Influence of thermal treatment on black currant (Ribes nigrum L.) juice aroma

The influence of thermal treatment on black currant juice aroma was investigated in temperature and time ranges relevant for black currant juice concentration processes, namely, 45, 60, 75, and 90 degrees C. Forty-nine aroma compounds were quantified, and the thermal treatment resulted in concentration increases of most terpenes, aldehydes, furans, and phenols, whereas the concentration of esters slightly decreased. Higher temperatures and longer exposure times had larger effects on the aroma compounds. Odor triangle tests showed no sensory difference between pasteurized juice and juice heated at 60 degrees C, whereas juice heated at 90 degrees C differed significantly from pasteurized juice. It is concluded that a 90 degrees C thermal treatment of black currant juice, which is in the temperature range used for conventional evaporation of black currant juice, has an effect on the aroma and sensory properties.     

Fatty acid content and juice characteristics in black currant (Ribes nigrum L.) genotypes

The fatty acid compositions of seeds from 29 black currant genotypes were determined using a rapid small-scale procedure. There was interest in alpha-linolenic, stearidonic, and, especially, gamma-linolenic acid (GLA) contents, and most samples showed values between 11.1 and 18.7%, between 2.5 and 4.5%, and between 11.6 and 17.4%, respectively. However, six genotypes exhibited gamma-linolenic contents >18%, and values >20% were recorded in four of these genotypes. The fatty acid contents of the six genotypes were also analyzed by using a conventional procedure, and only slight differences in fatty acid composition were found between the two methods. Although GLA content was not strongly correlated with juice parameters, some genotypes had both high GLA contents and desirable juice characteristics. The results obtained provide evidence that it is possible to select for GLA contents without negatively affecting juice quality, and both aspects can be combined in a single cultivar, thereby increasing the added value of the whole fruit.     

Preparative-scale isolation of four anthocyanin components of black currant (Ribes nigrum L.) fruits

Four anthocyanin components of black currant, delphinidin 3-O-beta-rutinoside (D3R), cyanidin 3-O-beta-rutinoside (C3R), delphinidin 3-O-beta-glucoside (D3G), and cyanidin 3-O-beta-glucoside (C3G), were successfully isolated as crystalline forms on a preparative scale. In this process, selective hydrolysis of the glucosides (D3G and C3G) and rhamnosides (D3R and C3R) was achieved by treatment with beta-glucosidase and hesperidinase (alpha-rhamnosidase), respectively, to improve resolution of anthocyanin components. Especially, selective conversion of the rutinosides into glucosides made the amounts of D3G and C3G increase about 4- and 7-fold, respectively. D3R, C3R, D3G, and C3G were isolated from enzymatic hydrolysates of black currant anthocyanins through Amberlite XAD-7HP absorption followed by preparative HPLC separation, and their crystals were obtained as the flavylium chloride.     

Anthocyanin-flavanol condensation products from black currant (Ribes nigrum L.)

Putative flavanol-anthocyanin condensation products were detected in a polyphenol-rich concentrate from black currant (Ribes nigrum L.). These compounds had UV-vis spectra similar to those of delphinidin-3-O-rutinoside and cyanidin-3-O-rutinoside, but eluted before all previously described anthocyanins on reversed phase HPLC. Mass spectrometric data indicated that they were rutinoside derivatives of novel aglycons 304 amu greater than delphinidin and cyanidin, respectively. The compounds were partly purified by semipreparative HPLC and gave MS and MS2 spectra consistent with anthocyanin rutinosides covalently linked to epigallocatechin or gallocatechin. These compounds are similar in structure to compounds thought to influence color and quality in red wines and strawberry juice products. There was also evidence for the presence of a range of other flavanol-anthocyanin condensation products. The compounds were present at differing levels in juices of 10 black currant varieties, which were roughly correlated to the content of the parent anthocyanins. The flavanol-anthocyanin products were present in polyphenol-enriched concentrates obtained by solid phase extraction, in commercially produced concentrates, and in fresh extracts of black currants. This suggests that the compounds were not artifacts formed during concentration or purification. However, differences in their comparative contents may be related to the lability of the parent anthocyanins during processing. Although present at low levels, the flavanol-anthocyanin products may influence color or quality parameters of black currant juices, and they may confer enhanced stability to the biological activities reported for their anthocyanin parents.     

