Search

In contrast to the hyperactive platinum electrode, ARS modified platinum electrode presents a remarkable inertness toward adsorption and surface processes and lends it for further voltammetric applications. Measuring pyrogallol levels in samples is significant for assessing their antioxidant activity, which is crucial for understanding their potential health benefits and ability to combat oxidative stress. In addition, the excess consumption of pyrogallol can have significant negative effects on human health. A voltammetric sensor has been developed for the determination of pyrogallol using ARS modified platinum electrode. The electrode was prepared by electrodeposition of alizarin red S on a platinum electrode using cyclic voltammetry with a potential scan range of - 0.4 to 1.2 V against an Ag/AgCl quasi reference electrode for 60 cycles as optimum number of cycles. The modified electrode was characterized by CV and SEM techniques. This modified alizarin red S platinum electrode showed remarkable electrocatalytic performance and stability, resulting in a significant increase in pyrogallol oxidation current by 11.05% compared to the pyrogallol oxidative current at the unmodified platinum electrode. A well-defined oxidation peak was observed at ~ 0.40 V. The sensor exhibited a low limit of detection (LOD) of 0.28 µM and a linear standard curve covering the ranges of 1.0-40 µM and 0.01-10.0 mM pyrogallol. Extensive studies were performed to evaluate possible interferences from various organic and inorganic compounds and yielded satisfactory results that confirm the selectivity of the developed sensor for pyrogallol determination. In addition, the ARS-Pt electrode provided consistently reliable results for the accurate detection of pyrogallol in water and tomato samples., (© 2024. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

The 1967 attempt of structural analysis of the solid-state complex of caffeine and pyrogallol was a pioneering structural investigation in the supramolecular chemistry of caffeine, of what today would easily be considered an archetype of a model pharmaceutical cocrystal. Re-investigating this historically important system demonstrates that this long overlooked complex is most likely a tetrahydrate with a different structure and composition than initially proposed, and provides the crystal structure of the anhydrous cocrystal.

This study aimed to explore the inhibitory effect of pyrogallol on AGE formation in the bovine serum albumin (BSA)/glucose system for 21 days at 37 °C. The AGEs formation was measured in terms of Amadori products, total AGEs, argpyrimidine, and pentosidine. Molecular docking was used to investigate the interaction between pyrogallol and BSA. According to the results, in the presence of pyrogallol, the formation of pentosidine and argpyrimidine AGEs decreased. The molecular interaction studies demonstrated that pyrogallol has a high affinity towards arginine residues of albumin. Finally, results proved pyrogallol is a vigorous antiglycation compound and fruitful for AGE inhibition.

This study was designed to investigate the effect of polyphenolic structure on the interaction strength and process between polyphenols (gallic acid (GA), epigallocatechin gallate (EGCG) and tannic acid (TA)) and amylose (AM). The results of Fourier transform infrared spectroscopy, isothermal titration calorimetry, X-ray photoelectron spectroscopy and molecular dynamic simulation (MD) suggested that the interactions between the three polyphenols and AM were noncovalent, spontaneous, low-energy and driven by enthalpy, which would be enhanced with increasing amounts of pyrogallol groups in the polyphenols. The results of turbidity, particle size and appearance of the complex solution showed that the interaction process between polyphenols and AM could be divided into three steps and would be advanced by increasing the number of pyrogallol groups in the polyphenols. At the same time, MD was intuitively employed to exhibit the interaction process between amylose and polyphenols, and it revealed that the interaction induced the aggregation of amylose and that the agglomeration degree of amylose increased with increasing number of pyrogallol groups at polyphenols. Last, the SEM and TGA results showed that TA/AM complexes had the tightest structure and the highest thermal stability (TA/AM˃EGCG/AM˃GA/AM), which could be attributed to TA having five pyrogallol groups., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Pharmaceutical cocrystals ( Regulatory Classification of Pharmaceutical Co-Crystals Guidance for Industry ; Food and Drug Administration, 2018) are crystalline solids produced through supramolecular chemistry to modulate the physicochemical properties of active pharmaceutical ingredients (APIs). Despite their extensive development in interdisciplinary sciences, this is a pioneering study on the efficacy of pharmaceutical cocrystals in wound healing and scar reducing. Curcumin-pyrogallol cocrystal (CUR-PYR) was accordingly cherry-picked since its superior physicochemical properties adequately compensate for limitative drawbacks of curcumin (CUR). CUR-PYR has been synthesized by a liquid-assisted grinding (LAG) method and characterized via FT-IR, DSC, and PXRD analyses. In vitro antibacterial study indicated that CUR-PYR cocrystal, CUR+PYR physical mixture (PM), and PYR are more effective against both Gram-negative ( Pseudomonas aeruginosa and Escherichia coli ) and Gram-positive ( Staphylococcus aureus and Bacillus subtilis ) bacteria in comparison with CUR. In vitro results also demonstrated that the viability of HDF and NIH-3T3 cells treated with CUR-PYR were improved more than those received CUR which is attributed to the effect of PYR in the form of cocrystal. The wound healing process has been monitored through a 15 day in vivo experiment on 75 male rats stratified into six groups: five groups treated by CUR-PYR+Vaseline (CUR-PYR.ung), CUR+PYR+Vaseline (CUR+PYR.ung), CUR+Vaseline (CUR.ung), PYR+Vaseline (PYR.ung), and Vaseline (VAS) ointments and a negative control group of 0.9% sodium chloride solution (NS). It was revealed that the wounds under CUR-PYR.ung treatment closed by day 12 postsurgery, while the wounds in other groups failed to reach the complete closure end point until the end of the experiment. Surprisingly, a diminutive scar (3.89 ± 0.97% of initial wound size) was observed in the CUR-PYR.ung treated wounds by day 15 after injury, followed by corresponding values for PYR.ung (12.08 ± 2.75%), CUR+PYR.ung (13.89 ± 5.02%), CUR.ung (16.24 ± 6.39%), VAS (18.97 ± 6.89%), and NS (20.33 ± 5.77%). Besides, investigating histopathological parameters including inflammation, granulation tissue, re-epithelialization, and collagen deposition signified outstandingly higher ability of CUR-PYR cocrystal in wound healing than either of its two constituents separately or their simple PM. It was concluded that desired solubility of the prepared cocrystal was essentially responsible for accelerating wound closure and promoting tissue regeneration which yielded minimal scarring. This prototype research suggests a promising application of pharmaceutical cocrystals for the purpose of wound healing.

Herein, we present the facile synthesis of poly(pyrogallol) biopolymers and their application as antibacterial agents. Pyrogallol is a class of phenolic compounds that can be found in various plants. Polymerization was performed by the auto-oxidation of pyrogallol under a hydrated condition. The microscopic image of poly(pyrogallol) shows a highly homogenous nanofibrous structure with a diameter of 100.3 ± 16.3 nm. Spectroscopic analysis by FT-IR spectroscopy, Raman spectroscopy, and XPS corroborated the formation of ether (C-O-C) bonds between the hydroxyl group and adjacent carbons of pyrogallol during polymerization. The FT-IR and XPS spectra also revealed redox-active gallol functional groups on poly(pyrogallol) nanofibers, which can be used to release free electrons and protons during oxidation followed by the generation of reactive oxygen species (ROS). The generated ROS from poly(pyrogallol) was used to inhibit the growth of bacteria, Escherichia coli , at a inhibition rates of 56.3 ± 9.7% and 95.5 ± 2.0% within 0.5 and 2 h, respectively. This finding suggests that poly(pyrogallol) can be used as a naturally occurring antibacterial agent for various biomedical and environmental applications.

