Phenolic cinnamic acid derivatives

The chemical formulae for a variety of plant phenols are given in Fig. 16.2, including examples of simpler phenols, such as cinnamic acid derivative, and of tocopherols, flavonoids, flavonoid glycosides and anthocyanidins. The flavonoids include the following subclasses flavanones (taxifolin), flavones (luteolin), flavonols (quercetin) and flavanols (catechin/epicatechin). The... 

Wine and by-products Cinnamic acid derivatives, anthocyanins and flavanols dominate (10 to 20 J,M gallic acid equivalents) Oil-in-water emulsion (dressing model) Red wine yields better protection, but phenols in white and rose wine seem more efficient on a molar basis Sanchez-Moreno et al., 2000... 

Arcmatic compounds phenols, phenolic acids, cinnamic acid derivatives, coumarins, flavonoids, quinones, and tannins, all of which are aromatic compounds, comprise the largest group of secondary plant products. They are often referred to as "phenolics" and have been identified as allelopathic agents in more instances than all of the other classes of compounds combined 5). 

Two hypotheses have been proposed to explain how phenolic acids directly increase membrane permeability. The first is that the compounds solubilize into cellular membranes, and thus cause a "loosening" of the membrane structure so that minerals can leak across the membrane (28-30, 42). Support for this hypothesis comes from the fact that the extent of inhibition of electrical potentials correlates with the log P (partition coefficient of a compound between octanol and water) for various benzoic and cinnamic acid derivatives (Figure 5). 

El-Basyouni, S.Z., A. C. Neish, andG. H. N. Towers The Phenolic Acids in Wlxeat III. Insoluble Derivatives of Phenolic Cinnamic Acids as Natural Intermediates in Lignin Biosynthesis. Phytochem. 3, 627—640 (1964). 

Figure 6.5 shows the structures of tra 5-cinnamic acid and four cinnamic acid derivatives (phenolic compounds) reported to be present in potatoes. Because potatoes are one of our major food plants, we validated with the aid of HPLC and LC/MS the content and distribution of antioxidative phenolic compounds in parts of the potato plant, in potato tubers, in the peel and flesh of tubers, in potatoes sold commercially in Korea and the United States, and in home-processed potatoes. The following discussion, based on our own studies, is followed by a brief overview of analytical methods for potato phenolic compounds by other investigators. 

Singleton and Esau (I) reviewed the methods for phenol analysis of wine. They pointed out that study would be greatly advanced if one could determine the total content of phenolic substances and express it in such a way that analysis of subclasses of phenols could be related to the original total and a balance sheet could be obtained. One could then say, for example, this wine has a total phenolic content of 1200 mg/liter calculated as gallic acid, and of that total, cinnamic acid derivatives account for 200 mg/liter, anthocyanins for 300 mg/liter, other small flavonoids for 200 mg/liter, and condensed tannins complete the total with 500 mg/liter of gallic acid equivalent. To accomplish this, the total phenol analysis not only must meet ordinary criteria of reproducibility and precision, but it also must be based on chemical relationships such that fractions determined separately can be converted to units of the total. Of course when clearcut fractionation can be accomplished by... 

The common phenolic acids have been detected at a single wavelength of 254 nm or 280 nm, by dual monitoring at 254 nm and 280 nm or at 280 nm and 320 nm, and by multiple-wavelength monitoring at 254 nm, 275 nm, and 300 nm. With detection at 320 nm, cinnamic acid derivatives can be detected without any interference from benzoic acid derivatives, which have a higher response at 254 nm. However, detection at 280 nm is at the best wavelength for the determination of both classes of phenolic compounds (10). 

However, due to the artifacts resulting from oxidation, hydrolysis of esters or ethers, or isomerization of phenolics during pretreatment of wines, as well as due to the low recovery rates of some phenolics, analysis of wine phenolics via direct injection of the filtered wine into the chromatographic column is often selected (80,82-84). For the red wine and musts (80), which were injected directly into the HPLC without sample preparation, a ternary-gradient system was often employed for phenolic compounds. Twenty-two phenolic compounds, including 10 anthocyanins, were analyzed from red wine. The separation of cinnamic acid derivatives (313 nm),... 

For the red wines (82-84), which were injected directly into the HPLC without sample preparation, a ternary-gradient system using aqueous acetic acid (1% and 5% or 6%), and acidified acetonitrile (acetonitrile-acetic acid-water, 30 5 6) was used for cinnamic acid derivatives, catechins, flavonols, flavonol glycosides, and proanthocyanidins. Due to the large number of peaks, the gradient was extended to 150 min for the resolution of many peaks of important phenolics. This direct injection method was able to separate phenolic acids and esters, catechins, proanthocyanidins, flavonols, flavonol glycosides, and other compounds (such as tyrosol, and rrans-resveratrol) in wine in a single analysis. However, use of acetic acid did not permit the detector (PDA) to be used to record the UV spectra of phenolics below 240 nm (84). 

Tannins and lignins are also derived from these pathways but are not included in Table 1. To make the list as simple as possible, all compounds of aromatic nature, viz., simple phenols, benzoic and cinnamic acid derivates, coumarins, flavonoids and quinones are condensed into one group - aromatic compounds. Thus I will attempt to cover systematically the secondary plant growth substances that fall into 11 major groups as shown in Table 1. 

