Paweł Stalica - Academia.edu (original) (raw)

Papers by Paweł Stalica

Research paper thumbnail of Profiles of Betacyanins in Epidermal Layers of Grafted and Light-Stressed Cacti Studied by LC-DAD-ESI-MS/MS

Journal of Agricultural and Food Chemistry, 2010

Profiles of betacyanins present in light-stressed stems of different cactus species and nonstress... more Profiles of betacyanins present in light-stressed stems of different cactus species and nonstressed but genetically aberrated red pigmented cacti of Gymnocalycium mihanovichii cv. ;Hibotan' Britton & Rose, which are known as grafted cacti, were compared. The identities of all the pigments in the cacti were characterized for the first time. The identification of acylated and nonacylated betacyanins was performed by means of mass spectrometry and UV-vis diode array detection coupled to high-performance liquid chromatography. The most indicative pigments of the stressed cacti, 5''-O-E-feruloyl-2'-O-beta-apiosyl-betanin and 5''-O-E-sinapoyl-2'-O-beta-apiosyl-betanin, as well as their diasteromers, were the prevailing betacyanins in Hylocereus polyrhizus , Epiphyllum phyllanthus , and Rhipsalis rhombea . Stressed Rhipsalis regnellii stems contained the sinapoylated betacyanins accompanied only by traces of the feruloylated derivatives. In addition, high contents of 2'-O-apiosyl-betanin were frequently observed in the samples with the highest concentration found in stressed Schlumbergera x buckleyi (T. Moore) Tjaden. These pigments were also detected, but at low levels, in the Hibotan pink, red, and violet scions, which were not light-stressed. In the Hibotan scions, the most abundant were the polar betacyanins: betanidin 5-O-beta-sophoroside and betanin. In most of the stressed samples, betanin was present at relatively low levels.

Research paper thumbnail of Antioxidant Activity of Betanidin: Electrochemical Study in Aqueous Media

Journal of Agricultural and Food Chemistry, 2011

The antioxidative mechanism of action of betalains is of significant interest because these pigme... more The antioxidative mechanism of action of betalains is of significant interest because these pigments are recently emerging as highly bio-active natural compounds with potential benefits to human health. Betanidin, the basic betacyanin, comprises the 5,6-dihydroxyl moiety, which results in its high antioxidant activity. Oxidation of betanidin by voltammetric techniques and chro matographic identification of the oxidation products with spectrophotometric and mass spectrometric detection (LC-DAD-MS/MS) were performed. Two main oxidation peaks for betanidin are observable at pH 3-5. These peaks become merged at higher pH, suggesting a different mechanism of oxidation at higher and lower pH values. The low oxidation potential of betanidin confirms its very strong reduction properties. The presence of two prominent oxidized products, 2-decarboxy-2,3-dehydrobetanidin and 2,17-bidecarboxy-2,3-dehydrobetanidin, indicates their generation through two reaction routes with two different quinonoid intermediates: dopachrome derivative and quinone methide. Both lead to the decarboxylative dehydrogenation of betanidin. Subsequent oxidation and rearrangement of the conjugated chromophoric system results in formation of 14,15-dehydrogenated derivatives.

Research paper thumbnail of Betalainic and nutritional profiles of pigment-enriched red beet root (Beta vulgaris L.) dried extracts

Food Chemistry, 2011

Betanin 2-Decarboxy-betanin 17-Decarboxy-betanin Neobetanin Decarboxylation Dehydrogenation Red b... more Betanin 2-Decarboxy-betanin 17-Decarboxy-betanin Neobetanin Decarboxylation Dehydrogenation Red beet root Spray-, air-, freeze-drying Beta vulgaris L.

