Varietal and interspecific influence on micronutrient contents in citrus from the Mediterranean area

To specify the genotypic variation of Mediterranean Citrus juices, the contents of carotenoids, flavonoids, and vitamin C were determined by high-performance liquid chromatography. A selection of orange varieties and Mandarin species from the Mediterranean area (Citrus sinensis, Citrus deliciosa Ten, and Citrus clementina Hort. ex Tan) was evaluated using carotenoid profiles and flavanones contents. Among the eight varieties of orange (Salustiana, Hamlin, Shamouti, Pera, Valencia, Maltaise, Sanguinelli, and Cara-cara) and two Mandarin species, only three cultivars (Pera, Sanguinelli, and Shamouti) and the two Mandarin species displayed a high content of vitamin A (374, 381, and 272 ER L(-1) for the three orange cultivars and 1156 and 960 retinol equivalent (RE) L(-1) for the Mandarins) due to a high content of beta-cryptoxanthin. These same Citrus were also rich in hesperidin (502, 537, 552, 767, and 754 mg L(-1), respectively). Principal component analysis allowed the Mediterranean orange varieties and Mandarin species to be differentiated on the basis of nutritional criteria. Strong correlations were observed between beta-cryptoxanthin and hesperidin (r = 0.92) and between beta-cryptoxanthin and beta-carotene (r = 0.98). In contrast, vitamin C content was not correlated with carotenoids and flavanone glycosides. The Mandarin and orange group was quite distinct. The orange varieties could be divided in two groups. In addition, a diversity tree allowed a genetic approach to differentiating Citrus cultivars on the basis of Euclidian distances. This representation showed that the hybrid Clementine was nearer to its parent Mandarin than to its parent orange, suggesting that beta-cryptoxanthin was a dominant genetic factor. With regard to vitamin A, Mandarin and its hybrid Clementine appeared to be the best Citrus species.     

Differentiation of several geographical origins in single-strength Valencia orange juices using quantitative comparison of carotenoid profiles.

Pure Valencia orange (Citrus sinensis) juices (64 samples) from Spain, Israel, Belize, Cuba, and Florida, harvested during two seasons (1996-1997 and 1997-1998), were analyzed for their carotenoid profiles. The detection of saponified carotenoid pigments has been achieved and quantitated using a photodiode array detection monitored at 350, 430, and 486 nm. Carotenoid pigments commonly found in the orange variety Valencia have been separated on a polymeric C-30 column using a ternary gradient as eluent. Pure Valencia juices from oranges grown in Mediterranean regions (Israel and Spain) have a high carotenoid content, expressed in beta-carotene (5-18 and 14-35 mg L(-)(1), respectively), compared to those grown in tropical and subtropical regions (Cuba, Belize, and Florida) (4-10, 2-8, and 5-10 mg L(-)(1), respectively). Quantitative results allowed the differentiation of Valencia variety geographical origins, in particular, the Mediterranean area from tropical and subtropical areas, using multidimensional analyses of carotenoid contents.     

Chemometric characterization of fruit juices from Spanish cultivars according to their phenolic compound contents: I. Citrus fruits

The data set composed by phenolic compound profiles of 83 Citrus juices (determined by HPLC-DAD-MS/MS) was evaluated by chemometrics to differentiate them according to Citrus species (sweet orange, tangerine, lemon, and grapefruit). Cluster analysis (CA) and principal component analysis (PCA) showed natural sample grouping among Citrus species and even the Citrus subclass. Most of the information contained in the full data set can be captured if only 15 phenolic compounds (concentration ≥10 mg/L), which can be quantified with fast and accurate methods in real samples, are introduced in the models; a good classification which allows the confirmation of the authenticity of juices is achieved by linear discriminant analysis. Using this reduced data set, fast and routine methods have been developed for predicting the percentage of grapefruit in adulterated sweet orange juices using principal component regression (PCR) and partial least-squares regression (PLS). The PLS model has provided suitable estimation errors.     

Characterization of paprika (Capsicum annuum) extract in orange juices by liquid chromatography of carotenoid profiles.

The carotenoid pigment profiles of authentic pure orange juices from Spain and Florida and an industrial paprika (Capsicum annuum) extract used for food coloring were obtained using reversed-phase liquid chromatography with a C18 packed column and an acetone/methanol/water eluent system. The procedure involving the carotenoid extraction is described. Both retention times and spectral properties using photodiode array detection for characterization of the major carotenoids at 430 and 519 nm are given. The influence of external addition of tangerine juice and/or paprika extract on orange juice color is described using the U.S. Department of Agriculture scale and adulterated orange juice. The procedure for quantitation of externally added paprika extract to orange juice is investigated, and the limit of quantitation, coefficient of variation, and recoveries are determined.     

