The origin of methylglyoxal in New Zealand manuka (Leptospermum scoparium) honey

Methylglyoxal in New Zealand manuka honey has been shown to originate from dihydroxyacetone, which is present in the nectar of manuka flowers in varying amounts. Manuka honey, which was freshly produced by bees, contained low levels of methylglyoxal and high levels of dihydroxyacetone. Storage of these honeys at 37 °C led to a decrease in the dihydroxyacetone content and a related increase in methylglyoxal. Addition of dihydroxyacetone to clover honey followed by incubation resulted in methylglyoxal levels similar to those found in manuka honey. Nectar washed from manuka flowers contained high levels of dihydroxyacetone and no detectable methylglyoxal.     

HPLC-Q-TOF/MS分析脐橙果实中的类黄酮

采用高效液相色谱分离、串联四极杆-飞行时间质谱正离子模式检测‘红肉脐橙’和‘清家脐橙’果实黄皮层、白皮层、囊衣和汁胞中的主要类黄酮。根据保留时间、精确质荷比、二级质谱以及标准品化合物验证,确定了脐橙不同组织中含量较高的甜橙黄酮、川陈皮素等13种类黄酮。依据峰面积比较相对含量,认为脐橙黄皮层中类黄酮含量丰富,白皮层和囊衣中类黄酮含量次之,汁胞中类黄酮相对含量较少。黄皮层中以甜橙黄酮、川陈皮素和橘皮素等多甲氧基黄酮为主,而白皮层、囊衣和汁胞中的类黄酮以橙皮苷、柚皮苷为主。脐橙相同组织如白皮层、囊衣和汁胞中类黄酮的相对含量在品种间无显著差异,但橙皮苷、3,5,6,7,3',4'-六甲氧基黄酮和橘皮素在两品种的黄皮层中相对含量差异显著。研究结果为进一步研究和综合利用脐橙的活性物质提供了科学依据。     

Isolation by HPLC and characterisation of the bioactive fraction of New Zealand manuka (Leptospermum scoparium) honey

Using HPLC a fraction of New Zealand manuka honey has been isolated, which gives rise to the non-peroxide antibacterial activity. This fraction proved to be methylglyoxal, a highly reactive precursor in the formation of advanced glycation endproducts (AGEs). Methylglyoxal concentrations in 49 manuka and 34 non-manuka honey samples were determined using a direct detection method and compared with values obtained using standard o-phenylenediamine derivatisation. Concentrations obtained using both the methods were similar and varied from 38 to 828 mg/kg.     

Flavonoids and phenolic acids from the aerial parts of Alyssum alyssoides L. (Brassicaceae)

Two phenolic acids (1 and 2) and seven flavonoids (3–9) were isolated from the aerial parts of Alyssum alyssoides (Brassicaceae). All these compounds (1–9) were isolated from this particular species for the first time. Their structures were identified, on the basis of MS and NMR spectra as: p-hydroxy-benzoic acid (1), 3-methoxy-4-hydroxybenzoic acid (vanillic acid) (2), kaempferol 3-O-β-D-glucopyranoside (astragalin) (3), kaempferol 3-O-(6″-α-L-rhamnopyranosyl)-β-D-glucopyranoside (nicotiflorin) (4), quercetin 3-O-β-D-glucopyranoside (isoquercetin) (5), quercetin 3-O-β-D-galactopyranoside (hyperoside) (6), isorhamnetin 3-O-β-D-glucopyranoside (7), isorhamnetin 3-O-β-D-galactopyranoside (8) and isorhamnetin 3-O-(6″-α-L-rhamnopyranosyl)-β-D-glucopyranoside (narcissin) (9). The chemotaxonomic significance of these compounds was summarized.     

Fatty acid derivatives and their use as CFPP additives in biodiesel

One of the main drawbacks of the use of biodiesel is its bad behavior at low temperatures. In this work, we show that it is possible to take profit of the presence of free fatty acids in the starting materials used for biodiesel production (i.e. reused oils) by synthesizing additives able to improve cold flow properties. The synthesis of fatty acid derivatives have been successfully carried out by esterification of stearic, oleic and linoleic acids with bulky linear and cyclic alcohols and by epoxidation of methyl oleate and subsequent ring-opening reaction with the same alcohols. The study of crystallization patterns of pure derivatives by DSC and optical microscopy revealed the improvement of cold properties of biodiesel. Blends of biodiesel with up to 5% of some of these compounds allowed a decrease of CFPP (Cold Filter Pour Point). Both observations reveal the utility of these compounds as cheap and renewable additives.     

