Synthesis of pyrraline reference material

A simplified and improved method is described for the preparation of pyrraline, a lysine derivative from the advanced Maillard reaction and potential indicator for heat treatment of foods. The compound was obtained in a high degree of purity and with a yield of 31% fromN -t-butyloxycarbonyl-L-lysine after heating with 3-deoxy-D-erythro-hexos-2-ulose for 2 h at 70°C in the dry state, preparative fractionation of the resultingN -t-butyloxycarbonyl pyrraline with reverse-phase liquid chromatography and final deprotection of the intermediate compound with acetic acid.     

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.     

Preparation of red jujube powder with high content of Amadori compounds and higher antioxidant activity by controlling the Maillard reaction

Amadori compounds (ACs) are stable compounds produced in the early stage of the Maillard reaction (MR) with health benefits such as immunomodulatory, antithrombosis, and tumor-preventive effects. Jujube is a medicinal and edible fruit in China. It is rich in free amino acids and reducing sugar, but traditionally, little attention was paid to the formation of ACs when jujube was processed, neither the influence of ACs on health effects. In this paper, we aimed to increase ACs through controlling the MR during different heating processes of jujube powder with adjusted water content and find the most effective AC that contributed to the antioxidant effects of jujube powder. The optimal dry-heating conditions to produce ACs were as follows: The water activity was 0.294, the heating temperature was 90°C, and the time was 120 min. After processing, the ACs content of jujube powder was 18.55 ± 0.19 mg/g dry weight (DW), which was more than 100 times of those in the unheated jujube powder (0.153 ± 0.003 mg/g DW). Besides, the antioxidant activity of jujube powder after dry-heating process was higher than that of unheated one. As the most abundant AC in the dry-heated jujube powder (12.90 ± 0.75 mg/g DW), N-(1-deoxy-d -fructose-1-yl) proline (Fru-Pro) showed the highest antioxidant activity (62% of equivalent l -ascorbic acid) among 12 ACs in ferric reducing antioxidant power assay. This result provided a method to produce jujube product with high content of ACs and confirmed the positive contribution of Fru-Pro to the antioxidant activity of the jujube powder.     

Optimisation of the extraction of phenolic compounds and antioxidant activity from aerial parts of Bidens pilosa L. using response surface methodology

Response surface methodology was used to find the optimum ethanol concentration and temperature which maximises the antioxidant activity (AA) of hydroalcoholic extracts from aerial parts of Bidens pilosa L. A rotatable central composite design was used, and the extracts were characterised by the determination of solid concentration (SC), total flavonoid (TFC) and total polyphenol content (TPC). AA was determined through 2,2′‐azinobis (3‐ethylbenzothiazoline‐6‐sulphonic acid) diammonium salt (ABTS) and 2,2‐diphenyl‐1‐pycrylhydrazyl (DPPH) radical scavenging activity. Mathematical models showed the significant effects of each variable and allowed to select the optimum conditions of ethanol concentration (62.7%) and extraction temperature (66.2 °C). The optimised extract presented an AA of 804.9 ± 12.2 Trolox equivalent antioxidant capacity (TEAC) dry base (d.b.) for DPPH and 515.8 ± 31.8 TEAC d.b. for ABTS. It was observed that both TFC and TPC showed a good correlation with AA of the extracts.     

On the reaction of glyoxal with proteins

 The reaction of arginine and arginine derivatives with glyoxal under mild conditions revealed the formation of a previously unknown amino acid, designated as “Glarg”. ¹H-, ¹⁵N- and ¹³C-NMR analysis of the new compound elucidated its structure to be 1-(4-amino-4-carboxybutyl)-2-imino-5-oxo-imidazolidine. Experiments with solutions containing N ^α -acetylarginine and glyoxal showed that “Glarg” is formed quickly under physiological conditions, but is labile at higher temperatures as well as at low pH values. After incubation of β-casein with glyoxal, the formation of protein-bound “Glarg” in enzymatic hydrolysates via amino acid analysis could be demonstrated. Due to the fast reaction of glyoxal with arginine residues, under physiological conditions, proteins may act as scavengers for glyoxal. Received: 8 November 1996 / Revised version: 10 January 1997     

