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Owning to the hydrophobic characteristics of microporous organic networks (MONs), their utilizations still largely limited in non- and weak-polar analytes. To expend their applications, here we reported the synthesis of a novel hollowed H-MON-PEI 1800 -2 composite via sacrifice template method and subsequent modification with polyethyleneimine (PEI) for efficient solid phase extraction of polar and ionic phenolic acid (PAs) from fruit juice samples. H-MON-PEI 1800 -2 exhibits large surface area, rapid extraction kinetics, remarkable chemical and thermal stabilities, and provides synergistic electrostatic, π-π, hydrogen bonding, and hydrophobic interaction sites for PAs. The developed method owns low limit of detection, wide linear range, large enrichment factors, and good reusability. The recoveries of H-MON-PEI 1800 -2 for PAs are 1-3 orders of magnitude higher than those of commercial adsorbents like activated carbon, C18 and Oasis HLB. This work highlights the prospects of functional H-MONs for enriching polar and ionic targets from complex sample matrices., 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.)

Bladder cancer (BC) is the 10th most common tumour with a high incidence and recurrence rate worldwide; however, the current therapies present limitations as, regularly, not all patients benefit from treatment. Therefore, the search for new, active marine phenolic acids with anti-tumour properties is imperative. In this study, we subjected marine phenolic acids to in silico investigations such as network pharmacology, molecular docking, and molecular dynamics simulation (MD) to identify a plausible pathway and the lead compound that inhibits BC. According to the network pharmacology analysis, eight hub genes (PLAU, MMP2, ITGB3, MAPK1, PTPN11, ESR1, TLR4, MMP9) were found and linked to the enrichment of hsa05205: proteoglycans in cancer, and four hub genes (MMP1, MMP2, MAPK1, MMP9) were involved in the enrichment of hsa05219: BC. Subsequently, molecular docking studies showed that the marine phenolic acids exhibit a strong binding affinity for the target protein, matrix metalloproteinase-9 (MPP9). Among these 14 marine phenolic acids, chicoric acid showed the highest binding affinity of -67.1445 kcal/mol and formed hydrogen bonds with the residues of Ala189, Gln227, Leu188, His226, Ala242, Arg249, Ala191, and Gly186 in the active site of the MPP9 protein. Then, molecular dynamics simulation revealed that chicoric acid formed a stable protein-ligand complex with RMSD and RMSF values of 0.72 nm and 0.53 nm, respectively. Furthermore, the PCA method was employed to understand the dynamical behaviour in the conformational space of MPP9 protein bound to chicoric acid, and the results showed the good conformational space behaviour of MPP9 protein. Moreover, chicoric acid showed a free binding energy value of -32.62 kcal/mol, which indicated it could be a BC inhibitor. Overall, chicoric acid demonstrated potential anti-BC activity through MPP9 protein inhibition., 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 Ltd. All rights reserved.)

In this study, the active food packaging film were prepared using hydroxypropyltrimethyl ammonium chloride chitosan with different substitution sites (O-HACC & N-HACC) and dialdehyde chitosan (DCS) grafted with protocatechuic acid (PA). To explore the effect of chitosan quaternization positions and crosslinking approaches on the slow-release and antibacterial properties, the double-crosslinked film were fabricated through the self-coupling reaction of PA and Schiff base reaction between amino groups on HACC and aldehyde groups on DCS. The HACC/DCS-based film exhibited stable porous three-dimensional networks with high nisin loading ratios (>90 %). With the participation of the catechol-catechol structure, the dense double-crosslinked film effectively restricted the diffusion of the water molecules, resulting in excellent slow-release properties fitting with the Korsmeyer-Peppas kinetic model. Especially, O-HACC/PA-g-DCS film, which had more reaction sites for Schiff base crosslinking than N-HACC, exhibited the equilibrium swelling ratio of 800 % at 60 h and could sustainably release nisin via non-Fickian diffusion behavior until 48 h. Moreover, the HACC/DCS-based double-crosslinked film performed good long-time antibacterial activity and preservation effects on salmon. On the 10th day of storage, the TVBN of N-HACC/PA-g-DCS and O-HACC/PA-g-DCS groups were only 28.26 ± 1.93 and 29.06 ± 1.68 mg/100 g and still lower than the thresholds., 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.)

A magnetic MXene aerogel (Fe 3 O 4 @MXene@PEI) was prepared by crosslinking amino modified MXene with polyethyleneimine using epichlorohydrin as a cross-linker. Adsorption properties of Fe 3 O 4 @MXene@PEI aerogel for phenolic acids were evaluated by adsorption kinetics and isotherms experiments, showing that the high adsorption affinity was governed by multilayer chemisorption process. An efficient MSPE/HPLC method was developed for the determination of phenolic acids with excellent selectivity, good linearity (0.025-5.0 μg mL -1 ), low LODs (0.007-0.017 μg mL -1 ), and satisfactory recoveries (80.0-120.0 %). Moreover, the antioxidant activity of the Fe 3 O 4 @MXene@PEI purified compounds was superior to that of the conventional method as demonstrated by the results of scavenging experiments on 2,2 -diphenyl-1-picrylhydrazyl radical scavenging assay. Finally, 65 organic acids were identified in the Fe 3 O 4 @MXene@PEI treated honeysuckle extracts by UHPLC-Q-Exactive Orbitrap MS/MS analysis. The proposed sorbent exhibits remarkable promise for the selective separation and purification of organic acids from herbal products., 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.)

