Comprehensive Evaluation of Amino Acids and Polyphenols in 69 Varieties of Green Cabbage (Brassica oleracea L. var. capitata L.) Based on Multivariate Statistical Analysis

The biological activities of the primary metabolites and secondary metabolites of 69 green cabbage varieties were tested. The LC-MS detection method was used to determine the content of 19 free amino acids (lysine, tryptophan, phenylalanine, methionine, threonine, isoleucine, leucine, valine, arginine, asparagine, glycine, proline, tyrosine, glutamine, alanine, aspartic acid, serine, and glutamate). The content of 10 polyphenols (chlorogenic acid, gallic acid, 4-coumaric acid, ferulic acid, gentisic acid, cymarin, erucic acid, benzoic acid, rutin, and kaempferol) was determined by the HPLC detection method. Considering the complexity of the data obtained, variance analysis, diversity analysis, correlation analysis, hierarchical cluster analysis (HCA), and principal component analysis (PCA) were used to process and correlate amino acid or polyphenol data, respectively. The results showed that there were significant differences between the different amino acids and polyphenols of the 69 cabbage varieties. The most abundant amino acids and polyphenols were Glu and rutin, respectively. Both amino acids and polyphenols had a high genetic diversity, and multiple groups of significant or extremely significant correlations. The 69 cabbage varieties were divided into two groups, according to 19 amino acid indexes, by PCA. Among them, seven varieties with high amino acid content all fell into the fourth quadrant. The HCA of amino acids also supports this view. Based on 10 polyphenols, the 69 cabbage varieties were divided into two groups by HCA. Based on 29 indexes of amino acids and polyphenols, 69 cabbage varieties were evaluated and ranked by PCA. Therefore, in this study, cabbage varieties were classified in accordance with the level of amino acids and polyphenols, which provided a theoretical basis for the genetic improvement of nutritional quality in cabbage.     

高效液相色谱-四极杆飞行时间质谱分析紫甘蓝和羽衣甘蓝中花色苷

应用高效液相色谱-电喷雾/四极杆飞行时间串联质谱联用技术分析了紫甘蓝和羽衣甘蓝中的花色苷成分.选用Agilent TC-C18色谱柱(250 mm×4.6 mm×5 μm),二元线性梯度洗脱,柱后流出液采用电喷雾四极杆飞行时间质谱的正、负离子模式进行检测.根据一级质谱的分子离子和二级质谱碎片离子,获得化合物的准确分子量...     

Determination of three major triterpenoids in epicuticular wax of cabbage (Brassica oleracea L.) by high-performance liquid chromatography with UV and mass spectrometric detection

Lupeol, together with alpha- and beta-amyrins in smaller quantities, has been found for the first time in the epicuticular wax of white cabbage (Brassica oleracea L. convar. capitata (L.) Alef. var. alba DC) leaf surface extract. The three triterpenoids were identified by a new high-performance liquid chromatographic (HPLC) method with UV and mass spectrometric (MS) detection using atmospheric pressure chemical ionization (APCI). All three isomeric compounds gave a parent ion peak at m/z 409 [M+H-18](+) and the relative intensities of some characteristic fragment ion peaks in tandem mass spectrometric (MS-MS) spectra of this parent ion enabled differentiation between the isomers. An additional peak at m/z 439 [M+H](+), which could be oleanonic or ursonic aldehyde, was detected by HPLC-APCI-MS. Saponification of cabbage leaf surface extract with 20% NaOH in methanol at 65 degrees C for 2h had no influence on lupeol, or alpha- or beta-amyrins, but lead to the formation of three additional compounds, which were not identified.     