Facile synthesis of (Z)-tetracos-5-enoic acid and racemic cis-4-(2-octadecylcyclopropane-1-yl)-butanoic acid

(Z)-tetracos-5-enoic acid and racemic cis-4-(2-octadecylcyclopropane-1-yl)-butanoic acid have been prepared from 1-eicosene by a new facile route. Periodic acid cleavage of the epoxide of 1-eicosene gave nonadecanal which was condensed with 4-carboxybutyltriphenylphosphonium bromide to give predominately (Z)-tetracos-5-enoic acid. Simmons-Smith type cyclopropanation of (Z)-tetracos-5-enoic acid gave a minor proportion of racemic cis-4-(2-octadecylcyclopropane-1-yl)-butanoic acid accompanied by major amounts of its methyl ester.     

Lipid, fatty acid and protein utilization during lecithotrophic larval development of Lithodes santolla (Molina) and Paralomis granulosa (Jacquinot)

During the larval development of the subantarctic king crab, Lithodes santolla, and stone crab, Paralomis granulosa, we compared changes in the carbon, fatty acid and protein contents of larvae reared under constant conditions from hatching to metamorphosis, either in presence or absence of food (Artemia spp. nauplii). In both species the feeding condition had no influence on any of the chemical parameters studied, indicating a fully lecithotrophic (i.e. non-feeding) mode of development from hatching of the first zoea to metamorphosis of the late megalopa. Dry mass and carbon contents at hatching were similar in the larvae of both species, but L. santolla contained initially higher total amounts of fatty acids and protein than P. granulosa. Both species utilized considerable portions of their total fatty acid pool which decreased logarithmically throughout the time of development. At metamorphosis, it was almost exhausted in P. granulosa, while L. santolla had consumed only about 60%. Protein utilization, in contrast, was higher in L. santolla (40%) than in P. granulosa (20%). Triacylglycerol was the principal storage lipid in both species, accounting initially for about 75% of the lipid fraction; it was strongly utilized during larval development. Phospholipid constituted the second largest lipid class; it also decreased in P. granulosa, but to a lesser extent in L. santolla. The major fatty acids of both species were 18:1(n−9), 20:5(n−3) and 16:0 as well as, in lower proportions, 18:1(n−7), 22:6(n−3), 16:1(n−7) and 18:0. Monounsaturated fatty acids represented the dominant group in L. santolla, whereas P. granulosa contained similar amounts of mono- and polyunsaturated fatty acids. In L. santolla, monounsaturated fatty acids, especially 16:1(n−7), were preferentially utilized as compared to polyunsaturates. Due to a particularly strong lipid utilization in P. granulosa, all individual fatty acids were largely depleted at metamorphosis, showing similar extents of consumption. L. santolla had higher initial lipid and protein stores that seem to be used more economically as compared to P. granulosa.     

Botanical and geographical origin of honey from the dry and humid Chaco ecoregions (Argentina)

To characterise the botanical and geographical origin of honey from the Chaco region (Argentina), 189 samples of honey were examined for pollen content using standard methodology. A general feature was the high representation of pollen from native arboreal plants, mainly of Fabaceae and the scarcity of pollen from herbaceous plants. One hundred and twenty-three samples proved to be unifloral. The most common were from: Prosopis alba, Helianthus annuus, Sarcomphalus mistol, Eugenia uniflora and Schinopsis balansae followed by those of Copernicia alba, Trithrinax schizophylla, Tessaria integrifolia, Baccharis-Eupatorium, Cynophalla retusa, Schinopsis lorentzii, Gleditsia amorphoides, Heimia salicifolia, Pisonia zapallo, Sagittaria montevidensis and Bulnesia sarmientoi. The pollen spectrum allowed the Dry and Humid Chaco ecoregions to be distinguished. The presence of pollen from cultivated crops and naturalised plants reflects a transitional complex between both ecoregions.     

