Functional lipid characteristics of Turkish Tombul hazelnut (Corylus avellana L.)

The quality of crude oil extracted from Tombul (Round) hazelnut, grown in the Giresun province of Turkey, was evaluated for its fatty acid, triacylglycerol (TAG), tocol, and phytosterol compositions. Oleic acid contributed 82.78% to the total fatty acids, followed by linoleic, palmitic, and stearic acids. Among 12 TAGs separated, 11 were identified (including one unknown): LLL, OLL, PLL, OOL, POL, PPL, OOO, POO, PPO, SOO, and PSO (where P, palmitoyl; S, stearoyl; O, oleoyl; and L, linoleoyl). The main components were OOO (71.31%), OOL (12.26%), and POO (9.45%), reflecting the high content of oleic acid present in hazelnut oil. Seven tocol isoforms (four tocopherols and three tocotrienols) and eight phytosterols as well as cholesterol were positively identified and quantified; among these, alpha-tocopherol (40.40 mg/100 g) and beta-sitosterol (134.05 mg/100 g) were predominant in hazelnut oil and contributed 78.74 and 81.28% to the total tocols and phytosterols present, respectively. Tocotrienols were detected in small amounts (1.02% to the total tocols). The crude hazelnut oil extracted from Turkish Tombul hazelnut, thus, serves as a good source of nutrients, bioactives, and health-promoting components.     

Antioxidant phytochemicals in hazelnut kernel (Corylus avellana L.) and hazelnut byproducts

Antioxidant efficacies of ethanol extracts of defatted raw hazelnut kernel and hazelnut byproducts (skin, hard shell, green leafy cover, and tree leaf) were evaluated by monitoring total antioxidant activity (TAA) and free-radical scavenging activity tests [hydrogen peroxide, superoxide radical, and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical], together with antioxidant activity in a beta-carotene-linoleate model system, inhibition of oxidation of human low-density lipoprotein (LDL) cholesterol, and inhibition of strand breaking of supercoiled deoxyribonucleic acid (DNA). In addition, yield, content of phenolics, and phenolic acid profiles (free and esterified fractions) were also examined. Generally, extracts of hazelnut byproducts (skin, hard shell, green leafy cover, and tree leaf) exhibited stronger activities than hazelnut kernel at all concentrations tested. Hazelnut extracts examined showed different antioxidative efficacies, expected to be related to the presence of phenolic compounds. Among samples, extracts of hazelnut skin, in general, showed superior antioxidative efficacy and higher phenolic content as compared to other extracts. Five phenolic acids (gallic acid, caffeic acid, p-coumaric acid, ferulic acid, and sinapic acid) were tentatively identified and quantified (both free and esterified forms). Extracts contained different levels of phenolic acids. These results suggest that hazelnut byproducts could potentially be considered as an excellent and readily available source of natural antioxidants.     

Turkish Tombul hazelnut (Corylus avellana L.). 1. Compositional characteristics

The quality of Tombul (Round) hazelnut, grown in the Giresun province of Turkey, was determined by measuring proximate composition, minerals, vitamins, dietary fiber, amino acids, and taste active components (free amino acids, sugars, and organic acids). Fat was the predominant component in Tombul hazelnut (approximately 61%). The major minerals were potassium, phosphorus, calcium, magnesium, and selenium. Hazelnut was also found to serve as an excellent source of vitamin E (24 mg/100 g) and a good source of water soluble (B complex) vitamins and dietary fiber. The major amino acids were glutamic acid, arginine, and aspartic acid. The three nonessential amino acids and the essential amino acids contributed 44.9 and 30.9% to the total amino acids present, respectively, while lysine and tryptophan were the limiting amino acids in Tombul hazelnut. Twenty-one free amino acids, six sugars, and six organic acids were positively identified; among these, arginine, sucrose, and malic acid predominated, respectively. These taste active components may play a significant role in the taste and flavor characteristics of hazelnut. Thus, the present results suggest that Tombul hazelnut serves as a good source of vital nutrients and taste active components.     

