Lipase-catalyzed synthesis of phloridzin esters
Authorized Users Only
2013
Authors
Milisavljević, AnaStojanović, Marija
Dinić, Ivana

Carević, Milica
Mihailović, Mladen
Milosavić, Nenad
Bezbradica, Dejan

Conference object (Published version)

Metadata
Show full item recordAbstract
Phloridzin is member of chemical class of dihydrochalcones, phenylpropanoids with
structure similar to chalcones, immediate flavonoid precursors, hence it is often classified
as flavonoid glucoside [1,2]. It is usually extracted from Malus species since it is very
abundant in young apple leaves and twigs. Due to its phenolic structure, phloridzin has
significant antioxidant activity and anti-UV properties, which makes it interesting for
application in food and cosmetics. Major limitation to wider application of phloridzin is its
low solubility in hydrophobic environment, which can be circumvented by synthesis of
physiologically active compounds derivatives by acylation of phloridzin. Synthesis of acyl
esters can be catalyzed by inorganic catalysts or enzymes, but chemical esterification is
not regioselective and results with unwanted functionalization of phenolic hydroxyl
groups responsible for antioxidative properties.
Therefore, in our study enzymatic esterification of phl...oridzin was performed using
immobilized lipase from Candida antarctica (Novozyme® 435). Several organic solvents
were tested and acetonitrile was proved to be the most adequate medium for this
reaction. Different acyl-donors were used with respect to chain length and saturation
level. Potential physiological activity of obtained esters was evaluated by determination of
their antioxidant activity using DPPH assay, so acyl donors were compared with respect to
both, product yields and antioxidant activity. After comparison of results of preliminary
study, phloridzyl oleate was selected as derivative with the best prospects and it used in
further experimental series for optimization of key experimental factors. Response surface
methodology was applied as statistical tool for optimization of product concentration (in
mM) as output and analyzed factors were: reaction time, temperature, enzyme
concentration, substrate molar ratio, and phloridzin concentration. After statistical
analysis each of examined experimental factors was found significant and second order
regression model was obtained. It was established that highest product concentration can
be expected at 68 oC, with 0.17 M of phloridzin, 2,5 % (w/v) of enzyme, 19-fold molar
excess of oleic acid after 7 days of reaction.
Source:
8th International Conference of the Chemical Societies of the South-East European Countries, Belgrade, Serbia, 2013, 254-Funding / projects:
Institution/Community
Tehnološko-metalurški fakultetTY - CONF AU - Milisavljević, Ana AU - Stojanović, Marija AU - Dinić, Ivana AU - Carević, Milica AU - Mihailović, Mladen AU - Milosavić, Nenad AU - Bezbradica, Dejan PY - 2013 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/6070 AB - Phloridzin is member of chemical class of dihydrochalcones, phenylpropanoids with structure similar to chalcones, immediate flavonoid precursors, hence it is often classified as flavonoid glucoside [1,2]. It is usually extracted from Malus species since it is very abundant in young apple leaves and twigs. Due to its phenolic structure, phloridzin has significant antioxidant activity and anti-UV properties, which makes it interesting for application in food and cosmetics. Major limitation to wider application of phloridzin is its low solubility in hydrophobic environment, which can be circumvented by synthesis of physiologically active compounds derivatives by acylation of phloridzin. Synthesis of acyl esters can be catalyzed by inorganic catalysts or enzymes, but chemical esterification is not regioselective and results with unwanted functionalization of phenolic hydroxyl groups responsible for antioxidative properties. Therefore, in our study enzymatic esterification of phloridzin was performed using immobilized lipase from Candida antarctica (Novozyme® 435). Several organic solvents were tested and acetonitrile was proved to be the most adequate medium for this reaction. Different acyl-donors were used with respect to chain length and saturation level. Potential physiological activity of obtained esters was evaluated by determination of their antioxidant activity using DPPH assay, so acyl donors were compared with respect to both, product yields and antioxidant activity. After comparison of results of preliminary study, phloridzyl oleate was selected as derivative with the best prospects and it used in