Marine-inspired phenolic compounds that exhibit underwater adhesion are used as biomedical adhesives under wet conditions. While these applications mainly use catechol and pyrogallol moieties that contain different numbers of hydroxyl groups on their benzene rings, how this difference affects adhesion and cohesion is not well understood. Herein, the chitosan backbone is functionalized with catechol and pyrogallol at similar modification rates (to give chitosan-catechol (CS-CA) and chitosan-pyrogallol (CS-GA), respectively) and their interaction energies are compared by using a surface forces apparatus (SFA). The phenolic moieties decrease the rigidity of the chitosan chain and increase solubility; consequently, CS-CA and CS-GA are more cohesive and adhesive than chitosan at pH 7.4. Moreover, the additional hydroxyl group of GA provides a further interacting chance; hence, CS-GA is more cohesive and adhesive than CS-CA. This study provides in-depth insight into interactions involving chitosan derivatives bearing introduced phenolic moieties that will help to develop biomedical adhesives., (© 2022 Wiley-VCH GmbH.)

The hexameric assemblies of resorcinarenes and pyrogallolarenes are fascinating structures that can serve as nanoreactors in which new chemistry and catalysis occur. Recently, it was suggested based on SANS or SAXS that C 11 -resorcin[4]arene ( 1 ) forms octameric aggregates of a micellar rather than capsular structure in toluene. Here, using NMR spectroscopy, diffusion NMR, and DOSY performed on solutions of C 11 -pyrogallol[4]arene ( 1 ), C 11 -pyrogallol[4]arene ( 2 ), and mixtures thereof in protonated and deuterated solvents, we found that, in benzene and toluene, 1 primarily formed hexameric capsules accompanied by a minor product with diffusion characteristics consistent with an octameric assembly. In chloroform, 1 formed hexameric capsules. In toluene, 2D NMR revealed two populations of encapsulated toluene molecules in the same capsule of 1 . The addition of tetrahexylammonium bromide to the assemblies of 1 in aromatic solvents drove the equilibrium toward the formation of the hexameric capsules. Interestingly, 2 formed only hexameric capsules in all solvents tested.

Spatial sequestration of molecules is a prerequisite for the complexity of biological systems, enabling the occurrence of numerous, often non-compatible chemical reactions and processes in one cell at the same time. Inspired by this compartmentalization concept, chemists design and synthesize artificial nanocontainers (capsules and cages) and use them to mimic the biological complexity and for new applications in recognition, separation, and catalysis. Here, we report the formation of large closed-shell species by interactions of well-known polyphenolic macrocycles with anions. It has been known since many years that C-alkyl resorcin[4]arenes ( R4C ) and C-alkyl pyrogallol[4]arenes ( P4C ) narcissistically self-assemble in nonpolar solvents to form hydrogen-bonded capsules. Here, we show a new interaction model that additionally involves anions as interacting partners and leads to even larger capsular species. Diffusion-ordered spectroscopy and titration experiments indicate that the anion-sealed species have a diameter of >26 Å and suggest stoichiometry ( M ) 6 (X - ) 24 and tight ion pairing with cations. This self-assembly is effective in a nonpolar environment (THF and benzene but not in chloroform), however, requires initiation by mechanochemistry (dry milling) in the case of non-compatible solubility. Notably, it is common among various polyphenolic macrocycles ( M ) having diverse geometries and various conformational lability.

In this study, we developed a novel colorimetric chemosensor for selective and sensitive recognition of Glutathione (GSH) using a simple binary mixture of commercially accessible and inexpensive metal receptors with names, Bromo Pyrogallol Red (BPR) and Xylenol Orange (XO). This procedure is based on the synergistic coordination of BPR and XO with cerium ion (Ce3+) for the recognition of GSH over other available competitive amino acids (AAs) especially thiol species in aqueous media. Generally, cysteine (Cys) and homocysteine (hCys) can seriously interfere with the detection of GSH among common biological species because they possess similar chemical behavior. Using all the information from 1HNMR and FT-IR studies, the proposed interaction is presented in which GSH acts as a tri-dentate ligand with three N donor atoms in conjunction with BPR and XO as mono and bi-dentate ligands respectively. This approach opens a path for selective detection of other AAs by argumentatively selecting the ensemble of mixed organic ligands from commercially available reagents, thereby eliminating the need for developing synthetic receptors, sample preparation, organic solvent mixtures, and expensive equipment. Evaluating the feasibility of the existing method was led to the determination of GSH in human plasma samples., (Copyright © 2021. Published by Elsevier Inc.)

Biomass valorization to building block chemicals in food and pharmaceutical industries has tremendously gained attention. To produce monophenolic compounds from palm empty fruit bunch (EFB), EFB was subjected to alkaline hydrothermal extraction using NaOH or K 2 CO 3 as a promotor. Subsequently, EFB-derived lignin was subjected to an oxidative depolymerization using Cu(II) and Fe(III) mixed metal oxides catalyst supported on γ-Al 2 O 3 or SiO 2 as the catalyst in the presence of hydrogen peroxide. The highest percentage of total phenolic compounds of 63.87 wt% was obtained from microwave-induced oxidative degradation of K 2 CO 3 extracted lignin catalyzed by Cu-Fe/SiO 2 catalyst. Main products from the aforementioned condition included 27.29 wt% of 2,4-di-tert-butylphenol, 19.21 wt% of syringol, 9.36 wt% of acetosyringone, 3.69 wt% of acetovanillone, 2.16 wt% of syringaldehyde, and 2.16 wt% of vanillin. Although the total phenolic compound from Cu-Fe/Al 2 O 3 catalyst was lower (49.52 wt%) compared with that from Cu-Fe/SiO 2 catalyst (63.87 wt%), Cu-Fe/Al 2 O 3 catalyst provided the greater selectivity of main two value-added products, syringol and acetosyrigone, at 54.64% and 23.65%, respectively (78.29% total selectivity of two products) from the NaOH extracted lignin. The findings suggested a promising method for syringol and acetosyringone production from the oxidative heterogeneous lignin depolymerization under low power intensity microwave heating within a short reaction time of 30 min.

The ongoing pandemic of coronavirus disease 2019 (COVID-19) caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) urgently needs an effective cure. 3CL protease (3CL pro ) is a highly conserved cysteine proteinase that is indispensable for coronavirus replication, providing an attractive target for developing broad-spectrum antiviral drugs. Here we describe the discovery of myricetin, a flavonoid found in many food sources, as a non-peptidomimetic and covalent inhibitor of the SARS-CoV-2 3CL pro . Crystal structures of the protease bound with myricetin and its derivatives unexpectedly revealed that the pyrogallol group worked as an electrophile to covalently modify the catalytic cysteine. Kinetic and selectivity characterization together with theoretical calculations comprehensively illustrated the covalent binding mechanism of myricetin with the protease and demonstrated that the pyrogallol can serve as an electrophile warhead. Structure-based optimization of myricetin led to the discovery of derivatives with good antiviral activity and the potential of oral administration. These results provide detailed mechanistic insights into the covalent mode of action by pyrogallol-containing natural products and a template for design of non-peptidomimetic covalent inhibitors against 3CL pro s, highlighting the potential of pyrogallol as an alternative warhead in design of targeted covalent ligands.

