Glass transition temperature of honey as a function of water content as determined by differential scanning calorimetry

The glass transition of pure and diluted honey and the glass transition of the maximally freeze-concentrated solution of honey were investigated by differential scanning calorimetry (DSC). The glass transition temperature, of the pure honey samples accepted as unadulterated varied between -42 and -51 degrees C. Dilution of honey to 90 wt % honey content resulted in a shift of the glass transition temperature by -13 to -20 degrees C. The concentration of the maximally freeze-concentrated honey solutions, as expressed in terms of honey content is approximately 102-103%, i.e., slightly more concentrated in sugars than honey itself. The application of DSC measurements of and in characterization of honey may be considered, but requires systematic study on a number of honeys.     

Use of differential scanning calorimetry to study lipid oxidation. 1. Oxidative stability of lecithin and linolenic acid

The oxidation of linolenic acid (LNA) and soy lecithin was studied by differential scanning calorimetry (DSC) with linear programmed heating rates (non-isothermal mode). The interpretation of the shape of DSC curves is discussed, and it has been concluded that temperatures of the extrapolated start of heat release are the most reliable data for the rapid estimation of the oxidative stability of lipid materials. The Ozawa-Flynn-Wall method was used to calculate the kinetic parameters of the process: for LNA autoxidation the activation energy, Ea, and pre-exponential factor, Z, are 66 +/- 4 kJ/mol and 1.5 x 10(7) s(-1), respectively, and the autoxidation of lecithin is described by Ea = 98 +/- 6 kJ/mol and Z = 9.1 x 10(10) s(-1). Values of Ea and Z can be applied for calculation of the overall first-order rate constant of autoxidation at various temperatures, k(T). For the two studied lipids the comparison of k(T) values shows the inversion of their oxidative stabilities; that is, below 167 degrees C lecithin is more stable than LNA, k(T)lecithin < k(T)LNA, and above that temperature (termed the isokinetic temperature) k(T)lecithin > k(T)LNA. The calculated inversion of oxidative stabilities can be an explanation of similar observations for other pairs of lipids if the results of accelerated tests measured at temperatures above 100 degrees C are compared with the results obtained at temperatures below 100 degrees C.     

Homogentisic acid: a phenolic acid as a marker of strawberry-tree (Arbutus unedo) honey.

Analysis of organic acids in strawberry-tree (Arbutus unedo) honey showed the presence of an unknown acid as the main constituent. This compound was isolated and identified as homogentisic acid (2, 5-dihydroxyphenylacetic acid) by MS and NMR techniques. Its average content in honey was 378 +/- 92 mg/kg. Analysis of nectar confirmed the floral origin of the compound found in honey. Since this acid was not detected in any of the different monofloral honeys, it could be used as a marker of strawberry-tree (A. unedo) honey.     

The question of high- or low-temperature glass transition in frozen fish. Construction of the supplemented state diagram for tuna muscle by differential scanning calorimetry

The thermal behavior of fresh tuna muscle, rehydrated freeze-dried tuna muscle, and tuna sarcoplasmic protein fraction was studied by three types of differential scanning calorimetry (DSC): conventional DSC, alternating DSC, and sensitive micro-DSC. The relationship between glass transition temperature, T(g), and water content was established. Only a low-temperature glass transition was detected for fresh tuna and freeze-dried tuna rehydrated to high water contents, whereas for sarcoplasmic protein fraction both a low-temperature and an apparent high-temperature glass transition were detected for samples of high water content. Construction of the supplemented state diagrams for whole tuna muscle and for tuna sarcoplasmic protein fraction confirmed the low-temperature transition to be glass transition of the maximally freeze-dehydrated phase. The apparent upper transition of sarcoplasmic protein fraction was shown not to be a glass transition but rather to originate from the onset of melting of ice, and the temperature of this event should be denoted T(m)'. The glass transition temperature and the concentration of the maximally freeze dehydrated tuna muscle are -74 degrees C and 79% (w/w), respectively.     