further experimental series for optimization of key experimental factors. Response surface methodology was applied as statistical tool for optimization of product concentration (in mM) as output and analyzed factors were: reaction time, temperature, enzyme concentration, substrate molar ratio, and phloridzin concentration. After statistical analysis each of examined experimental factors was found significant and second order regression model was obtained. It was established that highest product concentration can be expected at 68 oC, with 0.17 M of phloridzin, 2,5 % (w/v) of enzyme, 19-fold molar excess of oleic acid after 7 days of reaction. C3 - 8th International Conference of the Chemical Societies of the South-East European Countries, Belgrade, Serbia T1 - Lipase-catalyzed synthesis of phloridzin esters SP - 254 UR - https://hdl.handle.net/21.15107/rcub_technorep_6070 ER -
@conference{ author = "Milisavljević, Ana and Stojanović, Marija and Dinić, Ivana and Carević, Milica and Mihailović, Mladen and Milosavić, Nenad and Bezbradica, Dejan", year = "2013", abstract = "Phloridzin is member of chemical class of dihydrochalcones, phenylpropanoids with structure similar to chalcones, immediate flavonoid precursors, hence it is often classified as flavonoid glucoside [1,2]. It is usually extracted from Malus species since it is very abundant in young apple leaves and twigs. Due to its phenolic structure, phloridzin has significant antioxidant activity and anti-UV properties, which makes it interesting for application in food and cosmetics. Major limitation to wider application of phloridzin is its low solubility in hydrophobic environment, which can be circumvented by synthesis of physiologically active compounds derivatives by acylation of phloridzin. Synthesis of acyl esters can be catalyzed by inorganic catalysts or enzymes, but chemical esterification is not regioselective and results with unwanted functionalization of phenolic hydroxyl groups responsible for antioxidative properties. Therefore, in our study enzymatic esterification of phloridzin was performed using immobilized lipase from Candida antarctica (Novozyme® 435). Several organic solvents were tested and acetonitrile was proved to be the most adequate medium for this reaction. Different acyl-donors were used with respect to chain length and saturation level. Potential physiological activity of obtained esters was evaluated by determination of their antioxidant activity using DPPH assay, so acyl donors were compared with respect to both, product yields and antioxidant activity. After comparison of results of preliminary study, phloridzyl oleate was selected as derivative with the best prospects and it used in further experimental series for optimization of key experimental factors. Response surface methodology was applied as statistical tool for optimization of product concentration (in mM) as output and analyzed factors were: reaction time, temperature, enzyme concentration, substrate molar ratio, and phloridzin concentration. After statistical analysis each of examined experimental factors was found significant and second order regression model was obtained. It was established that highest product concentration can be expected at 68 oC, with 0.17 M of phloridzin, 2,5 % (w/v) of enzyme, 19-fold molar excess of oleic acid after 7 days of reaction.", journal = "8th International Conference of the Chemical Societies of the South-East European Countries, Belgrade, Serbia", title = "Lipase-catalyzed synthesis of phloridzin esters", pages = "254", url = "https://hdl.handle.net/21.15107/rcub_technorep_6070" }
Milisavljević, A., Stojanović, M., Dinić, I., Carević, M., Mihailović, M., Milosavić, N.,& Bezbradica, D.. (2013). Lipase-catalyzed synthesis of phloridzin esters. in 8th International Conference of the Chemical Societies of the South-East European Countries, Belgrade, Serbia, 254. https://hdl.handle.net/21.15107/rcub_technorep_6070
Milisavljević A, Stojanović M, Dinić I, Carević M, Mihailović M, Milosavić N, Bezbradica D. Lipase-catalyzed synthesis of phloridzin esters. in 8th International Conference of the Chemical Societies of the South-East European Countries, Belgrade, Serbia. 2013;:254. https://hdl.handle.net/21.15107/rcub_technorep_6070 .
Milisavljević, Ana, Stojanović, Marija, Dinić, Ivana, Carević, Milica, Mihailović, Mladen, Milosavić, Nenad, Bezbradica, Dejan, "Lipase-catalyzed synthesis of phloridzin esters" in 8th International Conference of the Chemical Societies of the South-East European Countries, Belgrade, Serbia (2013):254, https://hdl.handle.net/21.15107/rcub_technorep_6070 .