基于核磁共振技术检测小麦植株水分分布和变化规律

为研究活体冬小麦植株水分的分布状况和连续变化过程,该研究利用核磁共振无损、非侵入的技术优势,分析了小麦各器官T2弛豫谱特征及其反映的代谢特性,分别推求出小麦叶片、茎秆和穗的信号幅值与被检测器官纯水含量以及鲜质量的回归函数关系,在此基础上建立了测量活体冬小麦植株各器官湿基含水率的检测方法。对活体植株各器官湿基含水率核磁共振检测方法的可靠性验证表明,由核磁共振法和烘干法测定的小麦叶片、茎秆和穗的湿基含水率均方根误差分别为：5.3%、3.5%、3.3%。然后将该检测方法用于监测同一株冬小麦各器官湿基含水率的长期变化和日变化过程,结果显示,乳熟期至成熟期,小麦各个器官的湿基含水率均逐渐减小,而叶片湿基含水率的日变化则呈现先减小后增大的趋势。乳熟期叶片的湿基含水率由8:00逐渐减少,且在14:00－16:00达到最低值后开始恢复,于20:00恢复至当日初始水平。成熟期叶片湿基含水率由8:00逐渐减少,但在20:00不能恢复至日内的初始水平。由于这套基于核磁共振技术的小麦湿基含水率检测方法能够对同一植株进行活体无损连续监测,因此该研究的结果能够更直接更准确地揭示冬小麦植株体内水分的连续变化规律和植株衰老过程,从而为研究冬小麦健康生长耗水规律和制定合理的灌溉制度提供理论基础。     

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.     

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。     

玉米种子萌发过程内部水分流动规律的低场核磁共振检测

为研究玉米种子萌发过程中内部水分的流动规律,分析其内部生理代谢状态,该文利用低场核磁共振技术,连续60 h对3个品种玉米种子的吸胀、萌动和发芽3个阶段的萌发过程进行动态监测。分别在萌发时间为0、12、36和60 h这4个典型的萌发时刻,对处于25和31℃的2个恒温萌发环境中的玉米种子进行核磁共振横向弛豫时间信号采集,并通过反演运算得到其横向弛豫时间T_2反演谱。试验结果表明:通过横向弛豫时间可以将玉米种子内部水分划分为结合水(0.1T_210 ms)、半结合水(10T_2100 ms)及自由水(100T_21 000 ms)3种水分相态;随着萌发时间的延长,3个品种玉米种子在2个不同温度的萌发环境中,结合水均呈现先迅速增加后逐渐降低的趋势,自由水均反映为先降低后不断增加的态势,而半结合水和总体水分含量则表现为持续增加的现象;外界温度对3种相态水分含量的影响不尽相同,但提高萌发温度可以明显促进玉米种子吸水,同时提高玉米种子的发芽率。本试验快速并直接揭示了玉米种子在萌发过程中的水分分布情况,可为玉米种子萌发过程的机理研究提供重要参考。     

Self-diffusion coefficient of water in tofu determined by pulsed field gradient nuclear magnetic resonance

The self-diffusion coefficient of water in soybean protein dispersion and tofu was measured by pulsed field gradient (PFG) NMR. A soy protein isolate (SPI) dispersion (6 and 12%, w/w) in water, calcium cross-linked precipitate, and tofu were used for comparison. The self-diffusion coefficient of water (D) in the SPI dispersion, 2.23 x 10(-9) m2/s, was estimated lower than that of free water, 2.6 x 10(-9) m2/s at 25 degrees C, and decreased as the SPI concentration increased. It further decreased by the addition of calcium chloride, reflecting the obstruction effect induced by the precipitates in addition to the hydration and hydrodynamic interaction in the protein dispersion. The two water regions in tofu were interpreted by the two-site K?rger model: D1 and D2 of soft tofu were 2.26 (+/-0.11) x 10(-9) and 6.84 (+/-0.34) x 10(-11) m2/s, respectively. The relative amount of proton (water) was p1 = 0.98 and p2 = 0.02 at 100 ms of diffusion time. The self-diffusion coefficients of water decreased in pressed tofu, and their relative amounts of water changed to p1 = 0.93 and p2 = 0.07. It was suggested that D1 corresponded to obstructed water in the network structure and D2 corresponded to hydrated water on the surface layer of pores formed in the protein network of tofu. The pore sizes estimated from the diffusion length of obstructed water were 21.3 microm in soft tofu and 20.8 microm in pressed tofu. The removal of fat from pressed tofu led to a decrease in D2 from 6.26 (+/-0.31) x 10(-11) to 3.53 (+/-0.18) x 10(-11) m2/s, and the relative amount of hydrated water increased from 0.07 to 0.14, which indicated hydrophobic hydration.     

