Aglycones analysis

Erythromycins. Erythromycin A (14, R = OH, R = CH3, R" = H), the most widely used macroHde antibiotic, was the principal product found in culture broths of Streptomjces eTythreus (39), now reclassified as Saccharopoljspora eythraea (40). It contains a highly substituted aglycone, erythronoHde A, (16, R = R = OH) to which desosamine (1, R = OH, R = H) and cladinose (8, R = CH ) are attached (41). The complete stereochemistry of erythromycin A was estabUshed by x-ray analysis of its hydroiodide dihydrate (42) total synthesis of erythromycin A was a landmark achievement (43), a task previously considered hopeless (44). 

Figure 10.2 MDGC-MS differentiation between the enantiomers of theaspiranes in an aglycone fraction from puiple passion fruit DB5 pre-column (25 m X 0.25 mm i.d., 0.25 p.m film thickness canier gas He, 0.66 ml/min oven temperature, 60-300 °C at 10 °C/min with a final hold of 25 min) permethylated /3-cyclodextrin column (25 m X 0.25 mm i.d., 0.25 p.m film thickness canier gas He, 1.96 ml/min 80 °C isothermal for 20 min and then programmed to 220 °C at 2 °C/min). Reprinted from Journal of High Resolution Chromatography, 16, G. Full et al., MDGC- MS a powerful tool for enantioselective flavor analysis , pp. 642-644, 1993, with permission from Wiley-VCH.

Knowledge of the identity of phenolic compounds in food facilitates the analysis and discussion of potential antioxidant effects. Thus studies of phenolic compounds as antioxidants in food should usually by accompanied by the identification and quantification of the phenols. Reversed-phase HPLC combined with UV-VIS or electrochemical detection is the most common method for quantification of individual flavonoids and phenolic acids in foods (Merken and Beecher, 2000 Mattila and Kumpulainen, 2002), whereas HPLC combined with mass spectrometry has been used for identification of phenolic compounds (Justesen et al, 1998). Normal-phase HPLC combined with mass spectrometry has been used to identify monomeric and dimeric proanthocyanidins (Lazarus et al, 1999). Flavonoids are usually quantified as aglycones by HPLC, and samples containing flavonoid glycosides are therefore hydrolysed before analysis (Nuutila et al, 2002). 

As we have seen above, anthocyanins comprise an aglycone fraction commonly known as anthocyanidin and a frequently acylated osidic substituent. This characteristic leads to two different approaches for the analysis of these pigments (1) a direct anthocyanin analysis without a hydrolysis stage requiring identification of a number of molecules (several hundreds in the plant kingdom) or (2) an analysis of the anthocyanidin fraction only after hydrolysis of the anthocyanins present in the medium. 

Howard-Jones, A.R., Kruger, R.G., Lu, W. et al. (2007) Kinetic analysis of teicoplanin glycosyltransferases and acyltransferase reveal ordered tailoring of aglycone scaffold to reconstitute mature teicoplanin. Journal of the American Chemical Society, 129, 10082-10083. 

G.C.H. Derksen, T.A. van Beek, JE. Groot and A. Capelle, High performance liquid chromato graphic method for the analysis of anthraquinone glycosides and aglycones in madder root (Rubia tinctorum L.), J. Chromatogr. A, 816, 277 281 (1998). 

Identification of flavonoids Quantification of individual flavonoids depends heavily on the availability of standard references. Only a limited number of common flavonoids are commercially available as standards. Standard references for flavonoid glycosides are particularly difficult to find thus direct quantification of the native glycosides is nearly impossible. Analysis of the aglycones after acid or enzymatic hydrolysis is therefore common practice. When standard flavonoids are not available, or when unknown compounds are encountered in a particular fruit or vegetable, use of a DAD... 

The aglycone part of erythromycin A (lb) can be considered as pseudosym-metric (i.e., the stereochemistry of fragment C-4 to C-6 and that of C-10 to C-12 can be regarded as the same). Retro synthetic analysis suggests that the... 

Scheme 7-1. Retro synthetic analysis of the aglycone of erythromycin A (la).

One special feature in the interpretation of the quantitative results seems not to have been exploited in practical analysis, and it certainly deserves attention. The result of the methylation analysis is sometimes complex, and can reveal the occurrence of 10 to 20 different methylated sugars. In this situation, it is not easy to decide, by simple inspection of the analytical data, whether the result could be caused by one complex, carbohydrate chain, or by a structure containing several saccharide chains bound to a common aglycon. In addition, it is not always easy to decide whether the result could fit any natural structure, or mixture of structures, or whether the complex result is attributable to undermethylation. 

It was stated that this combined technique (HPLC-DAD, HPLC-ESI-MS, GC-MS) allows the safe identification of flavonol aglycones and glycosides and can be used for the analysis of these compounds in berries [161]. 

Retrosynthetic analysis of the callypeltoside aglycon based on the Paterson synthesis... 

There have been many survey studies of citrus flavonoids, yet by no means has an exhaustive analysis been performed for all species and cultivars. Surveys often are initiated by hydrolysis of tissue extracts and identification of the flavonoid aglycones present in the tissues. This provides a basis for subsequent identification of the glycosylated compounds present... 

---