NMR状态图并计算转折点温度,同时在不同温度下进行储藏实验,考察体系中葡萄糖的变化,评估不同储藏温度下的Maillard反应速率.结果表明:模型食品体系含水量不同、非反应组分含量不同,其NMR转折点温度有所不同.低水分含量的体系具有相对高的NMR转折点温度.即使在相同的储藏温度下,含水量相同而非反应组分含量不同的情况下,体系的Maillard反应速率也有所不同.储藏温度处于体系的NMR转折点之下时,体系的Maillard反应速率明显要比在NMR转折点温度之上要慢.由此,可以通过改变食品的配方、含水量等改变体系的NMR转折点温度,可以有效地延长食品的货架期.因此,核磁共振状态图对于评估最佳的储藏温度,以及通过配方设计来延长食品的货价期具有指导意义.     

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.     

NMR relaxation and water self-diffusion studies in whey protein solutions and gels

The changes in water proton transverse relaxation behavior induced by aggregation of whey proteins are explained in terms of the simple molecular processes of diffusion and chemical exchange. The water self-diffusion coefficient was measured in whey protein solutions and gels by the pulsed field gradient NMR method. As expected, water self-diffusion was reduced with increased protein concentrations. Whatever the concentration, the water molecules were free to diffuse over distances varying from 15 to 47 mum. Water diffusion was constant over these distances, demonstrating that no restrictions were found to explain the water hindrance. The modification in protein structure by gelation induced a decrease in water diffusion. The effects of protein concentration on water diffusion are discussed and modeled. Two approaches were compared, the obstruction effect induced by a spherical particle and the cell model, which considered two water compartments with specific self-diffusion coefficients.     

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.     

Diffusion coefficient of CO(2) molecules as determined by (13)C NMR in various carbonated beverages

In this paper, the NMR technique was used, for the first time, to accurately determine the diffusion coefficient D of CO(2)-dissolved molecules in various carbonated beverages, including champagne and sparkling wines. This parameter plays an important role concerning the bubble growth during its rise through the liquid (see ref 3). The diffusion coefficient of CO(2)-dissolved molecules D was compared with that deduced from the well-known Stokes-Einstein equation and found to significantly deviate from the general trend expected from Stokes-Einstein theory, i.e, D(SE) proportional, variant 1/eta, where D(SE) is the Stokes-Einstein diffusion coefficient and eta the viscosity of the liquid medium.     

低场NMR对羊肉贮藏过程中pH值和TVB-N的预测及验证

为探讨不同贮藏条件下羊肉新鲜度检测的方法,采用低场核磁共振(LF-NMR)技术通过分析冷冻(-18℃)与冷藏(4℃)条件下羊肉的LF-NMR弛豫特性变化,及测定羊肉的pH值和挥发性盐基氮(TVB-N)含量的变化对其新鲜度进行分析检测。在此基础上,利用多元回归分析建立羊肉pH值、TVBN含量与其LF-NMR弛豫特性的相关性模型,并对其进行验证。结果表明,不同贮藏条件下,随着贮藏时间的增加,羊肉中pH值、TVB-N含量均逐渐增大并符合二项式关系,且相关系数分别为R~20.99和R~20.97。横向弛豫时间T_(22)、T_(23)随贮藏时间的延长显著缩短,T_(22)与贮藏时间呈线性关系(R~20.98),T_(23)与贮藏时间呈良好二项式关系(R~20.97),T_(2b)、T_(21)变化无规律且不显著。随贮藏时间的延长,峰面积比例S_(22)逐渐下降、S_(23)呈上升趋势(R~20.97),S_(2b)、S_(21)无明显变化规律。由多元线性回归分析可知,TVB-N含量与T_(23)、T_2,pH值与T_(22)、T_2可建立良好的相关性模型(R~20.96)。模型验证合理,表明利用LF-NMR弛豫特性对不同贮藏条件下羊肉pH和TVB-N含量预测是可行的,这为通过LF-NMR弛豫特性对羊肉的新鲜度的检测提供了一定的理论依据。     

