Antioxidant activity of protocatechuates evaluated by DPPH, ORAC, and CAT methods.

Hibiscus sabdariffa L. is a worldwide consumed plant, principally after infusion of its dried sepals and calyces, which are usually discarded. Nevertheless, they represent a potential source of natural bioactive compounds, e.g. polyphenols, which could add value to this under-exploited plant. Protocatechuic acid (PA) was chosen as a model of the phenolic acids that can be extracted from H. sabdariffa. In order to modify PA hydrophilic character, which limits its use in lipid-rich food products, PA was esterified to C1-C18 alcohols, and the impact of lipophilization on its antioxidant activity was evaluated in both, an homogeneous (DPPH and ORAC methods) and an heterogeneous (CAT method) system. Results herein obtained showed that, depending on the grafted alkyl chain length, lipophilization could positively affect the antioxidant activity of PA in heterogeneous media; therefore, support its use as an innovative way to synthesize molecules with an improved antioxidant capacity and potential to be used as multifunctional preservatives in food.

[1]  P. Villeneuve,et al.  Ability of surface-active antioxidants to inhibit lipid oxidation in oil-in-water emulsion. , 2007, Journal of agricultural and food chemistry.

[2]  B. Sarriá,et al.  Synthesis and antioxidant activity of nitrohydroxytyrosol and its acyl derivatives. , 2014, Journal of agricultural and food chemistry.

[3]  F. Kolisis,et al.  Studies on the enzymatic synthesis of lipophilic derivatives of natural antioxidants , 1999 .

[4]  G. Cabello,et al.  Does hydrophobicity always enhance antioxidant drugs? A cut‐off effect of the chain length of functionalized chlorogenate esters on ROS‐overexpressing fibroblasts , 2011, The Journal of pharmacy and pharmacology.

[5]  H. Paul "Hibiscus sabdariffa" L , 1995 .

[6]  J. Kawabata,et al.  DPPH (= 2,2‐Diphenyl‐1‐picrylhydrazyl) Radical‐Scavenging Reaction of Protocatechuic Acid (= 3,4‐Dihydroxybenzoic Acid): Difference in Reactivity between Acids and Their Esters , 2006 .

[7]  P. Villeneuve,et al.  Relationship between hydrophobicity and antioxidant ability of "phenolipids" in emulsion: a parabolic effect of the chain length of rosmarinate esters. , 2010, Journal of agricultural and food chemistry.

[8]  S. P. Moulik,et al.  Absorption and emission spectroscopic studies of fluorescein dye in alkanol, micellar and microemulsion media , 1999 .

[9]  N. Milhazes,et al.  Structure-property-activity relationship of phenolic acids and derivatives. Protocatechuic acid alkyl esters. , 2010, Journal of agricultural and food chemistry.

[10]  P. Villeneuve,et al.  Chain length affects antioxidant properties of chlorogenate esters in emulsion: the cutoff theory behind the polar paradox. , 2009, Journal of agricultural and food chemistry.

[11]  J. Kawabata,et al.  Effects of Alcoholic Solvents on Antiradical Abilities of Protocatechuic Acid and Its Alkyl Esters , 2004, Bioscience, biotechnology, and biochemistry.

[12]  I. Kubo,et al.  Rational design of antimicrobial agents: antifungal activity of alk(en)yl dihydroxybenzoates and dihydroxyphenyl alkanoates. , 2003, Bioorganic & medicinal chemistry letters.

[13]  A. Scalbert,et al.  Polyphenols: antioxidants and beyond 1-3 , 2005 .

[14]  M. Yin,et al.  Antibacterial effects of roselle calyx extracts and protocatechuic acid in ground beef and apple juice. , 2009, Foodborne pathogens and disease.

[15]  C. Berset,et al.  Use of a Free Radical Method to Evaluate Antioxidant Activity , 1995 .

