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.     

基于低场核磁和差示量热扫描的面条面团水分状态研究

为了解低水分面条面团中水分的存在状态,明确真空度及和面时间对水分状态的影响,该研究以3个小麦品种（济麦20、宁春4号、济麦22）磨制的面粉为材料,采用真空和面制作低水分面条面团（含水率35%）,采用低场核磁共振技术（LF-NMR,low-field nuclear magnetic resonance）和差示量热扫描（DSC,differential scanning calorimetry）2种技术,测定不同真空度（0、0.06、0.09 MPa）和搅拌时间（4、8、12 min）下面团中水分的形态和分布,并进一步分析2种技术测定水分形态结果的相关性。结果表明,在低水分面条面团中,水分主要以弱结合水形态存在。不同品种的小麦粉面团的水分形态及分布存在差异,强筋小麦粉（济麦20）制作面团的水分自由度较低。真空和面（0.06 MPa）可以促进水分与面筋蛋白的相互作用,降低面团中水分子流动性,促进水分结构化;而非真空或过高真空度均会导致面团中水分自由度增加。济麦20、济麦22小麦粉和面时间为8 min时,面团水分流动性较低;而宁春4号小麦粉面团在4 min时,水分自由度较低;继续搅拌,深层结合水减少、弱结合水增多。LF-NMR和DSC测得面团水分状态的结果具有一致性。LF-NMR测得的弱结合水峰面积百分比与DSC测得的可冻结水百分比具有相同的变化趋势（r=0.695）,且深层结合水峰面积百分比与非冻结水百分比具有相同的变化趋势（r=0.564）。研究结果为认识制面过程中水分的作用,优化和面工艺和调整产品特性提供参考。     

Relationship between meat structure, water mobility, and distribution: a low-field nuclear magnetic resonance study

Nuclear magnetic resonance (NMR) measurements were carried out on pork longissimus muscle, which pre rigor had been manipulated to various muscle lengths, to investigate the relationship between the microstructure of meat and the NMR T(2) relaxation. Distributed exponential analysis of the NMR T(2) relaxation data revealed the existence of three distinct water populations: T(2b), T(21), and T(22). A high, significant correlation was found between the T(21) time constant and the sarcomere length (r = 0.84) and calculated ration of myofilament lattice volume in the I-band and A-band regions, respectively (r = 0.84), considering sigmoid relationships. The result implies that the T(21) time constant mainly is determined by the structure of the myofilament lattice and so strongly supports a previously proposed theory that the T(21) population corresponds to water located within a highly organized myofibrillar protein matrix including actin and myosin filament structures. A high correlation was also found between the T(22) population and the water-holding capacity (WHC) (r = 0.76), which suggests that the WHC is mainly determined by the amount of loosely bound extramyofibrillar water. However, the correlation between NMR T(2) parameters and WHC was further increased (r = 0.84) by including the T(21) time constant in the correlation analysis. This implies that the formation of drip loss is an ongoing process involving the transfer of water from myofibrils to the extracellular space and is affected by structural features at several levels of organization within the muscle tissue. This study demonstrates the advantages of NMR T(2) relaxation as an effective technique for obtaining further understanding of the relationship between the microstructure of meat, its WHC, water mobility, and water distribution.     

Effect of solutes and matrix structure on water mobility in glycerol-agar-water gel systems: a nuclear magnetic resonance approach

Nuclear magnetic resonance spectroscopy (NMR) has been widely used to determine water molecular mobility in food systems. This study aimed to examine the effects of matrix structure and solutes on the dynamics of water molecules in model mixed systems, glycerol-agar-water gels, using low- and high-resolution NMR. Simple models to explain water relaxation rates and self-diffusion coefficients in mixed systems were developed using the experimental values obtained for the individual binary systems (glycerol-water solutions and agar-water gels). The spin-lattice relaxation of mixed systems was influenced by interactions of both glycerol and agar with water, while the spin-spin relaxation of mixed systems was dominated by the interaction of agar with water. Water diffusion was influenced by not only molecular interactions between all components but also the gel matrix structure. These models are able to differentiate the effect of solutes from that of matrix structure on water molecular dynamics.     

