Technical note: Fourier transform infrared spectral analysis in tandem with 31P nuclear magnetic resonance spectroscopy elaborates detailed insights into phosphate partitioning during skimmed milk microfiltration and diafiltration

Our previous study identified peaks in the ³¹P nuclear magnetic resonance (³¹P NMR) spectra of skim milk, denoting the interaction of different phosphate species such as inorganic and casein-associated phosphate during the separation of colloidal and serum phases of skim milk by microfiltration (MF) and diafiltration (DF). In the current study, we investigated the same samples generated by the aforementioned separation using attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy analysis. The results confirmed that the technique was not only capable of differentiating between the mineral equilibrium of the casein phosphate nanocluster (CPN) and milk serum, but also complemented the application of ³¹P NMR. An ATR-FTIR broad band in the region of 1,055 to 1,036 cm^?1 and a specific band at 1,076 cm^?1 were identified as sensitive to the repartitioning of different phosphate species in milk in accordance with the ³¹P NMR signals representing casein-associated phosphate and inorganic phosphate in the serum. A third ATR-FTIR signal at 1,034 cm^?1 in milk, representing precipitated inorganic calcium phosphate, had not previously been detected by ³¹P NMR. Thus, the results indicate that a combination of ATR-FTIR and ³¹P NMR spectroscopies may be optimally used to follow mineral and protein phase changes in milk during membrane processing.     

Use of micellar casein concentrate for Greek-style yogurt manufacturing: Effects on processing and product properties

The objective of this work was to develop and optimize an alternative make process for Greek-style yogurt (GSY), in which the desired level of protein was reached by fortification with micellar casein concentrate (MCC) obtained from milk by microfiltration. Two MCC preparations with 58 and 88% total protein (MCC-58 and MCC-88) were used to fortify yogurt milk to 9.80% (wt/wt) protein. Strained GSY of similar protein content was used as the control. Yogurt milk bases were inoculated with 0.02% (wt/wt) or 0.04% (wt/wt) direct vat set starter culture and fermented until pH 4.5. The acidification rate was faster for the MCC-fortified GSY than for the control, regardless of the inoculation level, which was attributed to the higher nonprotein nitrogen content in the MCC-fortified milk. Steady shear rate rheological analysis indicated a shear-thinning behavior for all GSY samples, which fitted well with the power law model. Dynamic rheological analysis at 5°C showed a weak frequency dependency of the elastic modulus (G′) and viscous modulus (G″) for all GSY samples, with G′ > G″, indicating a weak gel structure. Differences in the magnitude of viscoelastic parameters between the 2 types of GSY were found, with G′ of MCC-fortified GSY < G′ of control, indicating a different extent ofprotein interactionsin the 2 types of yogurt. Differences were also noticed in water-holding capacity, which was lower for the MCC-fortified GSY compared with the control, attributed to lower serum protein content in the former. Despite some differences in the physicochemical characteristics of the final product compared with GSY manufactured by straining, the alternative process developed here is a feasible alternative to the traditional GSY make process, with environmental and possibly financial benefits to the dairy industry.     

基于低场核磁共振技术的奶粉品牌快速判别

目的：采用低场核磁共振技术对6个不同品牌的270个奶粉样品进行检测判别。方法：采用主成分分析（PCA）、偏最小二乘判别分析（PLS-DA）、误差反传人工神经网络（BP-ANN）等化学计量学方法对样品数据进行处理。结果：采用PCA方法的主成分三维投影图无法达到对奶粉品牌快速判别的目的;PLS-DA方法的训练集和预测集的正确识别率分别为66.1%,52.2%,可信度较低,也难以实现奶粉品牌的快速判别;BP-ANN方法的训练集和预测集的正确识别率分别为99.4%, 100.0%。结论：低场核磁共振与BP-ANN结合可以很好地识别奶粉品牌。     

定量核磁共振磷谱在食品分析检测中的研究进展

文章综述了近年来定量核磁共振磷谱在食品活性磷脂、磷酸盐、有机磷农药、标准品纯度鉴定等方面的研究进展,对其定量分析的影响因素进行了分析,并对其未来发展方向进行了展望.     

Nuclear magnetic resonance and mass spectrometry-based milk metabolomics in dairy cows during early and late lactation

Milk production in dairy cows has dramatically increased over the past few decades. The selection for higher milk yield affects the partitioning of available nutrients, with more energy being allocated to milk synthesis and less to physiological processes essential to fertility and fitness. In this study, the abundance of numerous milk metabolites in early and late lactation was systematically investigated, with an emphasis on metabolites related to energy metabolism. The aim of the study was the identification and correlation of milk constituents to the metabolic status of the cows. To investigate the influence of lactation stage on physiological and metabolic variables, 2 breeds of different productivity were selected for investigation by high-resolution nuclear magnetic resonance spectroscopy and gas chromatography-mass spectrometry. We could reliably quantify 44 different milk metabolites. The results show that biomarkers such as acetone and β-hydroxybutyrate are clearly correlated to the metabolic status of the individual cows during early lactation. Based on these data, the selection of cows that cope well with the metabolic stress of early lactation should become an option.     