Human activities, especially in industry, have contributed to soil contamination with heavy or toxic metals. The objective of this study was to determine the chelating effect and antioxidant activity of pyrogallol, as well as to evaluate its cytoprotective activity in prokaryotic and eukaryotic models, animal and plant, respectively, against toxic mercury chloride action. Antioxidant activity was determined by DPPH where pyrogallol showed considerable action, chelating even iron ions. For the microbiologic activity assays, microdilution was performed to obtain the minimal inhibitory concentration, minimum bactericidal and minimum fungicide concentration, from which the sub-inhibitory concentrations were determined. The product did not conferred cytoprotection to the tested bacteria and fungi. To evaluate plant cytoprotection, Lactuta sativa seeds were used together with the product at a sub-allelopathic concentration with different HgCl 2 concentrations. In this case, the tannin conferred cytoprotection to the plant model, allowing the best growth and development of caulicles and radicles, thus preserving tissues necessary for plant survival. From the results, it is observable that pyrogallol possesses cytoprotective action in the eukaryotic plant model, this action being useful as an alternative which favors the growth of plants in contaminated areas, as the recovering of crop fields or reforestation projects.

Multifunctional hydrogels that integrate stretchability, adhesion, self-healing, and antibacterial properties may find use in a variety of fields including electronic skin, wound dressings, and wearable devices; however, traditional hydrogels often exhibit short-term adhesiveness, poor mechanical properties, and a lack of antibacterial activity. Herein, a plant-inspired polyacrylamide-soybean protein isolate-pyrogallol/borax (PAM-SPI-P/B) hydrogel has been developed using a facile green method based on dynamic coordination cross-linking between pyrogallol (PG) and borax. The PG-borax dynamic bonds adjusted the network structure of the hydrogels to provide greater structural integrity to the PAM-SPI double network. This hydrogel possessed a high mechanical strength (large elongation up to 760% and compressive strength up to 1.25 MPa at 80% strain), low swelling ratio, and self-healing properties. Inspired by natural polyphenols that contain adhesive molecules, the addition of pyrogallol provided the hydrogel excellent adhesion to various hydrophilic and hydrophobic substrates. And with the inhibition of pyrogallol autoxidation due to the borax protection, the hydrogel showed repeatable and durable adhesion over 20 cycles. The obtained hydrogels also exhibited good antibacterial activities against Escherichia coli and Staphylococcus aureus because they were based on pyrogallol and borax, which have antibacterial properties. Accordingly, we envision that the PAM-SPI-P/B hydrogels have great potential for use in biomimetic tissues and biosensors.

Bis(demethoxy)curcumin (BDMC) is one of the main active components found in turmeric. Major drawbacks for its usage are its low aqueous solubility, and the challenging separation from other curcuminoids present in turmeric. Co-crystallization can be applied to alter the physicochemical properties of BDMC in a desired manner. A co-crystal screening of BDMC with four hydroxybenzenes was carried out using four different methods of co-crystal production: crystallization from solution by slow solvent evaporation (SSE), and rapid solvent removal (RSR), liquid-assisted grinding (LAG), and crystallization from the melt phase. Two co-crystal phases of BDMC were obtained with pyrogallol (PYR), and hydroxyquinol (HYQ). PYR-BDMC co-crystals can be obtained only from the melt, while HYQ-BDMC co-crystals could also be produced by LAG. Both co-crystals possess an equimolar composition and reveal an incongruent melting behavior. Infrared spectroscopy demonstrated the presence of BDMC in the diketo form in the PYR co-crystals, while it is in a more stable keto-enol form in the HYQ co-crystals. Solubility measurements in ethanol and an ethanol-water mixture revealed an increase of solubility in the latter, but a slightly negative effect on ethanol solubility. These results are useful for a prospective development of crystallization-based separation processes of chemical similar substances through co-crystallization.

Syringol and syringaldehyde are widely present pollutants in atmosphere and wastewater due to lignin pyrolysis and draining of pulp mill effluents. The hydroxylation degradation mechanisms and kinetics and health effect assessment of them under high and low-NO x regimes in atmosphere and wastewater have been studied theoretically. The effect of pH on reaction mechanisms and rate constants in their ·OH-initiated degradation processes has been fully investigated. Results have suggested that aqueous solution played a positive role in the ·OH-initiated degradation reactions by decreasing the energy barriers of most reactions and changing the reactivity order of initial reactions. For Sy - and Sya - (anionic species of syringol and syringaldehyde), most initial reaction routes were more likely to occur than that of HSy and Hsya (neutral species of syringol and syringaldehyde). As the pH increased from 1 to 14, the overall rate constants (at 298 K) of syringol and syringaldehyde with ·OH in wastewater increased from 5.43 × 10 10 to 9.87 × 10 10  M -1  s -1 and from 3.70 × 10 10 to 1.14 × 10 11  M -1  s -1 , respectively. In the NO x -rich environment, 4-nitrosyringol was the most favorable product, while ring-opening oxygenated chemicals were the most favorable products in the NO x -poor environment. On the whole, the NO x -poor environment could decrease the toxicities during the hydroxylation processes of syringol and syringaldehyde, which was the opposite in a NO x -rich environment. ·OH played an important role in the methoxyphenols degradation and its conversion into harmless compounds in the NO x -poor environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Toll-like receptors (TLRs) build the first barrier in the innate immune response and therefore represent promising targets for the modulation of inflammatory processes. Recently, the pyrogallol-containing TLR2 antagonists CU-CPT22 and MMG-11 were reported; however, their 1,2,3-triphenol motif renders them highly susceptible to oxidation and excludes them from use in extended experiments under aerobic conditions. Therefore, we have developed a set of novel TLR2 antagonists (1-9) based on the systematic variation of substructures, linker elements, and the hydrogen-bonding pattern of the pyrogallol precursors by using chemically robust building blocks. The novel series of chemically stable and synthetically accessible TLR2 antagonists (1-9) was pharmacologically characterized, and the potential binding modes of the active compounds were evaluated structurally. Our results provide new insights into structure-activity relationships and allow rationalization of structural binding characteristics. Moreover, they support the hypothesis that this class of TLR ligands bind solely to TLR2 and do not directly interact with TLR1 or TLR6 of the functional heterodimer. The most active compound from this series (6), is chemically stable, nontoxic, TLR2-selective, and shows a similar activity with regard to the pyrogallol starting points, thus indicating the variability of the hydrogen bonding pattern., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

In this work, a tunicate-inspired gelatin-based hydrogel is prepared by simply mixing 2,3,4-trihydroxybenzaldehyde (THB)-tethered gelatin solution with a small amount of Fe 3+ ions via the Schiff-base reaction and simultaneous formation of hexavalent Fe-complexes. The resulting hydrogel (termed GelTHB-Fe) exhibits not only tunable gelation time, rheological properties and self-healing ability by adjusting the composition, but also robust adhesion to a variety of materials, with an average adhesion strength of 136.7 kPa, 147.3 kPa, 153.7 kPa, 92.9 kPa, and 56.5 kPa to PMMA, iron, ceramics, glass and pigskin, respectively. Intriguingly, the pyrogallol moieties impart an antibacterial activity to the GelTHB-Fe hydrogel, which is shown to reduce infection and promote wound healing in a diabetic rat model. This GelTHB-Fe hydrogel holds great potential as a promising tissue adhesive.

