米ぬか熱水抽出液中のラジカル消去活性とフェノール酸類の関与

Simple SummaryIn the context of international commitments to reduce the environmental impact of herbicides, ecologically more favorable control method approaches must be explored. This is particularly important for allergenic Ambrosia artemisiifolia L., one of the most harmful species in the world. Secondary plant metabolites and, in particular, some phenolic compounds are known to have a strong allelopathic effect on weed growth. In this study we investigated whether phenolic acids (chlorogenic acid, caffeic acid, ferulic acid, gallic acid, protocatechuic acid, p-hydroxybenzoic acid, syringic acid, vanillic acid, and p-coumaric acid) can inhibit the early growth of A. artemisiifolia. Phenolic acids were tested at five different dose levels that were up to 16 times than those naturally occurring in plants. The results show that the suppression of the early growth of A. artemisiifolia is strongly dependent on phenolic acid and its dose. Treating seeds with ferulic acid, vanillic acid, p-coumaric acid, p-hydroxybenzoic acid, or a mixture of all phenolic acids resulted in significantly better inhibition of early growth parameters than other phenolic acids. However, none of the phenolic acids tested were effective as bioherbicides at their naturally occurring doses in plants. Therefore, selected doses of phenolic acids with significantly reduced herbicide doses should be further explored to effectively control A. artemisiifolia.This study aimed to investigate whether different doses of specific phenolic acids (chlorogenic acid, caffeic acid, ferulic acid, gallic acid, protocatechuic acid, p-hydroxybenzoic acid, syringic acid, vanillic acid, and p-coumaric acid), alone or in combination, can inhibit the early growth of the common ragweed (Ambrosia artemisiifolia L., Asterales: Asteraceae). A seed bioassay was performed in Petri dishes and placed in a climate chamber to assess the effects of five dose levels of phenolic acids to radicle and shoot length, as well seedling biomass of A. artemisiifolia. The lowest dose of phenolic acid corresponded to the natural phenolic acid concentration previously reported in dry plant tissue samples from Brassicaceae cover crop plants. Results show that the inhibition of the early growth of A. artemisiifolia depends strongly on phenolic acid. Across different treatments, high doses of phenolic acids significantly shortened shoots and radicles, as well as reduced seedling biomass. Treating seeds with ferulic acid alone, vanillic acid alone, p-hydroxybenzoic acid alone, or a mixture of all phenolic acids significantly reduced all early growth parameters. The estimated effective dose for the 50% inhibition (ED50) of radicle growth in A. artemisiifolia seedlings was 368.39 ± 59.85 × 10−8 mol with ferulic acid, 135.41 ± 17.65 × 10−8 mol with p-coumaric acid, 810.36 ± 134.15 × 10−8 mol with p-hydroxybenzoic acid, and 160.11 ± 12.30 × 10−8 mol with the combination of all phenolic acids.

ABSTRACTSimple phenolic acid levels were determined on pooled millstreams of five different classes of Canadian wheat milled to ~75, 80, and 85% extraction. Pooled flours and whole grain were analyzed by reversed‐phase high‐performance liquid chromatography (RP‐HPLC) to establish endogenous levels of insoluble bound, soluble esterified, and free phenolic acids. Only ferulic acid was detected in the insoluble bound category, which accounted for >80% of the total phenolic acids present in every flour. The soluble esterified phenolic acids accounted for up to 17% of the overall total phenolic acid content within a flour. The major constituents were sinapic, ferulic, and vanillic acids, with minor amounts of coumaric, caffeic, and syringic acids. Free phenolic acids accounted for a maximum of 6% of the total phenolic content of any prepared flour. Ferulic acid was the major free phenolic acid, while sinapic acid was not detected in any flour. Significant correlations (r = 0.64–0.97, P < 0.05) were observed between insoluble bound ferulic acid, individual soluble esterified acids, and most free acids with polyphenol oxidase activity, as well as color and ash content for each class.

