Capsaicinoids products

The intermediates for the branched chain fatty acid production have been detected in tissues [69], The saturated and desaturated forms of the branched chain acyl-ACP and acyl-CoA are in the same relative amounts as in the final capsaicinoid products, as demonstrated for two different cultivated species, habanero (C. chinense) and jalapeno (C. annuum). From these results the authors indicate that the desaturation step occurs prior to release from the FAS complex. 

Screening for no-heat mutants in Capsicum collections and populations is a common practice for pepper breeders, as capsaicinoid accumulation is unique to the members of genus. A second locus for control of capsaicinoid production exists in at least two other species, C. chinense and C. chacoense [82], and the mutation that revealed this second locus is called loss of vesicle (Lov). The blisters on the placental surface that fill with capsaicinoids are absent in these no-heat mutants. The gene product and map location of this mutation are not known. 

Terashima S, Shimizu M, Horie S, Morita N (1991) Studies on aldose reductase inhibitors from natural products. IV. Constituents and aldose reductase inhibitory effect of Chrysanthemum morifolium, Bixa orellana and Ipomoea batatas. Chem Pharm Bull 39 3346-3347 Tewksbury JJ, Manchego C, Haak DC, Levey DJ (2006) Where did the chUi get its spice Biogeography of capsaicinoid production in ancestral wild chili species. J Chem Ecol 32 547-564... 

Capsaicinoids Are Products of the Phenylpropanoid Pathway and the Branched Chain Fatty Acid Pathway... 

Validation of the role of femloyl-CoA in the synthesis of the vanillin precursor will be detection of the appropriate intermediates and/or enzyme activities in placental extracts that could account for the production of the predicted levels of capsaicinoids. The presence of low levels of monolignol intermediates could be explained by lignin biosynthesis. An alternate route from phenylalanine to vanillin has been considered by some investigators Orlova et al. [68] demonstrated the role of the benzenoid pathway in petunia flowers for the biosynthesis of phenylpropanoid/benzenoid volatiles. 

Stored under continuous light, and placental extracts from non-pungent fruit could synthesize capsaicinoids if vanillylamine and isocapric acid are provided. Together, these results raise the possibility that the gene product at Pml is a regulatory gene or a structural gene upstream in either the phenylpropanoid pathway or the branched chain fatty acid pathway and not capsaicinoid synthase. 

Paprika can be extracted to recover carotenoids, not only with CO2 but also with other gases. For example, by using ethane or ethylene, better results were obtained for the yield, extraction time, and quality of product. The solubilities of carotenoids are better in these gases, which is why the consumption of solvent and the extraction time were reduced. Practically water-free dye-concentrate was recovered by supercritical fluid ethane (under the conditions extraction 250 bar, 45°C separation 46 bar, 45 °C). The separation of pungent substances (capsaicinoids, free fatty acids) from the pigments can be carried out effectively in a continuous, counter-current extraction column with a large number of theoretical plates. 

Reilly, C.A., Crouch, D.J. and Yost, G.S. (2001) Quantitative analysis of capsaicinoids in fresh peppers, oleoresin capsicum and pepper spray products. Journal of Forensic Sciences 46(3), 502-509. 

The combination of these elements generates the diversity of capsaicinoids reported to date. Generally, the major constituent of the capsaicinoid soup are capsaicin (la) and its dihydroderivative (lb). Commercial capsaicin potvder is an approximately 5 1 mixture of capsaicin and dihydrocapsaicin, while analytical (>95 %) capsaicin contains mainly nonivamide as impurity. Despite its trivial name of synthetic capsaicin, nonivamide is a natural trace constituent of capsicum oleoresin, and concentration >3 % are indicative of adulteration [26]. The addition of nonivamide to capsicum oleoresin has been detected in products from both the food and the pharmaceutical markets. Some of them have been found to contain exclusively nonivamide, even though capsaicin is the only individual constituent of capsicum oleoresin to be approved by the FDA for human use [26]. 

