基于高效液相色谱指纹图谱的玛咖及其制品真实性识别

玛咖及其制品的真实性是保障品质的关键。为了研究玛咖及其制品的差异,对玛咖制品进行真实性鉴别,分别以不同产地、色型的玛咖及玛咖制品为供试材料,对其进行高效液相色谱(high performance liquid chromatography,HPLC)指纹图谱不同识别方法的研究。采用Waters Symmetry Shield TM C18(250 mm×4.6 mm,5μm)色谱柱,乙腈-水为流动相梯度洗脱,检测波长210 nm,体积流量0.80 m L/min,各成分得到较好分离。经方法学验证,方法具有较好的精密度、重复性和稳定性。对19个玛咖样品和6个玛咖制品HPLC指纹图谱进行分析,确定了15个色谱峰为玛咖和其制品的特征指纹峰,建立了玛咖及其制品的指纹图谱。以数字化指纹图谱为基础,分别进行主成分分析、判别分析和相似度分析。结果表明,3种方法均能使玛咖与玛咖制品得到较为一致的模式识别结果。主成分二维平面图和判别分析能够区分玛咖和玛咖制品,具有简便、直观的特点,玛咖与玛咖制品相似度分析差异显著(P0.05),分别为0.916和0.668,不同来源和色型的玛咖、玛咖制品间相似度均无显著差异(P0.05)。结果显示玛咖制品具有玛咖的特征峰,但含量存在差异。3种方法均能准确地体现指纹图谱的一致性和特征性,为玛咖和玛咖制品的区分及玛咖制品真实性保障提供了参考。利用HPLC指纹图谱可对玛咖及其制品的真实性进行鉴别。     

Weathering of gneiss in Calabria,Southern Italy

The effects of weathering in a Mediterranean climate on the mineralogy and microfabric of Paleozoic gneiss of the Sila Massif, Calabria, southern Italy, have been studied. Field observations show highly weathered rock forms a residual soil. Micromorphological and mineralogical properties of bedrock and saprolite show that the weathering process is characterized by at least two major stages, having two distinct rock microfabrics. In the first stage, the morphological features of the original rock are preserved and weathering is manifested mainly by microfracturing, and large portions of the rock remain unaltered. The second stage of weathering involves further development of microcracks and progressive chemical attack on the minerals. This latter stage occurs along both compositional and microstructural discontinuities, with etch pitting of feldspar, and neoformation of clay minerals and ferruginous products replacing feldspar, biotite, and iron-bearing garnet. The determination of quantitative petrographic indices provides a measure of the various stages of weathering.     

Authenticity of the traditional cypriot spirit "zivania" on the basis of 1h NMR spectroscopy diagnostic parameters and statistical analysis

A previous publication (Kokkinofta et al. J. Agric. Food Chem. 2003, 51, 6233-6239) discussed the use of inductively coupled plasma spectroscopy to differentiate between the traditional Cypriot alcoholic beverage zivania and other spirits similar in alcoholic content collected from different countries. In the present paper (1)H NMR spectroscopy is applied to confirm the previous conclusions and to obtain additional physical-chemical characteristics that may be used to differentiate zivania from other similar beverages. NMR spectroscopy gave a satisfactory degree of prediction and classification between zivanias and other distillings. The validity of quantification of the method was tested using comparative GC data. It appears that chemical analysis can be very helpful for identifying the unique geological and climatic conditions existing in the island of Cyprus that lead to an authentic product.     

Classification of German white wines with certified brand of origin by multielement quantitation and pattern recognition techniques

A procedure is proposed for the determination of the authenticity of white wines from four German wine-growing regions (Baden, Rheingau, Rheinhessen, and Pfalz) based on their content of some major, trace, and ultratrace elements. One hundred and twenty-seven white wine samples possessing a certificate of origin, all of the 2000 vintage, were analyzed. The concentrations of 13 elements (Li, B, Mg, Ca, V, Mn, Co, Fe, Zn, Rb, Sr, Cs, and Pb) were determined in wine diluted 1:20 by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS). Indium was routinely used as internal standard. Supervised pattern recognition techniques such as discriminant analysis and classification trees were applied for the interpretation of the data. A quadratic discriminant analysis (QDA) allowed the four regions to be discriminated with 83% accuracy when using only eight variables (Li, B, Mg, Fe, Zn, Sr, Cs, and Pb), and the prediction ability for classifying new samples was 76%. By use of a second method, a decision tree, the classification of samples coming from the four regions could be performed with an accuracy of 84% when only four elements were used: Li (very low in samples from Baden), Zn (abnormally low in the samples from the Rheingau), and Mg and Sr (both important for the differentiation between Pfalz and Rheinhessen samples). For this method, the prediction ability was only 74% in the identification of unknown samples. The robustness of the QDA model was not good enough, and therefore the tree is better recommended for the classification of new wine samples from these areas of German wine production.     