Main phospholipids and their fatty acid composition in muscle and cephalothorax of the edible Mediterranean crustacean Palinurus vulgaris (spiny lobster)

The total lipids of muscle and cephalothorax of Mediterranean lobster Palinurus vulgaris were found to be 1.0% and 2.4% of the wet tissue of which the phospholipids represented 66.5% and 47.5%, respectively. The main PhL saturated, monounsaturated and polyunsaturated fatty acids in muscle and cephalothorax were C16:0, C18:0, C18:1ω-9, C18:1ω-7, C20:4ω-6, C20:5ω-3 and C22:6ω-3. 2-OH C14:0 and cyclo-17:0 fatty acids were also identified though in low percentages. The main individual PhL in muscle were found to be phosphatidylcholine (53.5%), 72.0% of which corresponded to the structure of 1,2-diacyl-glycerocholine while the rest 28.0% to 1-O-alkyl-2-acyl-glycerocholine or 1-O-(1-alkenyl)-2-acyl-glycerocholine and phosphatidylethanolamine (19.3%), 75.0% of which corresponded to the structure of 1,2-diacyl-glyceroethanolamine and 25% to 1-O-alkyl-2-acyl-glyceroethanolamine or 1-O-(1-alkenyl)-2-acyl-glyceroethanolamine. Cephalothorax main PhL were found to be PC and PE (66.4% and 18.8%, respectively). In muscle and cephalothorax PC ω-3 fatty acids amounted 7.78% and 8.60%, while in PE amounted 30.77% and 23.65% respectively. Furthermore, in both tissues PhL, cardiolipine phosphatidylserine, phosphatidylinositol, sphingomyelin and lysophosphatidylcholine, were also found.     

UPLC/MS based method for quantitative determination of fatty acid composition in Gram-negative and Gram-positive bacteria

Quantitative fatty acid composition of microorganisms at various growth space points is required for understanding membrane associated processes of cells, but the majority of the relevant publications still restrict to the relative compositions. In the current study, a simple and reliable method for quantitative measurement of fatty acid content in bacterial biomass without prior derivatization using ultra performance liquid chromatography-electrospray ionization mass spectrometry was developed. The method was applied for investigating the influence of specific growth rate and pH on the fatty acid profiles of two biotechnologically important microorganisms — Gram-negative bacteria Escherichia coli and Gram-positive bacteria Lactococcus lactis grown in controlled physiological states. It was found that the membranes of slowly growing cells are more rigid and that the fatty acid fraction of the cells of L. lactis diminishes considerably with increasing growth rate.     

Oviposition deterrents from eggs of the cotton bollworm, Helicoverpa armigera (Lepidoptera: Noctuidae): chemical identification and analysis by electroantennogram

Our previous results showed that an extract of the abdomens of mated females of the cotton bollworm, Helicoverpa armigera, deterred oviposition of conspecifics. In this paper, we found that the extract, in addition to reducing conspecifics’ oviposition, could elicit strong electroantennogram responses from mated females. The EAG elicitors mainly came from mature chorionated eggs in the ovarioles. Laid eggs or their surface extract evoked similar EAG responses. The main chemical components of the EAG elicitors from mature chorionated and laid eggs were myristic, palmitic, stearic, and oleic acids. A blend of authentic fatty acids at the ratio found in the laid eggs and in an amount equivalent to 100 laid eggs mimicked the EAG response and deterring effect. Moreover, these four oviposition-deterring fatty acids and their corresponding methyl esters evoked significantly higher EAG responses from both mated females and males than hexane blank and background. The EAG values differed among the test chemicals and between sexes. These results demonstrate that the four fatty acids from eggs are at least partially responsible for the oviposition-deterring effect of the extract from the abdomens of mated female H. armigera and that the moths may detect these chemicals olfactorily by antennae.     