Preliminary chemometric study on the use of honey as an environmental marker in Galicia (northwestern Spain)

Thirteen metal elements were determined in 40 honey samples from Galicia with different environmental origins: rural, urban, and industrial areas. The data set of the honey metallic profiles was studied with a double purpose: first, to make a preliminary evaluation of honey as an environmental indicator in Galicia with the aim of monitoring pollution and, second, to compare the different capabilities of diverse pattern recognition prediction procedures for modeling the environmental surrounding of the hive. A certain level of similarity for urban and industrial samples was obtained using principal component analysis and cluster analysis, whereas significant differences for urban and industrial honeys were found in relation to rural honey samples. Different classification rules to associate metal content of honeys with their environmental surrounding were obtained by chemometric pattern recognition procedures. In general, the classification methods developed by neural networks provided better results than the traditional pattern recognition procedures. The metal profiles of honey seem to provide sufficient information to enable categorization criteria for classifying samples according to their environmental surrounding. Thus, honey could be a potential pollution indicator for the Galician area.     

Direct electron paramagnetic resonance study of tobacco. 1. Manganese(ii) as a marker

Three categories of tobacco products were studied using electron paramagnetic resonance (EPR) spectroscopy: Cuban cigar brand name Montecristo, four international trademark cigarettes, and three types of Middle Eastern tobacco blends called Al-Moassal or Jurak. The Montecristo Cuban cigar is used as standard of high-quality tobacco. Mainly two EPR signals from all of the studied samples are observed: a very weak sharp EPR signal superimposed on a broad signal. The broad EPR signal is attributed to a manganese(II) complex. The intensity of the manganese(II) EPR signal is found to be related to the quality of the tobacco content. The sharp signal, which is characteristic of semiquinone radicals, is observed at room temperature, and its intensity increases drastically with temperature.     

Use of nootkatone as a senescence indicator for Rouge La Toma Cv. grapefruit (Citrus paradisi Macf.)

The objective of this research was to study the usefulness of nootkatone as a senescence indicator for Rouge La Toma cv. grapefruit (Citrus paradisi Macf.), simulating different treatments that included the normal postharvest handling of citrus fruits: temperature conditioning, cold storage, shipment periods to overseas markets such as Japan and the U.S., marketing conditions, and storage at nonchilling temperature (control treatments). The highest nootkatone levels, determined by GLC-MS analyses, were detected in fruits subjected to control treatments. No significant differences were observed in nootkatone levels between treatments either with or without temperature conditioning prior to the start of the cold storage. Levels of nootkatone increased throughout time for all assayed treatments. The linear regressions of nootkatone levels showed correlation coefficients of 0.80 and 0.83 with storage time (29 and 42 days, respectively). Therefore, nootkatone appears to be a good indicator of senescence for Rouge La Toma grapefruit.     

Identification of a new form of lipid transfer protein (LTP1) in wheat seeds

Recently, this laboratory has isolated from barley and beer extract an isoform of lipid transfer protein (LTP1), which was not fully sequenced (Jégou, S.; Douliez, J. P.; Mollé, D.; Boivin, P.; Marion, D. J. Agric. Food Chem. 2000, 48, 5023--5029). It was named LTP1b and exhibited a molecular weight 294 Da higher than that of the known LTP1. This paper reports the finding of an LTP1 isoform in wheat that also exhibits an excess of 294 Da compared to the native protein. Amino acid sequencing, reduction and alkylation, and mass spectrometry showed that this new LTP1b possesses the same N-terminal sequence as the native LTP1, suggesting that the difference resides in the binding of an adduct which has a molecular weight of 294 Da. The aim of the present paper is to highlight various biophysical techniques that afford the identification of such an isoform-like LTP1 and to correlate this finding with other isoforms of LTP1 that were isolated from other plants but not fully sequenced.     

Using a modified ferrous oxidation-xylenol orange (FOX) assay for detection of lipid hydroperoxides in plant tissue.