Since hot pepper is important for the food and the pharmaceutical industries, a range of different methods have been developed for the analysis of capsaicinoids in plant material and finished products. The separation of CPS (la) and nonivamide (11) is especially challenging, since these compounds have similar behavior in many chromatographic conditions. Since synthetic nonivamide is the most common adulterant of capsicum oleoresin, various strategies have been suggested to overcome this problem. Capillary GC does not require previous derivatization of capsaicinoids, but its separatory power seems lower than that of HPLC, currently the most popular technique for the quantization of capsaicinoids. GC is, however, the method of choice for the analysis of the acyl moieties of capsaicinoids as methyl esters. These can be directly produced from capsaicinoids by oxidative N-dealkylation with DDQ (2,3-dichloro-5,6-dicyanobenzoquinone), followed by alcoholysis of the resulting amides with methanol in the presence of an acidic resin (Scheme 4.4) [41]. 

Even in its simplified form, the Nelson protocol will deter the most enthusiast natural-product chemist. Unsurprisingly, alternative protocols have been described in the proprietary literature, and their sheer number testify to the ingenuity and commitment of chemists to solve what is still today a daunting task. Some modern modifications to the Nelson method from the proprietary literature include the use of supercritical carbon dioxide to reduce the extraction of pigments in the preparation of the oleoresin [54], and the recourse to macroporous adsorption resins [55] or to repeated extraction with aqueous silver nitrate to trap capsaicinoids and reduce the number of partition steps [56]. 

In all these protocols, chemoselective amidation of vanillamine with NMA was achieved in satisfactory yield (about 80 %) by activation of the add to its corresponding chloride, followed by condensation with free vanillamine. Free vanillamine is much less stable than its corresponding chloride, and, owing to its polarity, it is difficult to extrad quantitatively from water solution, with loss of about 20 % of the product routinely observed in the desalification step [59]. Furthermore, the preparation of chlorides from polyunsaturated fatty acids is not trivial, and therefore alternative coupling protocols were investigated in a series of systematic studies dedicated to the structure-adivity relationships of capsaicinoids. 

Eor an investigation on the molecular basis of the effect of water stress on the production of capsaicinoids, see ... 

Oleoresin capsicum (OC) is an oily resin derivative from capsicums and composed of several related compounds. Capsicums are solanaceous (nightshade species) plants from the genus Capsicum. More than 20 species fall within the genus. Capsaicinoids are considered the active ingredients of OC. These active compounds are endocrine products of glands found in the plant placenta and are a mixture of two unsaturated and three saturated homologs... 

Capsaicin and capsaicinoids undergo Phase I metabolic bioconversion to catechol metabolites via hydroxylation of the vanillyl ring moiety (Lee and Kumar, 1980 Miller et al, 1983). Metabohsm involves oxidative, in addition to non-oxidative, mechanisms. An example of oxidative conversion involves the liver mixed-function oxidase system to convert capsaicin to an electrophilic epoxide, a reactive metabolite (Olajos, 2004). Surh and Lee (1995) have also demonstrated the formation of a phenoxy radical and quinine product the quinine pathway leads to formation of a highly reactive methyl radical (Reilly et al, 2003). The alkyl side chain of capsaicin also undergoes rapid oxidative deamination (Wehmeyer et al, 1990) or hydroxylation (Surh et al, 1995 Reilly et al, 2003) to hydroxycapsaicin as a detoxification pathway. An example of nonoxidative metabolism of capsaicin is hydrolysis of the acid-amide bond to yield vanillylamide and fatty acyl groups (Kawada et al, 1984 Oi et al, 1992). 

Capsaicin, the major capsaicinoid, is the N-vanillyl amide of 8-methyl-6-nonenoic acid. Related dihydro-, homo-, and dihydrohomo- isomers have also been reported. Most research efforts on red pepper have been concerned with determining the capsaicinoid makeup and concentration in various red pepper varieties and products 0 8). 

Stage that requires high efficiency as well as speed, due to the complexity of the sample matrix, and hence it is particularly challenging to achieve the goals. Therefore, the development of a rapid, sensitive, and reproducible method has been required for separation and determination of capsaicinoid compounds. The addition of ultraperformance liquid chromatography-mass spectrometry (UPLC-MS) method fulfilled these aforementioned demands and showed some complementary advantages to the conventional HPLC-MS, u-HPLC methods in terms of shorter analysis times, low sample volume, and much improved sensitivity [71]. Therefore, nowadays this UPLC-MS technique is routinely performed in pharmaceutical industries and related contract research institutes, laboratories concerned with biochemistry, biotechnology, environmental analysis, natural product research, and several other research fields. The UPLC-MS method has successfully been applied for the determination of n-DHC, C, DHC, h-C, and h-DHC present in the varieties of hot peppers [71]. 

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