Chromatographic investigation on acyl migration in betacyanins and their decarboxylated derivatives

Wybraniec, Sławomir

doi:10.1016/j.jchromb.2007.11.023

Cited by 13 publications

(22 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Compounds 6 , 14 , 15 and 16 , lacking the acetate moiety at C13 hydroxyl group, suffer a paulic acid migration to that position, thus becoming shunt products: 6-hydroxyl-13- O -paulyl-paulinone ( 6′ ), 13- O -deacetyl-13- O -paulyl-paulomycin E ( 14′ ), 13- O -deacetyl-13- O -paulyl-paulomycin B ( 15′ ) and 13- O -deacetyl-13- O -paulyl-paulomycin A ( 16′ ). Migration of acyl groups in aqueous solutions has been demonstrated to occur in other compounds such as betacyanins where glucose 6′- O -position is always favored [ 43 ], thuggacins that suffer acyl migrations of their lactone group [ 44 ], and chloramphenicol that undergoes an intra molecular rearrangement of an acetyl group from 3-hydroxyl to 1-hydroxyl group [ 45 ]. It has been demonstrated that acyl migration occurs to primary hydroxyl groups, which is the most stable position for acyl moieties [ 46 , 47 ].…”

Section: Discussionmentioning

confidence: 99%

New insights into paulomycin biosynthesis pathway in Streptomyces albus J1074 and generation of novel derivatives by combinatorial biosynthesis

et al. 2016

View full text Add to dashboard Cite

BackgroundStreptomyces albus J1074 produces glycosylated antibiotics paulomycin A, B and E that derive from chorismate and contain an isothiocyanate residue in form of paulic acid. Paulomycins biosynthesis pathway involves two glycosyltransferases, three acyltransferases, enzymes required for paulic acid biosynthesis (in particular an aminotransferase and a sulfotransferase), and enzymes involved in the biosynthesis of two deoxysugar moieties: D-allose and L-paulomycose.ResultsInactivation of genes encoding enzymes involved in deoxysugar biosynthesis, paulic acid biosynthesis, deoxysugar transfer, and acyl moieties transfer has allowed the identification of several biosynthetic intermediates and shunt products, derived from paulomycin intermediates, and to propose a refined version of the paulomycin biosynthesis pathway. Furthermore, several novel bioactive derivatives of paulomycins carrying modifications in the L-paulomycose moiety have been generated by combinatorial biosynthesis using different plasmids that direct the biosynthesis of alternative deoxyhexoses.ConclusionsThe paulomycins biosynthesis pathway has been defined by inactivation of genes encoding glycosyltransferases, acyltransferases and enzymes involved in paulic acid and L-paulomycose biosynthesis. These experiments have allowed the assignment of each of these genes to specific paulomycin biosynthesis steps based on characterization of products accumulated by the corresponding mutant strains. In addition, novel derivatives of paulomycin A and B containing L-paulomycose modified moieties were generated by combinatorial biosynthesis. The production of such derivatives shows that L-paulomycosyl glycosyltransferase Plm12 possesses a certain degree of flexibility for the transfer of different deoxysugars. In addition, the pyruvate dehydrogenase system form by Plm8 and Plm9 is also flexible to catalyze the attachment of a two-carbon side chain, derived from pyruvate, into both 2,6-dideoxyhexoses and 2,3,6-trideoxyhexoses. The activity of the novel paulomycin derivatives carrying modifications in the L-paulomycose moiety is lower than the original compounds pointing to some interesting structure–activity relationships.Electronic supplementary materialThe online version of this article (doi:10.1186/s12934-016-0452-4) contains supplementary material, which is available to authorized users.

show abstract

Section: Discussionmentioning

confidence: 99%

New insights into paulomycin biosynthesis pathway in Streptomyces albus J1074 and generation of novel derivatives by combinatorial biosynthesis

et al. 2016

View full text Add to dashboard Cite

show abstract

“…There were clearly two extra peaks displaying [M+H] + at m/z 637 next to phyllocactin/isophyllocactin where their MS/MS fragments at m/z 551 and 389 through neutral loss of Δm/z 86 could indicate the structure of 4'-malonylbetanins (15S/15R). Wybraniec (2008) proposed the formation pathway of these malonyl-betanin isomers by the acyl migration between two adjacent hydroxyl groups at C-4' and C-5' of the glucose units within phyllocactins/isophylocactin structures. [19] 15S/15R betanidin 5-O-β-sophoroside (m/z 713, 4/4 ' ) was also detected in the fraction 22 through the neutral loss of two hexose units (Δm/z 162).…”

Section: Hpccc Elution Profile Of Target Pigmentsmentioning

confidence: 99%

“…Wybraniec (2008) proposed the formation pathway of these malonyl-betanin isomers by the acyl migration between two adjacent hydroxyl groups at C-4' and C-5' of the glucose units within phyllocactins/isophylocactin structures. [19] 15S/15R betanidin 5-O-β-sophoroside (m/z 713, 4/4 ' ) was also detected in the fraction 22 through the neutral loss of two hexose units (Δm/z 162). The overlapping of 4/4 ' and 5/5 ' was seen in a previous high speed CCC separation of Wybraniec et al (2009) [18] where the polar sugar moieties are responsible for a high polarity and lead to early elution in the 'head-to-tail' mode.…”