Authenticity of the traditional cypriot spirit "zivania" on the basis of metal content using a combination of coupled plasma spectroscopy and statistical analysis

Sixty-eight alcoholic beverages ranging in alcoholic degree between 40 and 55 from different countries were analyzed for their 16 most abundant metal elements using inductively coupled plasma (ICP) spectroscopy. The results were analyzed statistically using two different types of analytical methods: canonical discriminant analysis and classification binary trees. The aim of this study was to investigate which of the metals analyzed constitute diagnostic parameters that establish authenticity of the traditional Cypriot spirit zivania. The two statistical methods revealed that Mg, Zn, and Cu are promising distinctive parameters capable of differentiating zivania from other spirits similar in alcoholic degree. It is believed that this differentiation in metals between the alcoholic beverages examined is related to the unique geological and climatic conditions existing on the island of Cyprus.     

Role of the cultivar in choosing Clementine fruits with a high level of health-promoting compounds

Thirteen cultivars and two hybrids of Clementine fruits (Citrus clementina Hort. Ex. Tan) cultivated in Italy were characterized according to pH, titratable acidity, total soluble solids, total polyphenols, carotenoids, vitamin C, hesperidin, rutin, narirutin and naringin and radical scavenging activity. The presence of rutin in Clementine fruit juice is reported for the first time here. The results indicated that all chemical parameters statistically differentiated each cultivar (P < 0.001). In particular, principal component analysis showed a clear discrimination of five cultivars from all the other varieties based on vitamin C and total polyphenols for the Caffin cultivar, which showed also the highest antioxidant activity; narirutin for the Etna hybrid cultivar; hesperidin, rutin and total soluble solids for the SRA 89 cultivar; and naringin, hesperidin and rutin for the Esbal cultivar. Moreover, the Mandalate hybrid cultivar showed the lowest antioxidant activity as well as vitamin C and total polyphenols content, while titratable acidity and naringin level were the highest. The antioxidant activity assessed in all the fruits was closely correlated with vitamin C and total polyphenols content, rather than with the flavonoid compounds.     

Authenticity assessment of estragole and methyl eugenol by on-line gas chromatography-isotope ratio mass spectrometry

On-line capillary gas chromatography-isotope ratio mass spectrometry was used in the combustion (HRGC-C-IRMS) and the pyrolysis (HRGC-P-IRMS) modes to determine delta(13)C(PDB), delta(2)H(SMOW), and delta(18)O(SMOW) data of estragole (1) and methyl eugenol (2) originating from various sources. For 1, similar delta(13)C values, i.e., ranging from -35.4 to -29.9 per thousand and from -36.4 to -28.8 per thousand for the product of synthetic and natural origins, respectively, were found. The delta(2)H values ranged from -155 to -3 per thousand for synthetic 1 and from -193 to -105 per thousand for 1 from natural origin, whereas the determination of delta(18)O data gave values from +1.8 to +24.8 per thousand and from +2.7 to +18.7 per thousand for 1 from synthetic and natural origins, respectively. As synthetic 2 is produced by methylation of natural eugenol, the IRMS techniques did not allow differentiation of synthetic 2 from the product of natural origin. The recorded data ranges were nearly identical, i.e., delta(13)C = -37.4 to -35.0 per thousand and -41.1 to -32.2 per thousand; delta(2)H = -155 to -126 per thousand and -217 to -107 per thousand; delta(18)O = +5.5 to +6.6 per thousand and +2.7 to +6.9 per thousand, each for 2 from synthetic and natural origins, respectively.     

Determination of the geographic origin of rice by chemometrics with strontium and lead isotope ratios and multielement concentrations

The objective of this study was to develop a technique for determining the country of origin of rice in the Japanese market. The rice samples included a total of 350 products grown in Japan (n = 200), the United States (n = 50), China (n = 50), and Thailand (n = 50). In this study, (87)Sr/(86)Sr and Pb isotope ((204)Pb, (206)Pb, (207)Pb, and (208)Pb) ratios and multielement concentrations (Al, Fe, Co, Ni, Cu, Rb, Sr, and Ba) were determined by high-resolution inductively coupled plasma mass spectrometry. By combining three chemometric techniques based on different principles and determination criteria, the countries of origin of rice were determined. The predictions made by 10-fold cross-validation were around 97% accurate. The presented method demonstrated the effectiveness of determining the geographic origin of an agricultural product by combining several chemometric techniques using heavy element isotope ratios and multielement concentrations.     