The ferrous oxidation-xylenol orange (FOX) assay was adapted for quantifying lipid hydroperoxides (LOOHs) in plant extracts. Excised pieces of several fruit and vegetable species were exposed to 83 kJ m(-2) day(-1) of biologically effective ultraviolet B irradiance (UV-B(BE)) for 10-12 days to induce cellular oxidation. The LOOH and thiobarbituric acid reactive substance (TBARS) concentrations of these plant tissues were assessed with the FOX and iodometric assays for the former and a modified TBARS assay for the latter. There was generally good agreement between the FOX and iodometric methods both prior to and following the UV exposure. However, the iodometric assay appeared to have some difficulty in consistently quantifying lower LOOH levels (<11 microM), whereas the FOX assay measured LOOH concentrations as low as 5 microM. All tissues exhibited UV-induced increases in TBARS, indicating a marked degree of cellular oxidation in the exposed tissue segments. Compared with the iodometric assay, the FOX method consistently generated less variable LOOH values. The presence of authentic linoleic acid-OOHs in spiked avocado and spinach samples (11 microM) was identified with liquid chromatography-mass spectrometry techniques, which validated corresponding FOX assay results. The FOX method is inexpensive, is not sensitive to ambient O2 or light levels, and can rapidly generate LOOH measurements. The physiological value of the FOX assay resides in its ability to measure initial rather than more advanced fatty acid oxidation; hence, early membrane-associated stress events in plant tissue can be detected.     

金属有机框架 (MOF) 类新型肥料在水稻上的应用初探

【目的】金属有机框架 (metal-organic framework,MOF) 是基于分子设计的一种新型团簇功能化合物,为实现多元化养分设计,生产环境友好的新型肥料提供了新的手段。本研究在水热条件下合成了两种MOF肥料,评估了这两种MOF材料作为新型肥料的潜力和可行性。【方法】以氯化铁 (FeCl₃·6H₂O)、硫酸锌 (ZnSO₄·7H₂O)、磷酸 (H₃PO₄)、草酸 (H₂C₂O₄·2H₂O) 和尿素 (CO(NH₂)₂) 为基础原料,在高压反应釜内100℃下合成MOF1和MOF2。MOF1和MOF2分别含Fe 18.6%、15.6%,P 15.7%、16.5%,N 5.16%、4.57%,C 4.61%、5.21%,MOF2还含Zn 2.89%。试验共设4个处理:不施肥 (CK)、常规施肥 (CF)、MOF1和MOF2。3个施肥处理为等氮磷钾设计,施肥水平为N 150 kg/hm2、P₂O₅ 200 kg/hm2和K₂O 150 kg/hm2。在水稻分蘖、拔节、孕穗及成熟期,采集土样,测定铵态氮、硝态氮、有效磷、有效铁、有效锌含量及pH。水稻成熟后,测定产量、千粒重、穗粒数、有效穗数和结实率。【结果】与CF相比,MOF1和MOF2处理的水稻产量分别增加了7.7%和6.3%,相关农艺性状也均有改善。MOF1和MOF2处理的水稻营养器官总干物质量和氮累积量均显著高于CF处理;CF处理的氮素利用率为32.8%,而MOF1和MOF2处理分别达到46.4%和43.0%,与CF差异显著。在成熟期,MOF1和MOF2处理的土壤铵态氮、硝态氮及有效铁含量较CF均显著增加。【结论】两个以磷和铁为主要养分的新型金属框架结构肥料不仅能提高水稻产量和氮素利用率,而且也可改善水稻相关农艺性状以及提高土壤养分含量,其作为新型肥料,具有广阔的应用潜力。     

Classification of edible oils by employing 31P and 1H NMR spectroscopy in combination with multivariate statistical analysis. A proposal for the detection of seed oil adulteration in virgin olive oils