Nutritional composition of hazelnut (Corylus avellana L.) as influenced by basic fertilization

Nitrogen (N), phosphorus (P), and potassium (K) deficiencies are a widespread phenomenon throughout the world, and are one of the most common nutritional disorders in Turkish hazelnut (Corylus avellana L.) cultivation. In this research, the effects of macronutrient fertilizers on mineral contents and some biochemical contents of ‘Tombul’ hazelnut (Corylus avellana L.) variety cultivated in the Black Sea Region of Turkey were investigated, and the contribution of these nuts to human nutrition was determined. The trials were carried out at ‘Tombul’ hazelnut orchards, and the hazelnuts were fertilized with five different doses of nitrogen, phosphorus, and potassium in each year for three consecutive years. The basic fertilizers (N, P₂O₅, and K₂O) significantly affected some biochemical contents and mineral compositions of the hazelnuts. In order to improve the biochemical and mineral compositions of hazelnut, 200 kg ha^?1 and 400 kg ha^?1 N fertilizations, 120 kg ha^?1 and 160 kg ha^?1 P₂O₅ fertilizations, and 400 kg ha^?1 and 600 kg ha^?1 K₂O fertilizations could be recommended for practice. According to the daily mineral element requirements, 100 g of hazelnuts provided about 43.5% P, 13.2% K, 19.4% Ca, 37.0% Mg, 0.2% Na, 53.8% Fe, 24.5% Zn, 14.5% B, and 66.7% Mo of the recommended dietary allowances. Cu and Mn contents of 100 g hazelnut were higher than the respective daily requirements. These results indicated that the mineral composition of hazelnut depended not only on the variety but also on the cultivation techniques such as soil condition and especially basic fertilization practices.     

Turkish Tombul hazelnut (Corylus avellana L.). 2. Lipid characteristics and oxidative stability

The quality of crude hazelnut oil extracted from Tombul (Round) hazelnut, grown in the Giresun province of Turkey, was determined by measuring lipid classes, fatty acids, and fat soluble bioactives (tocopherols and phytosterols). Oxygen uptake, peroxide value, thiobarbituric acid reactive substances, and alpha-tocopherol levels of stripped and crude hazelnut oils in bulk and oil-in-water (o/w) emulsion systems were also evaluated as indices of lipid oxidation over a 21 day storage period at 60 degrees C in the dark. The total lipid content of Tombul hazelnut was 61.2%, of which 98.8% were nonpolar and 1.2% polar constituents. Triacylglycerols were the major nonpolar lipid class and contributed nearly 100% to the total amount. Phosphatidylcholine, phosphatidylethanolamine, and phosphatidylinositol were the most abundant polar lipids, respectively. Sixteen fatty acids were identified, among which oleic acid contributed 82.7% to the total, followed by linoleic, palmitic, and stearic acids. Unsaturated fatty acids accounted for 92.2% of the total fatty acids present. Among oil soluble bioactives, alpha-tocopherol (38.2 mg/100 g) and beta-sitosterol (105.5 mg/100 g) were predominant in hazelnut oil and comprised 88 and 93% of the total tocopherols and phytosterols present, respectively. The results also showed that both stripped and crude hazelnut oils were more stable in terms of lipid oxidation in the bulk oil as compared to those in an o/w emulsion.     

Effects of roasting on the antioxidant status and phenolic profiles of commercial Turkish hazelnut varieties (Corylus avellana L.)

The effect of roasting on the antioxidant status and phenolic profiles of seven commercial Turkish hazelnut varieties (namely, ?ak?ldak, Fo?a, Karaf?nd?k, Mincane, Palaz, Sivri, and Tombul) was assessed. Samples were examined for their total phenolics, oxygen radical absorbance capacity (ORAC) values, condensed tannins, and phenolic acids (free and bound forms). Significant losses (p < 0.05) in total phenolics (~66.3%), ORAC values (~41.6%), condensed tannins (~75.2), and phenolic acids (~42.7) were noted when the hazelnuts were roasted. Some variations both between and within natural and roasted hazelnuts were observed (p < 0.05). Phenolic acids were mainly found in the bound form. Gallic, protocatechuic, p-coumaric, and ferulic + sinapic acids were present in all hazelnut varieties, albeit to different extents, and the first two were dominant. Mincane, in roasted form, had the highest total phenolics, ORAC values, condensed tannins, and phenolic acids. This was due to the presence of some skin in roasted Mincane. No skin was left in all other varieties upon roasting. The present work suggests that roasting results in a significant loss in the antioxidant status and phenolic profiles because of the removal of the skin, which is a rich source of phenolics. It is highly recommended to consume natural hazelnut instead of the roasted counterpart to take advantage of all of the functional benefits of this nut.     

