Cyclodimers of p-coumaric and ferulic acids in the cell walls of tropical grasses

Cell walls from leaves and stems of three tropical grasses (Setaria anceps cv Nandi (Schumach) Moss), pangola grass Digitara decumbens Stent and spear grass Heteropogon contortus (L) Beauv ex Roemer & Schultes were extracted with alkali, and ether-soluble fractions were prepared from the acidified solutions. Cyclobutane dimers derived from p-coumaric acid (CA: 3-(4-hydroxypheny) propenoic acid) and ferulic acid (FA: 3-(4-hydroxy-3-methoxyphenyl) propenoic acid) were found in all plant residues. Structural information on the dimers was obtained by gas chromatography-mass spectrometry. Stem cell walls differed from those of leaf in having major dimer components which contained residues tentatively identified as coniferyl alcohol (3-(4-hydroxy-3-methoxyphenyl)-2-propen-l-ol). Species differences in leaf cell wall cyclodimers were evident. Pangola and setaria grasses had dimers mainly derived from FA, whereas spear grass had over 70% of dimers derived from CA. Di-esterification of some dimers in the cell walls was confirmed by the release of dimers containing the reduced forms of CA and FA (coumaryl and coniferyl alcohols respectively) when leaf cell walls were extracted with borohydride. Head to tail dimerisation giving derivatives of truxillic acid (t-2, c-4-diphenyl-r-l, t-3-cyclobutanedicarboxylic acid) predominated, although evidence was obtained for the presence of head-to-head coumaric acid dimers (derivatives of truxinic acid, t-3, t-4-diphenyl-rl, c-2-cyclobutanedicarboxylic acid) in setaria stem and spear grass leaf. The results suggested that cyclodimers in grass cell walls occurred in cross-linking structures of varying complexity between macromolecules, where they would possibly contribute to fibre strength and thus have an adverse efect on the nutritional value of forage.     

Monomeric and dimeric phenolic constituents of plant cell walls—possible factors influencing wall biodegradability

A range of plant cell walls fiom graminaceous and leguminous plants were examined qualitatively and quantitatively for monomeric and dimeric phenolic constituents that were released by treatment with sodium hydroxide. The total amounts of phenolics released fiom the walls of the graminaceous plants varied fiom 8 to 28 mg g^?1 walls compared with less than 3 mg g^?1 walls jiom the legumes. p-Coumaric and ferulic acids were the major components of the monomeric fraction. The cell walls also contained substituted cyclobutanes having molecular weights equal to two p-coumaric acid molecules, two ferulic acid molecules or one p-coumaric plus one ferulic acid molecule, All the walls contained dehydrodiferulic acid. If it is assumed that the substituted cyclobutanes and dehydrodiferulic acid arise from dimerisation of feruloyl and p-coumaroyl groups linked to cell wall polysaccharides, then, for the graminaceous walls, it is calculated that between 5 and 14% of these groups had converted to dimers. This dimerisation process may limit the biodegradability of the wall polysaccharides.     

Phenolic constituents of cell wall types of normal and brown midrib mutants of pearl millet (Pennisetum glaucum (L) R Br) in relation to wall biodegradability

The cell walls of parenchyma, rind and vascular bundle fractions of pearl millet (Pennisetum glaucum (L) R Br) were isolated from two brown midrib mutants (bmr) 5753 and 5778 and from their normal (N) near-isogenic line. The cell wall content of parenchyma was lower than that of vascular bundle which, in turn, was lower than that of rind. The amounts of ferulic and p-coumaric acids released by NaOH treatment of the cell walls were in the ranges 3-7 mg g^?1 and 2-26 mg g^?1, respectively. Parenchyma cell walls of the N line had the highest content of p-coumaric acid (26 mg g^?1). This content of p-coumaric acid in the N line contrasts with that of bmr 5753 parenchyma (2 mg acid g^?1 walls) and bmr 5778 (7 mg acid g^?1 walls). The concentration of p-coumaric acid was highest in parenchyma cell walls that had been found to be the least digested. Parenchyma, rind and vascular bundle cells walls of the N line had much higher ratios of p-coumaric acid to ferulic acid than the mutants; rind and vascular bundle walls were less digestible than parenchyma. Small amounts of truxillic acid dimers were released by NaOH from the parenchyma walls of bmr 5778. Treatment of parenchyma, rind and vascular bundle cells walls with purified ‘driselase’ (containing xylanases and cellulases) released p-coumaroyl and feruloyl trisaccharides. Between 25 and 53% of the ferulic acid that was released by the NaOH treatment could be accounted for as feruloyl trisaccharide, but only 1-19% of the p-coumaric acid was accounted for as p-coumaroyl trisaccharide.     

