Metabolomics of thrips resistance in pepper capsicum spp. Peyssonnosides ab, unusual diterpene glycosides with a. Salvia divinorum yields salvinorin a, a psychotropic drug. Schuman,a,1 matthias schoettner,a purba mukerjee,a,2 beatrice berger,a,3 bernd schneider,b amir r. A novel acyclic diterpene glycoside, capsianside a, from. Acyclic diterpene glycosides, capsianosides c, d, e, f and. The leaves of stevia contain a natural complex mixture of eight sweet diterpene glycosides, including isosteviol. Acyclic diterpenoids from the leaves of capsicum annuum. Acyclic 17hydroxygeranylinalool glycosides from solanaceae family act as important resistant compounds against herbivorous insects, while enzymes responsible for their glycosylation remain unclear. Two new diterpene glycosides in addition to five known glycosides have been isolated from a commercial extract of the leaves of stevia rebaudiana. Two new acyclic diterpene glycosides from fruits of habanero capsicum chinense four acyclic diterpene glycosides were extracted from habanero, the fruits of. A novel diterpene glycoside with nine glucose units from. Pdf a new acyclic monoterpene glucoside from viscum.
Sweet entkaurene diterpene glycosides of stevia rebaudiana. Structureactivity relationship study of acyclic terpenes. The chemical structure was established in 1952 as a diterpene glycoside. Anatomical and morphological structures see more details of c. Papuamides ad are cyclic depsipeptides from theonella sp. Monomer and dimer acyclic diterpene glycosides capsianosides were pinpointed as metabolites that were related to thrips resistance. Direct analysis of stevia leaves for diterpene glycosides. Hydrolysis of terpenyl glycosides in grape juice and. A new acyclic diterpene glycoside from nicotiana attenuata with a mild deterrent effect on feeding manduca sexta larvae by a. Several entkaurenoid diterpene glycosides with steviol as a common aglycon. Moreover, metabolomic profiles of resistant and susceptible accessions differed. A new acyclic diterpene glycoside from nicotiana attenuata with a mild deterrent effect on feeding manduca sexta larvae. Diterpene glycosides, an abundant and effective direct defense against herbivores in nicotiana attenuata w sven heiling,a,1 meredith c.
Novel acyclic diterpene glycosides, capsianosides af and iv. Expired fee related application number us09256,066 inventor james h. They are produced by plants as part of their selfdefense mechanism 6 with important subclasses including ginsenosides 7 and eleutherosides. Pdf a new acyclic diterpene glycoside from nicotiana. Three new acyclic diterpene glycosides from the aerial parts of paprika and pimiento find, read and cite. In a study of the watersoluble constituents of the fruits of three varieties of c. A sterol glycoside from marine green alga codium iyengarii. They are biosynthesized by plants, animals and fungi via the hmgcoa reductase pathway, with geranylgeranyl pyrophosphate being a primary intermediate. Acyclic diterpene glycosides, named capsianosides i, ii, iii 1, c 2, d 3, e 4 and f 5, have been isolated from the dried hot red pepper fruits of capsicum annuum l. Three of these diterpene alcohols were already known compounds, while other three are new.
Pdf hosted at the radboud repository of the radboud university. Mauri et al 35 employed a capillary electrophoresis method to analyze stevia rebaudiana glycosides where they obtained rebaudioside a and steviolbioside using a semi preparative hplc. Diterpene glycoside an overview sciencedirect topics. This study provides an example of the application of desi to direct screening of plant materials, in this case diterpene glycosides. Sucrose and malonylated flavone glycosides were related to susceptibility. Us6228996b1 process for extracting sweet diterpene. Jasmonate and pphsystemin regulate key malonylation. Acyclic diterpene alcohols isolated from four algae of. We obtained novel acyclic diterpene glycosides, named. Pdf metabolomics of thrips resistance in pepper capsicum spp. The enthalpies of hydrolysis of acyclic, monocyclic, and. We selected 11 capsicum accessions from a group of 40 accessions that were screened for resistance to the western flower thrips f. Umbellulone is another example of bicyclic monoterpene ketone natural roles. Diterpene glycosides from korean fermented red pepper paste.