Studies on melanoidin-type colorants generated from the Maillard reaction of protein-bound lysine and furan-2-carboxaldehyde – chemical characterisation of a red coloured domaine

 The identification of a coloured substructure of melanoidin-type colorants is reported in the present paper. Brown-orange melanoidins with mass >10000 daltons were isolated from a thermally treated aqueous solution of casein and furan-2-carboxaldehyde using ultracentrifugation. After complete enzymatic digestion of the protein skeleton, two intense red coloured compounds were detected in the melanoidin hydrolysate by HPLC. These compounds were identified as the previously unknown chromophoric amino acid (S)-2-amino-6-{4-[(E)-1-formyl-2-(2-furyl)ethenyl]-5-(2-furyl)-2-[(E)-(2-furyl) methylidene]-2,3-dihydro-3-oxo-1H-pyrrol-1-yl}hexanoic acid and its 2-[(Z)-(2-furyl)methylidene] isomer, by using several NMR techniques, by MS, UV, and IR spectroscopy. The identification of these novel compounds verifies the idea that melanoidin-type colorants can be generated by a cross-linking reaction between a low molecular weight chromophore and a non-coloured high molecular weight biopolymer. Received: 19 August 1997 / Revised version: 24 October 1997     

Studies on melanoidin-type colorants generated from the Maillard reaction of protein-bound lysine and furan-2-carboxaldehyde – chemical characterisation of a red coloured domaine

 The identification of a coloured substructure of melanoidin-type colorants is reported in the present paper. Brown-orange melanoidins with mass >10000 daltons were isolated from a thermally treated aqueous solution of casein and furan-2-carboxaldehyde using ultracentrifugation. After complete enzymatic digestion of the protein skeleton, two intense red coloured compounds were detected in the melanoidin hydrolysate by HPLC. These compounds were identified as the previously unknown chromophoric amino acid (S)-2-amino-6-{4-[(E)-1-formyl-2-(2-furyl)ethenyl]-5-(2-furyl)-2-[(E)-(2-furyl) methylidene]-2,3-dihydro-3-oxo-1H-pyrrol-1-yl}hexanoic acid and its 2-[(Z)-(2-furyl)methylidene] isomer, by using several NMR techniques, by MS, UV, and IR spectroscopy. The identification of these novel compounds verifies the idea that melanoidin-type colorants can be generated by a cross-linking reaction between a low molecular weight chromophore and a non-coloured high molecular weight biopolymer. Received: 19 August 1997 / Revised version: 24 October 1997     

Residues of DDT and HCH in wheat samples collected from different states of India and their dietary exposure: A multicentre study

Under a multicentre study conducted by the Indian Council of Medical Research, 1712 samples of wheat grain/flour were collected from urban and rural areas in 11 states representing different geographical regions of India. These samples were analysed for residues of DDT (2,2-bis (p-chlorophenyl)-1,1,1-trichloro ethane) and different isomers of HCH (1,2,3,4,5,6-hexachloro cyclohexane, a mixture of isomers) by gas-liquid chromatography. Residues of DDT were detected in 59.4% of 1080 samples of wheat grain and in 78.2% of 632 samples of wheat flour. Different isomers of HCH were present in about 45-80% of the samples of wheat grain/flour. Medians of DDT and total HCH, respectively, for pooled samples of wheat grain were 0.013 and 0.035 mg kg^-1, while those for wheat flour were 0.01 and 0.02 mg kg^-1. Estimated daily intakes of DDT and different isomers of HCH through the consumption of wheat contaminated at their median and 90th percentiles constituted a small proportion of their acceptable daily intakes. Amongst the pesticide residues analysed, statutory maximum residue limits have been fixed only for γ-HCH in wheat in India, as 0.1 mg kg^-1 in wheat grain and zero in wheat flour. Residue levels of γ-HCH exceeded these maximum residue limits in five of 1080 samples of wheat grain and in 340 of 632 samples of wheat flour. The failure to meet the requirement of the γ-HCH maximum residue limit in large number of wheat flour samples was attributed to the fixation of practically unachievable zero limit. Comparing the previous studies and the present one, the levels of residues of DDT and HCH in wheat were significantly decreased.     