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.     

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.     

Classification of Ilex species based on metabolomic fingerprinting using nuclear magnetic resonance and multivariate data analysis

The metabolomic analysis of 11 Ilex species, I. argentina, I. brasiliensis, I. brevicuspis, I. dumosavar. dumosa, I. dumosa var. guaranina, I. integerrima, I. microdonta, I. paraguariensis var. paraguariensis, I. pseudobuxus, I. taubertiana, and I. theezans, was carried out by NMR spectroscopy and multivariate data analysis. The analysis using principal component analysis and classification of the (1)H NMR spectra showed a clear discrimination of those samples based on the metabolites present in the organic and aqueous fractions. The major metabolites that contribute to the discrimination are arbutin, caffeine, phenylpropanoids, and theobromine. Among those metabolites, arbutin, which has not been reported yet as a constituent of Ilex species, was found to be a biomarker for I. argentina,I. brasiliensis, I. brevicuspis, I. integerrima, I. microdonta, I. pseudobuxus, I. taubertiana, and I. theezans. This reliable method based on the determination of a large number of metabolites makes the chemotaxonomical analysis of Ilex species possible.     

Soil organic matter maps by nuclear magnetic resonance

Preliminary studies are reported on a soil and a litter fraction which have the aim of exploring the potential of two-dimensional ¹³C nuclear magnetic resonance spectroscopy for the analysis of soil organic matter structure. It has been shown that contour plots can be obtained in which one co-ordinate gives chemical shift information and the other the magnitude of the dipolar interaction. For aromatic and oxygenated aliphatic carbon, the latter parameter is a measure of the degree of protonation. Hence the method is useful for distinguishing between soils containing highly substituted and condensed aromatic structures and those with protonated aromatic carbon. Likewise, it is possible to distinguish between soils containing dioxygenated carbon which is. protonated (e.g. ketal).     

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.     

利用低场核磁共振及其成像技术分析水稻浸种过程水分传递

为研究水稻种子浸种过程中内部水分流动情况,可视化内部水分传递过程,利用低场核磁共振及其成像技术,监测沈农9816号、七山占及秀子糯3个品种水稻种子48 h浸种过程。每6 h时间间隔利用自旋回波（spin echo,SE）脉冲序列获取样品的质子密度加权像,利用硬脉冲自旋回波（carr-purcell-meiboomgill sequence,CPMG）序列获取样品的横向弛豫时间T2反演谱,从而分析浸种过程对水稻种子内部水分分布的影响。试验结果表明：核磁共振是一种有效的水分检测技术,可以实现浸种过程中种子内部水分的快速、准确、无损的检测。利用水稻种子的质子密度加权像,能够直观检测到种子内部水分分布情况,动态的监测到种子内部水分流动过程,分析发现水分最初是从胚进入种子内部,继而通过种皮的渗透,最后到达胚乳部分。根据T2反演谱信号幅值计算得到的水稻种子吸水率,发现3个品种在相同浸种时间的各个监测点均反映出秀子糯吸水率最高,沈农9816号吸水率最低,试验结果验证了支链淀粉的吸水性优于直链淀粉。研究结果可以为水稻种子浸种过程中水分传递的理论模型构建提供数据支持。     

Quantification of inositol phosphates using (31)P nuclear magnetic resonance spectroscopy in animal nutrition

A (31)P NMR method for quantitative determination of inositol phosphates in simple incubation samples of sodium phytate and Aspergillus niger phytase and in different types of complex samples, such as diets, digesta, and feces, is described. The inositol phosphates in complex samples were extracted with HCl, concentrated, and purified using freeze-drying and filtration and subsequently determined at pH 12.6 in aqueous solution using a (31)P NMR method. The (31)P NMR technique has as its main advantages over the HPLC techniques that it does not necessitate standards that may cause background matrix effects and that the spectra of inositol phosphates and orthophosphate appear in the same run without further sampling errors. The results of inositol hexaphosphate analysis with HPLC can be confirmed by this (31)P NMR method. Contents of inositol tetra-, tri-, di-, and monophosphate in the biological samples appear to be quantitatively not important. The (31)P NMR method can be applied for use in animal nutrition in general and studies of using phytase in diets for farm animals in particular, by measuring the content of inositol phosphates in feed ingredients, complete feeds, ileal contents, and feces of pigs and poultry.     

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.     

Soil phosphorus characterisation by 31p nuclear magnetic resonance

Abstract

Five New Zealand topsoils, including three sampled under introduced pasture and two in native tussock grasslands, were extracted with 0.5 M NaOH, and the different classes of phosphorus compounds in the extracts distinguished by ³¹p nuclear magnetic resonance (n.m.r.).