Regioand enantioselective functionalization of acyclic polyprenoids. Specific decorations of 17hydroxygeranyllinalool diterpene. Other diterpene glycosides are frequently reported in lamiales genus isodon, salvia, gentianales genus coffea, gardenia and solanales plants. Jun 08, 2019 putative acyclic diterpene glycosides detected in negative mode were confirmed by ms analysis in positive mode based on the presence of their common fragment with specific accurate mz 271. Hhere are different types of glycosides depending on the atom through which the linkage is done. Pharmacokvica activity 2 there including regulation, protection and sanitary health function. Biological template based on entkaurane diterpenoid. Makapugay 34 quantified the diterpene glycosides by hplc using soxhlet extraction. In our untargeted metabolomics analyses, we detected double charged fragments that were correlated with thrips resistance. Pdf two new acyclic diterpene glycosides from fruits of. A new diterpene glycoside from rabdosia rubescens hongmin liu,a xuebin yan, afumiyuki kiuchi,b,1 and zhenzhong liu department of chemistry, zhengzhou university,a zhengzhou 450052, china and faculty of pharmaceutical sciences, kanazawa university,b takaramachi, kanazawa 9200934, japan.
These insects can cause extensive damage to fruits, flowers and leaves on field and greenhouse grown plants worldwide. In the near future, terpene glucosides will become com. Introduction to glycosides philadelphia university. Cyclic peptides, acyclic diterpene glycosides and other compounds from lycium chinense mill. We obtained novel acyclic diterpene glycosides, named capsianosides af 16 and iv 7, 1b, 10, 9, 8 from various fruits of the capsicum annuum species and their structures were elucidated by. The physicochemical and spectroscopic analyses including nmr, eims, and ir indicated that the three. Structureactivity relationship study of acyclic terpenes in. Cyclic peptides, acyclic diterpene glycosides and other. Linalool is an acyclic monoterpenoid bicyclic monoterpenes include carene, sabinene, camphene, and thujene.
Structural characterization of the degradation products of a. To our knowledge, this is the first time that dimer capsianosides of pepper have been linked to insect resistance. Leaves of tobacco introduction ti165 were found to be resistant to tobacco budworm heliothis virescens f. Capsicum species are very important plants used as vegetable foods, spices and external medicines. Glycosides may be phenol, alcohol, or sulfur compounds.
Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed. These compounds are all glycosides of the diterpene enthydroxykaur16en19oic acid known as steviol 3,4. Pdf occurrence, biological activities and synthesis of kaurane. Hplc profiles of leaf extracts showed that ti165 had relatively high levels of two components a and b that were absent in susceptible varieties. For example, the abundance of monomers and dimers of capsianosides is correlated with thrips resistance in pepper capsicum spp macel et al. They are characterized by sugar proteins attached by a special bond to one or more nonsugar proteins. The structures of these compounds have been revised in the sugar connectivities by 1d and 2dnmr spectroscopic and chemical methods. In comparison with similar monoterpene glycosides, c6 z. Biosynthesis of the phenolic monoterpenes, thymol and carvacrol. Three acyclic diterpenoids were isolated from the etoac fraction through repeated silica gel column chromatography. Results and discussion the watersoluble layer of the aqueous acetone extract was subjected to rp18. A major thrips resistance qtl in capsicum was finemapped to a region of 0. Most are multicyclic structures with oxygencontaining functional groups.