Antioxidant and antiradical activities in extracts of hazelnut kernel (Corylus avellana L.) and hazelnut green leafy cover

Phenolic compounds in the aqueous systems were extracted, from hazelnut kernel (HK) and hazelnut green leafy cover (HGLC), with 80% (v/v) ethanol (HKe and HGLCe) or 80% (v/v) acetone (HKa and HGLCa). The extracts were examined for their phenolic and condensed tannin contents and phenolic acid profiles (free and esterified fractions) as well as antioxidant and antiradical activities by total antioxidant activity (TAA), antioxidant activity in a beta-carotene-linoleate model system, scavenging of DPPH (2,2-diphenyl-1-picrylhydrazyl) radical, and reducing power. Significant differences (p < 0.05) in the contents of total phenolics, condensed tannins, and TAA existed among the extracts that were examined. HGLCa extract had the highest content of total phenolics (201 mg of catechin equivalents/g of extract), condensed tannins (542 mg of catechin equivalents/g of extract), and TAA (1.29 mmol of Trolox equivalents/g of extract) followed by HGLCe, HKa, and HKe extracts, respectively. Five phenolic acids (gallic acid, caffeic acid, p-coumaric acid, ferulic acid, and sinapic acid) were tentatively identified and quantified, among which gallic acid was the most abundant in both free and esterified forms. The order of antioxidant activity in a beta-carotene-linoleate model system, the scavenging effect on DPPH radical, and the reducing power in all extracts were in the following order: HGLCa > HGLCe > HKa > HKe. These results suggest that both 80% ethanol and acetone are capable of extracting phenolics, but 80% acetone was a more effective solvent for the extraction process. HGLC exhibited stronger antioxidant and antiradical activities than HK itself in both extracts and could potentially be considered as an inexpensive source of natural antioxidants.     

Triacylglycerol and phospholipid composition of hazelnut (Corylus avellana L.) lipid fraction during fruit development

We analyzed the triacylglycerol and phospholipid contents of hazelnuts from early development to maturity. Both were analyzed by high-performance liquid chromatography coupled to a light scattering detector. Trioleylglycerol, linoleyl-dioleylglycerol, and palmitoyl-dioleylglycerol were the most predominant triacylglycerols throughout development. Triacylglycerols showed small variation during hazelnut development. Phosphatidylcholine, phosphatidylethanolamine, and phosphatidylinositol were the most abundant phospholipids. Traces of phosphatidic acid were also detected. The statistical analysis showed that the positive correlation among the individual phospholipid contents was significant. Phospholipid contents showed a steep decrease during hazelnut development. Triacylgycerols and phosphatidylcholine were isolated by preparative thin-layer chromatography, and their fatty acid profile was determined by gas-liquid chromatography. Triacylglycerols showed a high percentage of monounsaturated fatty acid moieties, whereas phosphatidylcholine had the highest percentage of saturated and monounsaturated fatty acid moieties. The polyunsaturated fatty acid moiety showed low percentages in the triacylglycerol and phospholipid backbone.     

Characterization of the key odorants in raw Italian hazelnuts ( Corylus avellana L. var. Tonda Romana) and roasted hazelnut paste by means of molecular sensory science

The concentrations of 19 odorants, recently characterized by GC-olfactometry and aroma extract dilution analysis as the most odor-active compounds in raw hazelnuts, were quantitated by stable isotope dilution assays (SIDA). Calculation of odor activity values (OAV) on the basis of odor thresholds in oil revealed high OAVs, in particular for linalool, 5-methyl-4-heptanone, 2-methoxy-3,5-dimethylpyrazine, and 4-methylphenol. A model mixture in sunflower oil containing the 13 odorants showing OAVs above 1 in their natural concentrations resulted in a good similarity compared to the overall nut-like, fruity aroma of the raw hazelnuts. Quantitation of the 25 most odor-active compounds in roasted hazelnut paste by SIDA showed clear changes in the concentrations of most odorants, and formation of new odor-active compounds induced by the roasting process was observed. The highest OAVs were calculated for 3-methylbutanal (malty), 2,3-pentanedione (buttery), 2-acetyl-1-pyrroline (popcorn), and (Z)-2-nonenal (fatty), followed by dimethyl trisulfide, 2-furfurylthiol, 2,3-butanedione, and 4-hydroxy-2,5-dimethyl-3(2H)-furanone. The aroma of a model mixture containing the 19 odorants with OAVs above 1 in their actual concentrations in the roasted nut material was judged to elicit a very good similarity to the popcorn-like, coffee-like, and sweet-smoky aroma of the roasted hazelnut paste. New SIDAs were developed for the quantitation of 5-methyl-4-heptanone, 5-methyl-(E)-2-hepten-4-one, 2-thenylthiol, and 3,5,5-trimethyl-2(5H)-furanone.     

Influence of Cultivar and Environmental Conditions on the Triacylglycerol Profile of Hazelnut (Corylus avellana L.)

