Electrospray ionization mass spectrometry fingerprinting of Brazilian artisan cachaça aged in different wood casks

We have investigated the capability of direct infusion electrospray ionization mass spectrometry in the negative ion mode, ESI(-)-MS, to differentiate representative samples of artisan cacha?a, a Brazilian sugar cane distillate of large production, aged in four different types of wood casks: amburana (Amburana cearensis), jequitibA (Cariniana estrellensis), balm (Myroxylon peruiferum), and oak (Quercus rubra). The ESI(-)-MS were found to be very characteristic, showing sets of diagnostic ions for each of the four types of samples: amburana (m/z 271, 313, 377), jequitibA (m/z 143, 171, 255), balm (m/z 137, 269, 283, 297), and oak (m/z 197, 301, 307). Furthermore, principal component (PCA) and hierarchical cluster analysis (HCA), applied to the ESI(-)-MS data, divided these samples into four definite categories. The influence of the aging time on the ESI(-)-MS fingerprints of the cacha?a samples stored in oak casks was also established. An inversion in the relative intensity of the diagnostic ions of m/z 307 and 301 is detected in the ESI(-)-MS as the aging time increased from 1 to 2 years. The chemical structures of the major cacha?a components were proposed on the basis of the following: (a) the comparison of the ESI(-)-MS/MS of the diagnostic anions with those of the authentic anions or (b) the interpretation of the fragmentation patterns of the previously unknown diagnostic anions. Hence, direct infusion ESI(-)-MS allows not only a rapid, simple, and accurate way to distinguish among cacha?a samples stored in different wood casks but also monitoring changes in their chemical composition according to the aging time.     

Profiles of polycyclic aromatic hydrocarbons in Brazilian sugar cane spirits: discrimination between Cachaças produced from nonburned and burned sugar cane crops

Cacha?a may be contaminated by a remarkable presence of polycyclic aromatic hydrocarbons (PAHs) when the sugar cane crop used for its production is burned before harvesting. The analysis of 15 PAHs by liquid chromatography coupled to a fluorescence detector in 131 cacha?a samples from burned and nonburned sugar cane crops is reported. Average contents of 21.1 and 1.91 microg L(-1) for total PAHs were observed for cacha?as originating from burned and nonburned sugar cane plantations, respectively. The main difference between these two classes of cacha?as is in the quantitative profile of the most potent carcinogenic PAH, benzo[a]pyrene, which is more abundant in cacha?a produced from burned sugar cane crops (4.54 x 10(-2) microg L(-1)) than in cacha?a produced from nonburned crops (9.02 x 10(-3) microg L(-1)). The contents of benzo[a]pyrene in both classes of cacha?a are lower than the legal limit established by the European Union (EU) at 2.00 microg L(-1) for food products. In relation to the total PAH content suggested by the German Society for Fat Science, both cacha?as from burned (21.1 microg L(-1)) and nonburned crops (1.91 microg L(-1)) are below the limit (25 microg L(-1)) for total PAH content. The analytical data for PAHs, when treated through the multivariate statistical methods principal component analysis and canonical discriminant analysis, provide a very good distinction between samples produced from burned and nonburned sugar cane crops with a certainty of 98.1%.     

Quantitative PCR detection of pork in raw and heated ground beef and pâté

Quantitative estimates are important to establish whether pork adulteration in ground beef and paté is accidental or intentional. A PCR procedure has been developed and evaluated to quantify pork in heated and nonheated meat and patés by densitometry using a specific and sensitive repetitive DNA element. Thirty, twenty-five, and twenty PCR cycles were carried out to find the best standard curve and correlation between pork content and band intensity. Twenty cycles showed the best results, quantifying degree contamination up to 1% pork in beef (heated and nonheated) and pork in duck paté with a minimum error. Finally, fraud was found in commercial patés.     

Identification of the effects of long-term application of nitrogen fertilizer on the availability of 11 elements in soils and their supply to ‘Jonathan’ apple trees by using simultaneous multi-element analysis

Abstract

The objective of this study was to investigate the effects of long-term application of ammoniacal N fertilizer for 43?years on the availability of 10 essential elements (B, N, Mg, K, Ca, Mn, Fe, Ni, Cu, and Zn) and Al in root-zone soils and their supply to ‘Jonathan’ apple trees. To achieve this objective, we used simultaneous multi-element analysis. To estimate the soil depth from which the apple trees took up these elements, we calculated the ratios of their concentrations in the N fertilized plot (N plot) to those in the no N plot (0?N plot) (N/0N ratio). Long-term N fertilization significantly increased the fruit and leaf N/0N ratios of N and Mn and significantly decreased that of K. These ratios in the fruits and leaves were similar to those in the 20–90?cm soil layer. This result suggests that N, K, and Mn in the fruits and leaves were supplied from the 20–90?cm soil layer. The N/0N ratios of all 11 elements in the fruits and leaves were significantly positively correlated with those in the 20–90?cm soil layer, but not in the 0–20?cm soil layer. Our findings indicate that long-term N fertilization altered the tree nutrition of not only N, but also K and Mn. These changes in the tree nutrition were ascribed to the fertilizer-induced changes in the availability of elements in the subsoils.     

Fast analysis of sugars, fruit acids, and vitamin C in sea buckthorn (Hippophaë rhamnoides L.) varieties

A fast, one-step gas chromatographic method was developed to analyze trimethylsilyl (TMS) derivatives of sugars, fruit acids, and ascorbic acid in sea buckthorn (Hippoha? rhamnoides L.) berries. The method was applied to berry press juice of sea buckthorn of different origins grown in Finland during the 2003 and 2004 seasons. The method gave reliable results for D-fructose, D-glucose, ethyl-D-glucose, and malic, quinic, and ascorbic acids, which are the major sugars and acids in sea buckthorn juice. For the first time in sea buckthorn and evidently in any berry, the presence of ethyl beta-D-glucopyranoside is reported. The structure of ethyl glucose was verified by high-performance liquid chromatography (HPLC), gas chromatography (GC), MS, and NMR analyses of both the isolated and the synthesized compounds. In the GC method, vitamin C was analyzed as ascorbic acid only, and dehydroascorbic acid was thus not taken into account.     

Comparative analysis of genetic diversity using molecular and morphometric markers in Andrographis paniculata (Burm. f.) Nees

Andrographis paniculata is a medicinal plant of immense therapeutic value. The present study was aimed to elucidate its genetic diversity based on morphochemical and RAPD markers from 53 accessions belonging to 5 eco-geographic regions. Analysis of variance and D ² statistics revealed significant differences in all the metric traits and sufficient inter-cluster distances indicating considerable diversity among the accessions. The complementary approach of RAPD was used to evaluate the genetic dissimilarities among all the accessions using 6 highly polymorphic primers. The average proportion of polymorphic loci across primers was 96.28%. The molecular genetic diversity based on Shannon index per primer averaged 5.585 with values ranging from 3.08 to 8.70 indicating towards wide genetic base. RAPD based UPGMA and D ² cluster analysis also revealed that various accessions available in different eco-geographic regions might have originated from native places of wild abundance. Similarity matrices were generated for molecular markers and morphometric data to determine the degree of congruence between the two. A highly significant but low correlation (r = 0.547, P < 0.001) was obtained thus implying the correspondence between the two. The species is hermaphroditic and a habitual inbreeder. The present study yielded a typical triangular congruence between its breeding system, morphometric traits and RAPD markers thus elucidating the usefulness of complementary approaches to make diversity analysis more explanatory and purposeful for optimum genetic amelioration and effective conservation of its genotypic variability.