A convenient wet digestion procedure for multielement analysis of plant materials

Abstract

For the determination of total element contents in plant material by atomic spectrometry after wet digestion, both dissolution and oxidation of the matrix are necessary. This was achieved by a sequential digestion procedure using first hydrogen fluoride (HF) for dissolution of silicate, followed by oxidation with nitric acid (HNO₃) and hydrogen peroxide (H₂O₂). The final solution is 0.2M HNO₃, and contains only traces of HF. Application of the method for the determination of aluminium (Al), boron (B), calcium (Ca), cadmium (Cd), copper (Cu), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), phosphorus (P), lead (Pb), sulfur (S), and zinc (Zn) in various materials showed good agreement with certified reference materials.     

利用SSR标记和SNP芯片对小麦EMS突变体进行真实性鉴定

为鉴定EMS突变的真实性,本研究利用SSR标记和90 K SNP芯片对小麦品系H261及其EMS突变体进行检测。SSR检测结果表明,H261与LF2010和LF2099的差异SSR标记为0个,但与LF2100的差异SSR标记为10个,多态性比例为47.62%。SNP芯片分析结果表明,H261与LF2010和LF2099之间的差异位点分别为66和12个,分别占总数的0.080 9%和0.014 7%,2个突变体与H261的纯合差异SNP数目均为0;而H261与LF2100之间的差异位点为2 846个,占总数的3.487 9%,二者之间纯合差异SNP为784,占总数的0.960 8%。综上所述,LF2010和LF2099突变体与亲本H261的遗传背景高度一致,是H261经过EMS诱变的后代,而LF2100是天然异交或机械混杂产生的假突变体。本研究结果为更好地发挥小麦突变体在遗传改良和功能基因组研究奠定了一定的理论基础。     

Evaluation of Mehlich 3 reagent as a multielement extractant in mine soils

The usefulness of Mehlich 3 (M3) reagent was evaluated as a method to extract numerous elements from coalmine soils in As Pontes (Spain) showing a wide range of physicochemical properties. Critical levels (deficiency and/or toxicity) were established for plant available elements extracted by this reagent. The M3 method was compared to 1M NH₄Cl, Olsen, acid oxalate, and DTPA methods as extractants for exchangeable Ca, Mg and K, available P, non-crystalline aluminium, and available heavy metals, respectively. The M3 method correlated significantly to NH₄Cl for Ca, Mg and K (r=0·76, 0·84 and 0·87, respectively), to Olsen P (r=0·77) and to oxalate Al (r=0·77). Significant correlations were found between Fe, Cu, Zn and Cd extracted by M3 and DTPA; for Mn, Ni, Co and Pb different relationship between methods were obtained for acid and alkaline samples, so that critical levels were established for M3 metals as a function of soil pH. Copyright © 1999 John Wiley & Sons, Ltd.     

Determining the geographic origin of wheat using multielement analysis and multivariate statistics

The element contents of wheat from four major wheat-producing regions of China were analyzed and used in multivariate statistical analysis to classify wheat according to geographical origin. The concentrations of 15 elements (Be, Na, Mg, Al, K, Ca, V, Mn, Fe, Cu, Zn, Mo, Cd, Ba, and Th) in 240 samples from the 2007/2008 and 2008/2009 harvests were determined by inductively coupled plasma mass spectrometry. The analysis of variance and linear discriminant analysis were applied to classify wheat origin, and the effects of region, variety, and harvest year on the element contents were analyzed in this study. It was concluded that the multielement analysis is a promising method to provide reliable origin information for wheat, although the element profiles and discriminant models were affected by wheat varieties, harvest years, and agricultural practices.     