Green biosynthesis,characterization, and cytotoxic effect of magnetic iron nanoparticles using Brassica Oleracea var capitata sub var rubra (red cabbage) aqueous peel extract

The green method of nanoparticle synthesis, which is an environment and living-friendly method, is an updated subject that has appeared as an alternative to conventional methods such as physical and chemical synthesis. In this presented study, the green synthesis of magnetic iron oxide nanoparticles (IONPs) from iron (III) chloride by using Brassica oleracea var. capitata sub.var. rubra aqueous peel extract has been reported. The prepared IONPs were characterized with fourier-transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-VIS), zeta potential, scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The cytotoxic effects of IONPs on MCF-7 breast cancer cell line were studied by MTT assay, and migrative effect of its were carried out by the wound healing assay. It was found that the mean particle size of IONPs was 675 ± 25 nm, and the polydispersity index was 0.265 PDI. It was also determined that these nanoparticles had an anti-proliferative impact on the MCF-7 breast cancer cell line depending on the dosage. Characterization results support the successful synthesis of nanoparticles, and the dose-dependent cytotoxic effects of nanoparticles on MCF-7 cells also make it a potential chemotherapeutic agent for breast cancer treatment.     

Characterisation of flavonols in broccoli (Brassica oleracea L. var. italica) by liquid chromatography-uV diode-array detection-electrospray ionisation mass spectrometry

The flavonoid composition of broccoli inflorescences has been studied by LC/UV-DAD/ESI-MSn. A large number of hydroxycinnamic acid esters of kaempferol and quercetin glucosides has been characterised. The structures of the flavonoid glycosides were analysed after alkaline hydrolysis, and were identified as 3-sophoroside/sophorotrioside-7-glucoside/sophoroside of kaempferol, quercetin and isorhamnetin (this last found in trace amount). These complex quercetin and isorhamnetin glucosides have not been previously characterised in nature. In addition, several less complex glucosides based on the same aglycones have been identified. The effect of sugar substitution and acylation on chromatographic mobility and ESI ionisation and fragmentation are discussed.     

Screening and identification of major phytochemical compounds in seeds,sprouts and leaves of Tuscan black kale Brassica oleracea (L.) ssp acephala (DC) var. sabellica L.

We report the spectrophotometric determination of total polyphenols, flavonoids, glucosinolates and antioxidant activity in seeds, seedlings and leaves of Tuscan black kale. The highest content of phytochemicals was observed in 10 days sprouts and antioxidant activity was maximum in 2, 4 days seedlings. Identification and characterisation of phytochemicals were performed by mass spectrometry (MS), high resolution and tandem MS with electrospray ionisation mode. Low-molecular-weight metabolites were evidenced in seeds while metabolites at high m/z range were detected in cotyledons and leaves. MS spectra evidenced different phenolic compounds (flavonoid caffeoyl glucose, hydroxycinnamic acid sinapine) and glucosinolates (glucoerucin, glucobrassicin and glucoraphanin) in function of developmental stage; galactolipids ω3 and ω6 were observed in leaves. Identification of stages with the highest phytochemicals content encourages the consumption of black kale sprouts and young leaves. Our research can support food and pharmaceutical industries for production of health promoting products from black kale.     

Prediction of white cabbage (Brassica oleracea var. capitata) self-incompatibility based on neural network and discriminant analysis of complex electrophoretic patterns

Self-incompatibility (SI) of white cabbage (Brassica oleracea var. capitata), a biological mechanism triggering the ability to pollinate plant ovules, is modelled based on the statistical analysis of electrophoretic patterns of stigma extracts. The patterns obtained for 72 plants grown in three different seasons (2003–2005) have been explored with discriminant analysis and non-linear neural networks. The NN models obtained perform a flawless classification of SI and provide a useful and fast technique for SI prediction before the end of the season. The discriminant analysis turns out to be less effective (74% of good predictions), but together with sensitivity analysis of NN, it points out the important markers of the SI process (peaks 1, 3, 5, 15 and 18).     

Biological Investigation and Chemical Study of Brassica villosa subsp. drepanensis (Brassicaeae) Leaves