Background: Researchers have investigated different techniques for synthesis of carbon dots. These techniques include Arc discharge, laser ablation, oxidation, water/solvothermal, and chemical vapor deposition. However, these techniques suffer from some limitations like the utilization of gaseous charged particles, high current, high temperature, potent oxidizing agents, non-environmentally friendly carbon sources, and the generation of uneven particle size. Therefore, there was a significant demand for the adoption of a new technology that combines the environmentally friendly aspects of both bio-based carbon sourcing and synthesis technique., Results: Medicago sativa L (alfalfa)-derived N, S-CDs have been successfully synthesized via microwave irradiation. The N,S-CDs exhibit strong fluorescence (λ ex/em of 320/420 nm) with fluorescence quantum yield of 2.2 % and high-water solubility. The produced N,S-CDs were characterized using TEM, EDX, Zeta potential analysis, IR, UV-Visible, and fluorescence spectroscopy. The average diameter of the produced N, S-CDs was 4.01 ± 1.2 nm, and the Zeta potential was -24.5 ± 6.63 mv. The stability of the produced nano sensors was also confirmed over wide pH range, long time, and in presence of different ions. The synthesized N, S-CDs were employed to quantify the antibacterial drug, nifuroxazide (NFZ), by fluorescence quenching via inner filter effect mechanism. The method was linear with NFZ concentration ranging from 1.0 to 30.0 μM. LOD and LOQ were 0.16 and 0.49 μM, respectively. The method was applied to quantify NFZ in simulated gastric juice (SGJ) with % recovery 99.59 ± 1.4 in addition to pharmaceutical dosage forms with % recovery 98.75 ± 0.61 for Antinal Capsules® and 100.63 ± 1.54 for Antinal suspension®. The Method validation was performed in compliance with the criteria outlined by ICH., Significance and Novelty: The suggested approach primarily centers on the first-time use of alfalfa, an ecologically sustainable source of dopped-CDs, and a cost-effective synthesis technique via microwave irradiation, which is characterized by low energy consumption, minimized reaction time, and the ability to control the size of the produced CDs. This is in line with the growing global recognition of the implementation of green analytical chemistry principles., 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.)

The physicochemical properties of starch and phenolic acid (PA) complexes largely depend on the effect of non-covalent interactions on the microstructure of starch. However, whether there are differences and commonalities in the interactions between various types of PAs and starch remains unclear. The physicochemical properties and digestive characteristics of the complexes were investigated by pre-gelatinization of 16 structurally different PAs and pullulanase-modified rice starches screened. FT-IR and XRD results revealed that PA complexed with debranched rice starch (DRS) through hydrogen bonding and hydrophobic interaction. Benzoic/phenylacetic acid with polyhydroxy groups could enter the helical cavities of the starch chains to promote the formation of V-shaped crystals, and cinnamic acid with p-hydroxyl structure acted between starch chains in a bridging manner, both of which increased the relative crystallinity of DRS, with DRS-ellagic acid increasing to 20.03 %. The digestion and hydrolysis results indicated that the acidification and methoxylation of PA synergistically decreased the enzyme activity leading to a decrease in the digestibility of the complexes, and the resistant starch content of the DRS-vanillic acid complexes increased from 28.27 % to 71.67 %. Therefore, the selection of structurally appropriate PAs can be used for the targeted preparation of starch-based foods and materials., 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.)

The molecular and colloidal-level interactions between two major phenolic acids, gallic and caffeic acid, with a major food polysaccharide, xanthan gum, were studied in binary systems aiming to correlate the stability of the binary systems as a function of pH and xanthan-polyphenol concentrations. Global stability diagrams were built, acting as roadmaps for examining the phase separation regimes followed by the fluorimetry-based thermodynamics of the interactions. The effects of noncovalent interactions on the macroscopic behavior of the binary systems were studied, using shear and extensional rheometry. The collected data for caffeic acid - xanthan gum mixtures showed that the main interactions were pH-independent volume exclusions, while gallic acid interacts with xanthan gum, especially at pH 7 with other mechanisms as well, improving the colloidal dispersion stability. A combination of fluorimetry, extensional rheology and stability measurements highlight the effect of gallic acid-induced aggregation of xanthan gum, both in structuring and de-structuring the binary systems. The above provide a coherent framework of the physicochemical aspect of binary systems, shedding light on the role of xanthan gum in its oral functions, such as in inducing texture, in model complex systems containing phenolic acids., Competing Interests: Declaration of competing interest We declare no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Farfarae Flos is a traditional herb widely employed for treating coughs, bronchitis, and asthmatic disorders. In the current study, we utilized SWATH and IDA data acquisition modes in combination with multiple data processing techniques to identify Farfarae Flos metabolites in mice serum. A total of 56 compounds were characterized, including 31 phenolic acids, 13 flavonoids, 11 sesquiterpenoids and 1 alkaloid. Further quantitative analysis was conducted on 12 absorbed metabolites, utilizing a newly developed and rigorously validated analytical method. Our approach demonstrated an acceptable level of specificity, accuracy, precision, and stability. When applied to compare the serum of mice treated with FF, all 12 metabolites showed the highest concentration at 0.5 h. Overall, this study presented a novel strategy for unraveling the active compounds of FF via serum pharmacochemistry analysis, which made a foundation for exploring the pharmacodynamic material basis of FF., 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.)

ATP citrate lyase (ACLY) is a key enzyme in glucolipid metabolism, and abnormally high expression of ACLY occurs in many diseases, including cancers, dyslipidemia and cardiovascular diseases. ACLY inhibitors are prospective treatments for these diseases. However, the scaffolds of ACLY inhibitors are insufficient with weak activity. The discovery of inhibitors with structural novelty and high activity continues to be a research hotpot. Acanthopanax senticosus (Rupr. & Maxim.) Harms is used for cardiovascular disease treatment, from which no ACLY inhibitors have ever been found. In this work, we discovered three novel ACLY inhibitors, and the most potent one was isochlorogenic acid C (ICC) with an IC 50 value of 0.14 ± 0.04 μM. We found dicaffeoylquinic acids with ortho-dihydroxyphenyl groups were important features for inhibition by studying ten phenolic acids. We further investigated interactions between the highly active compound ICC and ACLY. Thermal shift assay revealed that ICC could directly bind to ACLY and improve its stability in the heating process. Enzymatic kinetic studies indicated ICC was a noncompetitive inhibitor of ACLY. Our work discovered novel ACLY inhibitors, provided valuable structure-activity patterns and deepened knowledge on the interactions between this targe tand its inhibitors., 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. Published by Elsevier B.V.)