Reveals monomer and dimer acyclic diterpene glycosides as potential chemical defenses june 2019 journal of. Characteristic constituents of the stevia plant are observed in both the positive and negative ion modes including a series of diterpene. Telmer southern crop protection and food research center, 91 sandford street, london, ont. Although sometimes used interchangeably with terpenes, terpenoids or isoprenoids are modified terpenes that contain additional functional groups, usually oxygencontaining. Structural elucidation by 2d nmr spectroscopy isolation and structure elucidation of the clerodanetype diterpene glycosides palmatosides c i and fii. Putative acyclic diterpene glycosides detected in negative mode were confirmed by ms analysis in positive mode based on the presence of their common fragment with specific accurate mz 271. Ca2758122c diterpene glycosides as natural solubilizers.
Geranyllinalool gl is an acyclic diterpene alcohol which is widely. A new acyclic diterpene glycoside from nicotiana attenuata. Acyclic diterpene glycosides, capsianosides viii, ix, x, xiii. In addition, myrcene, one of the acyclic monoterpene alcohols showed a negative. In this sense, the steviol is a constituent from stevia rebaudiana, a plant native to certain regions of south america paraguay and brazil. Geranyllinalool synthases in solanaceae and other angiosperms. The chemical structures of four cyclic peptides, lyciumins ad 14, three acyclic diterpene glycosides, lyciumosides iiii 57 and other three compounds, a tryptophan derivative glycoside 8, a monoterpene glycoside 9 and a steroidal glycoside 10 isolated from lycium chinense, have been elu. Their structures were elucidated by spectroscopic and chemical means. Recently we have reported the isolation and sensory evaluation of rebaudioside m 1, also known as rebaudioside x, a minor. Monoterpenes are found in many parts of different plants, such as barks. Compounds a and b were isolated from ti165 by a combination of preparative c18, silicic acid column, and centrifugal thinlayer. Diterpenes form the basis for biologically important compounds such as retinol, retinal, and phytol.
Two diterpene glycosides rebaudiosides t and u, minor c19 xylopyranosyl. Minor diterpene glycosides from the leaves of stevia. Hydroxygeranyllinalool glycosides from tobacco exhibit. Some authors use the term terpene more broadly, to include the terpenoids. Therefore, we have isolated and characterised acyclic diterpene alcohols from four siphonaceous. In addition, the presence of characteristic glycosides in an allnatural commercial stevia dietary supplement was confirmed. Twelve terpenoids were evaluated in the treatment of type 2 diabetes mellitus. About 60% of known natural products are terpenoids. Triterpenoid saponins are triterpenes which belong to the saponin group of compounds, making them triterpenoid glycosides.
Functions of glycosides in the plant formation of glycosides in different parts of plants has. Three novel diterpene glycosides were isolated for the first time from the commercial extract of the leaves of stevia rebaudiana, along with several known steviol glycosides, namely stevioside, rebaudiosides af, rubusoside and dulcoside a. Reveals monomer and dimer acyclic diterpene glycosides as potential chemical defenses. A novel acyclic diterpene glycoside was obtained from the part of the polar ingredients in the fresh fruits of capsicum annuum l. Twelve novel acyclic diterpene glycosides, named capsianosides, were isolated from fruits of c. This property has fostered interest in their biosynthesis and metabolism. Fine mapping of a thrips resistance qtl in capsicum and. The capsianosides were classified into 2 groups, monomeric diterpene glycosides capsianosides iv and their dimeric esters capsianosides af. Jasmonate and pphsystemin regulate key malonylation steps in. Obicyclooctane may be con sidered an analog for cyclic 2. Pdf a new acyclic monoterpene glucoside from viscum album.
Diterpene glycosides from korean fermented red pepper. For this reason, most glycosides can be classified as prodrugs as they remain inactive until they are hydrolyzed. Bicyclic monoterpenes include carene, sabinene, camphene, and thujene. Twelve novel acyclic diterpene glycosides glycosides subject category. Interestingly, various acyclic diterpene glycosides including capsianoside f 2 have been identified from red pepper izumitani et al.