Research paper thumbnail of Separation of polar betalain pigments from cacti fruits of Hylocereus polyrhizus by ion-pair high-speed countercurrent chromatography

Journal of Chromatography A, 2009

Polar betacyanin pigments together with betaxanthins from ripe cactus fruits of Hylocereus polyrh... more Polar betacyanin pigments together with betaxanthins from ripe cactus fruits of Hylocereus polyrhizus (Cactaceae) were fractionated by means of preparative ion-pair high-speed countercurrent chromatography (IP-HSCCC) also using the elution-extrusion (EE) approach for a complete pigment recovery. HSCCC separations were operated in the classical 'head-to-tail' mode with an aqueous mobile phase. Different CCC solvent systems were evaluated in respect of influence and effectiveness of fractionation capabilities to separate the occurring pigment profile of H. polyrhizus. For that reason, the additions of two different volatile ion-pair forming perfluorinated carboxylic acids (PFCA) were investigated. For a direct comparison, five samples of Hylocereus pigment extract were run on preparative scale (900 mg) in 1-butanol-acetonitrile-aqueous TFA 0.7% (5:1:6, v/v/v) and the modified systems tert.-butyl methyl ether-1-butanol-acetonitrile-aqueous PFCA (2:2:1:5, v/v/v/v) using 0.7% and 1.0% trifluoroacetic acid (TFA) or heptafluorobutyric acid (HFBA) in the aqueous phase, respectively. The chemical affinity to the organic stationary CCC solvent phases and in consequence the retention of these highly polar betalain pigments was significantly increased by the use of the more lipophilic fluorinated ion-pair reagent HFBA instead of TFA. The HFBA additions separated more effectively the typical cacti pigments phyllocactin and hylocerenin from betanin as well as their iso-forms. Unfortunately, similar K D ratios and selectivity factors˛around 1.0-1.1 in all tested solvent systems proved that the corresponding diastereomers, 15S-type pigments cannot be resolved from the 15R-epimers (iso-forms). Surprisingly, additions of the stronger ion-pair reagent (HFBA) resulted in a partial separation of hylocerenin from phyllocactin which were not resolved in the other solvent systems. The pigments were detected by means of HPLC-DAD and HPLC-electrospray ionization-MS using also authentic reference materials.

Research paper thumbnail of Profiles of Betacyanins in Epidermal Layers of Grafted and Light-Stressed Cacti Studied by LC-DAD-ESI-MS/MS

Journal of Agricultural and Food Chemistry, 2010

Profiles of betacyanins present in light-stressed stems of different cactus species and nonstress... more Profiles of betacyanins present in light-stressed stems of different cactus species and nonstressed but genetically aberrated red pigmented cacti of Gymnocalycium mihanovichii cv. ;Hibotan' Britton & Rose, which are known as grafted cacti, were compared. The identities of all the pigments in the cacti were characterized for the first time. The identification of acylated and nonacylated betacyanins was performed by means of mass spectrometry and UV-vis diode array detection coupled to high-performance liquid chromatography. The most indicative pigments of the stressed cacti, 5''-O-E-feruloyl-2'-O-beta-apiosyl-betanin and 5''-O-E-sinapoyl-2'-O-beta-apiosyl-betanin, as well as their diasteromers, were the prevailing betacyanins in Hylocereus polyrhizus , Epiphyllum phyllanthus , and Rhipsalis rhombea . Stressed Rhipsalis regnellii stems contained the sinapoylated betacyanins accompanied only by traces of the feruloylated derivatives. In addition, high contents of 2'-O-apiosyl-betanin were frequently observed in the samples with the highest concentration found in stressed Schlumbergera x buckleyi (T. Moore) Tjaden. These pigments were also detected, but at low levels, in the Hibotan pink, red, and violet scions, which were not light-stressed. In the Hibotan scions, the most abundant were the polar betacyanins: betanidin 5-O-beta-sophoroside and betanin. In most of the stressed samples, betanin was present at relatively low levels.