Carotenoids, color, and ascorbic acid content of a novel frozen-marketed orange juice

A recently developed food, the so-called ultrafrozen orange juice (UFOJ), has been characterized in terms of carotenoid pigments, ascorbic acid, and color. The juice, obtained from Valencia late oranges, is frozen immediately after the squeezing of the oranges, which makes it a product showing good organoleptic and nutritional quality. In relation to the carotenoid profile, it was observed that the 5,6-epoxy carotenoids violaxanthin and antheraxanthin (specifically (9Z)-violaxanthin and (9Z)- or (9'Z)-antheraxanthin), were by far the major pigments and that dihydroxycarotenoids predominate over monohydroxycarotenoids. As far as color was concerned, it was seen that there were little differences among the juices analyzed. The hue of the samples, ranging from 77.19 degrees to 80.15 degrees and from 79.99 degrees to 83.04 degrees depending on the kind of instrumental measurement, and their chroma (ranging from 63.06 to 72.25 and from 44.40 to 58.38) revealed readily that the juice surveyed exhibited a deep orangeish coloration, the color coordinate best correlated with the total carotenoid content being b*. The levels of ascorbic acid ranged from 332.64 to 441.44 mg/L, with an average content of 391.06 +/- 28.86 mg/L.     

Betaines in fruits of Citrus genus plants

Numerous compounds, many of them osmolytes, were quantified in natural juices and in frozen concentrate juices from fruits of plants of the Citrus genus. L-proline, N-methyl-L-proline (hygric acid), N,N-dimethyl-L-proline (stachydrine), 4-hydroxy-L-prolinebetaine (betonicine), 4-hydroxy-L-proline, γ-aminobutyric acid (Gaba), 3-carboxypropyltrimethylammonium (GabaBet), N-methylnicotinic acid (trigonelline), and choline in the fruit juices of yellow orange, blood orange, lemon, mandarin, bitter orange (Citrus aurantium), chinotto (Citrus myrtifolia), and grapefruit were analyzed by sensitive HPLC-ESI-tandem mass spectrometry procedure. It was found that the most represented osmolytes in the juices, that is, L-proline, stachydrine, and betonicine, can be quantified with minimal sample preparation and short analysis time (about 1 min) also by flow injection analysis (FIA) ESI-MS/MS with the same results as obtained by HPLC ESI-MS/MS. In all of the juices, discrete amounts of choline and trigonelline were present. Conversely, GabaBet was always below detection limits. Notably, N-methyl-L-proline and 4-hydroxy-L-prolinebetaine, which were discovered for the first time in the juice of bergamot (Citrus bergamia Risso et Poit), are also present in all of the citrus juices examined.     

Effect of orange juice's processing on the color, particle size, and bioaccessibility of carotenoids

This study was aimed at assessing the differences between industrially processed and hand-squeezed orange juices (OJs) in relation to their color, particle size, carotenoid content, and carotenoid bioaccessibility. Specifically, industrial samples of fresh squeezed OJs after the finishing steps (FISO) and the same OJs after pasteurization (PISO), as well as hand-squeezed OJs (HSO) were studied. The results showed that the HSO and PISO were different (p < 0.05) in terms of color (darker and more reddish vs brighter, more yellowish and colorful), particle size (volume and surface area mean diameter), and total carotenoid content (29 ± 5 and 22 ± 3 mg/L, respectively). On the other hand, the industrial extraction of OJs reduced the particle size distribution, and accordingly, the relative bioaccessibility of bioactive carotenoids increased (p < 0.01). Independently of the type of OJ, the bioaccessibility of carotenoids in decreasing order was the following: α-carotene > β-cryptoxanthin > β-carotene > zeaxanthin > lutein.     

电子舌信号与理化指标的信息融合区分不同养殖水的研究

为优化金鱼的养殖环境,应用电子舌结合理化指标对不同的金鱼养殖水进行了跟踪分析和研究。采用离子选择型电子舌对金鱼养殖水进行了检测,同时采用化学方法检测了养殖水的常用理化指标;通过主成份分析、聚类分析和典型判别分析3种模式识别方法,对不同养殖密度和不同养殖天数的金鱼养殖水进行了分析和区分,并探讨了电子舌信号与理化指标进行融合区分不同金鱼养殖水的能力。结果表明:将电子舌信号与理化指标的融合可有效区分不同的金鱼养殖水。在选取适当的模式识别方法的前提下,单独使用电子舌信号即可有效区分不同养殖密度和不同养殖天数的金鱼养殖水:采用典型判别分析方法,电子舌具有极强的区分不同养殖密度和不同养殖天数的养殖水的能力;而采用主成份分析方法,电子舌基本具有区分不同养殖密度和不同养殖天数养殖水的能力,若将电子舌信号与理化指标进行融合,则其区分能力将大大增强;采用聚类分析方法,电子舌信号、电子舌信号与理化指标融合的区分能力均最差。该文研究结果可为金鱼的养殖环境的检测分析提供参考。     

