A molecular modelling study to rationalize the regioselectivity in acylation of flavonoid glycosides catalyzed by Candida antarctica lipase B

Oliveira, Eduardo Basílio de; Humeau, Catherine; Chebil, Latifa; Maia, Elaine Rose; Dagognet, François; Maigret, Bernard; Ghoul, Mohamed; Engasser, Jean‐Marc

doi:10.1016/j.molcatb.2009.01.011

Cited by 53 publications

(26 citation statements)

References 46 publications

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“…Nevertheless, previous studies demonstrated that monoesters are regioselectively formed due to the preferential acylation of the primary –OH present on the glucose moiety (more precisely on the C6 carbon atom; 6''–OH) of other glycosides (Chebil et al ., ; Xanthakis et al ., ). Recent in silico molecular modelling studies have brought an explanation for this fact, based on the case of isoquercitrin (quercetin‐3‐O‐glucoside) (De Oliveira et al ., , ): this glycosylated molecule docks in the CALB catalytic pocket in such a way that the aglycon part is anchored in the cavity entrance, while the sugar moiety is projected towards the of the catalytic residues. The primary 6''–OH group is the only one that reaches a productive position, comprised between the catalytic residues Ser105 and His224.…”

Section: Resultsmentioning

confidence: 99%

Extraction, identification and enzymatic synthesis of acylated derivatives of anthocyanins from jaboticaba (Myrciaria cauliflora) fruits

Castro

Silva

Oliveira

et al. 2013

Int J of Food Sci Tech

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International audiencePolyphenols were extracted from the skin of jabuticaba fruits (Myrciaria cauliflora). Their total concentration and in vitro antioxidant activity were analysed by the DPPH and ABTS methods. The corresponding results (dry basis) were 1290mg gallic acid equivalent (GAE).(100g)(-1), 98% of DPPH radical inhibition and 120m TEAC.g(-1) (ABTS method). All these values are at least as higher as average values reported in the literature for other fruits. A more specific analysis of the fractions of phenolic compounds was also performed by HPLC-MS. Ellagic acid, quercetin, rutin, delphinidin-3-glucoside and cyanidin-3-glucoside were the main compounds detected; the latter two were the most abundant. The crude extract was subjected to enzymatic acylation assays in order to synthesise new esters with new potential techno-functionalities. Palmitic acid was used as acyl donor and lipase B of Candida antactica (CALB) as biocatalyst. HPLC-MS evidenced the formation of palmitic monoesters in connection with the delphinidin-3-glucoside and cyanidin-3-glucoside fractions

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Section: Resultsmentioning

confidence: 99%

Extraction, identification and enzymatic synthesis of acylated derivatives of anthocyanins from jaboticaba (Myrciaria cauliflora) fruits

Castro

Silva

Oliveira

et al. 2013

Int J of Food Sci Tech

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“…The effect of substrate concentration [44,45,52,56], enzyme amount and reaction temperature [51] on conversion yield and regioselectivity were also investigated. More recently, De Oliveira et al (2009) employed a combined docking, molecular mechanics, and molecular dynamics approach in order to explain the observed regioselectivity of C. antarctica lipase B at a molecular level [57].…”

Section: Resultsmentioning

confidence: 99%

Enzymatic transformation of flavonoids and terpenoids: Structural and functional diversity of the novel derivatives