Peroxidovanadium(V) and oxidovanadium(IV) compounds have been tested as peroxidase-similar compounds. Their catalytic performance was tested on phenol red and pyrogallol substrates. Bromination kinetic studies revealed Michaelis-Menten behavior with respect to phenol red for both complexes. Catalytic efficiency is ~ 10 4 M -1 min -1 . Both vanadium complexes showed the capacity to oxidize pyrogallol, but only the oxidovanadium (IV) complex follows Michaelis-Menten kinetics with respect to this substrate (K m = 1.05 × 10 -3 M). Peroxidovanadium(V) complex displayed a more complex mechanism, and further studies became necessary to elucidate it. The structure-activity relationship was also assessed.

The synthesis of phenyl-resorcinarenes and pyrogallolarenes is known to produce a conformational mixture of cone and chair isomers. Depending on the synthesis conditions the composition of the conformational mixture is variable; however, the cone conformer is the greatest proportion of phenyl-resorcin[4]arenes and chair conformer of pyrogallol[4]arenes. The experimental evidence suggests that phenyl-substituted resorcinarene and pyrogallolarene exist as a dynamic boat in solution.

Phosphate buffered saline (PBS) is a commonly used buffer in biological research. Herein, the stability of a series of flavonoids, i.e. myricetin, kaempferol, baicalein, luteolin and quercetin, were assessed in PBS within 5 s. Apigenin proved very stable in PBS and was therefore used as a control. Kaempferol and baicalein were less stable with small amounts of oxidized and hydroxylated products being detected. The other flavonoids were unstable and their dimers were identified in PBS at 4 °C under normal atmospheric conditions. Flavonols with a catechol or pyrogallol substitution pattern on ring B readily formed stable dimers and oxidized products in PBS (pH = 7.4) at 4 °C within 5 s. The chosen experimental conditions improved the stability of dimers and allowed their detection., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Demands for safe depigmentation compounds are constantly increasing in the pharmaceutical and cosmetic industry, since the numerous relevant compounds reported to date have shown undesirable side effects or low anti-melanogenic effects. In this study, we reported three novel inhibitors of tyrosinase, which is the key enzyme in melanogenesis, identified using docking-based high throughput virtual screening of an in-house natural compound library followed by mushroom tyrosinase inhibition assay. Of the three compounds, gallacetophenone showed high anti-melanogenic effect in both human epidermal melanocytes and a 3D human skin model, MelanoDerm. The inhibitory effect of gallacetophenone on tyrosinase was elucidated by computational molecular modeling at the atomic level. Binding of gallacetophenone to the active site of tyrosinase was found to be stabilized by hydrophobic interactions with His367, Ile368, and Val377; hydrogen bonding with Ser380 and a water molecule bridging the copper ions. Thus, our results strongly suggested gallacetophenone as an anti-melanogenic ingredient that inhibits tyrosinase.

The lignin pyrolysis products generated by biomass combustion make an essential contribution to the formation of secondary organic aerosols (SOAs). The ozone-initiated oxidation of guaiacol, syringol and creosol, major constituents of biomass burning, were investigated theoretically by using the density functional theory (DFT) method at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. Six primary addition reaction pathways and further decomposition routes with corresponding thermodynamic values were proposed. The Criegee intermediates can be excited by small molecules, such as NO x , H 2 O in the atmosphere, and would further proceed via self-decomposition or isomerization. The most predominant product for ozonation of guaiacol is the monomethyl muconate (P1). At 295 K and atmospheric pressure, the rate constant is 1.10 × 10 -19 cm 3 molecule -1 s -1 , which is lies a factor of 4 smaller than the previous experimental study. The branching ratios of the six channels are calculated based on corresponding rate coefficient. The present work mainly provides a more comprehensive and detailed theoretical research on the ozonation of methoxyphenol, which aspires to offer novel insights and reference for future experimental and theoretical work and control techniques of SOAs caused by lignin pyrolysis products.

Elemicin, an alkenylbenzene constituent of natural oils of several plant species, is widely distributed in food, dietary supplements, and medicinal plants. 1'-Hydroxylation is known to cause metabolic activation of alkenylbenzenes leading to their potential toxicity. The aim of this study was to explore the relationship between elemicin metabolism and its toxicity through comparing the metabolic maps between elemicin and 1'-hydroxyelemicin. Elemicin was transformed into a reactive metabolite of 1'-hydroxyelemicin, which was subsequently conjugated with cysteine (Cys) and N -acetylcysteine (NAC). Administration of NAC could significantly ameliorate the elemicin- and 1'-hydroxyelemicin-induced cytotoxicity of HepG2 cells, while depletion of Cys with diethyl maleate (DEM) increased cytotoxicity. Recombinant human CYP screening and CYP inhibition experiments revealed that multiple CYPs, notably CYP1A1, CYP1A2, and CYP3A4, were responsible for the metabolic activation of elemicin. This study revealed that metabolic activation plays a critical role in elemicin cytotoxicity.

Microbial conversion of aromatic compounds is an emerging and promising strategy for valorization of the plant biopolymer lignin. A critical and often rate-limiting reaction in aromatic catabolism is O -aryl-demethylation of the abundant aromatic methoxy groups in lignin to form diols, which enables subsequent oxidative aromatic ring-opening. Recently, a cytochrome P450 system, GcoAB, was discovered to demethylate guaiacol (2-methoxyphenol), which can be produced from coniferyl alcohol-derived lignin, to form catechol. However, native GcoAB has minimal ability to demethylate syringol (2,6-dimethoxyphenol), the analogous compound that can be produced from sinapyl alcohol-derived lignin. Despite the abundance of sinapyl alcohol-based lignin in plants, no pathway for syringol catabolism has been reported to date. Here we used structure-guided protein engineering to enable microbial syringol utilization with GcoAB. Specifically, a phenylalanine residue (GcoA-F169) interferes with the binding of syringol in the active site, and on mutation to smaller amino acids, efficient syringol O -demethylation is achieved. Crystallography indicates that syringol adopts a productive binding pose in the variant, which molecular dynamics simulations trace to the elimination of steric clash between the highly flexible side chain of GcoA-F169 and the additional methoxy group of syringol. Finally, we demonstrate in vivo syringol turnover in Pseudomonas putida KT2440 with the GcoA-F169A variant. Taken together, our findings highlight the significant potential and plasticity of cytochrome P450 aromatic O -demethylases in the biological conversion of lignin-derived aromatic compounds., Competing Interests: The authors declare no conflict of interest., (Copyright © 2019 the Author(s). Published by PNAS.)

In the present study, the interaction of Pyrogallol (PG) with human serum albumin (HSA) was investigated by UV, fluorescence, Circular dichroism (CD), and molecular docking methods. The results of fluorescence experiments showed that the quenching of intrinsic fluorescence of HSA by PG was due to a static quenching. The calculated binding constants ( K ) for PG-HSA at different temperatures were in the order of 10 4  M -1 , and the corresponding numbers of binding sites, n were approximately equal to unity. The thermodynamic parameters, Δ H and Δ S were calculated to be negative, which indicated that the interaction of PG with HSA was driven mainly by van der Waals forces and hydrogen bonds. The negative value was obtained for Δ G showed that the reaction was spontaneous. In addition, the effect of PG on the secondary structure of HSA was analyzed by performing UV-vis, synchronous fluorescence, and CD experiments. The results indicated that PG induced conformational changes in the structure of HSA. According to Förster no-radiation energy transfer theory, the binding distance of HSA to PG was calculated to be 1.93 nm. The results of molecular docking calculations clarified the binding mode and the binding sites which were in good agreement with the results of experiments. Communicated by Ramaswamy H. Sarma.