Extraction of polyphenols from processed black currant (Ribes nigrum L.) residues

The total phenol and anthocyanin contents of black currant pomace and black currant press residue (BPR) extracts, extracted with formic acid in methanol or with methanol/water/acetic acid, were studied. Anthocyanins and other phenols were identified by means of reversed phase HPLC, and differences between the two plant materials were monitored. In all BPR extracts, phenol levels, determined by the Folin-Ciocalteu method, were 8-9 times higher than in the pomace extracts. Acid hydrolysis liberated a much higher concentration of phenols from the pomace than from the black currant press residue. HPLC analysis revealed that delphinidin-3-O-glucoside, delphinidin-3-O-rutinoside, cyanidin-3-O-glucoside, and cyanidin-3-O-rutinoside were the major anthocyanins and constituted the main phenol class ( approximately 90%) in both types of black currant tissues tested. However, anthocyanins were present in considerably lower amounts in the pomace than in the BPR. In accordance with the total phenol content, the antioxidant activity determined by scavenging of 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation, the ABTS(*)(+) assay, showed that BPR extracts prepared by solvent extraction exhibited significantly higher (7-10 times) radical scavenging activity than the pomace extracts, and BPR anthocyanins contributed significantly (74 and 77%) to the observed high radical scavenging capacity of the corresponding extracts.     

Volatile monoterpenes in black currant (Ribes nigrum L.) juice: effects of heating and enzymatic treatment by beta-glucosidase

Changes of terpenes in black currant juice induced by the action of heat were investigated in the present study. Limonene, alpha-terpinene, linalool, alpha-terpineol, 4-terpineol, and menthol added to either black currant juice or a model system were thermally treated at 90 degrees C for 30 min. Similar heat-induced decreases in the concentration of the terpenes were observed in the two systems. The concentration of a range of terpene hydrocarbons and oxygenated terpenes increased, alpha-terpineol being a main conversion product of most of the examined compounds. In the main, the measured loss of compounds exceeded the detected concentrations of products formed. In addition, determination of glycosidically bound terpenes in the juice was carried out by two methods of enzymatic hydrolysis, namely, addition of beta-glucosidase to an Amberlite XAD-2 isolate or directly to black currant juice. The two methods gave the same patterns of seven released volatile aglyconic terpenes. However, none of the released terpenes are important for the odor of black currant juice.     

Enzyme-assisted extraction of antioxidative phenols from black currant juice press residues (Ribes nigrum).

Enzymatic release of phenolic compounds from pomace remaining from black currant (Ribes nigrum) juice production was examined. Treatment with each of the commercial pectinolytic enzyme preparations Grindamyl pectinase, Macer8 FJ, Macer8 R, and Pectinex BE, as well as treatment with Novozym 89 protease, significantly increased plant cell wall breakdown of the pomace. Each of the tested enzyme preparations except Grindamyl pectinase also significantly enhanced the amount of phenols extracted from the pomace. Macer8 FJ and Macer8 R decreased the extraction yields of anthocyanins, whereas Pectinex BE and Novozym 89 protease showed no effect. A decrease in pomace particle sizes from 500-1000 microm to <125 microm increased the phenol yields 1.6-5 times. Black currant pomace devoid of seeds gave significantly higher yields of phenols than pomace with seeds and seedless wine pomace. Four selected black currant pomace extracts all exerted a pronounced antioxidant activity against human LDL oxidation in vitro when tested at equimolar phenol concentrations of 7.5-10 microM.     