Monomeric and dimeric phenolic acids released from cell walls of grasses by sequential treatment with sodium hydroxide

Cell walls of tall fescue Festuca arundinacea Schreb and coastal bermudagrass Cynodon dactylon L Pers were treated sequentially with increasing concentrations of sodium hydroxide (0·1 M to 10 M) to release monomeric and dimeric phenolic acids. (E)-p-Coumaric and (E)-ferulic acids were the major monomers released. Most of the saponifiable feruloyl groups (97% for tall fescue, 89% for coastal bermudagrass) were released with 0·1 M sodium hydroxide. Much lower proportions of saponifiable p-coumaroyl groups (67% for tall fescue, 46% for coastal bermudagrass) were released with this treatment. The major dimers from both grasses were 4,4′-dihydroxy-α-truxillic, 4,4′-dihydroxy-3-methoxy-α-truxillic, and 4,4′-dihydroxy-3,3′-dimethoxy-α-truxillic acids, and were mainly released with 0·1 M sodium hydroxide. Similar proportions of the monomers and dimers were released from the cell walls of each grass with the 0·1 M and 1 M sodium hydroxide sequential treatments. It is probable that most if not all of the monomers and dimers released by the sequential alkali treatments were originally ester linked to the cell walls. If it is assumed that the cell wall bound dimers are formed photochemically from p-coumaroyl and feruloyl groups during plant growth, it is calculated that, for the two grasses, between 12 and 17% of the monomer units were converted to dimers.     

Identification of ferulate oligomers from corn stover

BACKGROUND: Cross‐links between plant cell wall polymers negatively impact forage digestibility. Hydroxycinnamates and their oligomers act as cross‐links between polysaccharides and/or polysaccharides and lignin. Higher ferulate oligomers such as dehydrotrimers were identified in cereal grains but not in vegetative organs of grasses. The aim of this study was to characterize ester‐linked hydroxycinnamate oligomers from corn stover with special emphasis on ferulate dehydrotrimers. RESULTS: With the exception of the 4‐O‐5‐dehydrodiferulic acid all known ferulate dehydrodimers, including the recently described 8‐8(tetrahydrofuran) dimer, were identified in the alkaline hydrolyzate of corn stover after chromatographic fractionation. Next to dehydrodimers, 18 cyclobutane dimers made up of ferulic acid and/or p‐coumaric acid were identified by GC‐MS of the dimeric size exclusion chromatography fraction. Ferulate dehydrotrimers were isolated by using multiple chromatographic procedures and identified by UV spectroscopy, MS and NMR. Four trimers were unambiguously identified as 5‐5/8‐O‐4‐, 8‐O‐4/8‐O‐4‐, 8‐8(aryltetralin)/8‐O‐4‐, and 8‐O‐4/8‐5‐dehydrotriferulic acids, a fifth tentatively as 8‐5/5‐5‐dehydrotriferulic acid. CONCLUSION: The formation of ferulate dehydrotrimers is not limited to reproductive organs of grasses but also contribute to network formation in the cell walls of vegetative organs. Although radically coupled hydroxycinnamate dimers and oligomers were in the focus of researchers over the last decade, the earlier described cyclobutane dimers significantly contribute to cell wall cross‐linking. Copyright © 2010 Society of Chemical Industry     

Phenolic acids released from bermudagrass (Cynodon dactylon) by sequential sodium hydroxide treatment in relation to biodegradation of cell types