Detection of bovine milk adulteration in caprine milk with N-acetyl carbohydrate biomarkers by using 1H nuclear magnetic resonance spectroscopy

In a return to tradition, the popularity of caprine milk is on the rise. However, particularly in countries with developed dairy industries based on bovine milk, there is the risk of adulteration with bovine milk, which is a cheaper alternative. Thus, a rapid, robust, and simple method for the detection of bovine milk added to caprine milk is necessary, and ¹H nuclear magnetic resonance spectroscopy appears to provide a solution. A matrix of 115 pure and artificially adulterated pasteurized milk samples was prepared and used to discover biomarkers of bovine milk that are independent of chemical and biological variation caused by factors such as genetics, diet, or seasonality. Principal component analysis and orthogonal projections to latent structures discriminant analysis of pure bovine milk and pure caprine milk revealed spectral features that were assigned to the resonances of 4 molecules. Of these, the peaks corresponding to protons in the N-acetylglucosamine and N-acetylgalactosamine acetyl moieties showed significant applicability for our method. Receiver operating characteristic curve analysis was used to evaluate the performance of the peak integrals as biomarkers of adulteration. This approach was able to distinguish caprine milk adulterated with 5% of bovine milk with 84.78% accuracy and with 10% of bovine milk an excellent 95.65% accuracy. This study demonstrates that N-acetyl carbohydrates could be used as biomarkers for the detection of bovine milk in caprine milk and could help in protecting caprine milk authenticity.     

基于核磁共振的物料内部水分检测及应用进展

物料内部水分含量、水分状态以及水分分布是物料干燥的重要特性,也是影响物料干燥过程的主要因素。干燥过程物料内部水分含量、水分状态及其分布的检测有助于真实反映干燥过程中物料内部的传质现象,并且为干燥工艺的优化和物料干燥数学模型的建立提供依据。综述了核磁共振技术在水分检测中的应用,并展望了核磁共振技术在果蔬干燥过程中物料内部水分无损检测中的意义和前景。     

低场核磁技术结合化学计量学法快速检测掺假牛奶

应用低场核磁共振技术结合主成分分析法(PCA)、偏最小二乘判别法(PLS-DA)、线性判别法(LDA)对掺水、食盐、尿素和蔗糖的牛奶及纯牛奶进行测定。结果表明:在主成分得分图中,不同掺假牛奶随掺假物质的掺假比例呈一定规律性分布,并得到了很好的区分。利用PLS-DA和LDA方法建立不同掺假牛奶的判别模型,对掺水、掺尿素牛奶的判别准确率均为100%,掺食盐牛奶的判别准确率分别为83.33%和100%,掺蔗糖牛奶的判别准确率分别为73.33%和76.67%。可见PCA法、PLS-DA法、LDA法可用于快速处理分析低场核磁共振数据,并且LDA法鉴别准确率最高。     

基于低场核磁共振技术检测秋刀鱼腌干制过程 水分状态变化

目的探讨腌干处理对秋刀鱼水分状态的影响,为秋刀鱼的高值化加工提供参考。方法秋刀鱼进行"三去"(去头、去尾、去内脏)处理,采用10%食盐溶液(料液比1:2)进行腌制,选取腌制2 h的样品进行40℃热风干燥,检测样品的水分含量、盐含量以及水分活度,利用低场核磁共振技术(low-field nuclear magnetic resonance,LF-NMR)测定腌干过程样品的水分存在状态。结果秋刀鱼样品腌干过程中均存在结合水、不易流动水和自由水3种状态水分。腌制10 h过程中样品的水分活度未低于0.90的细菌生长临界值。结合水比例呈现先增大后减小的变化趋势,自由水比例相对降低,不易流动水比例增大,表明腌制处理使得部分结合水与自由水转化为不易流动水。随干制时间的延长,样品的水分含量和水分活度均显著降低(P0.05),结合水变化较小,不易流动水比例呈降低趋势,表明干制处理一方面使得秋刀鱼组织内不易流动水流失,另一方面使其部分转移成其他相态的水。同时,核磁共振成像灰度图和伪彩图深色区域面积逐渐增大,表明干制过程伴随油脂的溢出。结论腌制和干制处理降低了秋刀鱼鱼肉的水分活度,同时改变了水分存在状态。核磁共振成像灰度图和伪彩图表明干制处理改变了秋刀鱼样品的油水平衡。     