Facial masks have become ubiquitous in our daily life to endow skin enough moisture and activated nutrition through mask nonwovens infused with skincare ingredients. However, the active nutrients in wet masks are prone to deterioration and deactivation. Herein, a novel multifunctional nanofiber dry mask was successfully prepared using aqueous-electrospun phenolic acid grafted chitosan/collagen peptides. When used, the functional nanofibers in the mask dissolve through spraying moisture, activating active ingredients in response to water and providing in-situ free radical scavenging, moisturizing and antibacterial effects to the skin. In this work, a series of gallic acid (GA), caffeic acid (CA), and protocatechuic acid (PA) have been studied to be grafted with chitosan to improve water solubility of chitosan (CS). Also, through aqueous electrospinning of phenolic acid-grafted chitosan/collagen peptides, a one-step green multifunctional nanofiber mask was obtained. The results showed that the mask had a 12.14 % moisturizing rate and a 94.09 % activity for removing free radicals from the skin after encountering moisture. Considering its high efficiency, controllable function release, and easy processability, the nanofiber multifunctional mask may provide a competitive alternative to facial masks and promote potential value-added applications of bio-based macro-molecules., 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.)

Hemicellulose extracted from ecalyptus APMP pulping waste liquor and undergoes etherification modification to produce carboxymethyl hemicellulose (CMHC). Subsequently, CMHC undergoes esterification reaction with p-hydroxybenzoic acid to synthesize a novel polysaccharide-based preservative known as carboxymethyl hemicellulose p-hydroxybenzoate (P-CMHC). The synthesis conditions of P-CMHC were optimized using the response surface methodology, resulting in an optimal esterification condition that achieved a degree of substitution of 0.232. P-CMHC exhibits excellent antioxidant activity, including 2,2-diphenyl-1-picrylhydrazyl (DPPH) and hydroxyl radical scavenging activities. Additionally, it demonstrates favorable hygroscopic and moisturizing properties. Thiazole blue (MTT) experiments evaluating cell proliferation rate indicate that P-CMHC possesses negligible cytotoxicity, making it a promising, safe, and healthy preservative. Consequently, it can be considered as a new material for applications in the fields of biomedicine, food, and cosmetics., Competing Interests: Declaration of competing interest We wish to draw the attention of the Editor to the following facts which may be considered as potential conflicts of interest and to significant financial contributions to this work. We confirm that the manuscript has been read and approved by all named authors and that there are no other persons who satisfied the criteria for authorship but are not listed. We further confirm that the order of authors listed in the manuscript has been approved by all of us. We confirm that we have given due consideration to the protection of intellectual property associated with this work and that there are no impediments to publication, including the timing of publication, with respect to intellectual property. In so doing we confirm that we have followed the regulations of our institutions concerning intellectual property., (Copyright © 2023. Published by Elsevier Ltd.)

Three phenolic acids including p-hydroxybenzoic acid (PHBA), 3,4-dihydroxybenzoic acid, (DHBA), and gallic acid (GA) were grafted onto native pectin (Na-Pe) through enzymatic method. Ultraviolet-visible spectrometry, Fourier transform infrared spectroscopy, and 1 H NMR analyses were used to explore the reaction mechanism. Results indicated that the p-hydroxyl of the phenolic acids reacted with the methoxycarbonyl of pectin through transesterification, and a covalent connection was formed. The phenolic acid contents of PHBA modified pectin (Ph-Pe), DHBA modified pectin (Dh-Pe), and GA modified pectin (Ga-Pe) were 20.18%, 18.87%, and 20.32%, respectively. After acylation with phenolic acids, the 1,1-diphenyl-2-picryl hydrazine clearance of pectin changed from 7.68% (Na-Pe) to 6.88% (Ph-Pe), 40.80% (Dh-Pe), and 90.30% (Ga-Pe), whereas its inhibition ratio of pectin increased from 3.11% (Na-Pe) to 35.02% (Ph-Pe), 66.36% (Dh-Pe), and 77.89% (Ga-Pe). Moreover, compared with Na-Pe, modified pectins exhibited better emulsification properties and stronger antibacterial activities against both Escherichia coli and Staphylococcus aureus., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Background: Epidemiological studies have reported lower risk of cardiovascular disease with moderate coffee consumption. In addition, emerging evidence indicates that consumption of coffee beverages enriched in chlorogenic acids (CGAs) may influence blood pressure and endothelial function, suggesting that the beneficial cardiovascular effect of coffee may relate to its CGA content., Objectives: We conducted a double-blind randomized crossover trial to test the effect of acute consumption of a decaffeinated green coffee extract (DGCE), rich in CGAs, on endothelial function in healthy subjects., Methods: We compared 3 different doses of DGCE (302, 604, and 906 mg, respectively) with a placebo. Endothelial function was defined as the percentage change in the internal diameter of the brachial artery in response to flow-mediated dilation (%FMD). In addition, we followed the plasma concentration-time profiles of 25 systemic CGA metabolites over 24 h after DGCE consumption and we explored the relation between systemic concentrations of CGAs and the effect on %FMD., Results: The DGCE formulations containing different amounts of CGAs resulted in dose-proportional increases in overall total polyphenol concentrations. The systemic appearance of total CGAs was biphasic, in agreement with previous results suggesting 2 sites of absorption in the gastrointestinal tract. Compared with the placebo group, a significant FMD increase (>1%) was observed 8.5, 10, and 24 h after consumption of 302 mg DGCE (∼156.4 mg CGAs). The differences with placebo observed in the other 2 groups were not statistically significant. Evaluation of the relation between phenolic exposure and %FMD showed a positive tendency toward a larger effect at higher concentrations and different behavior of CGA metabolites depending on the conjugated chemical position., Conclusions: We demonstrated an acute improvement in %FMD over time after ingestion of a DGCE, explained at least partly by the presence in the blood circulation of CGAs and their metabolites. This trial was registered at clinicaltrials.gov as NCT03520452., (© The Author(s) 2020. Published by Oxford University Press on behalf of the American Society for Nutrition.)