Measurement of soluble solids contents and pH in orange juice using chemometrics and vis-NIRS

The potential of visible and near-infrared reflectance spectroscopy (vis-NIRS) was investigated for its ability to nondestructively detect soluble solids contents (SSC) and pH in orange juices. A total of 104 orange juice samples were used for vis-NIRS at 325-1075 nm using a field spectroradiometer. Wavelet packet transform, standard normal variate transformation (SNV), and Savitzky-Golay first-derivative transformation were applied for the preprocessing of spectral data. The chemometrics of partial least-squares (PLS) regression analysis was performed on the processed spectral data. The evaluation of SSC and pH in orange juices by PLS regression with SNV showed the highest accuracy of the three preprocessing methods. The correlation coefficient (r), standard error of prediction, and the root-mean-square error of prediction for SSC were 0.98, 0.68, and 0.73, respectively, whereas those values for pH were 0.96, 0.06, and 0.06, respectively. The "fingerprint" representing features of orange juices or reflecting sensitivity to some elements at a certain band was proposed on the basis of regression coefficients. It is very useful in the field of food chemistry and further research on other materials. It is concluded that the vis-NIRS technique combined with chemometrics is promising for the fast and nondestructive detection of chemical components in orange juices or other materials.     

Seasonal changes of carotenoid pigments and color in Hamlin, Earlygold, and budd blood orange juices

The developmental patterns of carotenoids in Hamlin, Earlygold (an early-maturing selection), and Budd Blood sweet orange juices were studied during the September to mid-January period of the 1996-97 and 1997-98 seasons. The carotenoid concentration of Earlygold increased by as much as 4.9 times during the color development compared to 3.9 times in Hamlin and 4.5 times in Budd Blood juice in the same period. For the profiles of carotenoid pigment, dramatic changes occurred among the pigments that were present in high concentrations at the beginning of the season, with lutein and violaxanthin noted as the predominant pigments in Hamlin fruit. A marked increase in the percentage of beta-cryptoxanthin allowed it to become a major pigment in the late stage of maturation. The color development in the new cultivar Earlygold was especially notable, reaching the 36 color number, which is grade A, by late October to mid-November whereas Hamlin juice did not reach this grade A color number until January. Budd Blood juice was similar in carotenoid pigment content and seasonal changes to Hamlin juice, but also, the development of red anthocyanin pigment in January significantly increased juice color.     

Phlorin screening in various citrus species and varieties

Phlorin (3,5-dihydroxyphenyl beta-D-glucopyranoside), an orange peel marker, has been searched in 45 species and varieties of Citrus. The phlorin content was determined by high-pressure liquid chromatography in juices and aqueous peel extracts of these different fruits. The phlorin content in C. reticulata peel extract varies from 0 to 1012 mg L(-)(1) with a mean of 162 mg L(-)(1). On the contrary, phlorin was not found in mandarin and clementine juices except for mandarin "Commune" and "Beauty" (33 and 30 mg L(-)(1), respectively). In the 14 species of oranges and varieties, phlorin was detected in juices and peel extracts with a mean of 22 and 492 mg L(-)(1), respectively, while for grapefruits, means were 108 mg L(-)(1) in juices and 982 mg L(-)(1) for peel extracts. Tangors and tangelos which are hybrids (C. reticulata x C. sinensis and C. reticulata x C. paradisi, respectively) are characterized by the systematic presence of phlorin in peels (mean: 406 and 659 mg L(-)(1), respectively) while in juices its presence could be variable (0-73 mg L(-)(1)). These heterogeneity and values may be explained by the genetic variability of these hybrids and the phlorin content of their parentage group.     