Elucidation of membrane destabilization in post-mortem muscles using an extracellular paramagnetic agent (Gd-DTPA): an NMR study

The effect of Gd-DTPA on the development in NMR relaxation of skeletal rabbit muscles post-mortem was investigated by dynamic low-field (0.47 T) relaxation measurements from 4 min post-mortem and until 23 h post-mortem. Twelve rabbits were included in the study, and half of the animals were administered 0.2 mmol of Gd-DTPA iv 15 min before sacrifice, while the other half was administered an isotonic salt solution. A significant effect of Gd-DTPA treatment corresponding to a 25% reduction in the T(1) relaxation time was observed. T(2) relaxation was decomposed into two components reflecting intra- and extracellular components (T(2)()alpha and T(2)()beta, respectively), and Gd-DTPA treatment was found to affect both components. However, around 150 min post-mortem a dramatic increase in the difference between control and Gd-DTPA-treated rabbits was observed in the relaxation time of the intracellular water population (T(2)()alpha). Electrical stimulation of the muscles resulted in a significantly earlier onset of the increased effect of Gd-DTPA on the T(2)()alpha population. The increased effect of Gd-DTPA treatment on the T(2)()alpha component is believed to reflect leakage of water from the muscle cells due to membrane destabilization, known to be promoted by electrical stimulation. Accordingly, the present study demonstrates how Gd-DTPA can be used for probing membrane integrity in post-mortem muscles known to be of importance for subsequent water distribution and final water-holding capacity.     

Mobility characterization of waxy corn starch using wide-line (1)H nuclear magnetic resonance

The molecular mobility of waxy corn starch was studied by using wide-line (1)H nuclear magnetic resonance (NMR) spectroscopy. A suite of NMR techniques was used to measure relaxation times (i.e., T(2), T(2), and T(1)) and to characterize water and solid (starch) mobility of waxy corn starch. It was observed that the spectrum of each sample includes a complex broad proton component upon which is superimposed a narrow proton component over water activity (a(w)) ranges from 0.33 to 0.97 (i.e., 10.-25.6% water content) at 25 degrees C. Line shape analysis and relaxation times of both broad and narrow components show that T(2) and T(2) values decrease (i.e., decreasing mobility) with increasing solid concentration and show a "break point" in a concentration range between 19.8 and 21.9% water content. The T(1) shows a "T(1) minimum" in the same concentration range. Starch samples change from the glassy to viscous rubbery state in this same concentration range. This demonstrates that wide-line (1)H NMR relaxation times (i.e., T(2), T(2), and T(1)) may be useful as indicators of glass transition for starch samples in the solid state. The results demonstrate that wide-line (1)H NMR spectroscopy is able to separate modes and quantitate the magnitude of molecular mobility in complex systems.     

NMR signal analysis to characterize solid, aqueous, and lipid phases in baked cakes

Proton mobility was studied in molecular fractions of some model systems and of cake using a 1H nuclear magnetic resonance (NMR) relaxation technique. For cake, five spin-spin relaxation times (T2) were obtained from transverse relaxation curves: T2 (1) approximately 20 micros, T2 (2) approximately 0.2 ms, T2 (3) approximately 3 ms, T2 (4) approximately 50 ms, and T2 (2) approximately 165 ms. The faster component was attributed to the solid phase, components 2 and 3 were associated with the aqueous phase, and the two slowest components were linked to the lipid phase. After cooking, the crust contained more fat but less water than the center part of the cake. The amount of gelatinized starch was lower in the crust, and water was more mobile due to less interaction with macromolecules. This preliminary study revealed different effects of storage on the center and crust.     

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.     

