Recent Advances in Polyphenol Research. Группа авторов
Читать онлайн книгу.Chemistry, 37: 5617–5626.
3 Basílio, N., and Pina, F. (2014). Flavylium network of chemical reactions in confined media: modulation of 3’,4’,7‐trihydroxyflavilium reactions by host–guest interactions with cucurbit[7]uril. ChemPhysChem, 15 (11): 2295–2302.
4 Bjorøy, Ø., Rayyan, S., Fossen, T., et al. (2009). Structural properties of anthocyanins: rearrangement of c‐glycosyl‐3 deoxyanthocyanidins in acidic aqueous solutions. Journal of Agricultural and Food Chemistry, 57 (15): 6668–6677.
5 Brouillard, R., and Dubois, J.E. (1977). Mechanism of structural transformations of anthocyanins in acidic media. Journal of the American Chemical Society, 99 (5): 1359–1364.
6 Brouillard, R., Iacobucci, G.A., and Sweeny, J.G. (1982). Chemistry of anthocyanin pigments. 9. UV‐visible spectrophotometric determination of the acidity constants of apigeninidin and three related 3‐deoxyflavylium salts. Journal of the American Chemical Society, 104 (26): 7585–7590.
7 Cruz, L., Basílio, N., Freitas, V., et al. (2016). Extending the study of the 6,8 rearrangment in flavylium compounds to higher pH values. Inter‐conversion between 6‐bromo and 8‐bromo‐apigeninidinin. Chemistry Open, 5 (3): 236–246.
8 Sousa, J.L., Gomes, V., Mateus, N., et al. (2017). Synthesis and equilibrium multistate of new pyrano‐3‐deoxyanthocyanin‐type pigments in aqueous solutions. Tetrahedron, 73 (41): 6021–6030.
9 Cruz, L., Sousa, J.L.C., Gomes, V., et al. (2017). Chemical equilibrium characterization of pyrano‐3‐deoxyanthocyanin derivatives. Tetrahedron 73: 6012–6030.
10 Dangles, O., Saito, N., and Brouillard, R. (1993). Kinetic and thermodynamic control of flavylium hydration in the pelargonidin‐cinnamic acid complexation. Origin of the extraordinary flower color diversity of Pharbitis nil. Journal of the American Chemical Society, 115 (8): 3125–3132.
11 Fernandes, A., Brás, N., Mateus, N., et al. (2015). A study of anthocyanin self‐association by NMR spectroscopy. New Journal of Chemistry, 39: 2602–2611.
12 Goto, T., and Kondo, T. (1991). Structure and molecular stacking of anthocyanins – Flower color variation. Angewandte Chemie International Edition, 30 (1): 17–33.
13 Jurd, L., (1963). Anthocyanins and related compounds. I. Structural transformations of flavylium salts in acidic solutions. The Journal of Organic Chemistry, 28 (4): 987–991.
14 Hondo, T., Yoshida, K., Nakagawa, A., et al. (1992). Structural basis of blue‐colour development in flower petals from Commelina communis. Nature, 358 (6386): 515–518.
15 Lehn, J.M. (1995). From molecular to supramolecular chemistry. In: Supramolecular Photochemistry: Concepts and Perspectives. Weinheim: Wiley‐VCH.
16 Mendoza, J., Basílio, N., Pina,F., et al. (2018). Rationalizing the color in heavenly blue anthocyanin. A complete kinetic and thermodynamic study. Journal of Physical Chemistry .B, 122 (19): 4982–4992.
17 Mendoza, J., Basílio, N., de Freitas, V., et al. (2019). New procedure to calculate all equilibrium constants in flavylium compounds: application to the copigmentation of anthocyanins. ACS omega, 4 (7): 12058–12070.
18 Petrov, V., Diniz, A.M., Cunha‐Silva, L., et al. (2013). Kinetic and thermodynamic study of 2’‐hydroxy–8‐methoxyflavylium. Reaction network interconverting flavylium cation and flavanone. RSC Advances, 3 (27): 10786–10794.