Carbonate radicals (CO 3 ) are generated by the bicarbonate-dependent peroxidase activity of cytosolic superoxide dismutase (Cu,Zn-SOD, SOD-1). The present work explored the use of bleaching of pyrogallol red (PGR) dye to quantify the rate of CO - ) are generated by the bicarbonate-dependent peroxidase activity of cytosolic superoxide dismutase (Cu,Zn-SOD, SOD-1). The present work explored the use of bleaching of pyrogallol red (PGR) dye to quantify the rate of CO 3 - formation from bovine and human SOD-1 (bSOD-1 and hSOD-1, respectively). This approach was compared to previously reported methods using electron paramagnetic resonance spin trapping with DMPO, and the oxidation of ABTS (2,2-azino-bis(3-ethylbenzothiazoline)-6-sulfonic acid). The kinetics of PGR consumption elicited by CO 3 - was followed by visible spectrophotometry. Solutions containing PGR (5-200 μM), SOD-1 (0.3-3 μM), H 2 O 2 (2 mM) in bicarbonate buffer (200 mM, pH 7.4) showed a rapid loss of the PGR absorption band centered at 540 nm. The initial consumption rate (R i ) gave values independent of the initial PGR concentration allowing an estimate to be made of the rate of CO 3 - release of 24.6 ± 4.3 μM min -1 for 3 μM bSOD-1. Both bSOD-1 and hSOD-1 showed a similar peroxidase activity, with enzymatic inactivation occurring over a period of 20 min. The single Trp residue (Trp 32 ) present in hSOD-1 was rapidly consumed (initial consumption rate 1.2 ± 0.1 μM min -1 ) with this occurring more rapidly than hSOD-1 inactivation, suggesting that these processes are not directly related. Added free Trp was rapidly oxidized in competition with PGR. These data indicate that PGR reacts rapidly and efficiently with CO 3 - resulting from the peroxidase activity of SOD-1, and that PGR-bleaching is a simple, fast and cheap method to quantify CO 3 - release from bSOD-1 and hSOD-1 peroxidase activity., (Copyright © 2019 The Authors. Published by Elsevier B.V. All rights reserved.)

In the western diet there is an oversupply of n-6 fatty acids. This adverse trend can be balanced by the consumption of rapeseed and flaxseed oils rich in α-linolenic acid (n-3). However, the high share of this fatty acid contributes to low oxidative stability of oil. Oxidation decreases n-3 fatty acid and other bioactive compounds contents, which adversely affects oil nutritional value. In this study, the impact of ferulic and sinapic acids vinyl derivatives on the fatty acids and oil terpenoids (sterols, tocols, carotenoids, squalene) retention at the end of induction period during accelerated oxidation of rapeseed and flaxseed cold-pressed oils was investigated. It was found that the use of 4-vinylsyringol (4-VS) or 4-vinylquaiacol (4-VQ) increased the retention of intact sterols and carotenoids (at least 2-fold) and squalene (at least 4-fold). The 4-VQ addition also inhibited the α-linolenic acid loss. Unfortunately, both phenolic derivatives favoured α-tocopherol decay in rapeseed oil., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Myristicin is widely distributed in spices and medicinal plants. The aim of this study was to explore the role of metabolic activation of myristicin in its potential toxicity through a metabolomic approach. The myristicin- N-acetylcysteine adduct was identified by comparing the metabolic maps of myristicin and 1'-hydroxymyristicin. The supplement of N-acetylcysteine could protect against the cytotoxicity of myristicin and 1'-hydroxymyristicin in primary mouse hepatocytes. When the depletion of intracellular N-acetylcysteine was pretreated with diethyl maleate in hepatocytes, the cytotoxicity induced by myristicin and 1'-hydroxymyristicin was deteriorated. It suggested that the N-acetylcysteine adduct resulting from myristicin bioactivation was closely associated with myristicin toxicity. Screening of human recombinant cytochrome P450s (CYPs) and treatment with CYP inhibitors revealed that CYP1A1 was mainly involved in the formation of 1'-hydroxymyristicin. Collectively, this study provided a global view of myristicin metabolism and identified the N-acetylcysteine adduct resulting from myristicin bioactivation, which could be used for understanding the mechanism of myristicin toxicity.

In this work, CdS nanoparticles (CdS NPs) biosynthesized through Arabidopsis thaliana phytochelatin synthase-modified Escherichia coli (CdS/AtPCS1-E. coli) with fluorescence (FL) performance for detection of pyrogallol and gallic acid was investigated. Through expression of the AtPCS1 gene inside E. coli cells by pET28b vector, biosynthesis of CdS NPs was greatly enhanced due to generation of phytochelatins (PCs, (γ-Glu-Cys) n -Gly, n ≥ 2) for efficient capture of Cd 2+ . The expression of AtPCS1 and concentration of glutathione (GSH) and PCs were detected by sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and high performance liquid chromatography (HPLC), respectively. The morphology and component were checked through scanning electron microscope (SEM), transmission electron microscopy (TEM) and energy dispersive spectrometer (EDS). FL effect with different experimental conditions were examined. In addition, it is also applied to determination of pyrogallol and gallic acid. These results revealed that multifunctional PCs could effectively facilitate biosynthesis of CdS NPs with higher yield, better distribution and lower cost while stronger FL intensity could be obtained for quantitative analysis., (Copyright © 2018. Published by Elsevier B.V.)

The nature-inspired fabrication of tissue adhesive and hemostatic hydrogels holds great potential for restoring damaged internal tissue in regenerative medicine. However, feeble adhesion, multifaceted systems, prohibitive costs, and toxicity impede their applications in the medical field. In order to solve this problem, we fabricated chitosan-based wet tissue adhesive with hemostatic functions inspired by the self-healing mechanism of the tunicate. In order to introduce pyrogallol moiety, gallic acids, which are broadly distributed in nature, were incorporated into chitosan backbone, a key residue for the self-healing process of tunichrome in tunicates. The in vitro adhesion test results of the tunicate-inspired hydrogel exhibited two-fold greater adhesion ability in wet condition than did fibrin glue, a commercially available surgical glue. Further, the tunicate-inspired hydrogel exhibited significantly more platelet adhesion and blood clotting ability than the parent polymer. We also demonstrated the ability of the derivative to completely mimic the tunicate's fibrous structure by fabricating an electrospun mat. The hemostatic function vis-à-vis the wet adhesiveness of the synthesized chitosan-based material may be useful for facilitating the shortcomings of the restorative tissue medicine. Additionally, the electrospinning capability will enable the modulate of the structure-property relationship and a three-dimensional design for its application site., (Copyright © 2018. Published by Elsevier Ltd.)

To explore whether and how glucuronidation affects pyrogallol-type phytophenols, scutellarein and scutellarin (scutellarein-7- O -glucuronide) were comparatively investigated using a set of antioxidant analyses, including spectrophotometric analysis, UV-vis spectra analysis, and ultra-performance liquid chromatography coupled with electrospray ionization-quadrupole time-of-flight tandem mass spectrometry (UPLC-ESI-Q-TOF-MS/MS) analysis. In spectrophotometric analyses of the scavenging of 1,1-diphenyl-2-picrylhydrazyl (DPPH • ), 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS +• ), and 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide radicals (PTIO • ) and the reduction of Cu 2+ ions, scutellarein showed lower IC 50 values than scutellarin. However, in • O₂ - -scavenging spectrophotometric analysis, scutellarein showed higher IC 50 value than scutellarin. The analysis of UV-Vis spectra obtained after the Fe 2+ -chelating reaction of scutellarin showed a typical UV-Vis peak (λ max = 611 nm), while scutellarein showed no typical peak. In UPLC-ESI-Q-TOF-MS/MS analysis, mixing of scutellarein with DPPH • yielded MS peaks ( m / z 678, 632, 615, 450, 420, 381, 329, 300, 288, 227, 196, 182, 161, and 117) corresponding to the scutellarein-DPPH adduct and an MS peak ( m / z 570) corresponding to the scutellarein-scutellarein dimer. Scutellarin, however, generated no MS peak. On the basis of these findings, it can be concluded that glucuronidation of pyrogallol-type phytophenol antioxidants has a dual effect. On the one hand, glucuronidation can decrease the antioxidant potentials (except for • O₂ - scavenging) and further lower the possibility of radical adduct formation (RAF), while on the other hand, it can enhance the • O₂ - -scavenging and Fe 2+ -chelating potentials.