Sections of solvent-extracted bermudagrass (Cynodon dactylon L Pers) leaf blades were treated sequentially with increasing concentrations of sodium hydroxide. The amounts of saponifiable phenolic acid monomers and cyclobutane dimers released and the digestibility of the treated blades (ie % dry weight loss) were determined. Leaf sections were examined by scanning electron microscopy for biodegradation of cell types and histochemically (light microscopy) for lignin after treatment with sodium hydroxide. Treatment with 0.1 m sodium hydroxide for 1 h resulted in only minor changes from untreated sections. However, this treatment for 24 h released 86% of the ferulic acid, 65% of the dimers, and c 50% of the p-coumaric acid. Digestibility was increased from 6.5% in the untreated control to 56.6%. Substantial loss of the slowly biodegradable tissues (ie epidermis and parenchyma bundle sheath) and partial biodegradation and disruption of the refractory tissues (ie sclerenchyma, xylem and mestome sheath) occurred; histochemical reactions for lignin were less intense after NaOH treatment. Treatment with 1 m sodium hydroxide for 24 h released 50% of the p-coumaric acid and the remainder of the alkali-extractable ferulic acid and dimers, increased digestibility to 72%, and increased biodegradation of mesophyll and phloem. Mestome sheath cell walls only gave a histochemical reaction for phenolics and the reaction was weak after 1 m NaOH treatment. Alkali treatment increased the biodegradation of all cell types, with lignified tissues reduced to single-cell fibres after 1 and 2 m treatments.     

Effects of storage conditions on the accumulation of ferulic acid derivatives in white asparagus cell walls

White asparagus cell walls have shown to contain important amounts of phenolics, including ferulic acid and its dimers and trimers. It has been suggested that these phenolic compounds are mainly responsible for cross‐linking the different cell wall polymers related to asparagus hardening. During post‐harvest storage, the asparagus texture and the amount of cell wall phenolics increased significantly. In the present work, the effect of post‐harvest storage conditions on the accumulation of ferulic acid and its derivatives has been investigated. Three different storage conditions were used: keeping the spears in aerobic conditions at room temperature (ART) and at 4 °C (A4 °C), and in anaerobic conditions at room temperature (AnRT). A direct relationship between phenol accumulation and increases in texture was observed, and these changes are dependent on temperature and storage atmosphere. An increase in temperature led to a higher amount of cell wall phenolics and the absence of oxygen in the storage atmosphere delayed their accumulation. The evolution of ferulic dimers during the three storage conditions suggests a relevant role of 8‐O‐4′‐diFA and 8,5′‐BAdiFA in white asparagus hardening. Copyright © 2006 Society of Chemical Industry     

Chemical characteristics,fatty acid composition and conjugated linoleic acid (CLA) content of traditional Greek yogurts

Many studies with conjugated linoleic acid (CLA) indicate that it has a protective effect against mammary cancer. Because dairy products are the most important dietary sources of CLA, we have investigated the CLA concentrations and additionally the fatty acid profiles and chemical composition of several commercial, traditional, Greek yogurts from different geographical origin. The fat content of yogurts was in the order of goat < cow < sheep. Cow, sheep and goat milk yogurts contain respectively 0.128–1.501, 0.405–1.250 and 0.433–0.976 g CLA/100 g fat. Low-fat milk yogurts showed lower values of c-9, t-11 CLA content on lipid basis compared to full-fat yogurts. Samples from mountain areas showed average c-9, t-11 CLA content higher than those from prairie districts. The highest amounts of saturated fatty acids (SFA) were found in low-fat yogurts, of monounsaturated fatty acids (MUFA) in sheep milk yogurts and of polyunsaturated fatty acid (PUFA) in low-fat cow milk yogurts.     