A class of phenolic-chitosan quaternary ammonium derivatives have been designed and synthesized. Three chitosan derivatives possess effective structure of hydroxycinnamic acid have been obtained through chemical modification to get chitosan derivatives owning high antioxidant activity and antitumor activity. In this study, the scavenging ability of DPPH, hydroxyl (•OH), and superoxide (O 2 •-) free radical and reducing power have been tested to evaluate the antioxidant activity of the synthesized chitosan derivatives. Base on the value of IC 50 , the chitosan derivatives have the best inhibitory property of 0.019 mg/mL (DPPH), 0.016 mg/mL (•OH), and 0.008 (O 2 •-), respectively; and the chitosan derivatives with conjugate structure of ferulic acid and sinapic acid (4b and 4c) show promising antitumor activity toward A549 cells with the IC 50 of 0.046 and 0.052 mg/mL. These data indicate that the chitosan derivatives with phenolic group give much stronger antioxidant activity and antitumor activity. On the other hand, the synthesized chitosan derivatives show no cytotoxicity for L929 cells at the testing concentrations. These results demonstrate that the introduction of phenol group improves the antioxidant activity of chitosan obviously, and the antioxidant or free radical scavenger based on nature polymers and phenol shows potentials application., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Extraction of polar acidic compounds is a challenging task in electromembrane extraction. In this study, gel-electromembrane extraction was employed for the extraction of phenolic acids as the polar acidic compounds from fruit juices. For this aim, the extraction of phenolic acids from the juice samples (4 mL, pH = 6.0) was carried out across the agarose gel membrane (concentration of agarose; 3% (w/v), pH of gel; 10.0, and thickness of membrane: 3 mm) into the acceptor solution (100 μL, pH = 12.0). Also, this extraction process was conducted by applying the optimum potential (25 V) for 15 min to the extraction system. Under the optimized condition, acceptable linearity (R 2  ≥ 0.993) over a concentration range of 10.0-2500 ng mL -1 was achieved. The limits of detection were between 3.0 and 15.2 ng mL -1 , while the corresponding repeatabilities ranged from 5.3 to 11.4% (n = 4). The recoveries achieved for the extraction of target compounds were ranged from 26.8 to 74.4%. The proposed method was used for the extraction of phenolic acids from orange, apple and kiwi juices, and the obtained relative recoveries in the range of 78.0-104.2% and RSDs in the range of 6.3 to 11.3% indicated successful extraction of phenolic acids., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Tragacanth gum is a polysaccharide-based complex with a good coating property. However, its use in postharvest storage of fresh fruits and vegetables is very limited. In the current work, the effect of tragacanth gum (1%) was investigated on postharvest quality of apricot fruits during storage at 20 ± 1 °C for 8 days. Apricot fruits coated with tragacanth gum coating showed significantly reduced weight loss, decay and electrolyte leakage, hydrogen peroxide and malondialdehyde production. Tragacanth gum coating suppressed increase in total soluble solids and showed higher titratable acidity compared with control. The coated fruits had higher total phenolics and ascorbic acid along with greater 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity in contrast with control. Postharvest application of tragacanth gum coating maintained markedly higher activities of ascorbate peroxidase (APX), catalase (CAT), superoxide dismutase (SOD) and peroxidase (POD) enzymes activities as compared with control. In addition, tragacanth gum application suppressed polygalacturonase (PG), pectin methylesterase (PME), and cellulase (CX) enzymes activities, thereby suppressed softening of apricot fruits. Sensory quality attributes such as taste, juiciness, aroma, appearance, and overall acceptability were also significantly higher in tragacanth gum coated fruits compared with control. In conclusion, tragacanth gum coating could be considered suitable for postharvest quality conservation of apricot fruits., Competing Interests: Declaration of competing interest None., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Hydrocolloid-based films containing natural phenolic antioxidants (gallic and trans-cinnamic acids at 5% w/wt of polymers) embedded in a gelatin/chitosan matrix were designed as sustainable active packaging. This work deals with characterizing the release mechanisms of the phenolic acids from the films immersed into food simulants (sugar or polyol solutions) having different water activities and viscosities. The films containing gallic acid exhibited higher antioxidant activities than the trans-cinnamic acid films. The use of sucrose or glycerol to reduce the water activity (aw) both decreases the iron chelating power (antioxidant) and the E Coli growth (antimicrobial). Interactions involved between macromolecules (chitosan and gelatin) and phenolic compounds influence the release kinetic parameters (diffusivity, convection and partition coefficients) that were studied according to the nature of solute, the water activity and the viscosity of the release media. Thermal analysis (TGA and DSC) revealed a plasticization by both sucrose and glycerol, which entered the film., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In polymer therapeutics, polymer-based carrier systems conjugated with antioxidants have been synthesized and studied to improve diagnosis and treatment of diseases, such as, in cancer and tumor. The natural bioactive compound hyaluronic acid (HA), which is essential in medical and pharmaceutical fields, is a linear polymer composed of repeating disaccharide units of β-1,3-N-acetyl glucosamine and β-1,4-glucuronic acid. In this study, HA fractions of enzyme-assisted glycosaminoglycans (GAGs) extract from Liparis tessellatus eggs were grafted with gallic acid (GA), caffeic acid (CA), and ferulic acid (FA) via a free radical-mediated method, and with nisin via amide bond formation. The modification has been confirmed through FTIR and 1 H NMR spectroscopy and quantified by Folin-Ciocalteu and Bradford assay. FTIR spectra of grafted HA samples exhibited the typical phenolic characteristics within 1450-1650 cm -1 , and the formation of amide bond in nisin-grafted HA was shown by absorption peak within 1545-1646 cm -1 . 1 H NMR spectra showed new peaks of phenyl protons at 6.3-7.7 ppm and new peaks at 0.9-2.9 ppm of amino acids residues protons. These results all confirmed the successful grafting of GA, CA, FA and nisin onto the HA backbone extracted from L. tessellatus eggs., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Elucidating the recognition mechanisms of the noncovalent interactions between pharmaceutical molecules and proteins is important for understanding drug delivery in vivo, and for the further rapid screening of clinical drug candidates and biomarkers. In this work, a strategy based on cold spray ionization mass spectrometry (CSI-MS), combined with fluorescence, circular dichroism (CD), Fourier transform infrared spectroscopy (FTIR), and molecular docking methods, was developed and applied to the study of the noncovalent interactions between phenolic acid and lysozyme (Lys). Based on the real characterization of noncovalent complex, the detailed binding parameters, as well as the protein conformational changes and specific binding sites could be obtained. CSI-MS and tandem mass spectrometry (MS/MS) technique were used to investigate the phenolic acid-Lys complexes and the structure-affinity relationship, and to assess their structural composition and gas phase stability. The binding affinity was obtained by direct and indirect MS methods. The fluorescence spectra showed that the intrinsic fluorescence quenching of Lys in solution was a static quenching mechanism caused by complex formation, which supported the MS results. The CD and FTIR spectra revealed that phenolic acid changed the secondary structure of Lys and increased the α-helix content, indicating an increase in the tryptophan (W) hydrophobicity near the protein binding site resulting in a conformational alteration of the protein. In addition, molecular docking studies were performed to investigate the binding sites and binding modes of phenolic acid on Lys. This strategy can more comprehensively and truly characterize the noncovalent interactions and can guide further research on the interactions of phenolic acid with other proteins., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The research of cost-efficient lignin-based adsorbents is a practical strategy for the recovery of cellulase. In this study, alkali lignin was modified to increase the phenolic hydroxyl (Ph-OH) content for cellulase adsorption applications. After phenolation, compared with the lignin reference, the maximum adsorption cellulase capacity of lignoresorcinol (LigR) and lignopyrogallol (LigP) was improved from 76.5 mg/g to 842.1 mg/g and 911.4 mg/g, respectively. The enzyme activity of the adsorbed cellulase on LigR was higher than that on LigP, which could migrate to the fresh substrates during enzymatic hydrolysis. The adsorbed cellulase could be easily recovered from two lignin-based adsorbents by adjusting pH. The distinct cellulase adsorption behavior of two lignin-based adsorbents was closely related to the high Ph-OH contents and low S/G ratio in phenolated lignin samples characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Heteronuclear Single Quantum Coherence-Nuclear Magnetic Resonance (HSQC-NMR)., (Copyright © 2020. Published by Elsevier B.V.)