Ecklonia cava ( E. cava ) can alleviate vascular dysfunction in diseases associated with poor circulation. E. cava contains various polyphenols with different functions, but few studies have compared the effects of these polyphenols. Here, we comparatively investigated four major compounds present in an ethanoic extract of E. cava . These four major compounds were isolated and their effects were examined on monocyte-associated vascular inflammation and dysfunctions. Pyrogallol-phloroglucinol-6,6-bieckol (PPB) significantly inhibited monocyte migration in vitro by reducing levels of inflammatory macrophage differentiation and of its related molecular factors. In addition, PPB protected against monocyte-associated endothelial cell death by increasing the phosphorylations of PI3K-AKT and AMPK, decreasing caspase levels, and reducing monocyte-associated vascular smooth muscle cell proliferation and migration by decreasing the phosphorylations of ERK and AKT. The results of this study show that four compounds were effective for reduction of monocyte-associated vascular inflammation and dysfunctions, but PPB might be more useful for the treatment of vascular dysfunction in diseases associated with poor circulation.

During investigations on the peroxidase-catalysed oxidation of polyhydroxylated monoaromatic substrates such as 5-methylpyrogallol, we observed a spectacular dimerisation proceeding by dearomatisation in contrast with most common reaction patterns involving phenolics oxidation and dimerization. A tetracyclic fused product featuring an unusual 2-oxatetracyclo [6.3.1.0 1,6 .0 4,12 ] dodecan-3-one core was obtained and characterized by combined NMR techniques and high resolution mass spectroscopy (HRMS). This is an example of a spontaneous cascade triggered by a simple enzymatic reaction that could provide new options for biosynthetic hypothesis and a synthetic method to access this complex core in one operation.

A new trend describes the development and validation of a simple, sensitive and selective kinetic spectrophotometric methods for the determination of sulfadiazine in pharmaceutical formulations has been conducted. In this paper, sulfadiazine was derivatized as a new organic compound 4(4-sulphophenylazo) pyrogallol, 4-SPAP, by coupling pyrogallol with diazotized sulfadiazine in medium of controlled pH. 4-SPAP was characterized by techniques of FT-IR, H-NMR, GC-Mass, TG and DSC thermal analysis methods. Solvatochromic behavior in solvents of various polarities was also investigated. The determination of sulfadiazine was accomplished by initial rate and fixed time methods. These methods were based on the reaction of the compound containing sulfadiazine, 4-SPAP, with Ca(II) to form colored product with a maximum absorbance at 520 nm. The two methods were adopted for constructing the calibration curves and examined for their suitability for the quantitation of sulfadiazine in pharmaceuticals. The limit of detection (LOD) and limit of quantification (LOQ) were found to be, by initial rate method, 0.35 and 1.05 μg·mL -1 and that by fixed time method were found to be 0.69 and 2.07 μg·mL -1 , respectively. The percent relative standard deviations (%RSD) for the results ranged from 1.04% to 1.76% and 0.85% to 1.42% for the initial rate and fixed time methods of the proposed kinetic spectrophotometric method, respectively. The existence of common excipients in the pharmaceutical formulation did not produce any significant interference. Statistical comparison was reported as indicated from the F- and t-test data of the proposed methods with that of reference method showing excellent agreement and indicating no significant difference in their accuracy and precision., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Toll-like receptor 2 (TLR2) induces early inflammatory responses to pathogen and damage-associated molecular patterns trough heterodimerization with either TLR1 or TLR6. Since overstimulation of TLR2 signaling is linked to several inflammatory and metabolic diseases, TLR2 antagonists may provide therapeutic benefits for the control of inflammatory conditions. We present virtual screening for the identification of novel TLR2 modulators, which combines analyses of known ligand sets with structure-based approaches. The 13 identified compounds were pharmacologically characterized in HEK293-hTLR2 cells, THP-1 macrophages and peripheral blood mononuclear cells for their ability to inhibit TLR2-mediated responses. Four out of 13 selected compounds show concentration-dependent activity, representing a hit rate of 31%. The most active compound is the pyrogallol derivative MMG-11 that inhibits both TLR2/1 and TLR2/6 signaling and shows a higher potency than the previously discovered CU-CPT22. Concentration ratio analysis identified both compounds as competitive antagonists of Pam 3 CSK 4 - and Pam 2 CSK 4 -induced responses. Schild plot analysis yielded apparent pA 2 values of 5.73 and 6.15 (TLR2/1), and 5.80 and 6.65 (TLR2/6) for CU-CPT22 and MMG-11, respectively. MMG-11 neither shows cellular toxicity nor interference with signaling induced by other TLR agonists, IL-1β or TNF. Taken together, we demonstrate that MMG-11 is a potent and selective TLR2 antagonist with low cytotoxicity rendering it a promising pharmacological tool for the investigation of TLR signaling and a suitable lead structure for further chemical optimization., (Copyright © 2018 Elsevier Inc. All rights reserved.)

In this study we conducted serial kinetic studies integrated with computational simulations to judge the inhibitory effect of pyrogallol on α-glucosidase, due to the association between this enzyme and the treatment of type 2 diabetes. As a result, we found that pyrogallol bound to the active site of α-glucosidase, interacting with several key residues, such as ASP68, MET69, TYR71, PHE157, PHE158, PHE177, GLN181, HIS348, ASP349, ASP406, VAL407, ASP408, ARG439, and ARG443, which was predicted by performing a protein-ligand docking simulation. Subsequently, we evaluated the inhibitory effect of pyrogallol on α-glucosidase, and found that it induced a mixed type of inhibition in a reversible and quick-binding manner. The relevant kinetic parameters were evaluated to be: IC 50 =0.72±0.051mM; K i =0.37±0.018mM. A tertiary conformational change was synchronized with pyrogallol inhibition and modulation of the shape of the active site was correspondingly observed. Our study provides insight into the functional inhibitory role of pyrogallol, which results from its triple-hydroxyl groups interacting with the active site of α-glucosidase. We suggest that compounds similar to pyrogallol (phenolic hydroxyl compounds) which target the key residues of the active site of α-glucosidase could be potential agents for α-glucosidase inhibition., (Copyright © 2018. Published by Elsevier B.V.)

