Ce(IV)-coordinated organogel-based assay for on-site monitoring of propyl gallate with turn-on fluorescence signal.

Propyl gallate (PG) is a commonly used synthetic phenolic antioxidant in foodstuffs and industrial products. Due to the potential health risk of PG, rapid and on-site detection in food and environment samples are important to guarantee human health. Herein, we demonstrated rapid monitoring of PG by a fluorescence turn-on strategy based on a specific fluorogenic reaction between PG and polyethyleneimine (PEI). Specifically, Ce4+ with oxidase-mimicking activity oxidized PG to its oxides, which then reacted with PEI through the Michael addition to generate the fluorescent compound. The proposed fluorogenic reaction had good specificity for PG, which could distinguish PG from other phenolic antioxidants and interferences. Furthermore, portable and low-cost organogel test kits were prepared using poly(ethylene glycol) diacrylate for quantitative and on-site detection of PG via a smartphone-based sensing platform. The organogel-based assay detection limit was 1.0 µg mL-1 with recoveries ranging from 80.2% to 106.2% in edible oils and surface water. Suitability of the developed assay was also validated by high-performance liquid chromatography. Our study provides an effective fluorescent approach to rapid, specific, and convenient monitoring of PG, which is useful for diminishing the risk of PG exposure.

Cu3(PO4)2/BiVO4 photoelectrochemical sensor for sensitive and selective determination of synthetic antioxidant propyl gallate.

Propyl gallate (PG) as one of the most important additives has been widely used to prevent or slow the oxidation of foods in the food industry. In this work, Cu3(PO4)2/BiVO4 composite is synthesized through two hydrothermal processes. With visible light irradiation, the Cu3(PO4)2/BiVO4 composites modified PEC platform displays a superior anode photocurrent signal. The PEC sensor showed a wide linear range from 1 × 10-10 to 1 × 10-3 mol L-1 with a detection limit as low as 0.05 × 10-10 mol L-1. The Cu3(PO4)2/BiVO4 photoelectrochemical (PEC) sensor is designed and characterized by electrochemical impedance. Compared with GCE/BiVO4 and GCE/Cu3(PO4)2, the GCE/Cu3(PO4)2/BiVO4 has a higher photocurrent response. In addition, the sensor is highly selective for samples containing other antioxidants. Furthermore, the sensor can be used to detect PG in edible oil samples with satisfactory results. The recoveries of propyl gallate in edible oil ranged from 95.5 to 101.8%. The results show that Cu3(PO4)2/BiVO4 composites can be used to analyze PG in different edible oil samples, which are beneficial for food quality monitoring and reduce the risk of PG overuse in food.

Investigation of the pectin grafting with gallic acid and propyl gallate and their antioxidant activities, antibacterial activities and fresh keeping performance.

In this paper, a method for the enzymatic modification of pectin, in which gallic acid (GA) and propyl gallate (PG) were grafted onto pectin molecules in an aqueous/organic two-phase system catalyzed by lipase, was proposed. The potential reaction mechanism was explored through UV-Vis, FTIR and 1H NMR spectroscopic methods and density functional theory. Results suggested that the lipase played a dual role during the modification by catalyzing the hydrolysis of methyl ester bonds of pectin in the aqueous phase and the esterification between the 4-OH of GA and PG and the -COOH of pectin in the organic phase. Moreover, the effects of GA and PG on the antioxidant and the antibacterial activities of pectin were evaluated, and results showed that the antioxidant and the antibacterial activities of modified pectin were better than those of native pectin. The effect of modified pectin on the quality of fresh bass (Lateolabrax maculatus) was further studied. Results suggested that, compared to control group, the total viable count, histamine level, malondialdehyde content and acid value of bass fillets treated with modified pectin were significantly reduced, whereas the sensory score was significantly increased.

Quality-by-Design-Based Development of n-Propyl-Gallate-Loaded Hyaluronic-Acid-Coated Liposomes for Intranasal Administration.