3‐Chloropropane‐1,2‐diol (3‐MCPD) in Soy Sauce: A Review on the Formation,Reduction, and Detection of This Potential Carcinogen

Soy sauce, a dark‐colored seasoning, is added to enhance the sensory properties of foods. Soy sauce can be consumed as a condiment or added during the preparation of food. There are 3 types of soy sauce: fermented, acid‐hydrolyzed vegetable protein (acid‐ HVP), and mixtures of these. 3‐Chloropropane‐1,2‐diol (3‐MCPD) is a heat‐produced contaminants formed during the preparation of soy sauce and was found to be a by‐product of acid‐HVP‐produced soy sauce in 1978. 3‐MCPD has been reported to be carcinogenic, nephrotoxic, and reproductively toxic in laboratory animal testing and has been registered as a chemosterilant for rodent control. 3‐MCPD is classified as a possible carcinogenic compound, and the maximum tolerated limit in food has been established at both national and international levels. The purpose of this review is to provide an overview on the detection of 3‐MCPD in soy sauce, its toxic effects, and the potential methods to reduce its concentration, especially during the production of acid‐HVP soy sauce. The methods of quantification are also critically reviewed with a focus on efficiency, suitability, and challenges encountered in analysis.     

A comparative study of the in vitro activity of iodopropynyl butylcarbamate and amphotericin B against Prototheca spp. isolates from European dairy herds

The objective of this study was to assess the in vitro effect of iodopropynyl butylcarbamate (IPBC) and amphotericin B (AMB) on Prototheca zopfii genotype 2 and Prototheca blaschkeae isolates recovered from dairy herds of Belgium, France, Italy, Germany, and Poland. The combination of IPBC with AMB on Prototheca isolates and toxicity of IPBC to the bovine mammary epithelial cells were also evaluated. The in vitro activity of IPBC and AMB against 96 isolates of P. zopfii genotype 2 and 42 isolates of P. blaschkeae was performed. Minimum inhibitory concentrations (MIC) and minimum algicidal concentrations (MAC) of IPBC and AMB were determined. To determine any synergistic, additive, or antagonistic effect of the combination of IPBC and AMB, 2-dimensional checkerboard combination tests were also performed to calculate fractional inhibitory concentrations. Cytotoxicity analysis of IPBC to the bovine mammary epithelial cell line was performed using a 3-(4,5-dimethyl-2-thiazol-2yl)-2,5-diphenyl tetrazolium bromide (MTT) assay. The MIC for 50 and 90% of isolates (MIC₅₀ and MIC₉₀, respectively) for IPBC were 4 and 8 mg/L versus 0.5 and 1 mg/L for AMB, respectively. The MIC profiles differed between P. zopfii genotype 2 and P. blaschkeae, with the latter species being more susceptible to both compounds. The MIC₅₀ and MIC₉₀ of IPBC were 4 and 8 mg/L for P. zopfii genotype 2 and 1 and 2 mg/L for P. blaschkeae, respectively. The MIC₅₀ and MIC₉₀ of AMB were both 1 mg/L for P. zopfii genotype 2 and 0.25 and 1 mg/L for P. blaschkeae, respectively. Both IPBC and AMB exhibited the ability to kill Prototheca spp. The MAC for 90% of isolates of IPBC was twice the MIC₉₀, whereas an 8-fold increase of the MIC₉₀ was algicidal in the case of AMB. Overall, the combined use of IPBC and AMB exhibited an increased algicidal effect, albeit the fractional inhibitory concentration index showed synergistic activity only against 3 P. zopfii genotype 2 isolates. For all the remaining isolates (87.5%), this combination produced only an additive effect. The MTT assay results showed both IPBC and AMB, at the concentrations employed in the study, to be nontoxic to the epithelial mammary gland cells (cell viability >90%). Notably, only IPBC at the highest concentration (i.e., 8 mg/L) exerted a slight cytotoxic effect on the cell line tested (mean cell viability: 88.54 ± 3.88 and 90.66 ± 3.0, after 2 and 4 h of MTT treatment, respectively). The anti-Prototheca activity of IPBC was here demonstrated for the first time. In addition, the combined use of IPBC with AMB enhanced each other's effect, creating an additive rather than synergistic interaction. Both agents, used at concentrations corresponding to MIC values against Prototheca spp., showed no toxic effect for the mammary epithelial cells. In conclusion, IPBC, used either alone or in combination with AMB, can be considered a promising option in the treatment armamentarium for protothecal mastitis in dairy cows.     