Rapid detection of Salmonella in milk by a nuclear magnetic resonance biosensor based on the streptavidin-biotin system and O-carboxymethyl chitosan target gadolinium probe

Rapid and sensitive detection of foodborne pathogens is of great importance for food safety. Here, a set of nuclear magnetic resonance (NMR) biosensors based on a O-carboxymethyl chitosan target gadolinium (Gd) probe was developed to quickly detect Salmonella in milk by combining NMR technology and bioimmunotechnology with membrane filtration technology. First, O-carboxymethyl chitosan (O-CMC) was biotinylated to prepare biotinylated O-carboxymethyl chitosan (biotin–O-CMC) through amide reaction, and biotinylated magnetic complexes (biotin–O-CMC–Gd) were obtained by using O-CMC, which has strong chelating adsorption on Gd. The target probe was obtained by combining biotin–O-CMC–Gd with the biotinylated antibody (biotin–antibody) via streptavidin (SA) by introducing the SA–biotin system. Then, Salmonella was captured by the target probe through antigen–antibody interaction. Finally, NMR was used to measure the longitudinal relaxation time (T₁) of the filtrate collected by membrane filtration. This NMR biosensor with good specificity and high efficiency can detect Salmonella with the sensitivity of 1.8 × 10³ cfu/mL within 2 h; in addition, it can realize the detection of complex samples because of its strong anti-interference capability and may open up a new method for rapid detection of Salmonella, which has a great application potential.     

基于低场核磁共振技术的鲜牛奶冷藏天数的鉴别

应用低场核磁共振技术结合简单分类算法（SIMCA）、线性判别法（LDA）和支持向量机法（SVM）对不同冷藏天数的鲜牛奶进行鉴别,并比较了SIMCA、LDA中不同函数及SVM中不同类型参数、不同核函数的建模效果。结果表明:LDA中Mahalanobis函数建立的模型优于Linear、Quadratic函数的模型;SVM中C-SVM类型的模型优于Nu-SVM类型的模型,径向基函数与线性函数的模型优于S型函数、多项式函数的模型。SIMCA模型的总识别准确率为95.83%,LDA中Mahalanobis函数建立的模型总识别准确率为100%,SVM中C-SVM类型的径向基函数建立的模型总识别准确率为87.50%。由此表明LDA中用Mahalanobis函数建立的模型最适合预测鲜牛奶的冷藏天数。      

Effects of pressure processing on strawberry studied by nuclear magnetic resonance

Two different nuclear magnetic resonance techniques, namely magnetic resonance imaging and ¹H-HR-MAS NMR spectroscopy, have been employed to study the extent of the damage caused by relatively low pressures (100–200 MPa) in strawberry. MRI maps showed important changes in the relaxation behavior of water molecules in pressurized samples. These differences increased with the pressure level applied. ADC values clearly showed the destruction of biological barriers and the loss of cell compartments produced by pressure. This induced major water redistribution in the tissues and; therefore, substantial changes in the interactions between water molecules and their environment. Relaxation times in T₁ and T₂ maps clearly depicted these pressure induced modifications. Moreover, NMR spectroscopy showed significant differences in the main sugars content in control and pressurized samples. Sucrose hydrolysis seems to be enhanced by the pressure treatment.

Industrial relevance

The research data presented in this paper show a deep insight into the phenomena which take place during pressure processing in a soft plant tissue. The Nuclear Magnetic Resonance (NMR) techniques employed offered the opportunity of studying the whole product without any preparative manipulation which could mask the pressure effects. The results obtained should be useful to understand how and why pressure causes damage to vegetal tissues and, therefore, to design optimized high-pressure treatments which minimize this damage.     

核磁共振技术在食品分析检测中的应用

核磁共振检测技术是一种新型的食品无损检测技术。介绍了核磁共振的基本原理和优势,综述了国内外核磁共振技术在食品中的水分、油脂、玻璃态转变、碳水化合物、蛋白质及品质鉴定等方面的研究进展,但该技术在实际应用中仍然存在一些问题,有待进一步研究。     

用低场核磁共振检测水稻浸种过程中种子水分的相态及分布特征

为研究水稻浸种过程中种子的水分相态及其分布特征,利用低场核磁共振快速、无损、准确的检测技术,通过硬脉冲回波序列CPMG(carr purcell meiboom gill sequence)测量水稻种子横向弛豫时间T2,根据横向弛豫时间T2的差异区分种子内部的水分相态及其变化规律。试验结果表明:通过T2反演谱横向弛豫时间T2长短的差异,发现水稻浸种过程中种子内部水分存在结合水、自由水2种水分状态,同时可区分出内层水、中层水、外层水3种水分分层;二者均能通过回归方程合理的估测水稻在浸种过程中种子的吸水率情况;通过T2反演谱信号幅值大小的差异,发现水稻浸种过程中的种子总水含量不断上升,但由于判定依据及划分方式的不同,二者在水分的流动方式上略显差异。低场核磁共振技术对水稻浸种过程中种子内部的水分变化进行了直观的揭示,提供了一种高效的种子水分检测方法。     