Research paper thumbnail of Antioxidant Activity of Betanidin: Electrochemical Study in Aqueous Media

Journal of Agricultural and Food Chemistry, 2011

The antioxidative mechanism of action of betalains is of significant interest because these pigme... more The antioxidative mechanism of action of betalains is of significant interest because these pigments are recently emerging as highly bio-active natural compounds with potential benefits to human health. Betanidin, the basic betacyanin, comprises the 5,6-dihydroxyl moiety, which results in its high antioxidant activity. Oxidation of betanidin by voltammetric techniques and chro matographic identification of the oxidation products with spectrophotometric and mass spectrometric detection (LC-DAD-MS/MS) were performed. Two main oxidation peaks for betanidin are observable at pH 3-5. These peaks become merged at higher pH, suggesting a different mechanism of oxidation at higher and lower pH values. The low oxidation potential of betanidin confirms its very strong reduction properties. The presence of two prominent oxidized products, 2-decarboxy-2,3-dehydrobetanidin and 2,17-bidecarboxy-2,3-dehydrobetanidin, indicates their generation through two reaction routes with two different quinonoid intermediates: dopachrome derivative and quinone methide. Both lead to the decarboxylative dehydrogenation of betanidin. Subsequent oxidation and rearrangement of the conjugated chromophoric system results in formation of 14,15-dehydrogenated derivatives.

Research paper thumbnail of Betalainic and nutritional profiles of pigment-enriched red beet root (Beta vulgaris L.) dried extracts

Food Chemistry, 2011

Betanin 2-Decarboxy-betanin 17-Decarboxy-betanin Neobetanin Decarboxylation Dehydrogenation Red b... more Betanin 2-Decarboxy-betanin 17-Decarboxy-betanin Neobetanin Decarboxylation Dehydrogenation Red beet root Spray-, air-, freeze-drying Beta vulgaris L.

Research paper thumbnail of Separation of polar betalain pigments from cacti fruits of Hylocereus polyrhizus by ion-pair high-speed countercurrent chromatography

Journal of Chromatography A, 2009

Polar betacyanin pigments together with betaxanthins from ripe cactus fruits of Hylocereus polyrh... more Polar betacyanin pigments together with betaxanthins from ripe cactus fruits of Hylocereus polyrhizus (Cactaceae) were fractionated by means of preparative ion-pair high-speed countercurrent chromatography (IP-HSCCC) also using the elution-extrusion (EE) approach for a complete pigment recovery. HSCCC separations were operated in the classical 'head-to-tail' mode with an aqueous mobile phase. Different CCC solvent systems were evaluated in respect of influence and effectiveness of fractionation capabilities to separate the occurring pigment profile of H. polyrhizus. For that reason, the additions of two different volatile ion-pair forming perfluorinated carboxylic acids (PFCA) were investigated. For a direct comparison, five samples of Hylocereus pigment extract were run on preparative scale (900 mg) in 1-butanol-acetonitrile-aqueous TFA 0.7% (5:1:6, v/v/v) and the modified systems tert.-butyl methyl ether-1-butanol-acetonitrile-aqueous PFCA (2:2:1:5, v/v/v/v) using 0.7% and 1.0% trifluoroacetic acid (TFA) or heptafluorobutyric acid (HFBA) in the aqueous phase, respectively. The chemical affinity to the organic stationary CCC solvent phases and in consequence the retention of these highly polar betalain pigments was significantly increased by the use of the more lipophilic fluorinated ion-pair reagent HFBA instead of TFA. The HFBA additions separated more effectively the typical cacti pigments phyllocactin and hylocerenin from betanin as well as their iso-forms. Unfortunately, similar K D ratios and selectivity factors˛around 1.0-1.1 in all tested solvent systems proved that the corresponding diastereomers, 15S-type pigments cannot be resolved from the 15R-epimers (iso-forms). Surprisingly, additions of the stronger ion-pair reagent (HFBA) resulted in a partial separation of hylocerenin from phyllocactin which were not resolved in the other solvent systems. The pigments were detected by means of HPLC-DAD and HPLC-electrospray ionization-MS using also authentic reference materials.