低场核磁共振分析聚乙二醇对萌发期水稻种子水分吸收的影响

为研究聚乙二醇(PEG,polyethylene glycol)处理下水稻种子萌发过程中内部水分分布和变化规律,进而揭示水稻耐旱性在水分吸收规律上的重要特征。应用低场核磁共振的T2弛豫谱和质子密度加权成像分析了PEG处理下水稻种子萌发过程中的水分变化,研究了利用蒸馏水(对照)和质量分数分别为10%、20%PEG6000处理对两个水稻品种旱9710、辽星1发芽指标的影响,以及对两个水稻品种萌发0、6、22、48、72 h吸水量的影响,确定单位质量核磁信号幅值与水稻种子湿基含水率的回归函数关系。发芽指标检测结果显示:旱9710耐旱性高于辽星1。质子密度加权成像结果显示:在水分吸收初期,水分子直接通过种子表面裂缝进入种子体内,胚乳中的淀粉粒等物质开始吸水膨胀,种子体积增大。24 h后,种子内营养物质向种胚流动。PEG处理下,水稻种子吸水量明显减少,发芽速度明显降低,且PEG质量分数越高,发芽速度越慢。基于核磁共振理论及T2弛豫谱的多组分特征,当反演频率为10 000时,水稻种子萌发过程中的水分分为束缚水与自由水两部分。T2弛豫谱结果表明:在蒸馏水和质量分数分别为10%、20%PEG处理下,种子湿基含水率和核磁信号幅值均逐渐增长。PEG处理下,核磁信号幅值增长相比对照处理显著降低(P0.05)。PEG处理抑制了两个水稻品种种子对水分的吸收,PEG质量分数越高,抑制作用越强。PEG处理24 h后,耐旱性强的水稻品种吸水率相比对照处理的降低幅度小于耐旱性弱的品种。回归分析表明,3种处理下,核磁信号幅值和湿基含水率具有一致的线性关系(R2=0.983),由回归方程可以求得水稻种子萌发过程中各状态水分的含量。试验为研究水稻种子萌发过程对干旱胁迫的反应机制,开发种子水分微观活体无损检测技术等方面的研究提供理论支持和数据参考。     

Effects of casein and fat content on water self-diffusion coefficients in casein systems: a pulsed field gradient nuclear magnetic resonance study

The water self-diffusion coefficients in casein matrixes were measured using a pulsed field gradient spin-echo nuclear magnetic resonance technique (PFG-SE NMR). The dependence of the water self-diffusion coefficient on the casein concentration and the aqueous phase composition is reported in both a rehydrated native phosphocaseinate dispersion and a concentrated casein retentate. A model has been proposed to explain the different behavior of the water self-diffusion coefficient in the two casein systems. This model demonstrates that the water self-diffusion cannot be simply explained by the water content only. So, taking into account the specific effect of each constituent of the aqueous dispersing phase, the water self-diffusion reduction induced by the casein micelle can be modeled. The effect of fat on the water self-diffusion coefficients was investigated. Anhydrous milk fat-reconstituted retentate samples were used in order to estimate the obstruction effect of fat globules in the modeling process. The dependence of the self-diffusion coefficient of water on the fat and casein content is reported. A general model included the effect of the aqueous phase composition, and the obstruction effects of casein micelles and fat globules were proposed. This model was validated for water self-diffusion coefficients in industrial fatty retentates.     

Extraction of chili,black pepper,and ginger with near-critical CO2, propane,and dimethyl ether: analysis of the extracts by quantitative nuclear magnetic resonance

Ginger, black pepper, and chili powder were extracted using near-critical carbon dioxide, propane, and dimethyl ether on a laboratory scale to determine the overall yield and extraction efficiency for selected pungent components. The temperature dependency of extraction yield and efficiency was also determined for black pepper and chili using propane and dimethyl ether. The pungency of the extracts was determined by using an NMR technique developed for this work. The volatiles contents of ginger and black pepper extracts were also determined. Extraction of all spice types was carried out with acetone to compare overall yields. Subcritical dimethyl ether was as effective at extracting the pungent principles from the spices as supercritical carbon dioxide, although a substantial amount of water was also extracted. Subcritical propane was the least effective solvent. All solvents quantitatively extracted the gingerols from ginger. The yields of capsaicins obtained by supercritical CO(2) and dimethyl ether were similar and approximately double that extracted by propane. The yield of piperines obtained by propane extraction of black pepper was low at approximately 10% of that achieved with dimethyl ether and CO(2), but improved with increasing extraction temperature.     