Compositional differences of phenolic compounds between black currant (Ribes nigrum L.) cultivars and their response to latitude and weather conditions

Phenolic compounds in black currants of three Finnish cultivars and their response to growth latitude and weather conditions were analyzed over a six-year period. 'Melalahti' had lower contents of total phenolic compounds (31.4% and 29.2% lower than 'Mortti' and 'Ola', respectively), total anthocyanins (32.6% and 30.5%), and total hydroxycinnamic acid derivatives (23.1% and 23.8%) (p < 0.05) and was less affected by growth latitude and weather conditions than 'Mortti' and 'Ola'. However, all the cultivars grown at higher latitude (66°34' N) had lower contents of total flavonols, total anthocyanins, and total phenolic compounds than those grown at lower latitude (60°23' N) (p < 0.05). The content of total hydroxycinnamic acid conjugates did not vary in 'Melalahti' (p > 0.05) but increased as the latitude increased in 'Mortti' and 'Ola' (p < 0.05). Temperature and radiation were the major weather variables influencing the composition of phenolic compounds. Delphinidin-3-O-glucoside, delphinidin-3-O-rutinoside, and myricetin-3-O-glucoside content showed positive correlations with temperature and radiation in all three cultivars. The study gives important guidelines for the selection of raw materials and growth sites as well as for the berry cultivation for commercial exploitation of black currant berries.     

High-performance liquid chromatography analysis of black currant (Ribes nigrum L.) fruit phenolics grown either conventionally or organically

Black currants (Ribes nigrum L.) contain a diverse range of phenolics and possess a high antioxidant activity, which makes them an interesting target for the functional food industry. In this study, phenolic profiles of organically and conventionally grown black currant fruits, collected from commercial farms within a climatically similar area, were compared. Compounds were identified using UV/vis and mass spectroscopy techniques and quantified with high-performance liquid chromatography equipped with UV/vis detection. Several different conjugates of hydroxycinnamic acids, flavonols, and anthocyanins were quantified. Statistically significant differences between farms were found for almost all compounds. Differences between the highest and the lowest measured values of major phenolic compounds of different phenolic classes ranged from 24 to 77%. Principal component analysis quite effectively separated farms from each other but did not cluster them according to cultivation technique. Thus, it was concluded that the biochemical quality of organically grown black currant fruits does not differ from those grown conventionally.     

Yield and fruit quality of black currant (Ribes nigrum L.) are favoured by precipitation and cool summer conditions

The aim of this study was to examine the genetic and climatic impact on yield parameters and fruit chemical composition of black currant cultivars (Ribes nigrum L.). Correlation analysis between fruit parameters and climatic conditions over a period of eight years revealed a positive correlation between yield and precipitation during fruit development, whereas summer temperatures and radiation were negatively correlated with yield. Higher soluble solid concentrations occurred in years with high summer temperatures and radiation, while anthocyanins concentrations were negatively correlated with summer temperature. Furthermore, a negative correlation between phenolic compounds and radiation in June and July was observed. Temperature and radiation in late spring and summer were also negatively correlated with ascorbic acid concentration, while precipitation during summer was highly positively correlated with this important vitamin. These results indicate that to achieve high yield of quality black currants, rich in phenolic compounds, anthocyanins and ascorbic acid, cool summer conditions with ample precipitation are desirable. The observed cultivar variation in the content of health-related phytochemicals provides a good potential for further breeding of new cultivars with improved fruit quality.     

Sensory-guided decomposition of red currant juice (Ribes rubrum) and structure determination of key astringent compounds