不同品种红葡萄酒花色苷高效液相色谱指纹图谱识别

利用高效液相色谱法建立了9个品种葡萄酒的花色苷指纹图谱,对不同品种葡萄酒进行识别。HPLC检测：采用反相C18柱,调整流动相pH值1.6,二元梯度洗脱,检测波长518 nm。指纹图谱建立方法：计算HPLC色谱峰的相对保留时间和相对峰面积,按相对保留时间排列相对应的相对峰面积。采用夹角余弦法计算相关系数,并使用SPSS11.0统计分析软件对指纹图谱进行系统聚类分析。结果表明：不同品种葡萄酒花色苷的HPLC指纹图谱存在着差异,山葡萄种及杂种葡萄酒具有区别于欧亚种葡萄酒的特征色谱峰;不同品种葡萄酒花色苷指纹图谱的相似性不同,不同种间品种葡萄酒相似性较差;系统聚类分析初步建立了不同品种葡萄酒花色苷识别模式,对葡萄酒进行了较好的识别。指纹图谱技术结合聚类分析是识别不同酿造品种葡萄酒的有效方法之一。     

Validating erosion rate estimates provided by caesium‐137 measurements for two small forested catchments in Calabria,southern Italy

Increasing concern for problems of soil degradation and the off‐site impacts of accelerated erosion has generated a need for improved methods of estimating rates and patterns of soil erosion by water. The use of environmental radionuclides, particularly ¹³⁷Cs, to estimate erosion rates has attracted increased attention and the approach has been shown to possess several important advantages. However, the use of ¹³⁷Cs measurements to estimate erosion rates introduces one important uncertainty, namely, the need to employ a conversion model or relationship to convert the measured reduction in the ¹³⁷Cs inventory to an estimate of the erosion rate. There have been few attempts to validate these theoretical conversion models and the resulting erosion rate estimates. However, there is an important need for such validation, if the ¹³⁷Cs approach is to be more widely applied and reliance is to be placed on the results obtained. This paper reports the results of a study aimed at validating the use of two theoretical conversion models, namely the exponential depth distribution model and the diffusion and migration model, that have been used in several recent studies to convert measurements of ¹³⁷Cs inventories on uncultivated soils to estimates of soil erosion rates. The study is based on data assembled for two small catchments (1.38 and 1.65 ha) in Calabria, southern Italy, for which measurements of sediment output are available for the catchment outlet. The two catchments differ in terms of the steepness of their terrain, and this difference is reflected by their sediment yields. Because there is no evidence of significant deposition within the two catchments, sediment delivery ratios close to 1.0 can be assumed. It is therefore possible to make a direct comparison between the estimates of the mean annual erosion rates within the two catchments derived from ¹³⁷Cs measurements and the measured sediment outputs. The results of the comparison show that the erosion rate estimates provided by both models are reasonably consistent with the measured sediment yields at the catchment outlets. However, more detailed assessment of the results shows that the validity of the erosion rate estimates is influenced by the magnitude of the erosion rates within the catchment. The exponential depth distribution model appears to perform better for the catchment with higher erosion rates and to overestimate erosion rates in the other catchment. Similarly, the basic migration and diffusion model performs better for the catchment with lower erosion rates and overestimates erosion rates in the other catchment. However, the improved migration and diffusion model appears to perform satisfactorily for both catchments. There is a need for further studies to extend such independent validation of the ¹³⁷Cs technique to other environments, including cultivated soils, and to other conversion models and procedures. Copyright © 2003 John Wiley & Sons, Ltd.     

品种纯度和真伪的DNA分子标记鉴定及其应用

本文阐述了品种纯度和真伪的ＤＮＡ分子标记鉴定的原理,优点及其应用研究概况,认为利用ＲＦＬＰ、ＲＡＰＤ和ＡＦＬＰ等ＤＮＡ分子标记可通过鉴定种子ＤＮＡ水平上的差异来鉴定品种纯度和真伪,具有准确可靠、成本较低、不受环境因素影响、便于实现鉴定自动化,且可鉴定表型上难于鉴别的品种等优点;已初步应用于多种作物的品种纯度和真伪鉴定,有些已实现商业化;本文还认为,利用ＤＮＡ分子标记鉴定品种纯度和真伪是品种鉴定的发     

基于二元Logistic回归分析的苹果汁鉴伪模型的建立

苹果汁中特征有机酸指纹图谱可以用来鉴别苹果汁掺假。本文共收集了170个中国产苹果样本,通过高效液相色谱法测定样本中有机酸的种类及含量。数据与现有文献中相关数据不完全吻合,但所得数据反应的是中国不同产区苹果中有机酸数据特征。在测得的有机酸种类和含量的基础上利用二元Logistic回归分析方法建立了一个判别模型,用以区别掺假苹果汁。模型为：π=1/[1+exp(79.545X1+14.255X2+ 3.4X3-5.02)],此模型的精确度和重现率分别为87.4%和94.51%。统计数据显示该模型判别效果良好,可用于苹果汁的质量控制。     