Lignin modification during Eucalyptus globulus kraft pulping followed by totally chlorine-free bleaching: a two-dimensional nuclear magnetic resonance, Fourier transform infrared, and pyrolysis-gas chromatography/mass spectrometry study

Chemical modification of eucalypt lignin was investigated during kraft pulping and chlorine-free bleaching by comparing milled wood lignin, kraft lignin, and pulp enzymatic residual lignins. The syringyl-to-guaiacyl ratio (S/G) from analytical pyrolysis slightly changed during pulping and bleaching (S/G, 3-4) but was higher in the kraft lignin. Semiquantitative heteronuclear single quantum correlation (HSQC) nuclear magnetic resonance (NMR) showed that the relative amount of beta-O-4' (around 80% side chains) and resinol type substructures (15%) was slightly modified during pulping and oxygen delignification. However, a decrease of resinol substructures (to only 6%) was found after alkaline peroxide bleaching. The relative amount of surviving linkages in the highly phenolic kraft lignin was dramatically modified; resinols were predominant. Oxygen delignification did not change interunit linkages, but a relative increase of oxidized units was found in the HSQC aromatic region, in agreement with the small increase of pyrolysis markers with oxidized side chains. NMR heteronuclear multiple bond correlations showed that the oxidized units after oxygen delignification bore conjugated ketone groups.     

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.     

Field compaction at different soil-water status: effects on pore size distribution and soil water characteristics of a Rhodic Ferralsol in Western Cuba

The level of compaction induced on cultivated fields through trafficking is strongly influenced by the prevailing soil-water status and, depending on the attendant soil degradation, vital soil hydraulic processes could be affected. Therefore, understanding the relationship between field soil-water status and the corresponding level of induced compaction for a given load is considered an imperative step toward a better control of the occurrence of traffic-induced field soil compaction. Pore size distribution, a fundamental and highly degradable soil property, was measured in a Rhodic Ferralsol, the most productive and extensively distributed soil in Western Cuba, to study the effects of three levels of soil compaction on soil water characteristic parameters. Soil bulk density and cone penetration index were used to measure compaction levels established by seven passes of a 10 Mg tractor at three soil-water statuses corresponding to the plastic (Fs), friable (Fc) and relatively dry soil (Ds) consistency states. Pore size distribution calculated from soil water characteristic curves was classified into three pore size categories on the basis of their hydraulic functioning: >50 μm (f_>50 μm), 50–0.5 μm (f_{50–0.5 μm}) and <0.5 μm (f_<0.5 μm). The greatest compaction levels were attained in the Fs and Fc soil water treatments, and a significant contribution to compaction was attributed to the existing soil water states under which the soil compaction was accomplished. Average cone index (CI) values in the range of 2.93–3.70 MPa reflected the accumulation of f_<0.5 μm pores, and incurred severe reductions in the volume of f_>50 μm pores in the Fs and Fc treatments, while an average CI value of 1.69 MPa indicated increments in the volume of f_{50–0.5 μm} in the Ds treatment. Despite the differential effects of soil compaction on the distribution of the different pore size categories, soil total porosity (f_Total) was not effective in reflecting treatment effects. Soil water desorption at the soil water potentials evaluated (0.0 to −15,000 cm H₂O) was adversely affected in the f_<0.5 μm dominated treatments; strong soil water retention was observed with the predominance of f_<0.5 μm, as was confirmed by the high water content at plant wilting point. Based on these findings, the use of field capacity water content as the upper limit of plant available soil water was therefore considered inappropriate for compacted soils.     