Effect of ripening on total conjugated linoleic acid and its isomers in buffalo Cheddar cheese

Cheese is a biologically and biochemically dynamic product in which a series of sequential changes take place throughout its manufacture and subsequent ripening. These changes improve nutritional value, body and texture and enrich the flavour. Conjugated linoleic acids (CLA), a group of naturally occurring geometrical and positional isomers of linoleic acid, are present in high concentration in dairy products and fat from ruminant animals. Six isomers of CLA have been separated and identified by gas liquid chromatography (GLC) analysis. Buffalo milk had higher 9c,11t-18:2 isomer (86.14%). Total CLA concentration of CLA isomers was increased significantly ( P <  0.05) on conversion of milk into cheese and subsequent storage. The concentration of the 9c,11t-18:2 isomer was decreased significantly ( P <  0.05), whereas that of trans , trans -isomers (12,14-; 11,13-; 10,12-; 9,11-) increased significantly ( P <  0.05).     

Diferulate cross-links impede the enzymatic degradation of non-lignified maize walls

We assessed the effect of ferulate substitution and diferulate cross-linking of xylans on the degradation of cell walls by two fungal enzyme mixtures, one of which contained feruloyl esterase and high xylanase activities. Non-lignified cell suspensions of maize (Zea mays) were grown with 0 or 40 μM 2-aminoindan-2-phosphonic acid to produce walls with normal (17·2 mg g⁻¹) or reduced (5·1 mg g⁻¹) ferulate concentrations. Walls were incubated with mercaptoethanol to inhibit diferulate formation or with hydrogen peroxide to stimulate diferulate formation by wall bound peroxidases. Varying the ferulate substitution of xylans did not affect cell wall hydrolysis. In contrast, increasing ferulate dimerisation from 18 to 40% reduced carbohydrate release by 94–122 mg g⁻¹ after 3 h and by 0–48 mg g⁻¹ after 54 h of enzymatic hydrolysis. Diferulate cross-links impeded the release of xylans, cellulose and pectins from walls. These results provide compelling evidence that diferulate cross-links reduce the rate and, to a lesser degree, the extent of wall hydrolysis by fungal enzymes. Our results also suggest that enzyme mixtures containing high xylanase activity but not feruloyl esterase activity can partially overcome the inhibitory effects of diferulate cross-linking on wall hydrolysis. © 1998 SCI.     

The phenolic acid and polysaccharide composition of cell walls of bran layers of mature wheat (Triticum aestivum L. cv. Avalon) grains

The purpose of this study was to examine the carbohydrate and phenolic‐ester composition of cell walls in wheat bran layers. Four defined layers of wheat bran were separated manually from mature grains of wheat (Triticum aestivum L. cv. Avalon) to give samples of beeswing bran (outer pericarp), cross cells, testa + nucellar epidermis and aleurone cells. The cell‐wall material from each layer, and from a sample of intact bran, was analysed for carbohydrates and wall‐bound esterified phenolic acids. The cell‐wall material of intact bran was rich in arabinose and xylose with significant quantities of glucose and uronic acid and a relatively small amount of galactose and mannose. The varying ratios of arabinose:xylose in cell walls of isolated bran layers indicated that the heteroxylans had tissue‐specific substitution patterns. HPLC analysis of phenolic acids identified significant amounts of esterified ferulic acid and 8‐8′‐ (aryltetralin form), 5‐8′‐, 5‐5′‐, 8‐0‐4′‐ and 5‐8′‐(benzofuran form)‐dehydrodiferulic acids in the isolated cell walls. Ferulic acid was highly concentrated in the aleurone layer, whereas dehydrodiferulates were concentrated in the beeswing bran and cross cells. The role of phenolic cross‐linking is discussed in relation to the architecture of the cell walls of wheat bran and to processing implications. Copyright © 2005 Society of Chemical Industry     

Studies on dimerisation of tocopherols under the influence of methyl linoleate peroxides

