Degradation of N‐(1‐Deoxy‐d‐xylulos‐1‐yl)glycine and N‐(1‐Deoxy‐d‐xylulos‐1‐yl)proline using thermal treatment

The formation and degradation of N‐(1‐Deoxy‐d ‐xylulos‐1‐yl)glycine and N‐(1‐Deoxy‐d ‐xylulos‐1‐yl)proline, derived from the secondary amine Maillard reaction in xylose‐amino acid model solutions, were detailed in this study. The identification and quantitative analysis of N‐(1‐Deoxy‐d‐ xylulos‐1‐yl)glycine and N‐(1‐Deoxy‐d‐ xylulos‐1‐yl)proline were carried out using high‐performance anion‐exchange chromatography and high‐performance liquid chromatography. The formation of intermediate and advanced products derived from N‐(1‐Deoxy‐d‐ xylulos‐1‐yl)glycine and N‐(1‐Deoxy‐d‐ xylulos‐1‐yl)proline was also tested using an UV‐Vis spectrophotometer to gain a better comparing of the degradation process of the two important Maillard reaction products using thermal treatment. Results showed that the degradation of N‐(1‐Deoxy‐d‐ xylulos‐1‐yl)glycine was more significant than N‐(1‐Deoxy‐d‐ xylulos‐1‐yl)proline. Moreover, xylose was tested in the degradation products of both N‐(1‐Deoxy‐d‐ xylulos‐1‐yl)glycine and N‐(1‐Deoxy‐d‐ xylulos‐1‐yl)proline, which indicated that the degradation of N‐substituted 1‐amino‐1‐deoxyketoses was a reversible reaction to form reducing sugar.     

Absorption of N-phenylpropenoyl-L-amino acids in healthy humans by oral administration of cocoa (Theobroma cacao)

Besides flavan-3-ols, a family of N-phenylpropenoyl-L-amino acids (NPAs) has been recently identified as polyphenol/amino acid conjugates in the seeds of Theobroma cacao as well as in a variety of herbal drugs. Stimulated by reports on their biological activity, the purpose of this study was to investigate if these amides are absorbed by healthy volunteers after administration of a cocoa drink. For the first time, 12 NPAs were quantified in human urine by means of a stable isotope dilution analysis with LC-MS/MS (MRM) detection. A maximum amount was found in the urine taken 2 h after the cocoa consumption. The highest absolute amount of NPAs excreted with the urine was found for N-[4'-hydroxy-(E)-cinnamoyl]-L-aspartic acid (5), but the highest recovery rate (57.3 and 22.8%), that means the percentage amount of ingested amides excreted with the urine, were determined for N-[4'-hydroxy-(E)-cinnamoyl]-L-glutamic acid (6) and N-[4'-hydroxy-3'-methoxy-(E)-cinnamoyl]-L-tyrosine (13). In order to gain first insights into the NPA metabolism in vivo, urine samples were analyzed by LC-MS/MS before and after beta-glucuronidase/sulfatase treatment. As independent of the enzyme treatment the same NPA amounts were found in urine, there is strong evidence that these amides are metabolized neither via their O-glucuronides nor their O-sulfates. In order to screen for caffeic acid O-glucuronides as potential NPA metabolites, urine samples were screened by means of LC-MS/MS for caffeic acid 3-O-beta-D-glucuronide and 4-O-beta-D-glucuronide. But not even trace amounts of one of these glucuronides were detectable, thus excluding them as major NPA metabolites and underlining the importance of future investigations on a potential O-methylation or reduction of the N-phenylpropenoyl moiety in NPAs.     

Urinary 2-ethyl-3-oxohexanoic acid as major metabolite of orally administered 2-ethylhexanoic acid in human

Human metabolism of 2-ethylhexanoic acid (2-EHA), which is a known metabolite of important phthalates, was investigated using 2-EHA-contaminated food. The results of our studies reveal that the major catabolic pathway of 2-EHA in human is beta-oxidation. The dominant final urinary metabolite was identified and quantified as 3-oxo-2-ethylhexanoic acid (3-oxo-2-EHA), but only after immediate methylation of the extract from urine and prior to GC-MS analysis. Former studies without the precaution of immediate methylation had found 4-heptanone as the major metabolite, which is obviously an artifact arising from the decarboxylation of 3-oxo-2-EHA.     