Phenolic compounds in the soils collected from 6 paddy fields and 9 forests were surveyed quantitatively by gas chromatography. The results are as follows: 1) p-Coumaric, ferulic, vanillic, p-hydroxybenzoic, syringic, salicylic, and protocatechuic acids were detected in all soils. Among these acids, p-coumaric acid was present in the largest quantity in most of the soils. Gallic, caffeic, and sinapic acids, resorcinol, and phloroglucinol were not detected. 2) The total amounts of individual phenolic acids in the forest soils (34-632 ppm) were markedly higher than those in the paddy soils (10-26 ppm). p-Coumaric acid content went up to 188 ppm in the forest soils and up to 7 ppm in the paddy soils. The average concentration of total phenolic acids per weight of organic matter in the forest soils was about 2 times as high as that in the paddy soils. 3) In the paddy soils, the concentrations of p-hydroxybenzoic, vanillik, syringic, p-coumarie, and ferulic acids, which have no chelating ability, were considerably related to the pH and the carbon content of the soil, but the concentrations of protocatechuic and salicylic acids, which are chelating agents, were not related to those of the soil. Also in A horizons of forest soils, the concentrations of many phenolic acids were related to carbon content, but not to pH. 4) In a forest soil surveyed, the concentrations of individual phenolics decreased with increasing depth. However, the ratios of the amounts of individual phenolics to the carbon content increased with depth.

Lignin-related phenolic acids have been implicated in rice sterility problem on peatlands in Southeast Asia. Therefore, a comparison was made of phenolic constituents in peat soils from three zones; tropical Malaysia, temperate Japan and boreal Finland. From peat samples were extracted lignin-derived phenolic acids: 4-hydroxybenzoic, vanillic, syringic, trans-4-hydroxycinnamic and ferulic acids. The amounts of all the phenolic acids were greater in the tropical and temperate peat soils than in the boreal peat. Between the tropical and temperate peats, there was a marked difference in the quantitative distribution of the five phenolic acids. The ratio of the total amount of trans-4-hydroxycinnamic and ferulic acids to that of 4-hydroxybenzoic, vanillic and syringic acids was 0.12 for tropical and 2.7 for temperate peats. The substituted hydroxycinnamic acids, therefore, occurred in a smaller amount in the tropical than in the temperate peat soils. The polymerisation of these phenolic acids may cause rice sterility problem in the tropical peat soils.