Brassica villosa subsp. drepanensis (Caruel) Raimondo & Mazzola, belonging to the Brassica oleracea complex, is a wild edible plant endemic to western Sicily and a relative of modern cultivated Brassica crops. In this study, the antioxidant properties, anti-inflammatory activities, enzymatic inhibition, and cytotoxicity in cancer cells of B. villosa subsp. drepanensis leaf ethanolic extract were analysed for the first time. In addition, its chemical profile was investigated partitioning the total 70% ethanol extract among ethyl acetate, n-butanol, and water to obtain three residues that were subjected to chromatographic separation. Two flavonol glycosides, a phenol glucoside, two amino acids, and purine/pyrimidine bases were obtained. The presence of the glucosinolate glucoiberin was detected in the water extract by UHPLC-MS analysis. The total polyphenol and flavonoid content of the 70% ethanol extract showed good antioxidant capacities and anti-inflammatory properties by reducing nitric oxide release and reactive oxygen species levels and increasing glutathione in lipopolysaccharide-stimulated RAW 264.7 cells. The extract inhibited the enzymatic activity of α-amylase, α-glucosidase, and, significantly, of lipase. The MTT assay showed that the extract did not affect the viability of normal HFF-1 and RAW 264.7 cells. Among the cancer cell lines tested, an antiproliferative action was only observed in CaCo-2. The cytotoxicity of the extract was further confirmed by LDH release assay and by the destabilization of the oxidative balance. Results confirmed the antioxidant properties of the crude extract responsible for the anti-inflammatory effect on healthy cells and cytotoxicity in cancer cells.     

Determination of fatty acids by high-performance liquid chromatography and fluorescence detection using precolumn derivatization with 9-fluorenylmethyl chloroformate

A new high-performance liquid chromatographic method is described for the determination of fatty acids in seed oils. The method was based on precolumn derivatization with 9-fluorenylmethyl chloroformate as a labeling agent and fluorescence detection. Fatty acids were extracted from the samples and subjected to derivatization with the reagent at 60°C for 10?min. The chromatographic separation of 14 fatty acids (C10–C22) was achieved on a combined loading compression octadecyl sulfate (CLC-ODS) column with a run time of 30?min. Three-step gradient elution of a mobile phase consisted of acetonitrile and water was used, and the signal was monitored at excitation and emission wavelengths of 265 and 315?nm, respectively. The method indicated favorable sensitivity and reproducibility for fatty acids’ derivatives. The detection limits, at a signal-to-noise ratio of 3, were 0.01–0.05?µg/ml and relative standard deviations (RSDs) were less than 0.27%. Excellent linear responses were observed with coefficients of 0.9995. This method was applied to quantify fatty acids in white, brown, and black sesame seeds’ oil.     

Identification of complex,naturally occurring flavonoid glycosides in kale (Brassica oleracea var. sabellica) by high‐performance liquid chromatography diode‐array detection/electrospray ionization multi‐stage mass spectrometry

Kale is a member of the Brassicaceae family and has a complex profile of flavonoid glycosides. Therefore, kale is a suitable matrix to discuss in a comprehensive study the different fragmentation patterns of flavonoid glycosides. The wide variety of glycosylation and acylation patterns determines the health‐promoting effects of these glycosides. The aim of this study is to investigate the naturally occurring flavonoids in kale. A total of 71 flavonoid glycosides of quercetin, kaempferol and isorhamnetin were identified using a high‐performance liquid chromatography diode‐array detection/electrospray ionization multi‐stage mass spectrometry (HPLC‐DAD/ESI‐MSⁿ) method. Of these 71 flavonol glycosides, 27 were non‐acylated, 30 were monoacylated and 14 were diacylated. Non‐acylated flavonol glycosides were present as mono‐, di‐, tri‐ and tetraglycosides. This is the first time that the occurrence of four different fragmentation patterns of non‐acylated flavonol triglycosides has been reported in one matrix simultaneously. In addition, 44 flavonol glycosides were acylated with p‐coumaric, caffeic, ferulic, hydroxyferulic or sinapic acid. While monoacylated glycosides existed as di‐, tri‐ and tetraglycosides, diacylated glycosides occurred as tetra‐ and pentaglycosides. To the best of our knowledge, 28 compounds in kale are reported here for the first time. These include three acylated isorhamnetin glycosides (isorhamnetin‐3‐O‐sinapoyl‐sophoroside‐7‐O‐D‐glucoside, isorhamnetin‐3‐O‐feruloyl‐sophoroside‐7‐O‐diglucoside and isorhamnetin‐3‐O‐disinapoyl‐triglucoside‐7‐O‐diglucoside) and seven non‐acylated isorhamnetin glycosides. Copyright © 2010 John Wiley & Sons, Ltd.     