Improved determination of D-glucosamine hydrochloride in health foods by HPLC using 7-fluoro-4-nitrobenzo-2-oxa-l,3-diazole as a derivative

Abstract: This article presents an improved method to detect d ‐glucosamine hydrochloride in health foods. A simple precolumn derivatization procedure with 7‐flouro‐4‐nitrobenzo‐2‐oxa‐1,3‐diazole (NBD‐F) reagent was employed. The separation of the derivatized d ‐glucosamine hydrochloride (NBD‐d ‐glucosamine hydrochloride) was performed using a mobile phase consisting of acetonitrile, potassium dihydrogen phosphate (0.01 mol/L), and trifluoroacetic acid (350:649.74:0.26, volume ratio) at a flow rate of 1.0 mL/min with the column temperature 35 °C. Under the optimum chromatographic conditions, the peak area of NBD‐d ‐glucosamine hydrochloride compared with its absolute value of the peak area of NBD‐d ‐glucosamine hydrochloride in a standard solution concentration range from 1.0 to 500.0 mg/L showed a good linear calibration (R = 0.9999). Recoveries, at spiked concentrations of 10.0, 40.0, and 500.0 mg/L, varied between 97.2% and 102.6% with relative standard deviations ranging from 0.4% to 1.5%. The present method provides sufficient sensitivity as reflected by the values of limit of detection (LOD) and limit of quantification (LOQ). LOD was determined from the signal‐to‐noise ratios (S/N) of NBD‐d ‐glucosamine hydrochloride peak of at least 3 in the recovery test at 0.02 mg/L, and the estimated LOQ was 0.06 mg/L (S/N = 10). The proposed method was successfully applicable to detect d ‐glucosamine hydrochloride in health foods and drugs containing a variety of complex materials.     

Identifications of inhibitors of IgE production by human lymphocytes isolated from ‘Cha Chuukanbohon Nou 6’ tea leaves

BACKGROUND: Tea (Camellia sinensis L.) is consumed all over the world and in especially large quantities in Japan and China, where it has been used not only as a daily beverage but also for medicinal purposes for thousands of years. Tea has been found to exhibit various bioregulatory activities, including antiallergic, anticarcinogenic, antimetastatic, antioxidative, antihypertensive, antihypercholesterolemic, anti‐dental caries and antibacterial effects, and to influence intestinal flora. RESULTS: Cha Chuukanbohon Nou 6 is a tea cultivar improved by the National Institute of Vegetable and Tea Science (NIVTS) in Japan. On comparing chemical constituents of 11 varieties of tea leaves by high‐performance liquid chromatography, we found two new major compounds in Cha Chuukanbohon Nou 6. Nuclear magnetic resonance spectroscopy revealed these compounds to be theogallin and 1,2‐di‐O‐galloyl‐4,6‐O‐(S)‐hexahydroxydiphenoyl‐β‐D ‐glucopyranose. The two were similar in chemical structure to strictinin, an inhibitor of immunoglobulin (Ig) production. Thus their effects on the production of Igs by peripheral blood lymphocytes were tested. Both compounds, like strictinin, inhibited IgE production. CONCLUSION: The results suggest Cha Chuukanbohon Nou 6 to be the basis of an antiallergic beverage. Copyright © 2009 Society of Chemical Industry     

The impact of the various chemical and physical factors on the degradation rate of bronopol

Bronopol (2‐bromo‐2‐nitropropane‐1,3‐diol) is used as preservative in cosmetic industry. Its main role in commercial products consists in protection of the cosmetic composition stability by inhibiting the development of micro‐organisms. Unfortunately, preservatives can also undergo the degradation processes. The aim of examinations was to prove that bronopol decomposes in aqueous solutions and storage conditions have a significance influence on its degradation rate. High‐performance liquid chromatography method (methanol/water with hydrochloric acid 5:95 v/v) with spectrophotometric detection (210 nm) was used for examining the decomposition rate of bronopol. The impact of chemical (addition of cosmetics components: citric acid and/or sodium dodecylsulfate) and physical (elevated and ambient temperature, sunlight or ultraviolet radiation and air access) factors has been elaborated. Bronopol decomposes most rapidly (independently on the sample surrounding conditions) when it is in solution with sodium dodecylsulfate, the inverse dependence is observed in the presence of two compounds – citric acid and sodium dodecylsulfate. Additionally, the elevated temperature causes the acceleration of decomposition. Bronopol degradation by‐products were also identified as methanol, formic acid, tris(hydroxymethyl)methane and 2‐bromo‐2‐nitroethanol.     