A combination of (1)H NMR and (31)P NMR spectroscopy and multivariate statistical analysis was used to classify 192 samples from 13 types of vegetable oils, namely, hazelnut, sunflower, corn, soybean, sesame, walnut, rapeseed, almond, palm, groundnut, safflower, coconut, and virgin olive oils from various regions of Greece. 1,2-Diglycerides, 1,3-diglycerides, the ratio of 1,2-diglycerides to total diglycerides, acidity, iodine value, and fatty acid composition determined upon analysis of the respective (1)H NMR and (31)P NMR spectra were selected as variables to establish a classification/prediction model by employing discriminant analysis. This model, obtained from the training set of 128 samples, resulted in a significant discrimination among the different classes of oils, whereas 100% of correct validated assignments for 64 samples were obtained. Different artificial mixtures of olive-hazelnut, olive-corn, olive-sunflower, and olive-soybean oils were prepared and analyzed by (1)H NMR and (31)P NMR spectroscopy. Subsequent discriminant analysis of the data allowed detection of adulteration as low as 5% w/w, provided that fresh virgin olive oil samples were used, as reflected by their high 1,2-diglycerides to total diglycerides ratio (D > or = 0.90).     

The Derivation and Use of a Dynamic Model for Mercury in Lake Fish Based on a Static (Regression) Model

This work presents a new regression model for mercuryin lake fish, which provides the highest r ²-valueso far reported for a predictive model for Hg in lakefish. A new method to transform static regressionmodels to dynamic (time-dependent) models is alsopresented. The method to mathematically transformregression models to dynamic model uses the ecologicalhalflife concept and two differential equations, onefor the target organism (the predator) and one for theprey. This method is generic and can be applied inanalogous cases. The practical use of the dynamicmodel is illustrated in two case studies involvinglake liming and fertilization as methods to reduce Hgin lake fish. The dynamic model is a tool to obtainrealistic expectations of the recovery process, whichis slow because Hg in lake fish has a relatively longecological halflife (about 3 yr).     

Use of two-dimensional electrophoresis to evaluate proteolysis in salmon (Salmo salar) muscle as affected by a lactic fermentation

Two-dimensional electrophoresis was used to study proteolysis in salmon fillets inoculated or not with the starter culture Lactobacillus sake LAD. Protein fragments appeared increasingly with time in both samples, indicating that the main quantitative changes were due to endogenous enzymes. In the most acidic zone (pI = 4-6. 20) particularly, proteolysis was overall independent from processing. In contrast, fermentation had a significant effect in the pH range 6.20-8.35, suggesting a specificity of the bacterial proteases of L. sake toward alkaline to slightly acidic proteins. Furthermore, fragments surrounding tropomyosin (apparent pI = 4.70) appeared in fermented samples, indicating that the protein may be a suitable substrate for the metabolism of L. sake LAD.     

Using kale (Brassica oleracea var. acephala) as a phytoremediation plant species for lead (Pb) and cadmium (Cd) removal in saline soils

Ornamental kale (Brassica oleracea var. Acephala) is usually planted from early autumn until late winter. Since most of the plants used for phytoremediation cannot be grown during this time, kale can be a suitable option for phytoremediation and utilized during autumn and winter in urban landscape, especially in metropolitan areas where high levels of cadmium (Cd) and lead (Pb) pollutions exist. Kale growth in saline soil at different growth stages (germination and vegetative growth stages) was studied in this investigation. A factorial experiment based on completely randomized design (CRD) with four replications was used in this study. Treatments included three levels of sodium chloride (NaCl) (0, 30, and 60 mg/kg), four levels of Cd (0, 4, 8, and 16 mg/kg), and four levels of Pb (0, 1, 5, and 10 mg/kg). Results indicated that increase in Cd and Pb concentrations in the soil decreased fresh and dry weights of the plants. The results of the various growth stages revealed that under salinity stress, kale plants were able to absorb more Pb than Cd and effectively remediate Pb in polluted and saline lands. Cd accumulation in control treatment was 6.2% more than that in the saline treatments, whereas, Pb accumulation in the highest NaCl level, 60 mg/kg salinity treatment was 7.64% more than that of the control condition. Also, proline content of the plants was significantly increased under Cd and Pb stress. From the results of this study, it was concluded that using kale plant is recommended for phytoremediation of saline soils with 10 and 16 mg/kg Pb and Cd contents, respectively.     