Section: Hpccc Elution Profile Of Target Pigmentsmentioning

confidence: 99%

The application of ion‐pair high performance countercurrent chromatography monitored by off‐line LC‐ESI‐MS/MS injections to study betalain metabolite from Vietnamese red dragon fruit (Hylocereus polyrhizus)

Thu

Jerz

Winterhalter

2019

Vietnam Journal of Chemistry

View full text Add to dashboard Cite

The pre‐purified betalain extract from Vietnamese red dragon fruits (Hylocereus polyrhizus) was fractionated by a high performance countercurrent chromatography (HPCCC) device using the ion‐pair forming biphasic solvent of tert‐butylmethylether/n‐butanol/acetonitrile/1% aqueous trifluoroacetic acid (2:2:1:5, v/v/v/v). The J‐type HPCCC centrifuge with a 240g centrifugal force field was able to fractionate seven pigments from a 350 mg enriched crude pigment fruit extract, resulting in purified fractions for qualitative identification by LC‐ESI‐MS/MS. This approach fractionated the main betacyanin epimers namely 15R/15S‐betanin (m/z 551), 15R/15S‐phyllocactin (m/z 637), and apiosyl‐15R/15S‐betanin (m/z 683) from the solely existing betaxanthin indicaxanthin. In addition, few minor betacyanins such as 2’‐apiosyl‐15R/15S‐phyllocactin (m/z 769) were concentrated in a few fractions. That method also allowed the better detection of cacti fruit pigment 15R/15S‐hylocerenin (m/z 695), and 15R/15S‐betanidin 5‐O‐β‐sophoroside (m/z 713). However, the separation of these highly polar compounds was incomplete due to insufficient force of the ion‐pairing effect of trifluoroacetic acid (TFA).

show abstract

“…Along with 3 / 3′ , accompanying isomers previously chromatographically assigned as acyl migration products, betanidin/isobetanidin 5- O -(4′- O -malonyl)-β-sophoroside 4 / 4′ , 29 , 35 , 49 , 50 were also identified in the Melocactus samples ( Tables 1 and 3 , Figures 3 and 4 ) according to their retention times and coelution with the authentic standards derived from fruits of Mammillaria species 35 as well as low- and high-resolution mass spectrometric experiments. As in the case of Mammillaria fruits, the characteristic profile of two pairs of structural isomers 3 / 4 and 3′ / 4′ presented already in the extensive acyl migration study 49 was confirmed here for the Melocactus fruits. For this aim, analyses of the 3 / 4 and 3′ / 4′ standard mixtures obtained from a Mammillaria fruit extract 35 were performed (data not shown) which enabled confirmation of retention times of 4 / 4′ .…”

Section: Resultsmentioning

confidence: 99%

Identification and Determination of Betacyanins in Fruit Extracts of Melocactus Species

Sutor

Wybraniec

2020

J. Agric. Food Chem.

Self Cite

View full text Add to dashboard Cite

Betacyanin pigments were studied in edible fruits of four Melocactus species, M. violaceus Pfeiff., M. bahiensis (Britton & Rose) Luetzelb, M. amoenus (Hoffm.) Pfeiff., and M. curvispinus Pfeiff., by means of chromatographic and mass spectrometric techniques. The main pigment constituent, melocactin, endogenously present in the Melocactus species, was identified as betanidin 5- O -β-sophoroside betacyanin, previously known as “bougainvillein-r-I”. The highest total concentration of betacyanins was found in fruits of M. amoenus (∼0.08 mg/g). Except for melocactin being the most abundant betacyanin (34.8–38.8%) in the analyzed species, a presence of its malonylated derivative, mammillarinin (15.2–19.9%), as well as more hydrophobic feruloyled and sinapoyled melocactins was confirmed by additional co-chromatographic experiments with authentic reference betacyanins. The acyl migration isomers of the malonylated betacyanins as well as a presence of 5′′- O - E -sinapoyl-2′- O -apiosyl-betanin (2.3–3.0%) found frequently in light-stressed cacti was also acknowledged.

show abstract

Chromatographic investigation on acyl migration in betacyanins and their decarboxylated derivatives

Cited by 13 publications

References 30 publications

New insights into paulomycin biosynthesis pathway in Streptomyces albus J1074 and generation of novel derivatives by combinatorial biosynthesis

New insights into paulomycin biosynthesis pathway in Streptomyces albus J1074 and generation of novel derivatives by combinatorial biosynthesis

The application of ion‐pair high performance countercurrent chromatography monitored by off‐line LC‐ESI‐MS/MS injections to study betalain metabolite from Vietnamese red dragon fruit (Hylocereus polyrhizus)

Identification and Determination of Betacyanins in Fruit Extracts of Melocactus Species

Contact Info

Product

Resources

About