Biogas and phosphorus recovery from waste activated sludge (WAS) with sequential homogeneous protocatechuic acid (PCA) enhanced Fenton pretreatment, anaerobic digestion (AD) and microbial electrolysis cell (MEC) were investigated. The cumulation of biogas production of WAS-Fenton-AD was 330.4 mL/g VS, which was 2.05-fold of the control without pretreatment (WAS-AD) during anaerobic digestion. Biogas production of 178 mL/L/d from WAS-Fenton-AD-MEC was achieved, which was 5.23-fold of the WAS-MEC, 2.28-fold of WAS-Fenton-MEC and 1.46-fold of WAS-AD-MEC, respectively. Enhanced phosphorus recovery in form of struvite reached 1.72 g/g TS (18.03% of total P) with a purity of 74.4%. Microbial community richness and diversity analysis revealed that the pretreatment process under circumneutral condition improved the diversity of microbial community, which was consisted of Bacteroidetes (33.90%), Proteobacteria (33.14%), and Chloroflexi (10.14%), compared to a majority of Firmicutes (70.81%) in WAS-AD. This study provides a feasible strategy for the recovery of biogas combined with phosphorus from WAS., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Lead (Pb), which widely recognized as a nonessential heavy metal and a major environmental contamination, is a growing threat to the ecosystem and human body. In the present study, Malus micromalus Makino cv. 'Dong Hong' phenolic extract (MMPE) has been used to antagonise Pb-induced erythrocyte injury, hepatic and renal dysfunction in mice. Six-week-old male Kunming mice were gavaged with PbCl 2 (20 mg/kg mouse/day) and/or MMPE (100 mg/kg mouse/day) by gavage administration for 10 days. We evaluated erythrocyte fragility, relative organ mass, biochemical parameters and histopathological changes to evaluate the protection effect of MMPE on the injury of liver and kidney in Pb-treated mice. MMPE significantly inhibited the increase of protein kinase C-α, B-cell lymphoma-2-associated X, cytochrome C and Caspase-3 protein levels and decreased calreticulin protein expression level in Pb-exposed mice. MMPE supplementation could maintain the integrity of erythrocyte membranes and ameliorate the endoplasmic reticulum stress in Pb-treated mice. It suggested MMPE as a natural nutritional supplement to alleviate Pb-induced hazardous effects in Pb-exposed humans., 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 © 2019 Elsevier Inc. All rights reserved.)