Sequential application of solvent extraction, gel permeation chromatography, and RP-HPLC in combination with taste dilution analyses, followed by LC-MS and 1D/2D NMR experiments, led to the discovery and structure determination of 25 key astringent compounds of red currant juice. Besides several flavonol glycosides, in particular, 3-carboxymethyl-indole-1-N-beta-D-glucopyranoside, 3-methylcarboxymethyl-indole-1-N-beta-D-glucopyranoside, and a family of previously not identified compounds, namely, 2-(4-hydroxybenzoyloxymethyl)-4-beta-D-glucopyranosyloxy-2(E)-butenenitrile, 2-(4-hydroxy-3-methoxybenzoyloxymethyl)-4-beta-D-glucopyranosyloxy-2(E)-butenenitrile, (E)-6-[3-hydroxy-4-(O-beta-D-glucopyranosyl)phenyl]-5-hexen-2-one named dehydrorubrumin, and (3E,5E)-6-[3-hydroxy-4-(O-beta-D-glucopyranosyl)phenyl]-3,5-hexadien-2-one named rubrumin, have been identified. Determination of the oral astringency thresholds by means of the half-tongue test revealed that the lowest thresholds of 0.3 and 1.0 nmol/L were found for the nitrogen-containing 3-carboxymethyl-indole-1-N-beta-D-glucopyranoside and 3-methylcarboxymethyl-indole-1-N-beta-D-glucopyranoside, which do not belong to the group of plant polyphenols.     

The influence of early yield on the accumulation of major taste and health-related compounds in black and red currant cultivars (Ribes spp.)

The focus of our study was to investigate the effect of crop load on the accumulation and composition of primary metabolites (sugars and organic acids), selected groups of flavonoids (anthocyanins and flavonols), and total phenolics in two subsequent years in four black currant cultivars ('Titania', 'Triton', 'Tsema', and 'Cacanska crna') and three red currant cultivars ('Junifer', 'Rolan', and 'Stanza'). For the determination and quantification of compounds, high-performance liquid chromatography-photodiode array with a mass spectrometer was used. Significant differences among cultivars were detected in all analyzed compounds. Anthocyanins were the predominant phenolic group and were more abundant in black currant cultivars as compared to red ones. Similar amounts of sugars and organic acids were measured in both Ribes species; however, vitamin C was 3-fold higher in black currants. A larger crop load in the second year had a negative effect on the sugar content of berries and promoted a higher degree of acids, with the exception of vitamin C, which was higher in the year with a lower crop load. On the other hand, the content of anthocyanins and flavonols was higher in the year with a larger crop load, while there were no differences in total phenolic content.     

Structural and sensory characterization of key pungent and tingling compounds from black pepper (Piper nigrum L.)

To gain a more comprehensive knowledge on whether, besides the well-known piperine, other compounds are responsible for the pungent and tingling oral impression imparted by black pepper, an ethanol extract prepared from black pepper (Piper nigrum L.) was screened for its key sensory-active nonvolatiles by application of taste dilution analysis (TDA). Purification of the compounds perceived with the highest sensory impact, followed by LC-MS and 1D/2D NMR experiments as well as synthesis, led to the structure determination of 25 key pungent and tingling phytochemicals, among which the eight amides 1-(octadeca-2E,4E,13Z-trienyl)piperidine, 1-(octadeca-2E,4E,13Z-trienyl)pyrrolidine, (2E,4E,13Z)-N-isobutyl-octadeca-2,4,13-trienamide, 1-(octadeca-2E,4E,12Z-trienoyl)-pyrrolidine, 1-(eicosa-2E,4E,15Z-trienyl)piperidine, 1-(eicosa-2E,4E,15Z-trienyl)pyrrolidine, (2E,4E,15Z)-N-isobutyl-eicosa-2,4,15-trienamide, and 1-(eicosa-2E,4E,14Z-trienoyl)-pyrrolidine were not yet reported in literature. Sensory studies by means of a modified half-tongue test revealed recognition thresholds ranging from 3.0 to 1150.2 nmol/cm2 for pungency and from 520.6 to 2162.1 nmol/cm2 for the tingling orosensation depending on their chemical structure.     

Genotype and climate conditions influence the drop off of flowers and premature berries of blackcurrant (Ribes nigrum L.)