After manual annotation, 1031 mz features were annotated as. Request pdf on sep 23, 2008, jonghyun lee and others published cheminform abstract. A steviol glycoside bearing nine glucose units is unprecedented in the literature, and could have an impact on the natural sweetener catalog. Many plants store chemicals in the form of inactive glycosides, which can be activated by enzyme hydrolysis polt, 1995. Camphor, borneol, eucalyptol and ascaridole are examples of bicyclic monoterpenoids containing ketone, alcohol, ether, and bridging peroxide functional groups, respectively. A new acyclic diterpene glycoside from nicotiana attenuata 19 pound 3 is a new natural product, isolated here for the. Feb 15, 2012 a novel acyclic diterpene glycoside 1, capsianoside xviii and capsianoside f 2 were isolated and identified from gochujang. Resistance to thrips is an important trait for pepper growers. Acyclic diterpene alcohols from algae 17 weeds table i. The enthalpies of hydrolysis of acyclic, monocyclic, and glycoside cyclic phosphate diesters have been measured by flow microcalorimetry using a phosphohydrolase isolated from enferobacfer aerogenes as catalyst. Acyclic diterpene glycosides, capsianosides viii, ix, x, xiii, xv and xvi from the fruits of paprika capsicum annuum l. Diterpenes are a class of chemical compounds composed of four isoprene units, often with the molecular formula c 20 h 32. Recently, glycosides of the kaurane diterpene known as steviol enthydroxykaur16en19oic acid have been employed as biological templates in the preparation of porous nanomaterials 4,7. The name terpene is a shortened form of terpentine, an obsolete spelling of turpentine.
This family of natural products possesses a diterpene core and has been used to sweeten food products for hundreds of years in south america 4. Direct analysis of stevia leaves for diterpene glycosides by. Chemicals and chemical groups see more details, named capsianosides, were isolated from fruits fruits subject category. The compound 1 exhibited the following spectral data. The values so ob tained kilocalories per mol at 25 for sodium salts are. Diterpene furan glucosides from tinospora 34 234 cordifolia. Dtg dereplication rules may still be applied to these novel acyclic diterpene glycosides, the ratios of the aglycone fragments and adducts appeared to be different. Novel acyclic diterpene glycosides, capsianosides af and. Although sometimes used interchangeably with terpenes. Geranyllinalool is an acyclic diterpene alcohol with a wide distribution in the plant kingdom. Two sulfated diterpene glycosides featuring a highly substituted and sterically.
Cyclic diterpenes result from two different biosynthetic cyclization processes from ggpp figures. The chemical structures of four cyclic peptides, lyciumins ad 14, three acyclic diterpene glycosides, lyciumosides iiii 57 and other three compounds, a tryptophan derivative glycoside 8, a monoterpene glycoside 9 and a steroidal glycoside 10 isolated from lycium chinense, have been elucidated by a combination of chemical, 1 h and cnmr, and mass spectrometric studies. The analysis of stevia leaves has been demonstrated without any sample preparation using desorption electrospray ionization desi mass spectrometry. By the early 21st century, only a limited number of the chemical structures of steviol glycosides in s. The terpenoids, sometimes called isoprenoids, are a large and diverse class of naturally occurring organic chemicals derived from the 5carbon compound isoprene, and the isoprene polymers called terpenes. Pathway elucidation and engineering of plantderived. The terpenoids, sometimes called isoprenoids, are a large and diverse class of naturally. Direct rapid analysis was achieved using minimal amounts of sample. Acyclic diterpene glycosides, capsianosides viii, ix, x. The chemical structures of four cyclic peptides, lyciumins ad 14, three acyclic diterpene glycosides, lyciumosides iiii 57 and other three compounds, a tryptophan derivative glycoside 8, a monoterpene glycoside 9 and a steroidal glycoside 10 isolated from lycium chinense, have been elucidated by a combination of chemical, 1h and cnmr, and mass spectrometric studies. Based on these evidences, the monoterpene structure should be 1hydroxylinalol.
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