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Studies on the constituents of Helleborus purpurascens: use of derivatives from calix[6]arene, homooxacalix[3]arene and homoazacalix[3]arene as extractant agents for amino acids from the aqueous extract

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Abstract

The task of this work was to investigate the extraction capacity of various calixarenes for free and esterified amino acids from aqueous acid phases. Furthermore, this method was applied to aqueous extracts of Helleborus purpurascens. Generally, it is known that calixarenes can be used as extractants for ammonium compounds due to π-cation and lone pair cation interactions. As first, tert-Butyl-calix[6]arene and derivatives thereof were used. They had already proven their worth in previous investigations. In addition, tert-Butyl-hexahomooxa-calix[3]arene was used also, which can also enter into lone pair cation interactions. In addition to these well-known calixarenes, new calixarenes were produced and tested. Based on the tert-Butyl-hexahomooxa-calix[3]arene, a phosphor(III)bridged derivative was prepared, combining the three aromatic hydroxyl groups to a phosphite. As a seldom-described class of calixarenes, tert-Butyl-hexahomoaza-calix[3]arene derivatives were used. The nitrogen analogues of tert-Butyl-hexahomooxa-calix[3]arene could be produced as N-benzyl derivatives. The structure of the esterified carboxymethylated derivative of N,N′,N″-Tribenzyl-tert-Butyl-hexahomoaza-calix[3]arene could be verified by X-ray structure analysis. It crystallized as a partial cone. The extraction capacity of the described calixarenes was investigated for amino acids from aqueous acidic solutions into an organic phase. For the testing were chosen asparagine, aspartic acid, tyrosine, tryptophane, phenylalanine and pipecolinic acid and their methyl esters. The amino acids and their methyl esters were dissolved in water at different pH values. The calixarenes were dissolved in dichloromethane (DCM) or chloroform. After this preparation, the aqueous acidic amino acid solutions were mixed with the solutions and shaken intensively. In addition, blank values were determined by extracting the aqueous stock solutions of the amino acids and their methyl esters with pure solvents. To determine the extraction rate, the phases were separated and each analysed using GC-FID, partially GC–MS(EI). The evaluation is performed in two ways. On the one hand the depletion in the aqueous phase and on the other hand the content in the organic phase was determined.

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Notes

  1. The term “hydroalcoholic” is not precisely but commonly used. Therefore, the term is also used by the authors for the extract which was generated with a mixture of water and ethanol.

  2. A congruence of retention time and fragmentation pattern between an unknown substance and an authentic material proves the identity of an unknown substance.

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Acknowledgements

The authors want to thank Ing. Geta Serbanescu and Ing. Draga Todorov (both S.C. Exhelios S.R.L.) for fruitful discussions and for the support of this work with rhizome and roots of H. purpurascens and an already prepared hydroalcoholic extract thereof. The authors want to thank also Dr. Macarie A. Corina and Dr. Ionel Balcu, (both: Institutul National de Cercetare Dezvoltare pentru Electrochimie si Materie Condensata, Timisoara, Romania) for their contributions for this publication and also Dr. Matthias Freytag (Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Braunschweig, Germany); the authors want to thank for the measuring of the x-ray structure. In addition, this work was supported by the Romanian National Authority for Scientific Research through the exploratory research program: “DEI-PCE-PROJECT NR. 341-/05.10.2011-Immunomodulatory Fluoroglycopeptide Molecular Architectures and PROJECT NR. 18360301, Contract: 42N/2018”.

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  1. Institutul National de Cercetare Dezvoltare pentru Electrochimie si Materie Condensata, Str. Dr. A. Paunescu Podeanu, Nr. 144, 300569, Timisoara, Romania

    M. Heiko Franz, Mirela Iorga, Catalin V. Maftei, Elena Maftei & Ion Neda

  2. InnoChemTech GmbH, Hagenring 30, 38106, Brunswick, Germany

    M. Heiko Franz

  3. Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106, Brunswick, Germany

    Catalin V. Maftei, Elena Maftei & Ion Neda

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  1. M. Heiko Franz
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  4. Elena Maftei
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Contributions

IN, MI and MHF contributed to the study conception and design. EM synthesised the Homoaza-calix[3]arene; IN and CVM synthesised the phosphorous-bridged Homooxa-calix[3]arene, MHF synthesised the esters of the amino acids; excepted the extractions and performed the GC analysis. The first draft of the manuscript was written by MHF and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Ion Neda.

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Franz, M.H., Iorga, M., Maftei, C.V. et al. Studies on the constituents of Helleborus purpurascens: use of derivatives from calix[6]arene, homooxacalix[3]arene and homoazacalix[3]arene as extractant agents for amino acids from the aqueous extract. Amino Acids 52, 55–72 (2020). https://doi.org/10.1007/s00726-019-02809-z

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