The stability of plant oils is related to the level of polyunsaturated fatty acids and the presence of native antioxidants--especially tocopherols. During storage, lipids or the fat products undergo oxidation and tocopherol dimers and trimers are formed. These compounds possess reducing and antioxidant properties and participate in oxidation clearly inhibiting this process. In the present study, the correlation between levels of peroxides formed during autoxidation of methyl linoleate and simultaneous decomposition of tocopherols was examined. The peroxide value was investigated. Quantities of decomposed tocopherols and formation of their dimers were determined by high-performance liquid chromatography (HPLC). Mass spectrum analysis confirmed thatthe analysed compounds were dimes. Dimerisation of gamma-T begins at the smaller quantity of the methyl linoleate peroxides than dimerisation of delta-T. At the beginning of methyl linoleate autoxidation dimerisation of gamma-T in relation to its loss was smaller. The quantity of gamma-T dimers with ether bonds in total dimers pointed to faster binding of phenoxy radicals than transformation into the phenyl ones. delta-T dimers with phenyl bonds constitute about 65% of the total. The quantity of peroxides in methyl linoleate, necessary for quantitative and qualitative changes of homologous tocopherols, decreased from delta-T to alpha-T.     

Formation of Trans Fatty Acids in Ground Beef and Frankfurters due to Irradiation

ABSTRACT:  This study was conducted to investigate possible formation of trans fatty acids due to irradiation of ground beef and frankfurters. Ground beef and frankfurter samples were irradiated at doses of 0, 1, and 5 kGy at 4 °C, and stored at 4 °C for 7 d (ground beef) or 3 mo (frankfurters). After irradiation and storage of the samples, trans fatty acids along with other fatty acids were analyzed using a modification of AOAC method 996.01. The results showed that 1 kGy irradiation did not induce any change in trans fatty acid content. However, 5 kGy irradiation caused a small but statistically significant ( P < 0.01) increase in the dominant trans fatty acid, C18:1 trans , which increased from 3.99% (of total fatty acid) for the nonirradiated ground beef to 4.05% for the 5 kGy sample, and from 1.21% for the nonirradiated frankfurter to 1.28% for the 5 kGy sample. Irradiation had no apparent effect on C16:1 and C18:2 trans fatty acids. In addition, irradiation slightly decreased the relative amount of poly-unsaturated fatty acid of ground beef and frankfurters, particularly after storage. Compared to variations in trans fatty acid content and fatty acid composition occurring naturally in meat and meat products, the changes due to irradiation were negligible.     

Antioxidant properties of commercial wild rice and analysis of soluble and insoluble phenolic acids

To investigate the antioxidant properties of commercial wild rice, identify and quantify soluble and insoluble phenolic acids in wild rice whole grain, the alkaline hydrolysates from crude methanol extracts (soluble fraction) and residues (insoluble fraction) were separately analysed by high performance liquid chromatography (HPLC) coupled with photodiode array detection (PAD) and quadrupole-time of flight (Q-TOF) mass spectrometry (LC–MS). The antioxidant activity of wild rice methanol extract was found to be up to 10 times greater than that of white rice (control sample) according to their 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity and oxygen radical absorbance capacity (ORAC). Ferulic acid was found as the most abundant phenolic acid (up to 355 mg/kg) followed by sinapic acid in wild rice. They both occurred mainly in the insoluble form. Other monomeric phenolic acids present in wild rice consisted of p-coumaric, vanillic, syringic, and p-hydroxybenzoic acids, along with two phenolic acid aldehydes (p-OH-benzaldehyde and vanillin). They were present in both soluble and insoluble forms. Phenolic acid dehydrodimers are cell wall bound and only appeared in the insoluble fractions featured by diferulic acids (DiFA) and disinapic acids (DiSA). The chemical structures of DiFA included 8-8′, 5-5′, 8-O-4′, and 8-5′ (benzofuran form) coupled dimers, with 8-O-4′ as the predominant form (up to 34 mg/kg). DiSA only appeared as 8-8′-coupled products with the linear isomers in the most quantities (up to 19 mg/kg). The DPPH free radical scavenging activities of soluble and insoluble fractions suggest that the antioxidant activity of wild rice is partially attributed to its phenolic acid profile.     