Volatile Variation of Theobroma cacao Malvaceae L. Beans Cultivated in Taiwan Affected by Processing via Fermentation and Roasting

After being harvested, cacao beans are usually subjected to very complex processes in order to improve their chemical and physical characteristics, like tastefulness with chocolate characteristic flavors. The traditional process consists of three major processing stages: fermentation, drying, and roasting, while most of the fermentation is carried out by an on-farm in-box process. In Taiwan, we have two major cocoa beans, the red and the yellow. We proposed that the major factor affecting the variation in tastes and colors in the finished cocoa might be the difference between cultivars. To uncover this, we examined the effect of the three major processes including fermentation, drying and roasting on these two cocoa beans. Results indicated that the two cultivars really behaved differently (despite before or after processing with fermentation, drying, and roasting) with respect to the patterns of fatty acids (palmitic, stearic, oleic, and arachidonic); triacylglycerols:1,2,3-trioleoyl-glycerol (OOO); 1-stearoyl-2,3-oleoyl-glycerol (SOO); 1-stearoyl-sn-2-oleoyl-3-arachidoyl- glycerol (SOA); 1,3-distearyol-sn-2-oleoyl-glycerol (SOS); organic acids (citric, tartaric, acetic, and malic); soluble sugars (glucose and fructose); amino acids; total phenolics; total flavonoids; and volatiles. Our findings suggest that to choose specific processing conditions for each specific cocoa genotype is the crucial point of processing cocoa with consistent taste and color.     

Impact of Hydrothermal Treatments on Nutritional Value and Mineral Bioaccessibility of Brussels Sprouts (Brassica oleracea var. gemmifera)

Hydrothermal treatment of Brussels sprouts (Brassica oleracea var. gemmifera) induces both physical and chemical changes in nutrients and non-nutrients. It also affects the bioaccessibility of individual compounds. The aim of this study was to investigate the influence of hydrothermal treatment (boiling, steaming, and sous vide technique) on the concentration of the selected nutrients and non-nutrients in Brussels sprouts and in vitro bioaccessibility of the mineral components. It has been shown that, in terms of the leaching of nutrients and non-nutrients into the aqueous medium, traditional cooking in water involves the greatest percentage loss (the highest decrease in dry matter (11.8%), ash (13.3%), protein (10.4%), crude fat (43.3%), dietary fiber (9.5%), digestible carbohydrates (12.2%), and most of mineral components (7.6–39.8%)). In contrast, steam cooking and sous vide cooking of Brussels sprouts allow a higher level of preservation of the individual compounds. By using reduced process temperatures and vacuum packaging, sous vide cooking can be an alternative to traditional cooking to preserve the higher nutritional value of Brassica oleracea var. gemmifera (preservation of dry matter, ash, crude fat, and most of the mineral components at the level of the raw sample p ≤ 0.05).     

Hemp Seeds of the Polish ‘Bialobrzeskie’ and ‘Henola’ Varieties (Cannabis sativa L. var. sativa) as Prospective Plant Sources for Food Production

This publication characterizes the nutritional value of the Polish hemp seeds of the ‘Bialobrzeskie’ and ‘Henola’ varieties, including the profile/content of fatty acids and amino acids. Hemp seeds were found to be rich in protein, fat, and dietary fiber. Polyunsaturated fatty acids (PUFA) dominated the unsaturated fatty acids (UFA) profile. Their average share within the total fatty acids (FA) was as high as 75%. Linoleic acid belonging to this group accounted for 55% of the total FA. Lipid profile indices (Σ n − 6/Σ n − 3, Σ PUFA/Σ SFA, the thrombogenicity index, the atherogenicity index and the hypocholesterolemic/hypercholesterolemic ratio) proved the high nutritional value of hemp oil. Considering the tyrosine + phenylalanine and histidine contents, hemp protein exhibited a great degree of similarity to egg protein, which is known and valued for its high biological value.     