Characterisation of ovine Bordetella parapertussis isolates by analysis of specific endotoxin (lipopolysaccharide) epitopes, filamentous haemagglutinin production, cellular fatty acid composition and antibiotic sensitivity

Abstract Isolates of Bordetella parapertussis , recovered from sheep or man, were characterised by reaction with specific anti- Bordetella lipopolysaccharide monoclonal antibodies, production of filamentous haemagglutinin, fatty acid patterns, and antibiotic sensitivity. Generally, the isolates lay within one of four groups, with separation of the ovine isolates into two groups. Reactions with specific monoclonal antibodies against lipopolysaccharide separated the ovine isolates into these two groupings. Analysis of the cellular fatty acid compositions by cluster analysis differentiated between the human and the ovine strains and also showed variation within the ovine isolates. When the production of filamentous haemagglutinin was analysed in an ELIS A system, a similar pattern emerged. Varying concentrations of filamentous haemagglutinin (11–429 ng (mg total protein)⁻¹) were extracted from the human isolates and the one group of ovine isolates with no significant protein detected in the other ovine group. These studies demonstrate variation between and within B. parapertussis isolates recovered from two mammalian sources.     

Solid-liquid phase behavior of binary fatty acid mixtures. 1. Oleic acid/stearic acid and oleic acid/behenic acid mixtures

Solid-liquid phase behavior of binary fatty acid mixtures was investigated by means of differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR) for the mixture composed of oleic acid (OA) and stearic acid (SA) and that composed of OA and behenic acid (BA). The DSC results provided a monotectic type T-X phase diagram for these mixtures, from which it was suggested that the two fatty acid species are completely immiscible in a solid phase regardless of the two polymorphs of OA, i.e., alpha-form or gamma-form. The solid phase immiscibility was confirmed by the FT-IR observation that the spectra obtained for the mixtures correspond to the superposition of the two spectra for respective components. Thermodynamic analysis of liquidus line demonstrated that OA and SA form an ideal mixture in a liquid phase, whereas the mixing of OA and BA in a liquid phase is slightly non-ideal.     

Simultaneous UPLC MS/MS analysis of endogenous jasmonic acid,salicylic acid,and their related compounds

Jasmonic acid (JA) and salicylic acid (SA) are plant hormones involved in plant growth and development. Recent studies demonstrated that presence of a complex interplay between JA and SA signaling pathways to response to pathogenesis attack and biotic stresses. To our best knowledge, no method has existed for simultaneous analyses of JA, SA, and their related compounds. Especially, the glucosides are thought to be the storages or the inactivated compounds, but their contribution should be considered for elucidating the amount of the aglycons. It is also valuable for measuring the endogenous amount of phenylalanine, cinnamic acid, and benzoic acid that are the biosynthetic intermediates of SA due to the existence of isochorismate pathway to synthesize SA. We established this method using deuterium labeled compounds as internal standards. This is the first report of simultaneous analysis of endogenous JA, SA, and their related compounds. Measuring the endogenous JA, SA, and their related compounds that had been accumulated in tobacco plants proved the practicality of the newly developed method. It was demonstrated that accumulation of JA, SA and their related compounds were induced in both case of TMV infection and abiotic stresses.     

Horse chestnut (Aesculus hippocastanum L.) seed fatty acids,flavonoids and heavy metals plasticity to different urban environments

Horse chestnut (Aesculus hippocastanum L.) is a deciduous tree which is widely used on urban green spaces in Serbia. Also, the seed of horse chestnut is an important raw material in pharmaceutical industry, owing to its medicinal properties. In this study, the content of fatty acids, flavonoids, aescin and heavy metals in seeds of 11 horse chestnut genotypes growing in urban conditions was investigated. A total of 16 fatty acids were identified. Unsaturated fatty acids in seed samples were the most abundat. Among the saturated fatty acids, palmitic acid was the dominant one, with a total average content of 8.12%. Oleic acid, with the total average content of 53.46%, was the most abundant unsaturated fatty acid. The results of this study indicated the presence of the following flavonoids: quercetin, kaempferol and rutin. Rutin was the most abundant, averagely contributing with 6.071 μg/g to the total quantified polyphenolics in all samples. The total aescin content ranged from 0.82% to 4.16%. Fruits of park and street trees from small- and middle-sized cities can be used in pharmaceutical industry as raw material. Differences between different urban site categories and localities were detected, which indicates the biochemical plasticity of the seeds to urban morphology.     