通过室内模拟试验，阐明阔叶红松林中已测得含量较高的3种酚酸物质（苯甲酸、丁香酸和香草酸）对红松种子萌发及苗木生长的影响，为探索阔叶红松林内化感作用机理及解决红松更新障碍问题提供科学依据。采用培养皿培养法及室内盆栽培养法，以红松种子和3年生红松苗为试验对象，设置不同浓度（2、20、200 mg/L）苯甲酸、丁香酸、香草酸处理液，以蒸馏水为对照（CK），进行红松种子萌发试验及红松苗木生长试验，研究3种酚酸物质对红松种子发芽、苗木生长、光合色素、抗氧化酶活性、膜脂过氧化作用及渗透调节物质的影响。结果表明，（1）不同浓度3种酚酸均抑制红松种子萌发，但酚酸浓度变化仅对红松种子发芽率影响差异显著。（2）3种酚酸对红松苗木生长及物质积累抑制作用显著。浓度变化对红松苗株高及地径影响不显著，对生物量、根干重和茎干重影响显著。（3）针叶叶绿素a、叶绿素b、类胡萝卜素含量变化对酚酸处理反应一致，20 mg/L的3种酚酸均显著抑制光合色素产生，而200 mg/L丁香酸溶液及2 mg/L香草酸溶液均显著促进叶绿素a和类胡萝卜素积累。（4）酚酸处理使红松苗针叶中POD、CAT活性降低，SOD活性增加。针叶中MDA含量显著增加，200 mg/L丁香酸溶液处理组针叶MDA含量高于CK处理组70.51%。（5）不同浓度苯甲酸溶液促进可溶性糖增加，抑制可溶性蛋白增加；不同浓度丁香酸溶液促进可溶性蛋白增加，而不同浓度香草酸溶液抑制可溶性蛋白增加，二者对可溶性糖含量影响受浓度变化影响显著。苯甲酸、丁香酸、香草酸影响红松种子萌发，通过对红松苗光合色素、抗氧化酶活性及渗透调节物质的影响导致其生长受抑制、生物量减少，产生膜脂过氧化伤害。因此，解决阔叶红松林内红松更新障碍问题时，凋落物及土壤中酚酸物质的化感作用不容忽视。;Through the relevant indoor simulation experiments, this research aims to clarify the effects of three phenolic acids (benzoic acid, syringic acid, and vanillic acid) with high content in broad-leaved Pinus koraiensis forest on the seed germination and seedling growth of Pinus koraiensis, so as to provide scientific basis for exploring the allelopathy mechanism of broad-leaved Pinus koraiensis forest and solving the problem of regeneration obstacle of Pinus koraiensis. The experiment adopts petri dish culture method and the indoor potted culture method. The Pinus koraiensis seeds and triennial Pinus koraiensis seedlings as experimental object were treated with different concentrations (2, 20, and 200 mg/L) of benzoic acid, syringic acid, vanillic acid solution, and distilled water was used as control. The germination experiment of Pinus koraiensis seed and the Pinus koraiensis seedling growth test were carried out to study the effects of three phenolic acids on germination, seedling growth, photosynthetic pigment, antioxidant enzyme activity, membrane lipid peroxidation, and osmoregulation substances of Pinus koraiensis seeds. The results show that: (1) all the three phenolic acids with different concentrations had the effects of inhibiting germination of Pinus koraiensis seeds, but the change of phenolic acid concentration only had a significant difference in the germination rate of Pinus koraiensis seeds. (2) The three phenolic acids had significant inhibitory effects on the growth and substance accumulation of Pinus koraiensis seedlings. Phenolic acid concentration had no significant effect on plant height and root length, but had significant effect on biomass, root weight and stem weight. (3) The changes in the contents of chlorophyll a, chlorophyll b, and carotenoids in needles had same reaction to the phenolic acid treatment. All the three phenolic acids of 20 mg/L had significant inhibition on the production of photosynthetic pigments, while the syringic acid solution of 200 mg/L and the vanillic acid solution of 2 mg/L had significant effects on promoting the accumulation of chlorophyll a and carotenoids. (4) Phenolic acid treatment reduced the activity of peroxidase and catalase and increased the activity of superoxide dismutase. The content of malondialdehyde in needles was significantly increased, while the content of MDA in needles treated with 200 mg/L syringic acid group was 70.51% higher than that in control group. (5) Benzoic acid solutions of different concentrations could promote the increase of soluble sugar and inhibit the increase of soluble protein. Different concentrations of syringic acid could promote the increase of soluble protein, while different concentrations of vanillic acid could inhibit the increase of soluble protein. The concentration changes of both had a significant influence on the change of soluble sugar content. Benzoic acid, syringic acid, and vanillic acid affected the germination of Pinus koraiensis seeds, which led to growth inhibition, biomass reduction and membrane lipid peroxidation of Pinus koraiensis seedlings by affecting photosynthetic pigment, antioxidant enzyme activity and osmotic regulation substances. Therefore, allelopathy of phenolic acids in litter and soil should not be ignored when solving the problem of Pinus koraiensis regeneration in broad-leaved Pinus koraiensis forests.

Phenolic acids are widely distributed in foods and raw materials. They are easily absorbed by humans due to their simplicity. Once they enter the blood plasma, they act as antioxidants. Beer can be a rich source of phenolic acids in the diet. The aim of this study was to determine the concentrations of phenolic acids in two experimental worts and beers as well as in nine market beers (using HPLC-UV). An examination of the total antiradical activities of phenolic acids with in vitro model systems (using ABTS and DPPH free radicals), at the concentrations comparable to those detected in beers, was performed. Only low fractions of the main phenolic acids present in barley malt (ferulic, vanillic and p-coumaric acid) were detected in the experimental worts. Moreover, the concentrations of phenolic acids significantly decreased until the last steps of beer production. The main beer phenolic acids (vanillic and ferulic acid) exerted a lower share of total antiradical activity against both free radicals (calculated as the sum of the individual activities of all acids detected in beer) than the minor phenolic acids (caffeic, chlorogenic, o-coumaric, sinapic or syringic acid). The synergies, between individual phenolic acids in pairs, were also studied with in vitro model solutions using free radicals. The total antiradical activity of the compounds studied in pairs, was at the most as high as the sum of the antiradical activity of the individual phenolic acids, but in most cases it was considerably lower (i.e. no synergy was detected).