Reduction of fumonisin B₁ in corn grits by twin-screw extrusion

Abstract: This study was designed to investigate the fate of fumonisins in flaking corn grits during twin‐screw extrusion by measuring fumonisin B₁ (FB₁) and its analogs with a mass balance approach. Food grade corn grits and 2 batches of grits contaminated with FB₁ at 10 and 50 μg/g by Fusarium verticillioides M‐2552 were processed with or without glucose supplementation (10%, w/w) with a twin‐screw extruder. Extrusion reduced FB₁ in contaminated grits by 64% to 72% without glucose and 89% to 94% with added glucose. In addition, extrusion alone resulted in 26% to 73% reduction in the levels of fumonisin B₂ and fumonisin B₃, while levels of both mycotoxins were reduced by >89% in extruded corn grits containing 10% glucose. Mass balance analysis showed that 38% to 46% of the FB₁ species detected in corn extruded with glucose was N‐(deoxy‐D‐fructos‐1‐yl)‐FB₁, while 23% to 37% of FB₁ species detected in extruded corn grits with and without added glucose was bound to the matrix. It was also found that the hydrolyzed form of FB₁ was a minor species in extruded corn grits with or without added glucose, representing <15% of the total FB₁ species present. Less than 46% of FB₁ originally present in corn grits could be detected in the fumonisin analogues measured in this study. Research is needed to identify the reaction products resulting from extrusion processing of fumonisin‐contaminated corn products. Practical Application: Twin‐screw extrusion is widely used in food industry for its versatility. This technology may reduce the level of fumonisins in corn particularly with added glucose.     

Thermodynamic characteristics of copigmentation reaction of acylated anthocyanin isolated from blue flowers of Scutellaria baicalensis Georgi with copigments

Anthocyanin extracts are increasingly used as food colorants. So far, anthocyanins have not been broadly used in foods and beverages, since they are not as stable as synthetic dyes. Copigmentation between anthocyanins and copigments is the main colour‐stabilizing mechanism. The process of copigmentation between isolated acylated anthocyanin and rutin, QSA or baicalin has been observed using UV–vis spectrophotometry. The thermodynamic parameters were correlated to the structure and position of the substituents in the interacting molecules. The acylated anthocyanin was isolated from cultivars of Scutellaria baicalensis Georgi flowers and purified by column chromatography by our own method and has been identified by ¹H‐/¹³C‐NMR spectroscopy and electrospray mass spectrometry as delphinidin‐3‐O‐(6‐O‐malonyl)‐β‐D ‐glucopyranosyl‐5‐O‐β‐D ‐glucopyranoside. Copyright © 2004 Society of Chemical Industry     

Increased ethylene biosynthesis elevates incidence of chilling injury in cold‐stored ‘Amber Jewel’ Japanese plum (Prunus salicina Lindl.) during fruit ripening

Mature ‘Amber Jewel’ Japanese plum fruit were stored at 0 or 5 °C for 3 and 6 weeks to investigate their effects on ethylene (C₂H₄) biosynthesis during ripening at ambient temperature in the development of chilling injury (CI) and fruit quality. CI (internal breakdown and browning) and fruit softening were higher during ripening, in the fruit stored at 5 °C than 0 °C, irrespective of storage period (SP). C₂H₄ production and activities of 1‐aminocyclopropane‐1‐carboxylic acid synthase (ACS) and 1‐aminocyclopropane‐1‐carboxylic acid oxidase (ACO) enzymes, and 1‐aminocyclopropane‐1‐carboxylic acid (ACC) content were higher during ripening in fruit stored at 5 °C than 0 °C. The fruit stored at 5 °C also exhibited higher respiration rate and higher soluble solids concentration/titratable acidity ratio. In conclusion, increase in storage temperature and SP elevates the activities of ACS and ACO enzymes and consequently C₂H₄ production which leads to the development of CI in plum fruit with advancement of ripening.     

In vitro antioxidant activity of different cultivars of banana flower (Musa paradicicus L.) extracts available in India

Abstract: Six different cultivars of banana flowers (Musa paradicicus) (Kathali, Bichi, Shingapuri, Kacha, Champa, and Kalabou) were analyzed for the content of polyphenol expressed as gallic acid equivalent and flavonoid expressed as quercetein equivalent, and the in vitro total antioxidative activities of the flower extracts were compared with standard and expressed as trolox equivalent. The reducing power, 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) and 2,2‐azinobis(3‐ethylbenzothiazoline‐6‐sulfonic acid) radical cation (ABTS?⁺) scavenging activities, inhibition of lipid peroxidation in a linoleic acid emulsion system, and liposome peroxidation system were measured and compared with respective standard antioxidants. Iron‐mediated Fenton reaction was carried out to evaluate the protective effect of the extract of banana flower (Kacha cultivar) against H₂O₂‐induced DNA damage. The Kacha variety contains the maximum amount of polyphenol (11.94 ± 0.03 mg of gallic acid equivalent/g of dry weight) and flavonoid (0.174 ± 0.001 g of quercetin equivalent/g of polyphenol). It also has the highest total antioxidant capacity, DPPH radical scavenging activity, and ABTS?⁺ radical scavenging activity with a least EC₅₀ value of 0.051 mg/mL. Hepatic cell damage in iron‐mediated Fenton reaction caused by free radicals is reduced by the banana flower extract. On the basis of the results obtained, the banana flowers are found to be a potential source of natural antioxidants. This is the first report on the antioxidant properties of the extracts from banana flowers. The study suggests that the flowers of M. paradicicus that are found in India and consumed as vegetable can provide valuable functional ingredients that help in the prevention of oxidative stress.