Phospholipid fatty acid and infra-red spectroscopic analysis of a sulphate-reducing consortium

Abstract In order to validate unusual fatty acids as biomarkers for sulphate-reducing bacteria, selective conditions were arranged for the enrichment of a marine glutamate-fermenting bacterium which made hydrogen and acetate available for oxidation via the respiration of sulphate. Under these conditions the complete oxidation of glutamate via sulphate reduction accounted for 84% of the available electron equivalents. Fatty acid biomarkers for hydrogen-oxidizing Desulfovibrio sp. (iso 17:1w7c and branched monoenoics) and for acetate-oxidizing Desulfobacter (10 methyl 16:0) were detected in the enrichment. These biomarkers were demonstrated in pure cultures of Desulfovibrio sp. and Desulfobacter sp. obtained from the enrichment. The predominant glutamate-fermenting bacterium isolated from the consortium contained no branched ester-linked phospholipid fatty acids, and produced acetate and hydrogen. With energy limitation the enriched consortium produced increased amounts of extracellular polysaccharide and the endogenous storage lipid poly-beta-hydroxybutyrate as detected with Fourier transform/infra-red (FT-IR) spectroscopy.     

Fatty acid composition in the central and peripheral adipose tissues of the sable (Martes zibellina)

Fatty acid composition was examined in the total lipids of the intraabdominal, subcutaneous and peripheral (paws, tail, nose) adipose tissues of a terrestrial mustelid, the sable Martes zibellina. The species inhabits the Palearctic taiga and is exposed to extreme cold during the winter. Although the paw pads and nose of the sable had higher proportions of total polyunsaturated fatty acids (PUFAs) compared to the adipose tissues of the trunk, the location of fat had only a little influence on the total percentages of saturated and monounsaturated fatty acids in the species. In this respect, the sable differs from its relative, the semiaquatic American mink Mustela vison, which has pronounced unsaturation of lipids towards the periphery. As observed previously in the mink, the sable deposits preferentially n-3 PUFAs in the appendages. The gradient of unsaturation is more modest in the sable possibly due to its terrestrial lifestyle. The results of the present study demonstrate that the average unsaturation of adipose tissue fatty acids does not increase towards the periphery in all northern mammals.     

Rapid stable isotope dilution analysis of very-long-chain fatty acids, pristanic acid and phytanic acid using gas chromatography–electron impact mass spectrometry

A common feature of most peroxisomal disorders is the accumulation of very-long-chain fatty acids (VLCFAs) and/or pristanic and phytanic acid in plasma. Previously described methods utilizing either gas chromatography alone or gas chromatography–mass spectrometry are, in general, time-consuming and unable to analyze VLCFAs, pristanic and phytanic acid within a single analysis. We describe a simple, reproducible and rapid method using gas chromatography/mass spectrometry with deuterated internal standards. The method was evaluated by analysing 30 control samples and samples from 35 patients with defined peroxisomal disorders and showed good discrimination between controls and patients. This method is suitable for routine screening for peroxisomal disorders.     

Isolation of chlorogenic acids and their derivatives from Stemona japonica by preparative HPLC and evaluation of their anti-AIV (H5N1) activity in vitro

Two chlorogenic acids and five chlorogenic acid derivatives were simultaneously separated and purified from Stemona japonica by preparative high-performance liquid chromatography. Five of the collected compounds were over 95% pure while the other two compounds were over 90% pure. Their structures were elucidated as 3-O-feruloylquinic acid (1), 4-O-feruloylquinic acid (2), methyl 3-O-feruloylquinate (3), methyl 5-O-caffeyolquinate (4), methyl 4-O-feruloylquinate (5), ethyl 3-O-feruloylquinate (6) and the new compound ethyl 4-O-feruloylquinate (7) by UV, NMR and ESI-MS. All compounds were obtained from Stemona species for the first time, however compounds 6 and 7 are believed to be artefacts from the ethanol extraction. The anti-AIV (H5N1) activities were evaluated by Neutral Red uptake assay. Compounds 3 and 4 exerted moderate inhibitory effect against AIV (H5N1) in vitro.