Xanthakis

Theodosiou

Magkouta

et al. 2010

Pure and Applied Chemistry

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Flavonoids and terpenoids are promising candidates for use as functional foods and novel therapeutics due to their prominent biological activities. However, the use of several bioactive plant compounds is limited by low stability and solubility problems. This review underlines the feasibility of enzymatic synthesis of novel bioactive analogs of selected flavonoids (silybin, rutin) and terpenoids (perillyl alcohol, POH) in nonconventional reaction systems. The effect of various parameters on the enzymatic acylation and/or glucosylation of these phytochemicals was studied. Also, the role of the structure of the novel molecules in relation to their biological function was investigated in various cancer cell lines. Biotransformations of the natural compoundsEnzymatic acylation of flavonoids Analytical-scale reactions of silybin esters synthesis were carried out in sealed round bottom flasks using acetone, tert-amyl alcohol, tert-butyl alcohol, or acetonitrile as reaction medium. Silybin and various acylation agents (fatty acids and corresponding vinyl or methyl esters) were solubilized in the organic solvent (10 ml) previously dehydrated with 3 Å molecular sieves. The acylation of silybin was performed in the presence of immobilized lipase (15 mg ml -1 , Novozym 435). In all cases studied, the flasks were incubated at 50 °C and stirred at 250 rpm. Rutin ester synthesis was carried out in sealed round-bottom flasks using acetone as reaction medium. Rutin (55 mg) was solubilized in acetone (9 ml) previously dehydrated with 3 Å molecular sieves. The acylation of rutin was performed in the presence of immobilized lipase (100 mg, Novozym 435). The acyl donor concentration was adjusted to have a flavonoid/acyl donor molar ratio of 1/5. The mixture was incubated at 50 °C and stirred at 175 rpm.E. XANTHAKIS et al.

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“…This parameter characterizes the extent of the conformational change of the enzyme backbone. For both of the TLL solvation runs, the value of RMSD of the TLL polypeptide amino acid residues' C a atoms ( % 1.5 in benzene and % 2.0 in methanol) is under the limit of RMSD (equal to 3.0 ) [34,37] that marks the degree of the enzyme deformation that may cause the loss of its catalytic activity. In the current case, an interesting result is the considerably large value determined for the RMSD divergence [46] of the corresponding C a atoms in methanol versus those of benzene that exceeds 2.5 at 4 ns and reaches the plateau of 2.7-2.9 at 11 ns of MD simulation.…”

Section: Deformation Of the Polypeptide Backbone Conformationmentioning

confidence: 99%

“…For instance, the regioselectivity of the lipase-catalyzed acylation of flavonoid glycosides has been prognosticated by means of docking. [37] MD simulation studies of lipase solvation in organic solvents [38,39] as well as in water have given useful information about conformational changes depending on medium [40,41] and, in particular, about lid opening in hydrophobic solvents and closing in water. [24] MD simulations have also been performed to explore substrate binding by the enzyme.…”

Section: Introductionmentioning

confidence: 99%

Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E₂

et al. 2014

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A lipase may catalyze either one or more of the three reactions of 11‐acetyl‐prostaglandin E2 in methanol‐containing reaction medium: esterification, deacetylation, and/or elimination. The catalytic performance depends on the lipase and on the methanol content. An increase in the methanol concentration in benzene from 5 % to 95 % leads to the exclusive switch of reactions from esterification to elimination catalyzed by Thermomyces lanuginosus lipase (TLL). To explain the switch, molecular dynamics simulations of solvation of TLL in benzene and in methanol were performed. Solvation in methanol leads to the closing of the lid. The repositioning of the oxyanion hole towards the catalytic triad blocks the catalysis of ester synthesis whereas enabling TLL to act as an acetyl‐β‐ketol eliminase. In benzene the lid is open, allowing esterification to occur. Docking analysis of 11‐acetyl‐prostaglandin E2 into the active site of the solvated TLL structures suggested the occurrence of reactions in accordance with the experiment.

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A molecular modelling study to rationalize the regioselectivity in acylation of flavonoid glycosides catalyzed by Candida antarctica lipase B

Cited by 53 publications

References 46 publications

Extraction, identification and enzymatic synthesis of acylated derivatives of anthocyanins from jaboticaba (Myrciaria cauliflora) fruits

Extraction, identification and enzymatic synthesis of acylated derivatives of anthocyanins from jaboticaba (Myrciaria cauliflora) fruits

Enzymatic transformation of flavonoids and terpenoids: Structural and functional diversity of the novel derivatives

Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E₂

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A molecular modelling study to rationalize the regioselectivity in acylation of flavonoid glycosides catalyzed by Candida antarctica lipase B

Cited by 53 publications

References 46 publications

Extraction, identification and enzymatic synthesis of acylated derivatives of anthocyanins from jaboticaba (Myrciaria cauliflora) fruits

Extraction, identification and enzymatic synthesis of acylated derivatives of anthocyanins from jaboticaba (Myrciaria cauliflora) fruits

Enzymatic transformation of flavonoids and terpenoids: Structural and functional diversity of the novel derivatives

Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E2

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Product

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Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E₂