The present study aimed to develop n-propyl gallate (PG)-encapsulated liposomes through a novel direct pouring method using the quality-by-design (QbD) approach. A further aim was to coat liposomes with hyaluronic acid (HA) to improve the stability of the formulation in nasal mucosa. The QbD method was used for the determination of critical quality attributes in the formulation of PG-loaded liposomes coated with HA. The optimized formulation was determined by applying the Box-Behnken design to investigate the effect of composition and process variables on particle size, polydispersity index (PDI), and zeta potential. Physiochemical characterization, in vitro release, and permeability tests, as well as accelerated stability studies, were performed with the optimized liposomal formulation. The optimized formulation resulted in 90 ± 3.6% encapsulation efficiency, 167.9 ± 3.5 nm average hydrodynamic diameter, 0.129 ± 0.002 PDI, and -33.9 ± 4.5 zeta potential. Coated liposomes showed significantly improved properties in 24 h in an in vitro release test (>60%), in vitro permeability measurement (420 µg/cm2) within 60 min, and also in accelerated stability studies compared to uncoated liposomes. A hydrogen-peroxide-scavenging assay showed improved stability of PG-containing liposomes. It can be concluded that the optimization of PG-encapsulated liposomes coated with HA has great potential for targeting several brain diseases.

Phenolic compounds as antioxidants to improve oxidative stability of menhaden oil-based structured lipid as butterfat analog.

Phenolic compounds, including propyl gallate, 1-o-galloylglycerol, ferulic, gallic, caffeic, rosmarinic, and carnosic acids, tocopherols, and butylated hydroxytoluene (BHT), were investigated as antioxidants to improve the oxidative stability of a structured lipid (SL) produced by the enzymatic acidolysis of menhaden oil with caprylic and stearic acids. SL had similar physical properties to butterfat but was more susceptible to oxidation. The above phenolic compounds were each added to SL as antioxidants. SL with 1-o-galloylglycerol, rosmarinic acid, or BHT showed the highest oxidative stability during an accelerated oxidation test with the total oxidation (TOTOX) value around 250 after 18 days. Oxidation induction time (OIT) using differential scanning calorimetry showed a good correlation with the accelerated oxidation test. A mixture of 1-o-galloylglycerol and tocopherols at 50:50 ppm had the strongest protective effect on SL (OIT = 115.1 min) compared to the other tested compounds or combinations at the same concentration (OIT < 100 min).

Protein Cohabitation: Improving the Photochemical Stability of R-Phycoerythrin in the Solid State.

The poor photochemical stability of R-phycoerythrin (R-PE) has been a bottleneck for its broad-spectrum applications. Inspired by nature, we studied a sustainable strategy of protein cohabitation to enhance R-PE stability by embedding it in a solid matrix of gelatin. Both pure R-PE and fresh phycobiliprotein (PBP) extracts recovered from Gracilaria gracilis were studied. The incorporation of R-PE in the gelatin-based films (gelatin-RPE and gelatin-PBPs) has improved its photochemical stability for at least 8 months, the longest time period reported so far. These results were evidenced by not only absorption but also emission quantum yield measurements (Φ). Moreover, the photostability of gelatin-RPE films upon continuous excitation with an AM1.5G solar simulator was tested and found to remain stable for 23 h after initial decreasing up to 250 min. In the end, another approach was established to allow 100% photostability for a 3 h exposure to an AM1.5G solar simulator by doping the gelatin-based film including R-Phycoerythrin with n-propyl gallate stabilized with Tween 80, allowing their use as naturally based optically active centers in photovoltaic applications.

Enzymatic synthesis of 1-o-galloylglycerol: Characterization and determination of its antioxidant properties.

1-o-Galloylglycerol (GG) was synthesized by the enzymatic glycerolysis of propyl gallate (PG) using a food-grade lipase (Lipozyme® 435). The reaction conditions affecting the yield of GG were optimized and a yield of 76.9% ±â€¯1.2% was obtained. GG was characterized by various techniques after being separated from the reaction mixture using liquid-liquid extraction. The water solubility and hydrophilicity of GG were significantly higher than those of gallic acid (GA) and PG. The antioxidant properties, measured by the ferric reducing antioxidant power (FRAP) and hydrogen peroxide (H2O2) scavenging assays, showed that GG exhibited the highest scavenging capacity (GG > GA > PG). From the results of the 1,1-diphenyl-2-picrylhydrazyl (DPPH•) and 2,2'-azinobis (3-ethylbenzthiazoline-6-sulfonic acid) (ABTS•+) assays, GG and GA exhibited greater scavenging capacity than PG (GG = GA > PG). These results suggest that GG may be used as a water-soluble antioxidant alternative to GA for food and cosmetic applications.

Application of Diethylzinc/propyl Gallate Catalytic System for Ring-Opening Copolymerization of rac-Lactide and ε-Caprolactone.