Alzheimer's disease is a severe neurodegenerative disease affecting elder worldwide and closely related to the neurotoxicity induced by amyloid β. To find efficient therapeutics, we have investigated the protective effects of cedrin from Cedrus deodara (Roxb.) G. Don on PC12 cells against the neurotoxicity induced by amyloid β 1-42 . The results have shown the viability of PC12 cells injured by amyloid β 1-42 can be improved by cedrin. Cedrin can reduce reacrive oxygen species overproduction, increase the activity of superoxide dismutase and decrease malondialdehyde content. Meanwhile, the loss of mitochondrial membrane potential and mitochondrial permeability transition pore opening in PC12 cells, and elevated Caspase-3 activity, downregulated Bcl-2 and upregulated Bax are meliorated. These results demonstrate the protective effect of cedrin is related to the inhibition of oxidative stress, improvement of mitochondrial dysfunction and suppression of apoptosis. This investigation gives evidences for the application of cedrin in practice and further investigation in vivo.

Reaction between pyrogallol and benzaldehyde results in a conformational mixture of C- tetra(phenyl)pyrogallol[4]arene (crown and chair). The conformer mixture was separated using crystallization procedures and the structures were determined using FTIR, ¹H-NMR, and 13 C-NMR. O -acetylation of C- tetra(phenyl)pyrogallol[4]arene (chair) with acetic anhydride, in pyridine results in the formation of dodecaacetyl-tetra(phenyl)pyrogallol[4]arene. The structure was determined using ¹H-NMR and 13 C-NMR finding that the product maintains the conformation of the starting conformer. On the other hand, the O -acetylation reaction of C- tetra(phenyl)pirogallol[4]arene (crown) under same conditions proceeded efficiently, and its structure was determined using ¹H-NMR and 13 C-NMR. Dynamic ¹H-NMR of acetylated pyrogallolarene was studied by means of variable temperature in DMSO- d ₆ solution, and it revealed that two conformers are formed in the solution. Boat conformations for acetylated pyrogallolarene showed a slow interconversion at room temperature.

The pyrogallol red (PR)-based Cu 2+ complex was proven to be an effective and selective colorimetric chemosensing ensemble for recognition of oxalate over other anions in a perfect aqueous solution. The addition of oxalate to the PR-Cu 2+ complex resulted in a colour change from purple to orange colour due to the regeneration of PR by the chelation of oxalate with Cu 2+ , while other anions did not induce any significant colour change. Moreover, it was revealed that no obvious interference was observed during the titrations with oxalate into each other anion. Therefore, the PR-Cu 2+ complex can be used as a simple and practical colorimetric chemosensor for detecting oxalate., (Copyright © 2017 John Wiley & Sons, Ltd.)

Background: Colon cancer is the most aggressive form of cancers, that causes 0.5 million deaths per year around the globe. Targeting colon cancer by conventional therapeutic options elicits toxicity. Traditional medicines take a lead to alleviate the existing clinical challenges., Objective: To investigate antibacterial activity against Helicobacter Pylori and in vitro anti-colon cancer activity by Acacia nilotica extract (ACE) and its active constituent pyrogallol., Methods: Pyrogallol isolated from A. nilotica by column chromatography and HPLC and structure was elucidated by spectral analysis. Antibacterial activity was done by flow cytometry. Cytotoxicity was measured by MTT assay. Apoptotic morphology and nuclear fragmentation were assessed with AO/ethidium bromide and DAPI staining. DNA fragmentation was done by electrophoresis. Western blot used to analyze the molecular mechanism of apoptosis. Cell cycle arrest was determined using flow cytometry of propidium iodide stained cells. Cell migration was determined by wound healing assay., Results: ACE (20 µg/ml) and pyrogallol (10 µg/ml) treatment reduced the survival of H.pylori at 61% and 62%, respectively. MTT results show that HT-29 cells are more sensitive to pyrogallol with an IC 50 value of 35μg/ml compared to ACE. Pyrogallol treated HT-29 cells reached dead state i.e. late apoptotic state with severe nuclear fragmentation. Pyrogallol elicits dose dependent DNA fragmentation in HT-29 cells. Pyrogallol induced apoptosis by simultaneous down-regulation of Bcl-2 and up-regulation of BAX and cytochrome c. Pyrogallol arrested HT-29 cells in S and G2/M phase of cell cycle. Further pyrogallol exhibited marked antimetastatic potential by inhibiting the migration of HT-29 cells dose dependently., Conclusion: Both ACE and pyrogallol repressed the growth of H.pylori and as significant anti-colon cancer agent., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

A simple and fast spectrophotometric methodology able to quantify superoxide released by NADPH oxidase from differentiated promyelocytic leukaemia (HL-60) cells using pyrogallol red is described.The latter is based on the known stoichiometry of the reaction between superoxide and pyrogallol red and the inability of pyrogallol red to react with hydrogen peroxide. In addition, we developed a 96-wells microplate-based method able to determine NADPH oxidase activity. Using this method, we determined pharmacological properties of the NADPH oxidase inhibitors VAS2870 and diphenyleneiodonium and the obtained IC50 values were in good agreement with previous reported data. NOX2 is highly expressed in differentiated promyelocytic leukaemia cells, whereas other isoforms are not detected or expressed at low amounts. Likewise, this methodology may be a useful assay for NOX2 inhibitor screening. NADPH oxidases are involved in several physiological and pathological processes, rendering its pharmacological modulation an attractive research target. In this context, this simple assay can be used for NADPH oxidase inhibitor screening as well as aiding in the study of different biological conditions that involve NADPH oxidase activity., (Copyright © 2017 Elsevier Inc. All rights reserved.)

This paper reports novel imidazole fluorescent poly(ionic liquid) nanoparticles (FPILNs) of poly(1-[(4-methyphenyl)methyl]-3-vinyl-imidazolium bromide (poly([MVI]Br) for selective and sensitive determination of pyrogallol. An imidazole ionic liquid of 1-[(4-methyphenyl)methyl]-3-vinyl-imidazolium bromide ([MVI]Br) was synthesized and used as the only monomer to obtain poly([MVI]Br) possessing phenyl fluorophores using a radical polymerization technique. The obtained poly([MVI]Br) can form nanoparticles in water. Scanning electron microscopy and dynamic light scattering results revealed majority of poly([MVI]Br) FPILNs with diameters ranging from 40 to 400nm. Although [MVI]Br showed weak fluorescence intensity, poly([MVI]Br) FPILNs exhibited strong fluorescence intensity with a quantum yield of 0.192, which is attributed to the presence of significant number of phenyl fluorophores and rigid construction. The selective and sensitive determination of pyrogallol was achieved through fluorescence quenching of poly([MVI]Br) FPILNs, and the quenching was attributed to the oxidation of poly([MVI]Br) FPILNs by O 2 ˙¯ produced by pyrogallol autoxidation. The poly([MVI]Br) FPILNs-based sensor demonstrated a good linear relationship between the extent of fluorescence quenching and the concentration of pyrogallol in a range of 0.05 - 10.0μM, achieving a detection limit of 0.01μM. Furthermore, the poly([MVI]Br) FPILNs-based assay detected pyrogallol in environmental water samples, suggesting its potential to be applied for practical purposes., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Hexane, dichloromethane and methanol extracts of the roots of Piper sarmentosum Roxb. were screened for toxicity towards Sitophilus oryzae (L.), Rhyzopertha dominica (F.), and Plodia interpunctella (Hübner) and the hexane extract exhibited the highest mortality percentage. Bioassay-guided fractionation of the hexane extract resulted in the isolation of asaricin 1, isoasarone 2, and trans-asarone 3. Asaricin 1 and isoasarone 2 were the most toxic compounds to Sitophilus oryzae, Rhyzopertha dominica, and Plodia interpunctella. Sitophilus oryzae and Rhyzopertha dominica exposed to asaricin 1 and isoasarone 2 required the lowest median lethal time. Insecticidal activity of trans-asarone 3 showed consistent toxicity throughout the 60 days towards all three insects as compared to asaricin 1 and isoasarone 2. Asaricin 1 and isoasarone 2 at different doses significantly reduced oviposition and adult emergence of the three insects in treated rice. Trans-asarone 3 had lowest toxicity with highest LC and LT values in all tested insects relative to its mild oviposition inhibition and progeny activity. Moreover, asaricin 1 and isoasarone 2 significantly inhibited acetylcholinesterase in comparison with trans-asarone 3 and the control. Acetylcholinesterase inhibition of Rhyzopertha dominica and Plodia interpunctella by asaricin 1 and isoasarone 2 were lower than that of Sitophilus oryzae, which correlated with their higher resistance.