Fresh Israeli Jaffa blond (Shamouti) orange and Israeli Jaffa red Star Ruby (Sunrise) grapefruit juices affect plasma lipid metabolism and antioxidant capacity in rats fed added cholesterol

The bioactivity of Israeli Jaffa blond (Shamouti) fresh orange and Israeli Jaffa red Star Ruby (Sunrise) grapefruit juices was investigated in vitro and in vivo. The contents of bioactive compounds of these juices were determined. The influence of bioactive compounds on plasma lipids and plasma antioxidant activity in rats fed cholesterol-containing and cholesterol-free diets was assessed. Significant differences in the contents of dietary fibers were not found. The contents of total polyphenols, flavonoids, and anthocyanins in fresh orange and grapefruit juices were 962.1 +/- 27.2 and 906.9 +/- 27.1; 50.1 +/- 3.3 and 44.8 +/- 3.2; and 69.9 +/- 5.6 and 68.7 +/- 5.5 microg/mL, respectively. The antioxidant potential measured by the scavenging activity against nitric oxide, the beta-carotene-linoleate model system (beta-carotene), and the 1,1-diphenyl-2-picrylhydrazyl and 2,2'-azino-bis(3-ethyl-benzothiazoline-6-sulfonic acid) diamonium salt assays was higher in orange juice but not significantly. A high level of correlation between contents of total polyphenols and flavonoids and antioxidant potential values of both juices was found. Diets supplemented with orange and to a lesser degree with grapefruit juices improved plasma lipid metabolism only in rats fed added cholesterol. However, an increase in the plasma antioxidant activity was observed in both groups. In conclusion, fresh orange and grapefruit juices contain high quantities of bioactive compounds, which guarantee their high antioxidant potential, and the positive influence on plasma lipid metabolism and plasma antioxidant activity could make fresh orange and grapefruit juices a valuable supplement for disease-preventing diets.     

Characterization of cider apples on the basis of their fatty acid profiles

In the current study, the fatty acids composition of 30 monovarietal apple juices from six cider apple varieties belonging to two categories was analyzed. The different apple juices were obtained from three consecutive harvests (1997, 1998, and 1999). The fatty acids concentration in apple juice together with chemometric techniques such as principal components analysis (PCA), soft independent modeling of class analogy (SIMCA), and linear discriminant analysis (LDA), allowed us to differentiate apple juices on the basis of the sweet or sharp category to which the cider apple variety belongs. Fatty acids such as the unsaturated oleic and linoleic acids, and saturated caprylic, capric, stearic, and palmitic acids were related to the sweet cider apple category, while pentadecanoic acid is related to the sharp class.     

Cryptoxanthin structural isomers in oranges, orange juice, and other fruits

Citrus fruits contain a wide range of bioactive compounds. Their carotenoid fraction is inter alia dominated by structural cryptoxanthin isomers as beta-cryptoxanthin and zeinoxanthin. Both xanthophylls were identified in saponified citrus fruit extracts by comparison to reference compounds extracted from corn and by their typical fragmentation pattern in LC-(APCI)MS analyses. alpha-Cryptoxanthin, another structural cryptoxanthin isomer usually found in carrot leaves, was not identified in the citrus fruits studied. Cryptoxanthin concentrations of direct orange juices (D) and reconstituted juices (C) were compared. Although the respective mean values [beta-cryptoxanthin, 62 (C) versus 110 microg/100 g (D); zeinoxanthin, 22 (C) versus 37 microg/100 g (D)] were statistically distinguishable (P < 0.05%), a doubtless classification is not possible because the concentration ranges overlap. To identify esters of structural cryptoxanthin isomers in native orange juice extracts, four saturated acyl esters were synthesized. LC-(APCI)MS studies revealed for the first time that the dominant acylation partners of both xanthophylls were C12:0, C14:0, and C16:0 in nearly equal amounts of roughly one-third, whereas C10:0 and C18:1 were present at lower extents of 5-14%; other acylation partners were not identified. The presented method is appropriate to gain deeper insight into the pattern of structural cryptoxanthin isomers of citrus fruits. Knowledge of acylated cryptoxanthin isomers may be important in the evaluation of the bioavailability of individual esters in future human digestion studies.     

Volatile constituents in fresh and processed juices from grapefruit and new grapefruit hybrids

Forty-five volatile constituents of juices from grapefruit and grapefruit hybrids were quantified by headspace gas chromatography. The three types of grapefruit juice analyzed include pasteurized juice not from concentrate, reconstituted single strength juice from concentrate, and fresh, unpasteurized juice. Principal component and discriminant analyses were carried out using 48 grapefruit juice samples, and the samples were classified into the three types of juice based on degree of processing. Discriminant analysis was superior to principal component analysis for this purpose. Juices from two recently developed grapefruit hybrids were classified similarly to unpasteurized grapefruit juices from commercial cultivars.     