Biodegradable polyesters gain significant attention because of their wide potential biomedical applications. The ring-opening polymerization method is widely used to obtain such polymers, due to high yields and advantageous properties of the obtained material. The preparation of new, effective, and bio-safe catalytic systems for the synthesis of biomedical polymers is one of the main directions of the research in modern medical chemistry. The new diethylzinc/propyl gallate catalytic system was first used in the copolymerization of ε-caprolactone and rac-lactide. In this paper, the activity of the new zinc-based catalytic system in the copolymerization of cyclic esters depending on the reaction conditions was described. The microstructure analysis of the obtained copolyesters and their toxicity studies were performed. Resulted copolyesters were characterized by low toxicity, moderate dispersity (1.19-1.71), varying randomness degree (0.18-0.83), and average molar mass (5300-9800 Da).

Scavenging of Acrolein by Food-Grade Antioxidant Propyl Gallate in a Model Reaction System and Cakes.

Reactive carbonyl species (RCS), such as acrolein (ACR), glyoxal (GO), and methylglyoxal (MGO), have received extensive attention recently as a result of their high activity and toxicity in vitro and in vivo. In the present study, propyl gallate (PG), a common food antioxidant, was found to effectively trap more ACR than butylated hydroxytoluene and butylated hydroxyanisole through the formation of mono-ACR adducts (PG-ACR) and di-ACR adducts (PG-2ACR). The two adducts were successfully purified, and their structures were elucidated on the basis of their high-resolution mass spectrometry and 1H, 13C, and two-dimensional nuclear magnetic resonance data. We further identified that PG-ACR had the ability to continue to trap GO and MGO to form PG-ACR-GO and PG-ACR-MGO, respectively, by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Furthermore, we verified that PG could inhibit the production of ACR, GO, and MGO via trapping these RCS simultaneously to form the corresponding adducts in pound cakes using LC-MS/MS.

Effect of laccase-catalyzed cross-linking on the structure and allergenicity of Paralichthys olivaceus parvalbumin mediated by propyl gallate.

The aim of the present study was to evaluate Paralichthys olivaceus parvalbumin (PV) following treatment by laccase (LAC) in the presence of propyl gallate (PG) on the structure and potential allergenicity. The structure of LAC + PG treated PV was analyzed through SDS-PAGE, CD, fluorescence, and allergenicity was analyzed by immunological and cell model. Our results showed that LAC + PG treatment can induce structural changes through PV cross-linking. Western blotting and indirect ELISA analysis revealed the decrease in IgG binding capacity of PV, corresponding with the structural changes. The results of in vitro digestion illustrate that LAC + PG treated PV showed more resistance to gastrointestinal digestion compared to untreated PV. The release rate of ß-hexosaminidase and histamine decreased by 35.6% and 66.9%, respectively, with LAC + PG treatment by RBL-2H3 cell assay. Considering the wide utilization of LAC in food industry, our treatment reveals its potential for creation of hypoallergenic fish products under mild reaction conditions.

Dietary antioxidants as a source of hydrogen peroxide.

Studies of 54 antioxidants revealed that 27 of them, mainly polyphenols, generated hydrogen peroxide (H2O2) when added to Dulbecco's modified Eagle's medium (DMEM), other media used for culture of mammalian and yeast cells and phosphate-buffered saline. The most active antioxidants were: propyl gallate (PG), (-)-epigallocatechin gallate (EGCG) and quercetin (Q). Chelex treatment and iron chelators decreased H2O2 generation suggesting that transition metal ions catalyze antioxidant autoxidation and H2O2 production. Green tea also generated H2O2; tea prepared on tap water generated significantly more H2O2 than tea prepared on deionized water. Ascorbic acid decreased H2O2 production although it generated H2O2 itself, in the absence of other additives. Lemon added to the tea significantly reduced generation of H2O2. Hydrogen peroxide generated in the medium contributed to the cytotoxicity of PG, EGCG and Q to human prostate carcinoma DU-145 cells, since catalase increased the survival of the cells subjected to these compounds in vitro.

Dual effects of propyl gallate and its methylglyoxal adduct on carbonyl stress and oxidative stress.

In the present study, we investigated the trapping of methylglyoxal (MGO) by propyl gallate (PG), a known food grade antioxidant, and the anti-carbonyl and anti-oxidative properties of the mono-MGO adduct of PG (MM-PG). Our result indicated that more than 77.5% MGO was suppressed by PG after a 30 min incubation of PG with MGO, which was much more effective than gallic acid (15.2%). For the first time, MM-PG was purified, and its structure was elucidated based on the analysis of its 1H, 13C, and 2D-NMR data. We also demonstrated that MM-PG had strong anti-oxidative and anti-carbonyl activities. Furthermore, PG could trap the MGO generated during the preparation of roasted pork, and both mono- and di- MGO adducts of PG were detected in the roasted pork system using LC/MS technique. Thus, PG could be widely applied in the food system for inhibiting the formation of both carbonyl species and oxidative species.