A review of malting and malt processing for whisky distillation

This paper encompasses a re‐evaluation of published literature and data regarding wort attenuation in malt distilleries raising questions and discussing how the conventional wisdom has changed over time and what questions still need to be answered. Current knowledge is summarized in the following four points: (a) Under normal malting conditions, starch granules are partially degraded by a combination of α‐amylase and α‐glucosidase. This complex can open up the granule at specific sites on the surface and create characteristic ‘pin‐hole’ lesions, which may be widened by secondary hydrolysis by α‐ and β‐amylase, limit dextrinase and α‐glucosidase (maltase). (b) All of these diastatic enzymes can survive mild kilning, probably by forming heat stable complexes on and within the starch granules and can continue a complete degradation of starch when mashed at ambient temperatures with glucose as the end product. (c) At normal mashing temperatures, starch granules gelatinize and dissolve with a concomitant rapid degradation to glucose, maltose, maltotriose and dextrins ranging from degree of polymerization (DP) 4 to > DP20. If there is immediate wort boiling after run‐off, this is the final composition of starch derived carbohydrates according to the conventional paradigm. (d) All malt worts also contain a small amount of panose, isopanose as well as glucosyl maltodextrins, based on a core of 6₂‐α‐glucosyl maltose (panose) or 6‐α‐maltosyl glucose (isopanose), which are remnants of the α‐amylase/glucosidase degradation of granular starch. These dextrins are resistant to the action of debranching enzymes and their concentration may vary between 4 and 8% of the malt extract, depending on the degree of modification of the host starch granules. They may be created at the active sites of this enzyme complex when the granule is gelatinized. In a conventional mash of unboiled distilling wort, the spectrum of wort dextrins produced from gelatinized starch is reduced to true ‘limit’ dextrins of DP4–8 by continued α‐amylolysis during early fermentation. These dextrins will contain side chains of either maltose or maltotriose residues surrounding the α‐1,6‐glucosidic linkage and can be debranched by limit dextrinase during late fermentation, leaving only the above glucosyl maltodextrins dextrins in the spent wash. Copyright © 2016 The Institute of Brewing & Distilling     

XIV. Yeast sequencing reports. A 43·5 kb segment of yeast chromosome XIV,which contains MFA2, MEP2, CAP/SRV2, NAM9, FKB1/FPR1/RBP1, MOM22 and CPT1, predicts an adenosine deaminase gene and 14 new open reading frames

A 43,481 bp fragment from the left arm of chromosome XIV of Saccharomyces cerevisiae was sequenced. A gene for tRNA^phe and 23 non-overlapping open reading frames (ORFs) were identified, seven of which correspond to known yeast genes: MFA2, MEP2, CAP/SRV2, NAM9, FKB1/FPR1/RBP1, MOM22 and CPT1. One ORF may correspond to the yet unindentified yeast adenosine deaminase gene. Among the 15 other ORFs, four exhibit known signatures, which include a protein tyrosine phosphatase, a cytoskeleton-associated protein and two ATP-binding proteins, four have similarities with putative proteins of yeast or proteins from other organisms and seven exibit no significant similarity with amino acid sequences described in data banks. One ORF is identical to yeast expressed sequence tags (EST) and therefore corresponds to an expressed gene. Six ORFs present similarities to human dbESTs, thus identifying motifs conserved during evolution. Nine ORFs are putative transmembrane proteins. In addition, one overlapping and three antisense ORFs, which are not likely to be functional, were detected. The sequence has been deposited in the EMBL data bank under Accession Number Z46843.     