19 Petrov, V., Gomes, R., Parola, A.J., et al. (2008). 2’‐hydroxyflavylium: introducing flavanones into the flavylium network of chemical reactions. Tetrahedron, 64 (4): 714–720.
20 Petrov, V., Parola, A.J., and Pina, F. (2012). Isomerization between 2‐(2,4‐Dihydroxystyryl)–1‐benzopyrylium and 7‐Hydroxy‐2‐(4‐hydroxystyryl)‐1‐benzopyrylium. Journal of Physical Chemistry, 116 (31): 8107–8118.
21 Petrov, V., Stanimirov, S., Petrov, I.K., et al. (2013). Emptying the β‐cyclodextrin cavity by light. Photochemical removal of the trans‐chalcone of 4’,7‐dihydroxyflavylium. Journal of Physical Chemistry, 117 (41): 10692–10701.
22 Pina, F. (2014a). Thermodynamic and kinetic processes of anthocyanins and related compounds and their bio‐inspired applications. In: Recent Advances in Polyphenols Research. Vol. 4, Chapter 11, (eds. Romani, A., Lattanzio, V., and Quideau, S.), 341–370. West Sussex: Wiley Blackwell.
23 Pina, F. (2014b). Anthocyanins and related compounds. Detecting the change of regime between rate control by hydration or tautomerization. Dyes and Pigments, 102: 308–314.
24 Pina, F., Melo, M.J., Maestri, M., et al. (1997). Photochromism of 4'‐methoxyflavylium perchlorate. A “write‐lock‐read‐unlock‐erase” molecular switching device. Journal of the American Chemical Society, 119 (24): 5556−5561.
25 Slavcheva, S., Mendoza, J., Stanimirov, S., et al. (2018). On the multistate of 2’‐hydroxyflavylium‐flavanone system. illustrating the concept of a timer with reset at the molecular level. Dyes and Pigments, 158: 465–473.
26 Sousa, A., Cabrita, L., Araújo, P., et al. (2014). Color stability and spectroscopic properties of deoxyvitisins in aqueous solution. New Journal of Chemistry, 38 (2): 539–544.
27 Yoshida, K., Kondo, T., Okazaki, Y., et al. (1995). Cause of blue petal colour. Nature, 373 (6512): 291.
28 Yoshida, K., Mori, M., and Kondo, T. (2009). Blue flower color development by anthocyanins: from chemical structure to cell physiology. Natural Product Reports, 26 (7): 884–915.
Endnotes
1 1 In previous work we have used the term mono ionized, in the sense of formation of ions. This was the term used for ions resulting from the acid‐base reactions and the respective constants were defined as ionization constants.
2 2 In any case, both processes are well separated in time and the respective amplitude can be obtained.
3 3 In the case of 4’‐hydroxyflavylium the trans‐chalcones are almost 100% of CB and thus equilibrium is achieved with AH+ and the trans‐chalcones.
4 4 Flash photolysis is applied when there is excited state flavylium/quinoidal base proton transfer.
5 5 In the case of two derivatives bearing one acylated unit, the compound with the three glucoside units has the highest effect.
6 6 It is possible to observe the blue color at pseudo‐equilibrium in other systems. The peculiar behavior of HBA1 is that the purplish and blue colors are observed at equilibrium.
7 7 In principle, other analytical techniques, such as nuclear magnetic resonance (NMR), can be used to access the ratio FLV/Ct. The timer can be used only for a certain time interval (a few hours), because the spectral variations at the end of the reaction become very small.
2 Proanthocyanidin Oligomers with Doubly Linked (A‐Type) Interflavan Connectivity : Structure and Synthesis
Ken Ohmori and Keisuke Suzuki
Department of Chemistry, Tokyo Institute of Technology, Japan
Keywords: A‐type, afzelechin; catechin; epiafzelechin; epicatechin; flavan; flavonoid; oligomer; proanthocyanidin; procyanidin;
2.1 Introduction
The oligomeric proanthocyanidins (PAs),