1H NMR diffusometry study of water in casein dispersions and gels

The self-diffusion coefficients of water in casein solutions and gels were measured using a pulsed-gradient spin-echo nuclear magnetic resonance technique (PGSE NMR). The dependence of the self-diffusion coefficient of water on the concentration and structure of casein is reported. The results were analyzed using a cell model. It was found that the water self-diffusion coefficient is insensitive to the structure of the casein in solution or in a gelled state. The influence of casein concentration on the water self-diffusion coefficient could be explained by obstruction from the casein molecule. Assuming a simple model with two water regions, each characterized by a specific water concentration and value of the water diffusion coefficient, the water mobility reduction induced by the casein can be rationalized.     

Cooking effects on water distribution in potatoes using nuclear magnetic resonance relaxation

Continuous low-field (LF) (1)H NMR relaxometry was used to monitor the structural changes during cooking of potatoes with two different dry matter (DM) contents. A principal component analysis of the relaxation decay curves revealed major events related to water mobility during cooking, which occur at 53 and 60 degrees C for potatoes with medium and low DM contents, respectively. Exponential analysis of the relaxation decays reveals two major water populations in the potato: a slow-relaxing (assigned to water in cytoplasm and extracellular cavities) water component, T(22) ( approximately 350-550 ms), and a fast-relaxing component (primarily assigned to water associated with starch and cell walls), T(21) ( approximately 45-65 ms). Significant DM dependent shifts in both the T(21) and T(22) relaxation time constants were observed during cooking, indicating that starch gelatinizes between 53 and 70 degrees C with water exchanging with the hydroxyls of starch (transition in T(21)) and cells start to disrupt with an increase in diffusion volumes at approximately 60 degrees C (transition in T(22)). The study reveals that continuous LF NMR measurement is an excellent and highly sensitive method to study changes in water mobility and water populations during the cooking of potatoes.     

Ingredient Characterization and Hardening of High‐Protein Food Bars: an NMR State Diagram Approach

A second‐degree simplex lattice mixture design was used to study the effects of soy, dairy, and soy‐dairy blends of powdered proteins in three high‐protein food bar models (sugar syrup, polyol syrup, and reduced‐sugar syrup). Overall protein performance was evaluated based on textural changes during accelerated storage, bar integrity, and dough stickiness and was a strong function of the syrup model used (R² = 92.33%). Nuclear magnetic resonance (NMR) relaxometry was used to measure relaxation times (T₂, T₂*, and T₁) at 20°C and to create state diagrams (temperature, T₂* curves) for the individual powdered proteins and syrups over a temperature range of –35 to 50°C. Increases in relaxation times for powdered protein samples were indicative of better overall protein performance, whereas increases in relaxation times for syrup samples were associated with increases in moisture content and concentration of polyols. Increases in water activity (a_w) of the bars during accelerated storage suggested an elevated rate of hardening for polyol‐containing bars that was caused by a decrease in the amount of water capable of acting as a plasticizer in the product. Proteins were separated into four types (A, B, C, and D) based on the shape of the state diagram curve. Predicted to be the most stable, type D proteins (SUPRO 313 and SUPRO 430) offered the most versatility and, when blended with other proteins, often induced synergistic softening effects in the nutrition bars which led to an extended product shelf life. The NMR state diagram technique appears to be a valuable tool for predicting overall performance of powdered proteins in sugar‐, polyol‐, and reduced‐sugar syrup based food bars.     

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   

Effects of ionic strength and denaturation time on polyethyleneglycol self-diffusion in whey protein solutions and gels visualized by nuclear magnetic resonance

Pulsed field gradient NMR spectroscopy was used to determine the poly(ethylene glycol) (PEG) self-diffusion coefficient (D(PEG)) as a function of NaCl concentration (C(NaCl)) and denaturation time (t(D)) in whey protein solutions and gels. D(PEG) in the gel decreased with increasing C(NaCl) concentrations and increased with increasing t(D); the increase ceased for all PEGs when the gel was fixed. This increase was more pronounced for the 82250 g/mol PEG than the 1080 g/mol PEG. Moreover, the diffusion coefficient of nonaggregated whey protein was measured and an increase for longer t(D) was also observed. Scanning electron microscopy images and (1)H spectra demonstrated that D(PEG) were related to the structure changes and to the percentage of beta-lactoglobulin denaturation.     