The effect of lead on photosynthesis, as determined by photoacoustics in Synechococcus leopoliensis (Cyanobacteria)

The effect of lead on photosynthetic light storage efficiency was measured by the photoacoustic method. The advantage of this method is in its directness, since the signal obtained by a hydrophone is proportional to that fraction of light energy that is dissipated as heat. This increases as less energy is stored photochemically if the photosynthetic apparatus is damaged. Cells of shape Synechococcus leopoliensis (Cyanobacteria) were grown in medium containing lead in concentrations of 0, 25, 50, 100, and 200 ppm. To avoid the co-precipitation of lead and phosphorus as lead phosphate, phosphorus was omitted from the media used during weeklong exposure to lead. Both chlorophyll concentration and photosynthetic energy storage efficiency decreased with time and with lead concentration. Reduction of photosynthesis progressed with time and increased with lead concentration, reaching up to 80% at the highest lead concentration after seven days.     

Development of a real-time PCR for the detection of lupine DNA (lupinus species) in foods

Lupine flour, protein, and fiber have become common ingredients in food products. The association of lupine-related allergic incidents with peanut allergy is a cause for concern as the latter may bring about severe reactions. In this study, a hybridization probe-based real-time PCR assay for the detection of lupine DNA in foods was developed. Particular attention was paid to the specificity of the method, which was verified by analysis of DNA extracts from more than 50 potential food ingredients such as legumes, cereals, seeds, nuts, spices, fruits, and meat. The limit of detection of the method was determined as 0.1 mg/kg. The successful detection of the presence/absence of lupine DNA in 20 samples proved the suitability of the assay for the analysis of frequently encountered food matrices.     

H(2)O(2)-mediated pigment decay in strawberry as a model system for studying color alterations in processed plant foods.

Phenolic and pigment (anthocyanin) stability in processing-ripe strawberries in response to aging under mildly oxidizing conditions, provoked by exogenous application of H(2)O(2), has been studied to design a simplified model system to study color alterations (pigment decay) that occur in strawberry-derived foods during processing and storage. The results showed that phenolic metabolism in strawberry slices during aging under mildly oxidizing conditions may be either oxidative (independent of exogenous H(2)O(2)) or peroxidative (dependent on exogenous H(2)O(2)), and that feeding strawberry slices with H(2)O(2) stimulates the oxidative phenomena which take place in their absence, such as the processes of anthocyanin and catechin degradation. The results also showed that because both (+)-catechin and anthocyanin levels in strawberry slices fall as H(2)O(2) increases, both p-hydroxybenzoic acid and brown polymeric compounds are formed. Comparison of these results with controls in the absence of H(2)O(2) suggests that peroxidase may play an important role in catechin consumption and in anthocyanin degradation and brown polymer formation during the aging of strawberry slices under mildly oxidizing conditions.     

Use of near-infrared spectroscopy for fast fraud detection in seafood: application to the authentication of wild European sea bass (Dicentrarchus labrax)

The possibility of using near-infrared spectroscopy (NIRS) for the authentication of wild European sea bass ( Dicentrarchus labrax ) was investigated in this study. Three different chemometric techniques to process the NIR spectra were developed, and their ability to discriminate between wild and farmed sea bass samples was evaluated. One approach used spectral information to directly build the discrimination model in a latent variable space; the second approach first used wavelets to transform the spectral information and subsequently derived the discrimination model using the transformed spectra; in the third approach a cascaded arrangement was proposed whereby very limited chemical information was first estimated from spectra using a regression model, and this estimated information was then used to build the discrimination model in a latent variable space. All techniques showed that NIRS can be used to reliably discriminate between wild and farmed sea bass, achieving the same classification performance as classification methods that use chemical properties and morphometric traits. However, compared to methods based on chemical analysis, NIRS-based classification methods do not require reagents and are simpler, faster, more economical, and environmentally safer. All proposed techniques indicated that the most predictive spectral regions were those related to the absorbance of groups CH, CH(2), CH(3), and H(2)O, which are related to fat, fatty acids, and water content.