Phenolic acids and tanshinones are the two groups of pharmaceutically active metabolites in Salvia miltiorrhiza Bunge. Their contents are the key quality indicator to evaluate S. miltiorrhiza. bHLH transcription factors have important roles in regulation of plant specialised metabolism. In this study, an endogenous bHLH transcription factor, SmbHLH3, was identified and functionally analyzed. SmbHLH3 was presented in all the six tissues and mostly expressed in fibrous roots and flowers. It was localized to the nucleus. Overexpression of SmbHLH3 decreased both phenolic acids and tanshinones contents. Contents of caffeic acid and rosmarinic acid were both decreased to 50% of the control. And accumulation of salvianolic acid B was decreased as much as 62%. Content of cryptotanshinone, dihydrotanshinone I, tanshinone I and tanshinone IIA in SmbHLH3-overexpression lines were reduced 97%, 62%, 86% and 91%, respectively. In the transgenic lines, expression of C4H1, TAT and HPPR in phenolic acids pathways were reduced to about 43%, 66% and 77% of the control, respectively. For tanshinone biosynthetic pathways, transcripts of DXS3, DXR, HMGR1, KSL1, CPS1 and CYP76AH1 were reduced to 46%, 65%, 78%, 57%, 27% and 62% of the control, respectively. There was an E/G-box specific binding site in SmbHLH3, which may bind the E/G-box present in promoter region of these biosynthetic pathway genes. Y1H results indicated that SmbHLH3 could bind the promoter of TAT, HPPR, KSL1 and CYP76AH1. These findings indicated that SmbHLH3 downregulate both phenolic acids and tanshinone accumulation through directly suppressing the transcription of key enzyme genes., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

A simple, rapid and selective high-performance thin-layer chromatographic (HPTLC) method has been developed and validated for simultaneous determination of three withanolides (withaferin A, withanone and withanolide A) and three phenolic acids (caffeic acid, ferulic acid and benzoic acid) from different parts (root, stem and leaf) of Withania somnifera and its two commercially available polyherbal formulations. The extraction efficiency of withanolides and phenolic acids were tested using two solvents, chloroform and methanol, respectively. HPTLC separation was performed on silica coated aluminium plates Si 60F 254 ; using toluene, ethyl acetate and acetic acid (60:40:4). The samples were quantitated at 231 nm. The purity and identity of peaks of all the six analytes were confirmed by matching Rf values and UV-spectrum with authentic standards. The identity of three withanolides was further confirmed by positive ion electrospray ionization mass spectrometry (ESI-MS/MS) analyses. The developed method was validated for sensitivity, linearity, reproducibility, accuracy, the limit of detection (LOD) and limit of quantification (LOQ) following the guidelines of the International Conference on Harmonization (ICH). The method was found to be linear (r > 0.99) in the range of 50-2000 ng/band for benzoic acid and 50-1000 ng/band for the other five studied metabolites. This simple and accurate HPTLC method provided enhanced resolution of studied analytes as compared to other phytoconstituents present in W. somnifera extracts. It has also been successfully applied in the analysis and quantification of two polyherbal formulations containing W. somnifera plant parts., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this study, the structural and antioxidant behavior of the three lichen-derived natural compounds such as atranorin (AT), evernic acid (EV) and diffractaic acid (DF) has been investigated in the gas and water phase using both B3LYP and M06-2X functional level of density functional theory (DFT) with two different basis sets 6-31+G (d, p) and 6-311++G (d, p). The intramolecular H-bonds (IHB) strength, aromaticity and noncovalent interactions (NCI) have been computed with the help of the quantum theory of atoms in molecules (QTAIM). This calculation gives major structural characteristics that indirectly influence the antioxidant behavior of the investigated compounds. The spin density (SD) delocalization of the unpaired electron is found to be the main stabilizing factor of neutral and cationic radical species. The main mechanisms, recommended in the literature, for the antioxidant action of polyphenols as radical scavengers such as hydrogen atom transfer (HAT), single electron transfer followed by proton transfer (SET-PT), and sequential proton loss electron transfer (SPLET), were examined. The result shows that the HAT and SPLET mechanism are the most conceivable one for the antioxidant action of this class of compounds in gas and water phase respectively. Preference of SPLET over HAT in water phase is due to the significantly lower value of proton affinity (PA) compared to the bond dissociation enthalpy (BDE) value. This study reveals that O 2 -H 3 , O 9 -H 26 and O 4 -H 45 respectively are the most favored site of AT, EV and DF for homolytic as well as heterolytic OH bond breaking., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Phenolic compounds are well known for their antimicrobial activity. They may provide an interesting solution to ensure food safety by preventing the growth of foodborne pathogens while addressing the wishes of consumers for the use of natural preservatives in food and favoring the reuse of agro-industry byproducts. However, their mechanism of action is still not very well understood. Here, we aimed to decipher the complex mechanism of action of eight phenolic acids by decomposing their effects, such as the general effect of the decrease of extracellular pH (γ(pH)) and specific inhibitory effects of the undissociated (γ(A u )) and dissociated (γ(A d )) forms. We thus developed three different models and applied them to a dataset of Listeria monocytogenes growth rates experimentally obtained in the presence of various concentrations of phenolic acids at several pHs. The model that best fits the dataset was selected for each phenolic acid to explore the potential mechanisms. The results show that the antimicrobial activity is mainly due to the effect of the undissociated forms, except for chlorogenic and gallic acids, for which the antimicrobial activity is mainly due to a decrease in extracellular pH. In addition, the dissociated forms of p-coumaric and ferulic acids show significant inhibitory activity., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Thymus vulgaris is used for various health benefits and culinary, nevertheless, report on its macromolecules is absent. Here, we report chemical compositions of the polysaccharides isolated from its leaf by sequential extraction with inorganic solvents. In particular, chemical profile of a unique rhamnogalacturonan I type polysaccharide containing ester linked phenolic acids has been described. Sugar compositional, TLC, UV-spectrometric and ESI-MS analyses of oligosaccharides generated from this polysaccharide by enzyme digestion, controlled acid hydrolysis and Smith degradation revealed atypical fine structural details. Biochemical analysis demonstrated dose-dependent antioxidant activity. A combination of large neutral side chains of the ramified region and ester linked phenolic acids are regarded as the functional sites. Ultraviolet spectrometric and fluorimetric analyses showed that this polysaccharide forms a homogeneous water-soluble complex with bovine serum albumin (binding constant, K = 2.91 × 10 6 /M). Consequently, water extraction affords a polysaccharide which induces pharmacological effect; this underlines the impact of thyme as natural dietetic antioxidant., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Core-shell magnetic nanoparticle synthesis offers the opportunity to engineering their physical properties for specific applications when the intrinsic magnetic properties can be associated with other interesting ones. The purpose of this study was to design, synthesize, and characterize core-shell magnetic nanoparticles that mimic superoxide dismutase activity offering the possibility of guidance and therapeutic action. We proposed, for the first time, the synthesis and characterization of the nanocarriers comprised of magnetite nanoparticles functionalized with branched polyethyleneimine of low molecular weight (1.8 kDa) permitting the loading of the protocatechuic acid or its inclusion complex with anionic sulfobutylether-β-cyclodextrin for active drug delivery, in order to combine the useful properties of the magnetite and the protocatechuic acid antioxidant effect. NMR and DSC analyses confirmed the formation of the inclusion complex between sulfobutylether-β-cyclodextrin and protocatechuic acid, while structural and compositional analyses (FT-IR, TEM, XRD) revealed the synthesis of the multifunctional magnetic systems. Due to the possibility of being formulated as blood system injectable suspensions, antioxidant activity (using DPPH test) and cytotoxicity (using MTS assay on normal human dermal fibroblasts cells) were also measured, showing adequate properties to be used in biomedical applications. Moreover, we proposed a nanocarrier that would be able to load unstable active principles and with very low solubility in biological fluids to increase their biological ability., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Covalent and non-covalent interactions between polyphenols and polysaccharides produced vital consequences on the sensory and nutritive qualities of the many foods. In the present study, the structure dependence of the non-covalent interactions between phenolic acids (PAs) and an arabinan-rich pectic polysaccharide from rapeseed meal (ARPP) was explored. Native RAPP and its hydrolysates as well as twenty-seven structurally diversified PAs were applied. The interaction was determined as the micrograms of PAs adsorbed by per milligram of polysaccharides (Q e , μg/mg). On one hand, the molecular weight (M w ) of ARPP displayed a significant effect on the Q e of ferulic acid and a highest value (412.28 μg/mg) was obtained for the ARPP hydrolysate having a M w of 76 kDa. On the other hand, the substituent profile of PAs greatly affected their Q e values onto ARPP, although the results are monomer and substituent specific. Specifically, in terms of Q e , hydroxylation favored the interaction by 35.78% to 271.22%, while methylation and esterification weakened the absorption by 44.78% to 230.71% and 16.48% to 78.68%, respectively. The case of esterification is more complicated that the attachment of OCH 3 at 3-position (-26.14% to -77.04%) is adverse but that at 5-position is highly favorable (156.96% to 190.70%) for the interactions., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A hydrate of co-crystal of piracetam and 3,5-dihydroxybenzoic acid was obtained via crystallization from water. Single-crystal X-ray data show that piracetam/3,5-dihydroxybenzoic acid tetrahydrate (P35TH) crystallizes in the triclinic system with a P1 space group. The physicochemical properties of co-crystal hydrate were characterized using powder X-ray diffractometry, differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA), and FTIR spectroscopy. The dehydration kinetics of P35TH was monitored at various temperatures and heating rates by DSC and TGA. Activation energy of P35TH dehydration was obtained using temperature ramp DSC, isothermal and nonisothermal TGA methods. Kinetic analysis of isothermal TGA data was fitted to various solid-state reaction models. Mechanistic models derived from isothermal dehydration kinetic data are best described as a 2-dimensional diffusion mechanism. A correlation was noted between the dehydration behavior and the bonding environment of the water molecules in the crystal structure. This study is a good demonstration of complexity of co-crystal hydrate and their dehydration behavior., (Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.)