The oil of several hazelnut (Corylus avellana L.) samples was extracted and evaluated for their triacylglycerol (TAG) composition. Trials were conducted in two Portuguese localities (Vila Real and Felgueiras) during three consecutive years and involved a total of 19 cultivars. The samples were analyzed by reversed-phase high-performance liquid chromatography with evaporative light-scattering detection. Sample preparation was fast and simple, consisting only of the dissolution of the oil in acetone, homogenization, and filtration, allowing this technique to be suitable for routine analyses. All samples presented a similar qualitative profile composed of eleven compounds: LLL, OLL, PLL, OOL, POL, PPL, OOO, POO, PPO, SOO and PSO (P, palmitoyl; S, stearoyl; O, oleoyl; and L, linoleoyl). The main components were OOO, LOO, and POO, reflecting the high content of oleic acid in hazelnut oils. A total of 79 different samples were studied, and the obtained data were statistically analyzed. Significant differences were verified in canonical variate plots when cultivars were grouped by country of origin. In general, the American cultivars were richer in TAGs with saturated fatty acids moieties, and the group of French, German, and English cultivars was richer in TAGs containing linoleic acid moieties. Differences were also significant when cultivars were grouped by year of production, showing that besides genetic factors, the TAG composition can be influenced by environmental factors.     

Detection of potentially allergenic hazelnut (Corylus avellana) residues in food: a comparative study with DNA PCR-ELISA and protein sandwich-ELISA

Allergen detection is of increasing interest for food labeling purposes. A comparative study with a commercial hazelnut-specific PCR-ELISA and a sandwich-type ELISA detecting hazelnut protein was performed to investigate to what extent immunochemical and DNA-based techniques would correlate in the detection of trace amounts of potentially allergenic hazelnut residues. Both methods were highly sensitive and allowed the detection of even <10 ppm of hazelnut in complex food matrixes. The protein-ELISA was highly specific for hazelnut. However, some foods could lead to false-positive results at the 10 ppm level. The PCR-ELISA did not show any cross-reactions with non-hazelnut foods, thus reducing the probability of having false positives at the trace level. Forty-one commercial food products with and without hazelnut components on their labels were analyzed for the presence of hazelnut. Of the 27 products in which hazelnut components were detected, two samples were not identified by the protein-ELISA, and only one sample, namely one white chocolate having <1 ppm of hazelnut protein, was not detected by PCR-ELISA. The good correlation of the results of PCR-ELISA and protein-ELISA suggested that both PCR-based and immunochemical techniques are suitable for reliable detection of potentially allergenic hazelnut residues in foods at the trace level.     

Structure determination and sensory analysis of bitter-tasting 4-vinylcatechol oligomers and their identification in roasted coffee by means of LC-MS/MS

Aimed at elucidating intense bitter-tasting molecules in coffee, various bean ingredients were thermally treated in model experiments and evaluated for their potential to produce bitter compounds. As caffeic acid was found to generate intense bitterness reminiscent of the bitter taste of a strongly roasted espresso-type coffee, the reaction products formed were screened for bitter compounds by means of taste dilution analysis, and the most bitter tastants were isolated and purified. LC-MS/MS as well as 1-D/2-D NMR experiments enabled the identification of 10 bitter compounds with rather low recognition threshold concentrations ranging between 23 and 178 micromol/L. These bitter compounds are the previously unreported 1,3-bis(3',4'-dihydroxyphenyl) butane, trans-1,3-bis(3',4'-dihydroxyphenyl)-1-butene, and eight multiply hydroxylated phenylindanes, among which five derivatives are reported for the first time. In addition, the occurrence of each of these bitter compounds in a coffee brew was verified by means of LC-MS/MS (ESI-) operating in the multiple reaction monitoring (MRM) mode. The structures of these bitter compounds show strong evidence that they are generated by oligomerization of 4-vinylcatechol released from caffeic acid moieties upon roasting.     

Group-type and fingerprint analysis of roasted food matrices (coffee and hazelnut samples) by comprehensive two-dimensional gas chromatography

The present study is focused on the volatile fraction of roasted hazelnut and coffee samples, differing in botanical origins, morphological characteristics, and roasting treatments, selected as challenging matrices. Volatile components, sampled by headspace solid phase microextraction (HS-SPME), were analyzed by GC x GC-qMS, and separation results were adopted to classify, correlate, and/or compare samples and evaluate processing effects. The high-complexity sample profiles were interpreted through different methods: a group-type characterization, a direct fingerprint comparison, and a template matching to extract useful and consistent information, and advantages and limits of each specific approach were critically evaluated. The group-type analysis, focused on several known botanical and technological markers, enabled sample comparison and characterization based on their quali-quantitative distribution; it is highly reliable, because of the authentic standard confirmation, and extends the comparative procedure to trace and minor components. Fingerprint approaches (i.e., direct fingerprint comparison and template matching), on the other hand, extended sample comparisons and correlations to the whole volatiles offering an increased discrimination potential and improved sensitivity due to the wider analyte pattern considered. This study demonstrates the ability of comprehensive GC to further explore the complexity of roasted samples and emphasizes the advantages of, and the need for, a comprehensive and multidisciplinary approach to interpret the increased level of information provided by GC x GC separation in its full complexity.     