Propyl gallate/cyclodextrin supramolecular complexes with enhanced solubility and radical scavenging capacity.

This study prepared and investigated the inclusion complexes of propyl gallate (PG) with beta-cyclodextrin (ß-CD) and its water-soluble derivatives dimethyl-beta-cyclodextrin (DM-ß-CD), hydroxypropyl-beta-cyclodextrin (HP-ß-CD), and sulfobutylether-beta-cyclodextrin (SBE-ß-CD). Phase solubility studies indicated that the formed complexes were in 1:1 stoichiometry. FT-IR, PXRD, DSC, 1H-NMR, ROESY-NMR, and SEM analysis results confirmed the formation of the complexes. The NMR results indicated that the aromatic ring of PG was embedded into the CD cavity. The aqueous solubility of PG was markedly improved, and that of the PG/DM-ß-CD complex increased by 365.3 times. In addition, the results of the antioxidant activity assay showed that the hydroxyl radical and superoxide radical scavenging capacities of the complexes increased by 3-11 times and 1-6.5 times, respectively, compared with those of PG under the same concentration. Therefore, CD/PG inclusion complexes with improved solubility and radical scavenging capacity can be used as water-soluble antioxidants in the food industry.

Biologically important hydrazide-containing fused azaisocytosines as antioxidant agents.

OBJECTIVES: Two important classes of hydrazide-containing fused azaisocytosines were evaluated as possible antioxidants and characterised by UV spectroscopy. METHODS: 2,2-Diphenyl-1-picrylhydazyl (DPPH), nitric oxide (NO), hydrogen peroxide (H2O2) scavenging potencies and reducing power of molecules were evaluated. RESULTS: The strongest DPPH scavengers were found to be 9, showing the potency superior to that of butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate (PG) and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox) and comparable to that of ascorbic acid (AA), and 6, revealing the antioxidant potency superior to that of BHA, BHT, PG and Trolox. In turn, 3 and 9 were the most promising NO scavengers, exhibiting the potency superior to that of BHA, BHT (3 and 9) and AA (3). The most potent H2O2 scavengers proved to be 10 and 9 showing similar or even better neutralising potency than that of Trolox, BHT and BHA. Simultaneously, the majority of hydrazides revealed higher ferric reducing abilities than that of AA and BHT. Some structure-activity relationships were explored. A possible mechanism for the DPPH radical scavenging ability of hydrazide-containing molecules was proposed. DISCUSSION: Hydrazides 3, 6 and 9 with an antioxidant potential better or comparable to that of the well-known antioxidants are proposed as new antioxidant candidates.

"Sign-on/off" sensing interface design and fabrication for propyl gallate recognition and sensitive detection.

A new strategy based on sign-on and sign-off was proposed for propyl gallate (PG) determination by an electrochemical sensor. The successively modified poly(thionine) (PTH) and molecular imprinted polymer (MIP) showed an obvious electrocatalysis and a good recognition toward PG, respectively. Furthermore, the rebound PG molecules in imprinted cavities not only were oxidized but also blocked the electron transmission channels for PTH redox. Thus, a sign-on from PG current and a sign-off from PTH current were combined as a dual-sign for PG detection. Meanwhile, the modified MIP endowed the sensor with recognition capacity. The electrochemical experimental results demonstrated that the prepared sensor possessed good selectivity and high sensitivity. A linear ranging from 5.0×10(-8) to 1.0×10(-4)mol/L for PG detection was obtained with a limit of detection of 2.4×10(-8)mol/L. And the sensor has been applied to analyze PG in real samples with satisfactory results. The simple, low cost, and effective strategy reported here can be further used to prepare electrochemical sensors for other compounds selective recognition and sensitive detection.

Method validation and measurement uncertainty for the simultaneous determination of synthetic phenolic antioxidants in edible oils commonly consumed in Korea.

This study investigated a method for the validation and determination of measurement uncertainty for the simultaneous determination of synthetic phenolic antioxidants (SPAs) such as propyl gallate (PG), octyl gallate (OG), dodecyl gallate (DG), 2,4,5-trihydroxy butyrophenone (THBP), tert-butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT) in edible oils commonly consumed in Korea. The validated method was able to extract SPA residues under the optimized HPLC-UV and LC-MS/MS conditions. Furthermore, the measurement of uncertainty was evaluated based on the precision study. For HPLC-UV analysis, the recoveries of SPAs ranged from 91.4% to 115.9% with relative standard deviations between 0.3% and 11.4%. In addition, the expanded uncertainties of the SPAs ranged from 0.15 to 5.91. These results indicate that the validated method is appropriate for the extraction and determination of SPAs and can be used to verify the safety of edible oil products containing SPAs residues.