Phytochemistry, traditional uses and pharmacology of Eugenia jambolana Lam. (black plum): A review

Eugenia jambolana Lam. (syn. Syzigium cumini (L.) SKEELS; S. jambolana DC; Family: Myrtaceae), commonly known as black plum or Jamun is a plant native to India. Annually the trees produce oblong or ellipsoid fruits (berries). They are green when raw and purplish black when fully ripe. The ripe fruits are sweetish sour to taste and are used to prepare health drinks, squashes, juices, jellies and wine. Studies have shown that the berries contain carbohydrates, minerals and the pharmacologically active phytochemicals like flavonoids, terpenes, and anthocyanins. Jamun is a plant with known ethnomedicinal uses. Before the discovery of insulin, Jamun was useful in the treatment of diabetes and is an integral part in the various alternative systems of medicine. Scientific studies have shown that the various extracts of Jamun possess a range of pharmacological properties such as antibacterial, antifungal, antiviral, anti-genotoxic, anti-inflammatory, anti-ulcerogenic, cardioprotective, anti-allergic, anticancer, chemopreventive, radioprotective, free radical scavenging, antioxidant, hepatoprotective, anti-diarrheal, hypoglycemic and antidiabetic effects. The present paper reviews these aspects and also addresses the lacunas in the existing knowledge.     

Efficiency and capacity of antioxidant rich foods in trapping peroxyl radicals: A full evaluation of radical scavenging activity

For the first time a variety of foods, characterized by high antioxidant activity, have been tested for the reactivity by which the system of antioxidants present in these foods competes for peroxyl radicals with poly-unsaturated fatty acids. The oxygraphic method we have used, on the basis of a rigorous kinetic model, permits to obtain the reactivity that is the Peroxyl Radical Trapping Efficiency (PRTE), beyond the Peroxyl Radical Trapping Capacity (PRTC) and to assign to each food characteristic values of these parameters, so facilitating their inter-comparison. In the analyzed foods the PRTE/PRTC ratio spans more than one order of magnitude, so reflecting the quality of antioxidants present in foods. According to the PRTE values and on the basis of the serving size the ranking of antioxidant food efficiency in trapping peroxyl radicals was blueberry > red chicory > coffee > pineapple ≈ red wine ≥ orange ≈ dark chocolate ≈ apple ≥ tea > pomegranate.     

The chemistry and medicinal uses of the underutilized Indian fruit tree Garcinia indica Choisy (kokum): A review

Garcinia indica Choisy Syn Brindonia indica, commonly known as kokum and belonging to Guttiferae family, is a plant native to certain regions of India. The trees yield fruits annually in the summer season during the months of March to May. The fruits are green when raw and red to dark purple when fully ripe. They are used to prepare juice, pickles and as acidulant in curries. In the traditional Indian system of medicine the Ayurveda and in various folk systems of medicine, the fruit rinds and leaves are used to treat various inflammatory ailments, rheumatic pain and bowel complaints. The kokum butter prepared from the seed is of both commercial and medicinal use. Chemical studies have shown that the rind contains protein, tannin, pectin, sugars, fat, organic acids like (−)-hydroxycitric acid, hydroxycitric acid lactone and citric acid; the anthocyanins, cyanidin-3-glucoside and cyanidin-3-sambubioside; and the polyisoprenylated phenolics garcinol and isogarcinol. Preclinical studies have shown that kokum or and some of its phytochemicals possess antibacterial, antifungal, anti-ulcerogenic, cardioprotective, anticancer, chemopreventive, free radical scavenging, antioxidant and anti-obesity effects. The present paper reviews the nutritional value, the phytochemical compounds, traditional uses and validated pharmacological properties of kokum.