Degradation of cereal bran polysaccharide-phenolic acid complexes by Aspergillus niger CFR 1105

Mulberries, Morus spp., grow in different growing regions of Turkey with a high diversity providing an opportunity to select superior accessions. The goal of the study was to determine the differences in phytochemical components and horticultural characteristics between white and black mulberry accessions in the Igdir province. Fruits of black and white mulberries collected from Igdir province were assayed for various horticultural characteristics including berry width, berry length, berry weight, and berry peduncle length. Samples were also assayed for vitamin C, organic acids (citric, tartaric, malic, succinic, and fumaric), sugars (glucose and fructose), phenolic acids (catechin, rutin, quercetin, chlorogenic, ferulic, o-coumaric, p-coumaric, caffeic, syringic, vanillic, and gallic acids), and antioxidant capacity [Trolox equivalent antioxidant capacity (TEAC) assay]. Differences (P < 0.05) were noted between accessions in berry length and berry weight. Malic acid was found to be the predominant organic acid regardless of species. Rutin (for black mulberry) and chlorogenic acid (for white mulberry) were the predominant phenolic acids. Black mulberry had higher glucose and fructose content than white mulberry. Analysis showed that black mulberry had higher content of tartaric acid, malic acid, TEAC, fructose, glucose, catechin, rutin, quercetin, o-coumaric acid, and caffeic acid compared with white mulberry (P < 0.01); however, white mulberry had higher content of succinic acid, vitamin C, chlorogenic acid, ferulic acid, p-coumaric acid, syringic acid, and gallic acid (P < 0.01). Our results provide a reference for further studies of mulberry fruits in detection of organic acids, sugars, antioxidant capacity, and phenolic compounds. Also, it is clear that we need standardized testing, extraction, and analysis protocols to compare genotypes grown in different countries.

Fresh and sun-dried dates of three native varieties from Oman, namely, Fard, Khasab, and Khalas, were examined for their antioxidant activity and total contents of anthocyanins, carotenoids, and phenolics, as well as free and bound phenolic acids. All results are expressed as mean value +/- standard deviation (n = 3) on a fresh weight basis. Fresh date varieties were found to be a good source of antioxidants (11687-20604 micromol of Trolox equiv/g), total contents of anthocyanins (0.24-1.52 mg of cyanidin 3-glucoside equiv/100 g), carotenoids (1.31-3.03 mg/100 g), phenolics (134-280 mg of ferulic acid equiv/100 g), free phenolic acids (2.61-12.27 mg/100 g), and bound phenolic acids (6.84-30.25 mg/100 g). A significant (p < 0.05) amount of antioxidants and carotenoids was lost after sun-drying of dates, whereas the total content of phenolics and free and bound phenolic acids increased significantly (p < 0.05). Anthocyanins were detected only in fresh dates. Date varieties had different levels and patterns of phenolic acids. Four free phenolic acids (protocatechuic acid, vanillic acid, syringic acid, and ferulic acid) and nine bound phenolic acids (gallic acid, protocatechuic acid, p-hydroxybenzoic acid, vanillic acid, caffeic acid, syringic acid, p-coumaric acid, ferulic acid, and o-coumaric acid) were tentatively identified. Of the date varieties studied, Khalas, which is considered to be premium quality, had higher antioxidant activity, total carotenoids, and bound phenolic acids than other varieties. These results suggest that all date varieties serve as a good source of natural antioxidants and could potentially be considered as a functional food or functional food ingredient, although some of their antioxidant constituents are lost during sun-drying.

The antioxidative properties of p‐hydroxy‐benzoic acid, vanillic acid, syringic acid, 3,4‐dihydroxy‐benzoic acid, p‐coumaric acid, ferulic acid, sinapic acid and caffeic acid in lard autoxidation at 100°C are compared. The effect of phenolic acids is investigated within the concentration range 0.02 – 0.20 wt %. It is proved that the derivatives of the benzoic acid have weaker inhibiting properties than is the case of the corresponding analogues of the cinnamic acid due to the more active participation of the inhibitor in the elementary reactions of propagation and initiation of the radical chain process. The activity (a complex parameter demonstrating the efficiency and strength of the antioxidant) of the phenolic acids investigated decreases in the sequence: caffeic acid &gt;3,4‐dihydroxy‐benzoic acid &gt; sinapic acid &gt; syringic acid&gt;ferulic acid&gt;p‐coumaric acid&gt;vanillic acid. The increase in concentration of the acids investigated is most advisable in the case of sinapic, syringic and ferulic acids which are not consumed in side reactions.