Inorganic orthophosphate and orthophosphate monoesters were the major forms of phosphorus in all soil extracts. The tussock‐grassland soil extracts showed the greatest diversity of phosphorus forms, and included compounds with n.m.r. signals ascribed to phosphonates, a previously unreported form of soil phosphorus.     

Nuclear magnetic resonance studies of water in tree sections

Non-invasive flow measuring techniques using nuclear magnetic resonance (NMR) have been described. Such techniques depend critically on the physical state of the protons in the moving liquid. This paper describes some preliminary NMR measurements of the protons in tree sections, made with conventional laboratory analysis instruments, in order to explore the possibility of designing a device for the non-invasive measurement of water flow in trees.     

Examination of molecular interaction sites of acetanilides with organic matter surrogates using nuclear magnetic resonance techniques

The dynamics of acetanilide pesticide interactions with organic matter (OM) surrogates were examined using nuclear magnetic resonance (NMR) spectroscopy. Differences in the relative changes in (13)C and (1)H spin-lattice relaxation times (T(1)) were measured at multiple molecular sites of metolachlor and the probe compound acetanilide to identify interaction sites and/or surfaces between the molecules and dissolved and colloidal OM surrogates. The decrease in T(1) at specific sites of acetanilide molecules was a function of the OM used and its concentration. High-affinity interactions at nonaromatic sites of metolachlor and acetanilide were observed with cellulose, chitin, and collagen, but interactions with lignin occurred with less site specificity and involved both aromatic and nonaromatic sites of the molecules. Changes in relaxation were compared to calculated and experimentally determined binding coefficients (K(oc)). The T(1) relaxation of the aromatic sites of acetanilides showed better relations with K(oc) than the nonaromatic sites. This study shows that NMR relaxation measurements can identify the high-affinity molecular interaction sites of acetanilides to OM surrogates.     

Measurement of the size distribution of water-filled pores at different matric potentials by stray field nuclear magnetic resonance

The water retention characteristic provides the traditional data set for the derivation of a soil's pore‐size distribution. However, the technique employed to achieve this requires that assumptions be made about the way pores interconnect. We explore an alternative approach based on stray field nuclear magnetic resonance (STRAFI‐NMR) to probe the water‐filled pores of both saturated and unsaturated soils, which does not require information relating to pore connectivity. We report the relative size distributions of water‐occupied pores in saturated and unsaturated samples of two sets of glass beads of known particle size, two sands, and three soils (a silty loam, a sandy loam and a loamy sand), using measurements of the NMR T₁ proton relaxation time of water. The T₁ values are linearly related to pore size and consequently measured T₁ distributions provide a measure of the pore‐size distribution. For both the sands and the glass beads at saturation the T₁ distributions are unimodal, and the samples with small particle sizes show a shift to small T₁ values indicating smaller voids relative to the samples with larger particles. Different matric potentials were used to reveal how the water‐occupied pore‐size distribution changes during drainage. These changes are inconsistent with, and demonstrate the inadequacies of, the commonly employed parallel‐capillary tube model of a soil pore space. We find that not all pores of the same size drain at the same matric potential. Further, we observe that the T₁ distribution is shifted to smaller values beyond the distribution at saturation. This shift is explained by a change in the weighted average of the relaxation rates as the proportion of water in the centre of water‐filled pores decreases. This is evidence for the presence of pendular structures resulting from incomplete drainage of pores. For the soils the results are similar except that at saturation the T₁ distributions are bimodal or asymmetrical, indicative of inter‐aggregate and intra‐aggregate pore spaces. We conclude that the NMR method provides a characterization of the water‐filled pore space which complements that derived from the water retention characteristic and which can provide insight into the way pore connectivity impacts on drainage.     

Oleuropein site selective hydrolysis by technomimetic nuclear magnetic resonance experiments

Technomimetic NMR experiments were performed in accordance with the lye treatment adopted during table olive industrial procedures for the debittering process causing oleuropein degradation. The site selective hydrolysis of the two ester groups, characterizing the biophenolic secoiridoid molecule, was shown to be dependent on the different reactivities of these functionalities. The process is controlled by the experimental conditions exerted on the olive pulp and determined by the buffering capacity of the olive mesocarp and by the epicarp molecular components influencing the reactant penetration into the fruit pulp. The overall hydrolytic process of oleuropein, the bitter principle of olives, using the technomimetic experimental mode, gave rise to its catabolic derivatives, hydroxytyrosol, 11-methyloleoside, and the monoterpene glucoside, technomimetically produced, isolated, and structurally characterized by (1)H, (13)C, and COSY spectroscopy as the oleoside.