[16]  P. Villeneuve,et al.  Antioxidant properties and efficacies of synthesized alkyl caffeates, ferulates, and coumarates. , 2014, Journal of agricultural and food chemistry.

[17]  H. Suh,et al.  Protective effect of protocatechuic acid isopropyl ester against murine models of sepsis: inhibition of TNF-alpha and nitric oxide production and augmentation of IL-10. , 2004, Biological & pharmaceutical bulletin.

[18]  Seema Patel Hibiscus sabdariffa: An ideal yet under-exploited candidate for nutraceutical applications , 2014 .

[19]  J. Graille,et al.  Esterification of phenolic acids from green coffee with an immobilized lipase from Candida antarctica in solvent-free medium , 1997, Biotechnology Letters.

[20]  A. Fusco-Almeida,et al.  Anti-Trichophyton Activity of Protocatechuates and Their Synergism with Fluconazole , 2014, Evidence-based complementary and alternative medicine : eCAM.

[21]  Z. Deng,et al.  Separation procedures for naturally occurring antioxidant phytochemicals. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[22]  D. Mcclements,et al.  What Makes Good Antioxidants in Lipid-Based Systems? The Next Theories Beyond the Polar Paradox , 2015, Critical reviews in food science and nutrition.

[23]  Mike Saltmarsh,et al.  Polyphenols: antioxidants and beyond. , 2005, The American journal of clinical nutrition.

[24]  P. Villeneuve,et al.  Conjugated autoxidizable triene (CAT) assay: a novel spectrophotometric method for determination of antioxidant capacity using triacylglycerol as ultraviolet probe. , 2008, Analytical biochemistry.

[25]  P. Villeneuve,et al.  Evaluation of the ability of antioxidants to counteract lipid oxidation: existing methods, new trends and challenges. , 2007, Progress in lipid research.

[26]  I. Kubo,et al.  Lipoxygenase inhibitory activity of alkyl protocatechuates. , 2014, Food chemistry.

[27]  G. Lóarca-Piña,et al.  Hibiscus sabdariffa L. extracts inhibit the mutagenicity in microsuspension assay and the proliferation of HeLa cells. , 2008, Journal of food science.

[28]  T. Tseng,et al.  Induction of apoptosis by hibiscus protocatechuic acid in human leukemia cells via reduction of retinoblastoma (RB) phosphorylation and Bcl-2 expression. , 2000, Biochemical pharmacology.

[29]  M. A. Tung,et al.  Relationship Between Hydrophobicity and Emulsifying Properties of Some Plant Proteins , 1980 .

[30]  Takahiro Tanaka,et al.  Potential Cancer Chemopreventive Activity of Protocatechuic Acid , 2011 .

[31]  R. Prior,et al.  Development and validation of an improved oxygen radical absorbance capacity assay using fluorescein as the fluorescent probe. , 2001, Journal of agricultural and food chemistry.

[32]  L. Lindqvist,et al.  The pH dependence of fluorescein fluorescence , 1975 .

[33]  P. Villeneuve,et al.  Synthesis, Characterization and Free Radical Scavenging Properties of Rosmarinic Acid Fatty Esters , 2010 .

[34]  Fereidoon Shahidi,et al.  Measuring antioxidant effectiveness in food. , 2005, Journal of agricultural and food chemistry.

[35]  P. Villeneuve,et al.  From phenolics to phenolipids: Optimizing antioxidants in lipid dispersions , 2013 .

[36]  Souravh Bais,et al.  A Review on Protocatechuic Acid and Its Pharmacological Potential , 2014, ISRN pharmacology.

[37]  I. Ferreira,et al.  Antibacterial activity of Veronica montana L. extract and of protocatechuic acid incorporated in a food system. , 2013, Food and chemical toxicology : an international journal published for the British Industrial Biological Research Association.

[38]  J. Bautista,et al.  Lipophilic hydroxytyrosyl esters. Antioxidant activity in lipid matrices and biological systems. , 2006, Journal of agricultural and food chemistry.