The substrates of the polyphenol oxidase enzymes are phenolic compounds present in plant tissues, mainly flavonoids. These include catechins, anthocyanidins, leucoantho-cyanidins, flavonols, and cinnamic acid derivatives. Polyphenol oxidases from different sources show distinct differences in their activity for different substrates. Some specific examples of polyphenolase substrates are chlorogenic acid, caffeic acid, dicatechol, protocatechuic acid, tyrosine, catechol, di-hydroxyphenylalanine, pyrogallol, and catechins. 

There is a growing interest in naturally occurring phenolic compounds that display biological antioxidant properties such as -hydroxycinnamic acid, ferulic zcid, caffeic acid/ and curcumin which are ubiquitous in plant food. It has been demonstrated that the interaction of the oxidizing OH adduct of DNA, poly-A and poly-G with hydrox-ycinnamic acid derivatives proceed via electron transfer. Cinnamic acid derivatives have been shown to be able to scavenge superoxide, peroxyl, and hydroxyl radicals. 

Cinnamic acid is well known for its role as a phenolic compound that gives the oil cinnamon its characteristic odor and flavor. It is soluble in water or ethanol and in nature cinnamic acid derivatives are known to... 

It was found that the treatment of spirodienone 322 with a H2SO4/ACOH mixture (1 50 v/v) results in an isomerization to form the cinnamic acid derivative 323 instead of the classical dienone-phenol rearrangement product (equation 154). 

In TFA solution, electron-rich examples of cinnamic acid derivatives and phenols give high yields of 4-aryl-3,4-dihydrocoumarins at room temperature with good regioselectivity <05JOC2881,05T9291>. 

The phenolic compounds present in these three commodities fall into two general classifications, cinnamic acid derivatives and flavonoids. Included in the former are chlorogenic acid and its isomers, free cinnamic acids such as caffeic and p-coumaric acid and various esters of those two acids. Included among the flavonoids are the following ... 

Figure 28 shows that substituted cinnamic acid derivatives have a relatively low absorption in the 310—320 nm region, so that they are relatively ineffective ultraviolet absorbers. Their main advantage is that they have no phenolic hydroxyl group which could be sensitive to alkali or heavy metal ions. The alkali sensitivity is a severe shortcoming for textile applications. On the other hand, with polyoxymethylene for instance, the thermal degradation can be catalysed by phenols, and with polyvinylchloride, side reactions can occur with metal stabilizers. 

In the last years, natural products have been used as antioxidative, melanogenesis inhibitors and sunscreen [48]. Lipid peroxidation is related to aging, membrane damage, heart disease, stroke and cancer in living organism. This oxidative mechanism could be stopped by the addition of synthetic anti-oxidants, but now it has been recognised that natural antioxidants are safe compared to tile synthetic compounds [49], Well-known natural anti-oxidants are represented by ubiquinones, tocopherols mid related compounds, flavonoids, cinnamic acid derivatives, licopene and related tetraterpenoids, and also by phenolic compounds [50]. 

Five soluble phenolic acids (free and esterifled), one of which is a hydroxylated derivative of benzoic acid (gallic acid) and four are cinnamic acid derivatives (caffeic, p-coumaric, ferulic, and sinapic acids), have been studied and tentatively identified in ethanolic extracts of hazelnut kernel and hazelnut by-products (Table 13.2) [31]. The order of total phenolic acid concentration was as follows hazelnut hard shell > hazelnut green leafy cover > hazelnut tree leaf > hazelnut skin > hazelnut kernel. Different phenolic acids predominate in each plant part examined. Among the identified phenolic acids, p-conmaric acid was most abundant in hazelnut kernel, hazelnut green leafy cover, and hazelnut tree leaf, whereas gallic acid was most abundant in hazelnut skin and hazelnut hard shell, possibly implying the presence and perhaps the dominance of tannins in the latter samples (Table 13.2). The same number, but different concentration, of phenolic acids have also been reported in hazelnnt kernel and hazelnut green leafy cover [30]. 

The main classes of phenolic compounds found in fruits are (1) phenolic acids, (2) stilbenes, (3) lignans, (4) flavonoids, and (5) tannins or proanthocyanidins. These classes are the most abundantly occurring phenolic compounds which are also an integral part of everyday dietary antioxidants in populations worldwide [7]. The most abundant phenolic compounds in the diet are phenolic acids (benzoic and cinnamic acid derivatives) and flavonoids which account for 60% and 30%, respectively, of total dietary phenolic compounds [7]. These phenolic compounds may be associated with various carbohydrates and organic acids and with one another (Figure 2 Table 1). 

Benzoic and cinnamic acid derivatives and flavonoids are the two most distributed phenolics within plants. Polyphenolic units are biosynthesized via shikimate pathway, resulting in cinnamic acids C -C phenylpropanoid building block that also contributes to other plant phenolics backbones such as those from flavonoids (Q-Ca-Ce), anthocyanidins (C6-C3-C6), and coumarins (C6-C3). Stilbeneoids (C6-C2-C6) and benzoic acid derivatives (Cfi-Ci) such as gallic and ellagic acids are also synthesized through this metabolic pathway (Fig. 1). 

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