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.     

Salt diffusion and distribution in meat studied by 23Na nuclear magnetic resonance imaging and relaxometry

This study introduces the use of combined 23Na magnetic resonance imaging (MRI) and 23Na NMR relaxometry for the study of meat curing. The diffusion of sodium ions into the meat was measured using 23Na MRI on a 1 kg meat sample brined in 10% w/w NaCl for 3-100 h. Calculations revealed a diffusion coefficient of 1 x 10(-5) cm2/s after 3 h of curing and subsequently decreasing to 8 x 10(-6) cm2/s at longer curing times, suggesting that changes occur in the microscopic structure of the meat during curing. The microscopic mobility and distribution of sodium was measured using 23Na relaxometry. Two sodium populations were observed, and with increasing length of curing time the relaxation times of these changed, reflecting a salt-induced swelling and increase in myofibrillar pore sizes. Accordingly, the present study demonstrated that pore size and thereby salt-induced swelling in meat can be assessed using 23Na relaxometry.     

Diffusion of oxygen in cork

This work reports measurements of effective oxygen diffusion coefficient in raw cork. Kinetics of oxygen transfer through cork is studied at 298 K thanks to a homemade manometric device composed of two gas compartments separated by a cork wafer sample. The first compartment contains oxygen, whereas the second one is kept under dynamic vacuum. The pressure decrease in the first compartment is recorded as a function of time. The effective diffusion coefficient D(eff) is obtained by applying Fick's law to transient state using a numerical method based on finite differences. An analytical model derived from Fick's law applied to steady state is also proposed. Results given by these two methods are in close agreement with each other. The harmonic average of the effective diffusion coefficients obtained from the distribution of 15 cork wafers of 3 mm thickness is 1.1 × 10(-9) m(2) s(-1) with a large distribution over four decades. The statistical analysis of the Gaussian distribution obtained on a 3 mm cork wafer is extrapolated to a 48 mm cork wafer, which length corresponds to a full cork stopper. In this case, the probability density distribution gives a mean value of D(eff) equal to 1.6 × 10(-9) m(2) s(-1). This result shows that it is possible to obtain the effective diffusion coefficient of oxygen through cork from short time (few days) measurements performed on a thin cork wafer, whereas months are required to obtain the diffusion coefficient for a full cork stopper. Permeability and oxygen transfer rate are also calculated for comparison with data from other studies.     

Investigation of binding behavior of alpha- and beta-ionones to beta-lactoglobulin at different pH values using a diffusion-based NOE pumping technique

Diffusion-based NMR techniques were employed to study effects of pH on beta-lactoglobulin (BLG) conformation and binding affinity to alpha- and beta-ionone. In the first part of the study, the influence of pH on the diffusion coefficient of BLG in D(2)O solution was investigated using a stimulated-echo NMR experiment. The diffusion coefficient of BLG decreased with increasing pH values. A significant decrease in the diffusion coefficient observed at pH 11 may be due to total unfolding (denaturation) of the protein, resulting in hydrophobically driven self-aggregation. A diffusion-based NOE pumping technique was then applied to determine the relative binding affinities between alpha- and beta-ionones and BLG at pH values varying from 3 to 11. An increase in signal intensities for beta-ionone with increasing molar concentration ratios between beta-ionone and BLG was observed at all pH ranges studied. The increased signal intensities reflect increased relative binding affinity. The greatest binding affinity occurred at pH 9 and the lowest at pH 11. alpha-Ionone showed binding evidence only at pH 9, and the binding was significantly weaker than that obtained for beta-ionone at the same pH. The high affinity observed for both aroma compounds at pH 9 may be due to a flexible conformation of BLG at this pH so that the flavor ligand accessibility increases. Conversely, alkaline denaturation occurring at pH 11 gives rise to relatively lower binding affinity compared to that observed at the other pH values.     

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.