The molecular complexes of 2-amino-1H-benzimidazolium 2-hydroxybenzoate (2ABHB) and 2-amino-1H-benzimidazolium pyridine 2-carboxylate (2ABP2C) were synthesised from a donor 2-aminobenzimidazole (2AB), and acceptors, 2-hydroxybenzoate (2HB) and pyridine 2-carboxylic acid (P2C) respectively. The brown colour single crystals were successfully grown by slow evaporation solution growth technique. The densities of grown crystals 2ABHB and 2ABP2C were measured by floatation method using carbon tetrachloride and xylene as solvents. The single crystal X-ray diffraction reveals the molecular structures of compounds 2ABHB and 2ABP2C. Both the structures contain positively charged 2-aminobenzimidazolium cation, 2ABHB contains negatively charged 2-hydroxybenzoate anion and 2ABP2C contains pyridine 2 carboxylic acid anions. 1 H and 13 C NMR spectral analyses were used to predict the presence of proton and carbon in the title compounds. The FTIR and Raman spectra have been recorded to detect the vibrational modes of functional groups present in the 2ABHB and 2ABP2C compounds. The proton transfer between the cation and anion was confirmed by UV-Vis spectra of both compounds. For both the compounds, thermal behaviour and stability of the crystals were studied using thermogravimetric and differential thermal analyses technique respectively. Further, the anti-bacterial activity of 2ABHB and 2ABP2C complex against Staphylococcus aureus, Klebsiella pneumonia, Pseudomonas eruginos and E. coli pathogens were investigated., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this work we demonstrate that aldose reductase (AR) interacts directly with tubulin and, was subjected to microtubule formation conditions, enzymatic AR activity increased more than sixfold. Since AR interacts mainly with tubulin that has 3-nitro-tyrosine in its carboxy-terminal, we evaluated whether tyrosine and other phenolic acid derivatives could prevent the interaction tubulin/AR and the enzymatic activation. The drugs evaluated have two characteristics in common: the presence of an aromatic ring and a carboxylic substituent. The 9 drugs tested were able to prevent both the interaction tubulin/AR and the enzymatic activation. In addition, we found that the induction of microtubule formation by high concentrations of glucose and the consequent activation of AR in cultured cells can be inhibited by phenolic acid derivates that prevent the interaction tubulin/AR. These results suggest that tubulin regulates the activation of AR through a direct interaction which can be controlled with phenolic derivates of carboxylic acids., (Copyright © 2018. Published by Elsevier Inc.)