DHPLC技术鉴定玉米杂交种真实性及纯度

变性高效液相色谱(denaturing high-performance liquid chromatography, DHPLC)技术可用于检测玉米(Zea mays)品种的单核苷酸多态性(single nucleotide polymorphism,SNP)和插入/缺失(Insertion/Deletion,InDel)的多态性遗传标记.为验证DHPLC技术在玉米分子标记分析中应用的可行性和可靠性,本研究基于公共数据库中的玉米基因信息,筛选2条DNA序列作为目标分析片段,利用DHPLC技术平台对10份玉米杂交种及其亲本进行检测.2条目标分析片段的DHPLC分析结果显示,玉米杂交种产生的DHPLC谱图具有多态性,基于Amp Ⅰ片段,10份玉米杂交种产生3类DHPLC图谱,基于AmpⅡ片段,可产生7种图谱类型,不同类型的DHPLC图谱在峰的数量和峰的保留时间上存在明显差异.测序结果显示DHPLC谱型与基因型一一对应,即使只有一个碱基差异的两种基因型样本,也将产生不同峰型特征的DHPLC图谱.10份玉米杂交种中,除3份杂交种的两条目标片段的DHPLC峰型均一致以外,其余7份杂交种相互之间至少存在一个DHPLC谱型的差异从而可以获得有效区分.实验结果也显示所有杂交种均与其亲本混合样本的DHPLC图谱一致.利用该特征,可以认为通过比对玉米杂交种子和育种亲本混合样本的DHPLC图谱峰型,实现对杂交种子真实性和纯度的鉴定.DHPLC分辨率高、快速、操作简单、安全等优点,将是杂交玉米种子真伪和纯度快速鉴定的有效手段.     

Collecting crop genetic resources in Italian towns of Albanian origin across the Molise,Calabria and Sicily regions

A project on collecting and safeguarding crop genetic resources in Italian linguistic islands by the Institute of Plant Genetics (IGV) of the National Research Council (CNR) of Bari (Italy) and the Institute of Crop Science of Kassel University (Germany) started in 1996 with a first mission in Italian towns (Basilicata region) of Albanian origin. In 2008 three other regions (Calabria, Molise and Sicily) were visited with the same aim. Ninety-six accessions belonging to 38 taxa were collected from 23 collecting sites. The Albanian linguistic islands still preserve valuable crop genetic resources that are severely threatened by genetic erosion. To halt this phenomenon a good example comes from Molise where the municipal government and scientific sector are starting to co-operate in the preservation of genetic diversity.     

基于矿物元素指纹图谱的黑龙江黄豆产地溯源

该研究探讨了矿物元素指纹分析技术对黑龙江黄豆产地溯源的可行性,筛选出判别黑龙江黄豆产地溯源的有效指标。利用电感耦合等离子体质谱仪(inductively coupled plasma mass spectrometry,ICP-MS)测定来自齐齐哈尔和北安2个地域50份黄豆样品中52种矿物元素的含量,并对数据进行了方差分析、主成分分析和判别分析。研究表明,46种矿物元素含量在地域间存在显著差异,通过逐步判别分析筛选出8项元素指标建立黄豆产地判别模型,所建立的模型对黄豆产地整体交叉检验判别率为95.7%。As、Ru、Gd含量在黄豆与土壤间呈显著正相关(P0.05),Tb含量在黄豆与土壤间呈极显著正相关(P0.01),由4种元素建立的判别模型对产地判别准确。因此,上述元素是黄豆矿物元素产地鉴别较可靠的指纹信息指标。     

Application of multielement stable isotope ratio analysis to the characterization of French, italian, and spanish cheeses

The stable isotope ratios (delta13C, delta15N, and delta34S of casein and delta13C and delta18O of glycerol) measured by IRMS of French, Italian, and Spanish cheeses are presented and discussed. Variability factors such as animal-feeding regimen, geographical origin, and climatic and seasonal conditions were studied to check the possibilities of cheese characterization offered by each isotopic parameter. Delta13C values of both casein and glycerol appeared to be strongly correlated to the amount of maize in the animal diet. Delta15N and delta34S of casein proved to be mostly influenced by the geoclimatic conditions of the area (aridity, closeness to the sea, altitude). Delta18O of glycerol was more dependent on the geographical origin of the cheeses and on climatic/seasonal parameters. By applying a multivariate stepwise canonical discriminant analysis, good discrimination possibilities for the different European cheeses were obtained, confirmed by the classification analysis, when >90% of the samples were correctly reclassified.