低场核磁共振技术测定石花菜对酸奶水分迁移及超微结构的影响

利用低场核磁共振及其成像技术对比了石花菜酸奶和酸奶水分迁移特性;并采用环境扫描电镜对石花菜酸奶超微形貌特征进行观察分析。结果表明,石花菜酸奶在发酵及储藏过程中的水分含量变化幅度小于不添加石花菜的酸奶,持水性增强;确定了前期发酵最优时间为6 h,冷藏后熟最优时间为24 h;通过环境扫描电镜观察发现石花菜酸奶中酪蛋白胶束与石花菜琼胶分子间相互缠结,蛋白链球颗粒粘结在致密的琼胶网络结构之中。     

基于低场核磁共振技术的冷冻猪背最长肌品质变化研究

采用低场核磁共振技术、核磁成像技术和一维空间频率编码技术,研究猪背最长肌在-18℃冻藏0d和1,3,6,9,12,15个月后水分含量和迁移变化规律;并测定猪肉贮藏过程中TVB-N、TBARS、汁液流失率、蛋白质溶解度的变化,将水分变化和品质指标变化进行相关性综合分析。结果表明:猪背最长肌中3种组分的水分分别为:结合水(T_(20))、不易流动水(T_(21))和自由水(T_(22)),随着冻藏时间的延长,肉样中T_(21)组分降低,T_(22)组分增加;MRI表明随着时间的延长,样品水分分布从最初分布均匀到样品边缘信号强,中间部位信号低。随着冻藏时间的再延长,又逐渐恢复均匀状态,15个月后水分分布较均匀;用一维频率编码扫描发现随着冻藏时间的延长,肉中水分的信号量(幅值)逐渐降低;相关性分析结果表明:T_(21)与冻藏时间、TVB-N、TBARS、汁液流失率、蛋白质溶解度都显著相关(P0.05),T_(22)与冻藏时间、TVB-N极显著相关(P0.01),T_(22)与TBARS、汁液流失率、蛋白质溶解度显著相关(P0.05),T_(21)、T_(22)都与肉中品质指标呈现较好的相关性。     

Optimization of nuclear magnetic resonance and gas chromatography-mass spectrometry-based fingerprinting methods to characterize goat milk powder

This study is the first to provide a comprehensive characterization of the liquid and volatile fractions of whole goat milk powder (GMP). Robust nuclear magnetic resonance (NMR)- and gas chromatography-mass spectrometry (GC-MS)-based chemical fingerprinting methods were optimized and implemented. The untargeted ¹H-NMR analysis resolved 44 metabolites in the liquid fractions of GMP. The NMR fingerprinting technique effectively identified metabolites coming from the aliphatic, sugar, and aromatic regions that can be important in defining the technological properties and quality of the GMP. The untargeted headspace gas chromatography-mass spectrometry fingerprinting was able to detect a total of 50 volatiles including alkanes, ketones, alcohols, aromatics, alkenes, aldehydes, esters, acid, and sulfur compounds. The GMP was dominated by volatiles in the alkane group, while only a few esters were detected. Goat milk is a premium product and vulnerable to fraudulent activities such as adulteration or counterfeit. Therefore, proper characterization and identification is a crucial first step to verify its authenticity and quality.     

基于核磁共振及成像技术研究速冻汤圆在冻融过程中的水分迁移变化

目的 研究冻融过程对速冻汤圆水分分布及迁移的影响。方法 采用低场核磁共振(low-field nuclear magnetic resonance, LF-NMR)及成像技术研究速冻汤圆在冻结和融化过程、反复冻融过程及储藏期间的水分分布变化。结果 在冻结状态下,速冻汤圆中强结合水含量高达95.85%,随着温度的升高,强结合水向弱结合水转化,当温度高于0℃时,体系中的水分以不易流动水为主,T22发生右移,水分自由度增加;另外,反复冻融造成汤圆水分的迁移损耗,核磁共振成像(magnetic resonance imaging,MRI)图进一步证实冻融循环导致汤圆体系中的结合水向不易流动水和自由水转化;随着储藏时间的延长,T₂₁由0.62ms增加为1.97ms,说明样品体系中结合水与基质结合的紧密度减低,但储藏期间结合水、不易流动水等含量变化并未呈现出规律变化。结论 冻融循环增加了体系水分的自由度;但在冻藏的过程中,保持储藏温度的稳定性有利于提高速冻汤圆体系中水分的稳定性。LF-NMR分析可以快速反映温度波动、反复冻融等对速冻汤圆水分分布造成的影响,进而评估速冻汤圆的品...