Effect of counter ions of arginine as an additive for the solubilization of protein and aromatic compounds.

Arginine is widely used in biotechnological application, but mostly with chloride counter ion. Here, we examined the effects of various anions on solubilization of aromatic compounds and reduced lysozyme and on refolding of the lysozyme. All arginine salts tested increased the solubility of propyl gallate with acetate much more effectively than chloride. The effects of arginine salts were compared with those of sodium or guanidine salts, indicating that the ability of anions to modulate the propyl gallate solubility is independent of the cation. Comparison of transfer free energy of propyl gallate between sodium and arginine salts indicates that the interaction of propyl gallate is more favorable with arginine than sodium. On the contrary, the solubility of aromatic amino acids is only slightly modulated by anions, implying that there is specific interaction between acetic acid and propyl gallate. Unlike their effects on the solubility of small aromatic compounds, the solubility of reduced lysozyme was much higher in arginine chloride than in arginine acetate or sulfate. Consistent with high solubility, refolding of reduced lysozyme was most effective in arginine chloride. These results suggest potential broader applications of arginine modulated by different anions.

Enzymatic Glycosylation of Phenolic Antioxidants: Phosphorylase-Mediated Synthesis and Characterization.

Although numerous biologically active molecules exist as glycosides in nature, information on the activity, stability, and solubility of glycosylated antioxidants is rather limited to date. In this work, a wide variety of antioxidants were glycosylated using different phosphorylase enzymes. The resulting antioxidant library, containing α/ß-glucosides, different regioisomers, cellobiosides, and cellotriosides, was then characterized. Glycosylation was found to significantly increase the solubility and stability of all evaluated compounds. Despite decreased radical-scavenging abilities, most glycosides were identified to be potent antioxidants, outperforming the commonly used 2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT). Moreover, the point of attachment, the anomeric configuration, and the glycosidic chain length were found to influence the properties of these phenolic glycosides.

Molecularly imprinted electrochemical sensor for propyl gallate based on PtAu bimetallic nanoparticles modified graphene-carbon nanotube composites.

A novel molecularly imprinted electrochemical sensor for propyl gallate (PG) determination was developed via electropolymerization of an o-phenylenediamine membrane in the presence of template molecules on glassy carbon electrode surface modified by PtAu bimetallic nanoparticles-capped graphene-carbon nanotubes composites (PtAu-GrCNTs). The modified electrodes were characterized by cyclic voltammetry, scanning electron microscope, x-ray diffraction and chronoamperometry. Moreover, experimental parameters such as scan cycles, incubation time, molar ratios of template molecules to functional monomers and extraction time were optimized. It was found that the PtAu-GrCNTs composite could effectively enhance the electron transfer efficiency and remarkably improve the sensitivity of the sensor. The results revealed the sensor displayed superb resistance to no-specific binding, very attractive detection limit as low as 2.51×10(-8) mol/L, and a wide linear range from 7×10(-8) mol/L to 1×10(-5) mol/L towards PG. Furthermore, the MIPs sensor was also successfully used for the detection of PG in food samples. Therefore, the MIPs-based electrochemical sensing strategy might provide a sensitive, rapid, and cost-effective method for PG determination and related food safety analysis.

Imprinted propyl gallate electrochemical sensor based on graphene/single walled carbon nanotubes/sol-gel film.

A novel imprinted sol-gel electrochemical sensor for the determination of propyl gallate (PG) was developed based on a composite of graphene and single walled carbon nanotubes (GR-SWCNTs). It was fabricated by stepwise modifying GR-SWCNTs and molecularly imprinted polymers and stored in 0.10 mol L(-1) phosphate buffer solution pH 6.0, which endowed the sensor good sensitivity and selective recognition towards template molecules. The morphology and specific adsorption capacity of the sensor was characterized by scanning electron microscope and electrochemical methods, respectively. Under the optimized conditions, a linear range of the sensor to PG was 8.0 × 10(-8)-2.6 × 10(-3)mo lL(-1) with a limit of detection of 5.0 × 10(-8)mol L(-1) (S/N=3). The sensor exhibited specificity and selectivity towards template molecules as well as excellent reproducibility, regeneration and stability. Furthermore, the sensor could be applied to determine PG in edible oils, instant noodles and cookies with satisfactory results.