Carotenoid profile modification during refrigerated storage in untreated and pasteurized orange juice and orange juice treated with high-intensity pulsed electric fields

A comparative study was made of the evolution and modification of various carotenoids and vitamin A in untreated orange juice, pasteurized orange juice (90 degrees C, 20 s), and orange juice processed with high-intensity pulsed electric fields (HIPEF) (30 kV/cm, 100 micros), during 7 weeks of storage at 2 and 10 degrees C. The concentration of total carotenoids in the untreated juice decreased by 12.6% when the juice was pasteurized, whereas the decrease was only 6.7% when the juice was treated with HIPEF. Vitamin A was greatest in the untreated orange juice, followed by orange juice treated with HIPEF (decrease of 7.52%) and, last, pasteurized orange juice (decrease of 15.62%). The decrease in the concentrations of total carotenoids and vitamin A during storage in refrigeration was greater in the untreated orange juice and the pasteurized juice than in the juice treated with HIPEF. During storage at 10 degrees C, auroxanthin formed in the untreated juice and in the juice treated with HIPEF. This carotenoid is a degradation product of violaxanthin. The concentration of antheraxanthin decreased during storage, and it was converted into mutatoxanthin, except in the untreated and pasteurized orange juices stored at 2 degrees C.     

Capillary electrophoresis for evaluating orange juice authenticity: a study on Spanish oranges

Fruit juices have very distinct organic acid profiles that can be used as fingerprints for establishing possible adulteration. Recently, our group developed and validated a capillary electrophoresis method using UV detection for determining citric, isocitric, tartaric, and malic acids in natural and commercial orange juices. Sample treatment consisted of only dilution and centrifugation or filtration. This method has been applied to evaluate these acids and their ratios in 63 samples of Navelina, the most common variety of Spanish oranges, over a three month period. This evaluation has been conducted to establish ranges of acid concentrations and to compare them with those found in commercial juices. The more reliable parameter, because of the lower variability in fresh samples, was found to be the citrate/isocitrate ratio with a value of 113 (RSD = 10%). Only one of nine ramdonly selected commercial juices presented values within the range of those of the population of just-pressed Navelina orange juice. Moreover, three of them had measurable tartrate values, which is not a natural component of orange juice, showing mixtures with cheaper fruits.     

Determination of vanillin in orange, grapefruit, tangerine, lemon, and lime juices using GC-olfactometry and GC-MS/MS

The presence of vanillin in orange, tangerine, lemon, lime, and grapefruit juices has been identified and confirmed using high-resolution GC retention index values, mass spectra, and aroma quality. The impact of vanillin on the flavor score for grapefruit juice is discussed and reported to be minimal. Vanillin concentrations are determined to be in the low parts-per-million range for the various citrus juices. The calculated concentrations in the orange, tangerine, lemon, lime, and grapefruit juices are 0.20, 0.35, 0.41, 0.35, and 0.60 ppm, respectively. Pasteurization produced an average 15% increase in the concentration of vanillin in grapefruit juices. Vanillin did not correlate well with the overall flavor score despite a rather intense signal using OSME gas chromatography-olfactometry software.     

Vitamin C,provitamin A carotenoids,and other carotenoids in high-pressurized orange juice during refrigerated storage

Vitamin C, provitamin A carotenoids, and other carotenoids were measured in freshly squeezed juices from oranges (Citrus sinensis L. var. Valencia late) that were subjected to high-pressure (HP) treatment. Also, the stability of these compounds was studied during refrigerated storage at 4 degrees C. HP treatment is an alternative to heat preservation methods for foods; therefore, it is essential to assess the impact of HP on bioactive compounds. Several processes that combine HP treatment with heat treatment for various time periods were assayed: T0, fresh juice (without treatment); T1, 100 MPa/60 degrees C/5 min; T2, 350 MPa/30 degrees C/2.5 min; T3, 400 MPa/40 degrees C/1 min. Fresh and treated samples were kept refrigerated (4 degrees C) over 10 days. After application of HP and during the refrigeration period, the qualitative and quantitative determination of vitamin C, provitamin A carotenoids (beta- and alpha-carotene; beta- and alpha-cryptoxanthin), and the xanthophylls zeaxanthin and lutein was achieved by high-performance liquid chromatography. T1 and T3 juices showed a decrease in ascorbic acid and total vitamin C just after HP treatment (D0) compared with T0 juices. On the contrary, T2 juices, just after HP treatment (D0), had the same levels of both compounds compared to untreated juices. T1, T2, and T3 treatments led to an increase in the extraction of carotenoids and provitamin A carotenoids. Total carotenoid content after the 10-day refrigerated storage period resulted in no significant quantitative changes in T1 juices, whereas in T2 and T3 juices small losses were found at the end of the storage period (20.56 and 9.16%, respectively). These losses could be influenced by the depleted protection of vitamin C toward carotenoid oxidation during the same period. A similar trend was found in provitamin A carotenoids for the different treated juices.