Determination of caffeoylquinic acids and flavonoids inCynara scolymus L. by high performance liquid chromatography

Summary The main phenolic compounds in dried extracts fromCynara scolymus (artichoke)—monocaffeoylquinic acids, dicaffeoylquinic acid, and flavonoids–have been separated by high-performance liquid chromatography. By use of a narrow bore C₁₈ column and an acidic mobile phase this HPLC method enabled improved separation within 31 min with significantly reduced solvent consumption compared with other methods. The method was validated to demonstrate its linearity, precision, accuracy, and robustness. Twelve commercial samples were analyzed. Monocaffeoylquinic acids were the most abundant phenolic compounds; the amounts present ranged from 0.48 to 4.24%. The amounts of dicaffeoylquinic acids and flavonoids were smaller—from 0.03 to 0.52%. The method is a good combination of efficiency and economy and should be especially useful for commercial applications.     

Determination of fatty acids in the seeds of Lepidium apetalum Willdenow,Descurainia sophia (L.) Webb ex Prantl,and Draba nemorosa L. by ultra-high-performance liquid chromatography equipped with a charged aerosol detector

Both the contents of fatty acids and the ratios of unsaturated to saturated fatty acids are important parameters for determining the nutritional values of oils. Thus, we herein evaluated the fatty acids present in the seed oils of Lepidium apetalum Willdenow, Descurainia sophia (L.) Webb ex Prantl, and Draba nemorosa L. as sources of Lepidii seu Descurainiae Semen seeds in Northeast Asian Countries. We developed a method based on ultra-high-performance liquid chromatography using a charged aerosol detector for the quantitative analysis of fatty acids in the seed oils. This technique is less time-consuming than previous methods as derivatization of the oils is not required. Our method was developed though the comparison of a UV detector with a charged aerosol detector, and various stationary phases and gradient programs were tested. In addition, method validation was carried out according to the International Conference on Harmonization guidelines with respect to linearity, precision, and accuracy. We found that the quantities of unsaturated fatty acids (6.051–282.376?mg/g) were higher than those of saturated fatty acids (0.855–12.548?mg/g) in all plant seed oils. The proposed method is reproducible and convenient, and therefore, is suitable for the quantitative analysis of fatty acids in plant oils.     

Chemical composition of volatile and fixed oils from of Salvia argentea L. (Lamiaceae) growing wild in Sicily

The chemical compositions of the essential oil and of the non-polar extracts (petroleum ether, dichloromethane) of the aerial parts (flowers, leaves and stems) of Salvia argentea L. were determined by GC-FID and gas chromatography–mass spectrometry analysis. 14-Hydroxy-α-humulene (40.1%) was recognised as the main constituents of the essential oil of S. argentea, together with 1,3,8-p-menthatriene (12.1%), globulol (7.4%) and β-sesquiphellandrene (5.8%). Tritriacontane (9.9% and 14.1%), heptacosane (8.4% and 10.5%), hentriacontane (8.3% and 10.9%), tetradecanal (8.4% and 10.2%) and methyldotriacontane (7.9% and 7.6%) were recognised as the main constituents of the extracts in petroleum ether and dichloromethane, respectively, whereas methyl linolenate (36.6% and 13.5%) and methyl myristoleate (10.5% and 18.5%) were recognised as the main constituents of the methylated extracts.     

Profiling of ornithine lipids in bacterial extracts of Rhodobacter sphaeroides by reversed-phase liquid chromatography with electrospray ionization and multistage mass spectrometry (RPLC-ESI-MS)