Antifungal Properties of Esters of Alkenoic and Alkynoic Acids

The antifungal property of the gas phases of a number of alkenoic and alkynoic acids and esters was investigated by placing the compounds in desiccators containing suspended bread. The following compounds inhibited mold development at a concentration of 20 mg per 2.6-liter desiccator: dimethyl fumarate, diethyl fumarate, propenoic acid, methyl and ethyl propenoate, methyl and ethyl propiolate, methyl-2,4-hexadienoate, 2,4- hexadien-1-ol, diethylethylidene malonate, 4-penten-1-ol, and 2-cyclohexen-1-one. Other compounds were active at 200 mg per desiccator: 3-methallyl alcohol; allyl acetone; diallyl ether; propiolic acid; methyl, ethyl, and vinyl crotonate; ethyl-2,4-hexadienoate; methyl and ethyl-2-hexenoate; ethyl-3-hexenoate; 1,5-hexadien-3-01; methylmaleic acid; methylmalonic acid; and 1-penten-3-ol.     

热处理激发油茶籽油中多酚与美拉德产物变化及互作研究

为分析热处理激发油茶籽毛油中多酚与美拉德产物含量变化、抗氧能力及互作关系，本文以油茶籽为原料进行热处理，采用HPLC分析比对酚类和美拉德产物种类及含量，氧化诱导时间测定抗氧能力并通过复配来测定协同百分比。结果表明，油茶籽毛油总酚中含有没食子酸（GA）、焦性没食子酸（PG）、3,4-二羟基苯乙酸（DOPAC）和反式肉桂酸（tCA），其含量随温度升高具有显著性变化；GA、PG、DOPAC抗氧能力随浓度增加而增加，tCA抗氧能力随浓度变化不显著。美拉德产物5-HMF、3-DG、MGO含量随着温度的升高其含量先降低后升高。5-HMF、3-DG抗氧能力随着浓度的升高先增加后降低，MGO抗氧能力随着浓度的变化先增加后趋于平缓。互作分析研究表明：在多酚两两复配中tCA+DOPAC为协同关系，其余为拮抗作用；三三复配中GA+DOPAC+PG为协同作用，其余为拮抗作用；全混时为协同作用。美拉德产物中5-HMF、3-DG、MGO两两复配和全混时均为拮抗作用。多酚与美拉德产物全混时为协同作用。     

紫外线辐照花生油贮藏过程中的脂肪酸组成分析

目的:紫外线辐照花生油在贮藏过程中变化情况。方法:将对照组花生油置于254 nm的紫外灯下辐照处理40 min,将紫外组和对照组花生油分别置于40、50和60 ℃的条件下加速氧化贮藏,对28 d贮藏过程中花生油的脂肪酸组成变化进行分析,通过主成分分析和相关性分析探究紫外线辐照花生油的脂肪酸组成在贮藏过程中的相互之间的关系。结果:经紫外线辐照花生油在加速氧化贮藏过程中饱和脂肪酸和单不饱和脂肪酸含量在贮藏21 d后呈迅速递增趋势,多不饱和脂肪酸在贮藏21 d后期呈迅速递减趋势,各种脂肪酸在贮藏过程中变化幅度比对照组大;温度越高,经紫外线辐照花生油各种脂肪酸组成在贮藏过程中变化幅度越大,当贮藏温度相对较低的时候,各种脂肪酸在贮藏过程中的变化不大;主成分分析和相关性分析表明,紫外线辐照花生油中亚油酸(C18:2n6)、亚麻酸(C18:3n3)与棕榈酸(C16:0)、硬脂酸(C18:0)、油酸(C18:1n9c)、花生酸(C20:0)、花生一烯酸(C20:1)、山嵛酸(C22:0)主要影响紫外组的脂肪酸组成,多不饱和脂肪酸与单不饱和脂肪酸、饱和脂肪酸存在极显著的负相关,单不饱和脂肪酸与饱和脂肪酸存在极显著的正相关。结论:紫外辐照花生油在贮藏过程中的脂肪酸组成比对照组的变化幅度大,较高的贮藏温度使紫外辐照花生油的脂肪酸组成和种类发生变化。     