Abstract

The aim of the present research was to study the extent of the drop off of blackcurrant flowers and young berries in the conditions of northern Europe, depending on particular genotypes and weather conditions. The study was carried out in southern Estonia in 2004–2007. The experiment involved nine recently selected genotypes from the blackcurrant breeding program of the Estonian University of Life Sciences Institute of Agricultural and Environmental Sciences Polli Horticultural Research Centre and 10 parent genotypes. Drop off is considerably influenced by the weather conditions during flowering (temperature, precipitation) and the particular genotype. Drop off is lower in genotypes ‘Ats’, 6-90-5, 1-90-15 and ‘Pilenai’, whereas it is high in genotypes ‘Zagadka’ and ‘Karri’. There is an average positive correlation between the cluster length, the number of flower buds in cluster and the extent of drop off. A strong negative correlation was found between the intra-flower fertilization ability of the genotype and drop off. There may be specimens with both similar as well as a very different extent of drop off among the genotypes originating from the same crossing combination. Drop off was lower among the genotypes where cultivar ‘Öjebyn’ was one of the parents.     

Quantitative analysis of aroma compounds in carrot (Daucus carota L.) cultivars by capillary gas chromatography using large-volume injection technique

Dynamic headspace sampling was used to collect aroma compounds from raw samples of four carrot (Daucus carota L.) cultivars (Brasilia, Duke, Fancy, and Cortez). The collected volatiles were analyzed by capillary GC-FID and GC-MS using large-volume cool on-column injection (LVI-COC). Of the 36 compounds identified, 6 had not been previously detected in carrots. Significant differences between the carrot cultivars were found for 31 of the identified volatiles as well as for total monoterpenes, sesquiterpenes, and total volatile content. Mono- and sesquiterpenes accounted for about 98% of the total volatile mass in all cultivars. LVI-COC injection was used to determine the loss of carrot volatiles during concentration of headspace samples under a stream of nitrogen. The loss among major monoterpenes in the concentrated samples varied from 16% for p-cymene to >40% for alpha-pinene as compared to nonconcentrated samples. The loss among high-boiling sesquiterpenes varied from not detectable (beta-caryophyllene, alpha-humulene, and caryophyllene oxide) to approximately 7% for (E)- and (Z)-gamma-bisabolene.     

Characterization of the aroma-active compounds in pink guava (Psidium guajava, L.) by application of the aroma extract dilution analysis

The volatiles present in fresh, pink-fleshed Colombian guavas ( Psidium guajava, L.), variety regional rojo, were carefully isolated by solvent extraction followed by solvent-assisted flavor evaporation, and the aroma-active areas in the gas chromatogram were screened by application of the aroma extract dilution analysis. The results of the identification experiments in combination with the FD factors revealed 4-methoxy-2,5-dimethyl-3(2 H)-furanone, 4-hydroxy-2,5-dimethyl-3(2 H)-furanone, 3-sulfanylhexyl acetate, and 3-sulfanyl-1-hexanol followed by 3-hydroxy-4,5-dimethyl-2(5 H)-furanone, ( Z)-3-hexenal, trans-4,5-epoxy-( E)-2-decenal, cinnamyl alcohol, ethyl butanoate, hexanal, methional, and cinnamyl acetate as important aroma contributors. Enantioselective gas chromatography revealed an enantiomeric distribution close to the racemate in 3-sulfanylhexyl acetate as well as in 3-sulfanyl-1-hexanol. In addition, two fruity smelling diastereomeric methyl 2-hydroxy-3-methylpentanoates were identified as the ( R,S)- and the ( S,S)-isomers, whereas the ( S,R)- and ( R,R)-isomers were absent. Seven odorants were identified for the first time in guavas, among them 3-sulfanylhexyl acetate, 3-sulfanyl-1-hexanol, 3-hydroxy-4,5-dimethyl-2(5 H)-furanone, trans-4,5-epoxy-( E)-2-decenal, and methional were the most odor-active.     

Prevention of photo-induced chlorophyll loss by the use of lime reflectant on the leaves of black pepper (Piper nigrum L.)