In this study, the mechanism of the xanthine oxidase (XO) inhibitory activity of pyrogallol, the main inhibitor found in roasted coffee, was investigated. Pyrogallol was unstable and readily converted to purpurogallin in a pH 7.4 solution, a physiological model of human body fluids. The XO inhibitory activity of the produced purpurogallin was higher than that of pyrogallol, as evidenced by comparing their IC 50 values (0.2µmolL -1 for purpurogallin, 1.6µmolL -1 for pyrogallol). The XO activity of pyrogallol was enhanced by pre-incubation in pH 7.4 solution. Although the initial XO inhibitory activity of 4-methylpyrogallol was weak (IC 50 33.3µmolL -1 ), its XO inhibitory activity was also enhanced by pre-incubation in the pH 7.4 solution. In contrast, 5-methylpyrogallol, which could not be transformed into corresponding purpurogallin derivatives, did not show XO inhibitory activity before or after incubation in pH 7.4 solution. Molecular docking simulations clarified that purpurogallins have stronger affinities for XO than corresponding pyrogallols. These results revealed that the potent XO inhibitory activity seemingly observed in pyrogallol is actually derived from its chemical conversion, under alkaline conditions, into purpurogallin., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Pyrogallol red (PGR) was identified as a novel optical probe for the detection of hydrogen peroxide (H 2 O 2 ) based on horseradish peroxidase (HRP)-catalyzed oxidation. Response surface methodology (RSM) was applied as a tool to optimize the concentrations of PGR (100µmolL -1 ), HRP (1UmL -1 ) and H 2 O 2 (250µmolL -1 ) and used to develop a sensitive PGR-based catalase (CAT) activity assay (PGR-CAT assay). N-ethylmaleimide -NEM- (102mmolL -1 ) was used to avoid interference produced by thiol groups while protecting CAT activity. Incubation time (30min) for samples or CAT used as standard and H 2 O 2 as well as signal stability (stable between 5 and 60min) were also evaluated. PGR-CAT assay was linear within the range of 0-4UmL -1 (R 2 =0.993) and very sensitive with limits of detection (LOD) of 0.005UmL -1 and quantitation (LOQ) of 0.01UmL -1 . PGR-CAT assay showed an adequate intra-day RSD=0.6-9.5% and inter-day RSD=2.4-8.9%. Bland-Altman analysis and Passing-Bablok and Pearson correlation analysis showed good agreement between CAT activity as measured by the PRG-CAT assay and the Amplex Red assay. The PGR-CAT assay is more sensitive than all the other colorimetric assays reported, particularly the Amplex Red assay, and the cost of PGR is a small fraction (about 1/1000) of that of an Amplex Red probe, so it can be expected to find wide use among scientists studying CAT activity in biological samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A novel and highly sensitive biosensor employing graphene oxide nano-sheets (GO), multiwalled carbon nanotubes (MWCNTs), and pyrogallol (PG) was fabricated and utilized for the sensitive determination of omeprazole (OME). The morphological and structural features of the composite material were characterized using different techniques. The modified electrode showed a remarkable improvement in the anodic oxidation activity of OME due to the enhancement in the current response compared to the bare carbon paste electrode (CPE). Sensor composition and measurement conditions were optimized using an experimental design. Differential pulse voltammetry (DPVs) exhibited two expanded linear dynamic ranges of 2.0×10 -10 -6.0×10 -6 M and 6.0×10 -6 -1.0×10 -4 M for OME at pH 7 with a detection limit of 1.02×10 -11 M. The practical analytical utilities of the modified electrode were demonstrated by the accurate determination of OME in pharmaceutical formulation and human serum samples with mean recoveries of 100.97% and 98.58%, respectively. The results clearly revealed that the proposed sensor is applicable to clinical analysis, quality control and routine determination of drugs in pharmaceutical formulations., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Cell nanoencapsulation, generating cell-in-shell structures ("artificial spores"), provides a chemical toolbox for controlling the cellular behaviors and functional characteristics of individual cells. Among the shell materials studied so far, naturally occurring polyphenolic compounds, including polydopamine and tannic acid, have intensively been employed in cell-surface engineering, because their material-independent coating property eliminates an extra priming step for inducing subsequent shell formation. Albeit successful in generating cell-in-shell structures, the coating of polyphenolic compounds generally requires alkaline conditions and/or high salt conditions, which are not compatible with certain cell types. In this work, we demonstrate that the nanocoating of individual cells with a plant-derived phenolic compound, pyrogallol (1,2,3-trihydroxybenzene), occurs at mildly alkaline pH of 7.8 in an isotonic buffer. Three different cell types (anucleate, microbial, and mammalian cells) are coated with pyrogallol without noticeable decrease in cell viability. The protocol developed in this work could be applied to other polyphenolic compounds, and, considering the many polyphenols identified as a coating material, provides an advanced chemical tool in cell-surface engineering., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Studies on tyrosinase have recently gained the attention of researchers due to the enzyme's biological functions and potential applications in food and cosmetic applications. In this present study, screening and kinetic evaluation of small molecules (>300Da) on human tyrosinase was carried out using surface plasmon resonance and molecular docking studies. Four molecules showed significant binding were further characterized. The binding constant K D (M) values obtained for crocin, curcumin, tannic acid, pyrogallol and hydroquinone are 5.60×10 -5 , 1.52×10 -3 , 6.45×10 -5 , 1.34×10 -5 and 2.433×10 -7 M respectively. In silico docking studies using autodock indicated significant binding and revealed the binding pocket residues for all molecules. The study shows the Biacore/SPR sensor's ability for screening and detection of inhibitors for human tyrosinase. This study can be used to rapidly screen and optimize various lead compounds as binders/inhibitors/modulators of human tyrosinase enzyme activity., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Numerous technologies have been used to reclaim valuable chemicals from bio-oil. In this study, a combination of the basification-acidification process and column chromatography was employed for the separation of high-purity syringol and acetosyringone from rice straw-derived bio-oil. The optimal conditions for the basification-acidification process and the possible precipitation mechanism of the basification were explored. The results showed the following as the optimal conditions for the basification process: mass ratio of calcium hydroxide (Ca(OH) 2 ) to bio-oil, 2.0; reaction temperature, 70°C; and reaction time, 30 min. The results also showed that 1.6 mol of hydrochloric acid (HCl) per gram of bio-oil was optimal for the acidification. The precipitation was found to proceed via a possible mechanism involving the reaction of the phenolic compounds in the bio-oil with Ca(OH) 2 to produce a precipitate. After further separation by column chromatography, purities of 91.4 and 96.2% (from gas chromatography-mass spectrometry) were obtained for syringol and acetosyringone, respectively. Their recoveries for the whole process were 73.0 and 39.3%, respectively., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)