Ferulic acid and its position among the phenolic compounds of wheat

Ferulic acid (3-methoxy-4-hydroxycinnamic acid) is the main phenolic acid occurring in cell walls of monocotyledones. Due to its blue-and-white fluorescence it is easily identified and is located in the cereal grain morphological parts. Its 40-fold greater concentration was found in the cells walls of the seed coat and aleuronic layer than in the cells walls of endosperm. Most often, it is linked by ester bonds with hemicellulose chains, mainly with arabinose residues and it also polymerizes with lignin through ether bonds. However, ferulic acid in the pentosane molecules forms specific complexes with proteins through chemical bonds with amino acids. It is interesting to mention the theory of the pentosane gel formation in which a great role is assigned to ferulic acid. An oxidized form of ferulic acid-diferulic acid-produces gel formation by linking two pentosane or protein molecules. The blue-and-white fluorescence of ferulic acid can be applied to determine flour contamination with grain coat particles and its ability to form complexes with pentosanes and proteins is important in the formation of dough texture with its semi-elastic properties.     

Characterisation of Lignin from Parenchyma and Sclerenchyma Cell Walls of the Maize Internode

Internodes of maize (Zea mays L, Co125), harvested 5 days after anthesis, were sectioned into five equal parts and samples of sclerenchyma and parenchyma cells mechanically isolated from each section. Phenolic acids and syringyl and guaiacyl degradation products of lignin were released from the walls of the two cell types by microwave digestion with 4 M NaOH. Aryl ether bonded units were selectively released by thioacidolysis. Total phenolic content of cell walls from the youngest (basal) sections were approximately two-thirds of those of the oldest, topmost sections (parenchyma 70·8–99·0 and sclerenchyma 72·5–114·1 mg g^-1) indicating that the process of lignification was already well advanced amongst most of the cell walls of the youngest section. The total phenolic content was marginally, but significantly, greater (P<0·05) in sclerenchyma walls than in parenchyma walls at all stages of maturity. There was no significant difference in phenolic acid concentrations between cell types from the same section but p-coumaric acid concentration increased with maturity (P<0·001) in walls from both cell types. The increase in p-coumarate with age was matched by an increased recovery of syringyl units resulting in a constant coumaroyl: syringyl molar ratio. Recovery of acetosyringone was significantly greater (P<0·001) from sclerenchyma than parenchyma walls and, in sclerenchyma, acetosyringone as a proportion of total syringyl recovery, increased significantly with age (P=0·015). Digestion with NaOH and thioacidolysis released comparable amounts of guaiacyl residues but NaOH digestion released approximately twice the amount of syringyl residues. This difference may be explained by the retention of the ester-bond between p-coumaric acid and syringyl units during thioacidolysis but not during digestion with 4 M alkali. The similarity in phenolic composition suggested that both cell types, despite their considerable anatomical differences, were exposed to a common flux of lignin precursors during the later stages of lignification as illustrated by the internode sections. Differences between cell walls arose because of differences in the regiochemistry of precursor incorporation. © 1997 SCI.     

Isolation and identification of one kind of yellow pigments from model reaction systems related to garlic greening

It was established that green pigment(s) responsible for garlic greening is composed of yellow and blue species, and pyruvic acid (a product from 1-PeCSO or 2-PeCSO under the action of alliinase) reacted with pigment precursor (PP) model compounds, 2-(1H-pyrrolyl) carboxylic acids to produce yellow pigments. However, the structure of the yellow pigments is unknown. In present paper, we identified three yellow pigments (Y1, Y2 and Y3) from three reaction systems containing pyruvic acid and 2-(1H-pyrrolyl) acetic acid (P-Gly) or 1-(2′-methyl-1′-carboxy-propyl) pyrrole (P-Val) or 1-(2′-methyl-1′-carboxy-butyl) pyrrole (P-Ile), respectively, by LC-ESI MS/MS and IT-TOF mass spectrometry. The three pigments have a UV/visible maximum absorbance between 400 and 434 nm and might be formed by dimerisation of the three corresponding PP under participation of pyruvic acid, molecular formula of which are C₁₆H₁₆N₂O₄ (Y1), C₂₂H₂₈N₂O₄ (Y2) and C₂₄H₃₂N₂O₄ (Y3), respectively.