A study was conducted to evaluate the adverse effect of direct solar radiation on irrigated pepper (Piper nigrum L.) vines and to determine whether lime could be applied as a reflectant to protect the exposed plants. It was found that even with favourable soil moisture conditions the leaves of the exposed plants developed the symptoms of the physiological disorder of leaf yellowing leading to the formation of necrotic patches. Leaves of the shaded plants remained dark green and healthy. Chlorophyll concentration in the exposed leaves was 44% less compared with the shaded leaves. However, the presence of lime coating on the surface of the exposed leaves resulted in the presence of 39% more chlorophyll content. A concept of Contact Shade Technology (CST) is suggested where reflectants can be used to artificially shade the shade-loving crop plants.     

Comparison of experimental methods for measuring infinite dilution volatilities of aroma compounds in water/ethanol mixtures

Several experimental methodologies exist for measuring volatilities; however, results show great dispersion and sometimes lack of agreement between different methods. The aim of our study was to compare the performance of three static headspace methods (vapor phase calibration, VPC; phase ratio variation, PRV; and liquid calibration static headspace, LC-SH) for determining gas/liquid partition coefficients of two aroma compounds in hydroalcoholic multicomponent solutions at infinite dilution. Comparison with literature data based on static and dynamic methods showed that PRV is simpler than VPC and LC-SH and that VPC and PRV are more accurate than LC-SH, which presented a significant bias (50% lower values).     

Characterization of odorants causing an atypical aroma in white pepper powder (Piper nigrum L.) based on quantitative measurements and orthonasal breakthrough thresholds

Application of the aroma extract dilution analysis on an extract of white pepper powder showing an intense fecal, cowshed-like off-flavor revealed 3-methylindole (fecal, swine-manure) and 4-methylphenol (fecal, horse-like) with the highest flavor dilution (FD) factors among the 22 odor-active compounds detected. In addition, high FD factors and/or undesirable odor qualities suggested 3-methylphenol (phenolic), butanoic acid (cheese-like), and 2- and 3-methylbutanoic acid (cheese-like) as well as pentanoic acid and hexanoic acid (cheese-like odors) as contributors to the malodor. Although the intensities of the off-note were clearly different in 50 commercial samples of white pepper, quantitation of 3-methylindole and 3- and 4-methylphenol as well as of the five short-chain acids by means of stable isotope dilution assays showed similar concentrations in most of the samples. Storage of a freshly ground white pepper powder for up to 7 months revealed a significant decrease in the typical odor qualities of white pepper and an increase in the fecal odor note with storage time. Because the concentrations of the odorants mentioned above were not much changed during storage, possibly very volatile odorants, such as alpha-pinene, which are able to mask the malodor, are lost during storage of, in particular, pepper powders. On the basis of odor activity values, which were calculated using breakthrough thresholds, in particular, 3-methylindole, 4-methylphenol, 3-methylphenol, and butanoic acid could be suggested as the main sources of the fecal off-flavor.     

Metabolite profiling using (1)H NMR spectroscopy for quality assessment of green tea, Camellia sinensis (L.)

A set of 191 green teas from different countries was collected and analyzed by (1)H NMR. It was proposed to establish if the teas could be discriminated according to the country of origin or with respect to quality. Both principal component analysis (PCA) and cluster analysis were applied to the data. Some separation of Chinese and non-Chinese teas was observed. The present results did not allow allocation of samples to individual countries, but cluster analysis suggested that it might be possible with an augmented sample set. The PCA did show a separation between the Longjing type (highest quality Chinese tea) and most other Chinese teas and indicated some metabolites that could be responsible for the difference. Longjing teas showed higher levels of theanine, gallic acid, caffeine, epigallocatechin gallate, and epicatechin gallate and lower levels of epigallocatechin when compared with other teas. These compounds have been mentioned previously in connection with quality, but it was also shown that higher levels of theogallin (5-galloyl quinic acid), theobromine, 2-O-(beta-l-arabinopyranosyl)-myo-inositol and some minor sugar-containing compounds were found in Longjing teas while higher levels of fatty acids and sucrose were found in the other teas. These new markers could prove to be useful for the authentication of bulk tea.