Investigating the origin of hazelnut (<Emphasis Type="Italic">Corylus avellana</Emphasis> L.) cultivars using chloroplast microsatellites

The place and time of European hazel (Corylus avellana L.) domestication is not clear, although it was already cultivated by the Romans. In this study, 75 accessions from Spain, Italy, Turkey, and Iran were analysed using 13 chloroplast microsatellite to investigate the origin and diffusion of hazelnut cultivars. Four loci were polymorphic and identified a total of four different chlorotypes. Their distribution was not uniform in each geographical group. The most frequent chlorotype A was present in all groups. An increase in chlorotype number and diversity from Spain eastward to Italy, Turkey, and Iran was observed. Results suggest that some spread of cultivars occurred from East to West and that hazelnut cultivation was not introduced from the eastern Mediterranean basin into Spain and southern Italy by Greeks or Arabs. Moreover, the results suggest considerable exchange of germplasm between Italy and Spain, probably by the Romans. Hazelnut appears to have been domesticated independently in three areas: the Mediterranean, Turkey, and Iran.     

Headspace GC and sensory analysis characterization of the influence of different milk additives on the flavor release of coffee beverages

Previous investigations of coffee flavor have been confined to the analysis of the aroma substances. These investigations showed that about 30 volatile compounds were substantially responsible for the coffee flavor. The aim of this study was to investigate the influence of different milk additives and one coffee whitener on the release of flavor impact compounds from coffee beverages. For the investigation of these effects an external static headspace technique was developed. With this technique the most potent odorants of the coffee beverage were determined. Analyses were performed by gas chromatography/olfactometry, flame ionization detection, and mass spectrometric detection. In addition, sensory studies of the odor profiles were performed. Milk and vegetable products as additives for coffee beverages affected the release of aroma substances in the brew through their lipid, protein, and carbohydrate components. All beverages with an additive showed reduced, but typical, odor profiles for each additive.     

Determination of advanced glycation endproducts by LC-MS/MS in raw and roasted almonds (Prunus dulcis)

A sensitive and reliable LC-(ESI)MS/MS method was developed and validated for the simultaneous analysis of five common advanced glycation endproducts (AGEs) after enzymatic digestion in raw and roasted almonds. AGEs included carboxymethyl-lysine (CML), carboxyethyl-lysine (CEL), pyralline (Pyr), argpyrimidine (Arg-p), and pentosidine (Pento-s). This method allows accurate quantitation of free and AGE-protein adducts of target AGEs. Results indicate that CML and CEL are found in both raw and roasted almonds. Pyr was identified for the first time in roasted almonds and accounted for 64.4% of free plus bound measured AGEs. Arg-p and Pento-s were below the limit of detection in all almond samples tested. Free AGEs accounted for 1.3-26.8% of free plus bound measured AGEs, indicating that protein-bound forms predominate. The roasting process significantly increased CML, CEL, and Pyr formation, but no significant correlation was observed between these AGEs and roasting temperature.     

Polyphenol screening of pomace from red and white grape varieties (Vitis vinifera L.) by HPLC-DAD-MS/MS

Phenolic compounds of 14 pomace samples originating from red and white winemaking were characterized by HPLC-MS. Up to 13 anthocyanins, 11 hydroxybenzoic and hydroxycinnamic acids, and 13 catechins and flavonols as well as 2 stilbenes were identified and quantified in the skins and seeds by HPLC-DAD. Large variabilities comprising all individual phenolic compounds were observed, depending on cultivar and vintage. Grape skins proved to be rich sources of anthocyanins, hydroxycinnamic acids, flavanols, and flavonol glycosides, whereas flavanols were mainly present in the seeds. However, besides the lack of anthocyanins in white grape pomace, no principal differences between red and white grape varieties were observed. This is the first study presenting comprehensive data on the contents of individual phenolic compounds comprising all polyphenolic subclasses of grapes including a comparison of several red and white pomaces from nine cultivars. The results obtained in the present study confirm that both skins and seeds of most grape cultivars constitute a promising source of polyphenolics.