Ornithine lipids (OLs), a sub-group of the large (and of emerging interest) family of lipoamino acids of bacterial origin, contain a 3-hydroxy fatty acyl chain linked via an amide bond to the α-amino group of ornithine and via an ester bond to a second fatty acyl chain. OLs in extracts of Rhodobacter sphaeroides (R. sphaeroides) were investigated by high-performance reversed phase liquid chromatography (RPLC) with electrospray ionization mass spectrometry (ESI-MS) in negative ion mode using a linear ion trap (LIT). The presence of OLs bearing both saturated (i.e, 16:0, 17:0, 18:0, 19:0 and 20:0) and unsaturated chains (i.e., 18:1, 19:1, 19:2 and 20:1) was ascertained and their identification, even for isomeric, low abundance and partially co-eluting species, was achieved by low-energy collision induced dissociation (CID) multistage mass spectrometry (MSⁿ, n = 2–4). OLs signatures found in two R. sphaeroides strains, i.e., wild type 2.4.1 and mutant R26, were examined and up to 16 and 17 different OL species were successfully identified, respectively. OLs in both bacterial strains were characterized by several combinations of fatty chains on ester-linked and amide-linked 3-OH fatty acids. Multistage MS spectra of monoenoic amide-linked 3-OH acyl chains, allowed the identification of positional isomer of OL containing 18:1 (i.e. 9-octadecenoic) and 20:1 (i.e. 11-eicosenoic) fatty acids. The most abundant OL ([M−H]⁻ at m/z 717.5) in R. sphaeroides R26 was identified as OL 3-OH 20:1/19:1 (i.e., 3-OH-eicosenoic acid amide-linked to ornithine and esterified to a nonadecenoic chain containing a cyclopropane ring). An unusual OL (m/z 689.5 for the [M−H]⁻ ion), most likely containing a cyclopropene ester-linked acyl chain (i.e., OL 3-OH 18:0/19:2), was retrieved only in the carotenoidless mutant strain R26. Based on the biosynthetic pathways already known for cyclopropa(e)ne ring-including acyl chains, a plausible explanation was invoked for the enzymatic generation of this ester-linked chain in R. sphaeroides.     

Effect of temperature on the separation of chlorophenoxy acids and carbamates by capillary high-performance liquid chromatography and UV (or diode array) detection

In this work, the effect of temperature in isothermal and programmed modes on several chromatographic parameters such as retention factor, selectivity, resolution and plate number has been discussed. A critical comparison of isocratic/isothermal, gradient/isothermal and isocratic/program temperature modes has been made. Two representative families of pesticides have been selected for this study. One includes ionisable chlorophenoxy acids and two of their esters, some of which show similar polarities. The other one contains several weakly polar carbamates. Analysis was carried out using a reversed-phase capillary high-performance liquid chromatography (HPLC) system and focusing technique with UV or diode array detection (DAD).     

Effect of Botanical Extracts on the Growth and Nutritional Quality of Field-Grown White Head Cabbage (Brassica oleracea var. capitata)

Nutraceuticals and functional foods are gaining more attention amongst consumers interested in nutritious food. The consumption of foodstuffs with a high content of phytochemicals has been proven to provide various health benefits. The application of biostimulants is a potential strategy to fortify cultivated plants with beneficial bioactive compounds. Nevertheless, it has not yet been established whether the proposed higher plants (St. John’s wort, giant goldenrod, common dandelion, red clover, nettle, and valerian) are appropriate for the production of potential bio-products enhancing the nutritional value of white cabbage. Therefore, this research examines the impact of botanical extracts on the growth and nutritional quality of cabbage grown under field conditions. Two extraction methods were used for the production of water-based bio-products, namely: ultrasound-assisted extraction and mechanical homogenisation. Bio-products were applied as foliar sprays to evaluate their impact on total yield, dry weight, photosynthetic pigments, polyphenols, antioxidant activity, vitamin C, nitrates, micro- and macroelements, volatile compounds, fatty acids, sterols, and sugars. Botanical extracts showed different effects on the examined parameters. The best results in terms of physiological and biochemical properties of cabbage were obtained for extracts from common dandelion, valerian, nettle, and giant goldenrod. When enriched with nutrients, vegetables can constitute a valuable component of functional food.     

高效液相色谱荧光测定及质谱鉴定分析血清中胆汁酸

利用新型荧光试剂1,2-苯并-3,4-二氢咔唑-9-乙基苯磺酸酯(BDEBS)作柱前衍生化试剂,在EclipseXDB-C8色谱柱上,采用梯度洗脱对10种胆汁酸(BAs)荧光衍生物进行了优化分离。95℃下在二甲基亚砜(DMSO)溶剂中以柠檬酸钾作催化剂,衍生反应35min后获得稳定的荧光产物,衍生反应完全。荧光激发和发射波长分别为λex=333nm,λem=390nm。采用大气压化学电离源(APCISource)正离子模式,实现了血清中胆汁酸的定性测定。分析物的定量测定采用荧光法进行。线性回归系数均在0.9996以上,检出限为22.36~44.57×10-15mol。