The degradation of 10 phenolic compounds including 9 phenolic acids (caffeic, chlorogenic, p‐coumaric, gallic, gentisic, p‐hydroxybenzoic, protocatechuic, syringic and vanillic acids) and one flavanol (catechin) in subcritical water at the initial concentration of 100 mg/L was investigated in a temperature range of 100–250°C for 30–120 min in a batch‐type vessel. The degradation process followed the first‐order kinetics model. After treatment at 250°C for 30 min, all the compounds completely disappeared. We also demonstrated that the subcritical water treatment of some phenolic compounds, especially, caffeic acid, resulted in products that were quite stable at high temperature and exhibited a high DPPH radical scavenging activity, that is retaining about 50% of the DPPH radical scavenging activity compared to the original caffeic acid solution after the treatment at 250°C for 120 min.

Influence of dietary phenolic acids on redox status of iron: Ferrous iron autoxidation and ferric iron reduction

Three sun-dried date varieties grown in Oman, namely Fard, Khasab, and Khalas, were examined for their proximate composition and functional constituents; dietary fiber, selenium, antioxidant, carotenoids, phenolics as well as phenolic acids. The study was conducted on dried dates due to their higher consumption compared with fresh dates. All results are expressed as mean value ± standard deviation (n= 3) on a fresh weight basis. Date varieties were found to be low in fat and protein, but rich in dietary fiber and antioxidants. They were found to be a high source of energy (278-301 kcal/100 g), due to the high carbohydrate content. Total dietary fiber content of dates varied from 6.26 to 8.44 g/100 g, of which 84-94 was insoluble fiber. Dates were found to be a good source of antioxidant constituents including selenium (0.356 to 0.528 mg/100 g), total antioxidants (8212-12543 I¼mol of Trolox equiv/g), carotenoids (0.92-2.91 mg/100 g), and phenolics (217-343 mg of ferulic acid equiv/100 g). Date varieties had different levels and patterns of phenolic acids. Nine phenolic acids (gallic, protocatechuic, p-hydroxybenzoic, vanillic, caffeic, syringic, pcoumaric, ferulic, and o-coumaric acid) were tentatively identified. Ferulic acid was the major phenolic acid for all date varieties. The total content of phenolic acids ranged between 20.24 mg/100g for Khasab and 63.41 mg/100g for Khalas. Of the date varieties studied, Khalas, which is considered to be of premium quality, had higher antioxidant activity, total carotenoids and phenolic acids than other varieties. These results suggest that all date varieties serve as a good source of natural antioxidants and could potentially be considered as a functional food or functional food ingredient.

Phenolic profile and antioxidant activity of various extracts from Citrullus colocynthis (L.) from the Pakistani flora

Flos Lamii albi has a high biological activity and is widely used in herbal medicine. The aim of the study was to characterize the secretory structures present in Lamium album subsp. album corolla and the location of phenolic compounds. Additionally, we carried out qualitative phytochemical analyses of flavonoids and phenolic acids. Light, fluorescence, and scanning electron microscopy were used to analyze the structure of the floral organs. The main classes of phenolic compounds and their localization were determined histochemically. Phytochemical analyses were performed with high-performance thin-layer chromatography (HPTLC) and high-performance liquid chromatography (HPLC). Six types of glandular trichomes were found which contained flavonoids, phenolic acids, and tannins. The phytochemical studies demonstrated the presence of caffeic, chlorogenic, ferulic, gallic, p-coumaric, protocatechuic, syringic, gentisic, and vanillic phenolic acids as well as rutoside, isoquercetin, and quercetin flavonoids. The corolla in L. album subsp. album has antioxidant properties due to the presence of various polyphenols, as shown by the histo- and phytochemical analyses. The distribution and morphology of trichomes and the content of phenolic compounds in the corolla have taxonomic, pharmacognostic, and practical importance, facilitating the identification of the raw material.