Heavy and light beer: a carbon isotope approach to detect C(4) carbon in beers of different origins,styles, and prices

The carbon isotope ratios (delta(13)C) of 160 beers from around the world ranged from -27.3 to -14.9 per thousand, primarily due to variation in the percentage of C(3) or C(4) plant carbon in the final product. Thirty-one percent of beers had a carbon signature of C(3) plants (barley, rice, etc.), whereas the remaining 69% contained some C(3)-C(4) mixture (mean of mixtures, 39 +/- 11% C(4) carbon). Use of C(4) carbon (corn, cane sugar, etc.) was not confined to beers from any particular region (Pacific Rim, Mexico, Brazil, Europe, Canada, and the United States). However, the delta(13)C of European beers indicated mostly C(3) plant carbon. In contrast, U.S. and Canadian beers contained either only C(3) or C(3)-C(4) mixtures; Brazilian, Mexican, and Pacific Rim beers were mostly C(3)-C(4) mixtures. Among different lagers, U.S.-style lagers generally contained more C(4) carbon than did imported pilsners. Among different ales, those brewed by large high-production breweries contained significant proportions of C(4) carbon, while C(4) carbon was not detected in microbrewery or home-brew ales. Furthermore, inexpensive beers generally contained more C(4) carbon than expensive beers.     

Emission of nitrous oxide and carbon dioxide and dynamics of mineral N in wastewater sludge,vermicompost or inorganic fertilizer amended soil at different water contents: A laboratory study

Liming or vermicomposting eliminates pathogens from wastewater sludge, but might affect CO₂ and N₂O emissions when added to soil. Soil incubated at 40%, 60%, 80% and 100% of its water holding capacity (WHC) was amended with limed or unlimed wastewater sludge, vermicompost or inorganic fertilizer, while emissions of N₂O and CO₂ and mineral N concentrations were monitored in aerobic incubation experiment for 7 days. Application of unlimed wastewater sludge significantly increased the emission of CO₂ compared to the unamended soil, but not the other treatments except when unlimed wastewater sludge was added to soil incubated at 60% WHC. The emission of CO₂, was generally largest in soil incubated at 60% WHC and lowest in soil incubated at 100% WHC. The emission of N₂O after 1 day was significantly larger in soil amended with unlimed wastewater sludge compared to the other treatments, but not when soil was incubated at 100% WHC. The emission of N₂O increased with increased soil water content. The concentration of NH₄⁺ was largest in soil amended with limed or unlimed wastewater sludge and lowest in the unamended soil and soil water content had no clear effect on it. In soil incubated at 40%, 60% and 80% WHC, the largest amount of NO₃⁻ was found in soil amended with inorganic fertilizer and vermicompost and the lowest in the soil amended with unlimed wastewater sludge. The concentration of NO₃⁻ in soil decreased when the soil water content increased in all treatments, except in the soil amended with unlimed wastewater sludge. It was found that water content affected the emission of CO₂ of N₂O and the concentration of NO₃⁻, but not the amount of NH₄⁺ and NO₂⁻ in soil. Application of unlimed wastewater sludge increased the emissions of CO₂ and N₂O and the concentrations of NH₄⁺, but decreased the amount of NO₃⁻ in soil.     

Changes in nutrient content,enzymatic activities and microbial properties of lateritic soil due to application of different vermicomposts: a comparative study of ergosterol and chitin to determine fungal biomass in soil

In this experiment, vermicomposts, prepared from five different waste materials, were applied to acid lateritic soil under field conditions and soil samples were collected after 90 days to study the effect of vermicomposts on different chemical and biochemical. Results suggest that vermicompost prepared from paddy straw is most effective to improve nutrient content, enzymatic activities and microbial properties of lateritic soil. Vermicompost application significantly (P ≤ 0.05) increased the concentration of organic C, mineralizable N, available P and exchangeable K in soil. Amylase, protease, urease and acid phosphatase activities were also significantly (P ≤ 0.05) higher in vermicompost treated soils compared with the control. Both basal and substrate‐induced microbial respiration, microbial biomass C and N and fungal population in lateritic soil were increased due to vermicompost application. Ergosterol and chitin content were significantly (P ≤ 0.05) higher in vermicompost treated soils over the control. Application of vermicompost increased the proportion of fungal biomass in total soil microorganisms.