Single-molecule (SM) microscopy is a powerful tool capable of visualizing individual molecules and events in real time. SM imaging may rely on proteins or nucleic acids labelled with a fluorophore. Unfortunately photobleaching of fluorophores leads to irreversible loss of signal, impacting the collection of data from SM experiments. Trace amounts of dissolved oxygen (O 2 ) are the main cause of photobleaching. Oxygen scavenging systems (OSS) have been developed that decrease dissolved O 2 . Commercial OSS enzyme preparations are frequently contaminated with nucleases that damage nucleic acid substrates. In this protocol, we purify highly active Pseudomonas putida protocatechuate 3,4-dioxygenase (PCD) without nuclease contaminations. Quantitation of Cy3 photostability revealed that PCD with its substrate protocatechuic acid (PCA) increased the fluorophore half-life 100-fold. This low cost purification method of recombinant PCD yields an enzyme superior to commercially available OSS that is effectively free of nuclease activity., (Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.)

Reversible benzoic acid decarboxylases are versatile biocatalysts by taking advantage of both decarboxylation and carboxylation reactions, especially for the biocatalytic Kolbe-Schmitt reaction. In the course of developing a benzoic acid decarboxylase tool-box, a putative benzoic acid decarboxylase gene from Fusarium oxysporum was heterologously over-expressed in Escherichia coli, the recombinant protein was purified and characterized. The purified enzyme exhibited relatively high catalytic efficiencies for the decarboxylation of 2, 3-dihydroxybenzoic acid and carboxylation of catechol (k cat /K m  = 2.03 × 10 2 and 1.88 mM -1  min -1 , respectively), and thus characterized as 2, 3-dihydroxybenzoic acid decarboxylase (2, 3-DHBD_Fo). The enzyme also catalyzed the decarboxylation of various substituted salicylic acids with different groups at varied positions except 5-position and the carboxylation of phenol and the substituted phenols. In a preparative reaction, catechol was carboxylated into 2, 3-dihydroxybenoic acid with 95% conversion by adding dodecyldimethylbenzylammonium chloride into the reaction system, and the product was isolated in 72% yield. These results demonstrate that 2, 3-DHBD_Fo is a valuable addition to the benzoic acid decarboxylase tool-box with potential practical applications., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Excessive free radicals can cause oxidative damage to human tissues, which results in a variety of diseases. Therefore, the development of antioxidant materials is one of the great projects in biomedical field. In this work, antioxidant protocatechuic acid (PCA) monomers were grafted onto chitosan (CS) backbones to develop a PCA grafted chitosan (PCA-g-CS) antioxidant copolymer via the method of free radical-induced grafting reaction. The formation of covalent bonds between PCA and CS were confirmed by FTIR, 1 H NMR, XRD and UV-vis. The antioxidant activity of PCA-g-CS was analyzed by 2, 2-diphenyl-1-picrylhydrazyl (DPPH) and hydroxyl radical scavenging assays. In addition, the cytotoxicity of PCA-g-CS on neuron-like rat phaeochromocytoma (PC12) cells was evaluated by using MTT assay. The neuroprotective effects against hydrogen peroxide (H 2 O 2 ) and l-glutamic acid (GLU) induced apoptosis in PC12 cells were also investigated. Our results demonstrated that the PCA-g-CS antioxidant copolymer had the ability to scavenge DPPH and hydroxyl radical in vitro. Furthermore, the PCA-g-CS was biocompatible and had neuroprotective effects against free radical-induced apoptosis in PC12 cells. This PCA-g-CS copolymer is firstly synthesized for neuroprotection and the results suggest the PCA-g-CS may be a potential antioxidant material in the treatment of oxidative damage related diseases., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Changes in the microenvironment of Trp in lysozyme are one of the key factors in the fibrillation process. Gallic acid through the oxidation of o-dhydroxy moiety into quinone was shown to inhibit lysozyme fibrillation by stabilizing the Trp microregions [Konar et al., Int. J. Biol. Macromol. 103 (2017) 1224-1231]. In this article we compare the inhibitory effects of several gallic acid-based phenolic compounds. The results show that pyrogallol, and 3,4-dihydroxy benzoic acid, each containing the o-dihydroxy moiety exhibited a significant inhibitory effect on lysozyme fibrillation which is further supported by docking studies. Interestingly, the inhibitory effect of pyrogallol is almost similar to that observed for gallic acid. The lower inhibitory effect of 3,5-dihydroxy benzoic acid and 4-hydroxy benzoic acid corroborates this finding as neither of the compounds can be transformed into quinone intermediates. The ineffectiveness of benzoic acid towards fibrillation questions the role of the COOH group in the inhibition. The IC 20 values determined show the similar trends. Results of the Thioflavin T binding assay and parameters from the docking studies reveal a strong correlation based on which a relation has been obtained that could be used to identify potential polyphenol based inhibitors by considering docking studies alone., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Correct adjustment of the mobile phase is equally important as the selection of the appropriate column for the separation of polar compounds in LC. Both solvophobic and selective polar interactions control the retention in the Reversed Phase and Hydrophilic Interaction modes. The retention models describing the effects of the volume fraction of the strong eluent component in binary mobile phases on the sample retention factors apply in a limited mobile phase composition range. We introduced a three-parameter retention model, which provides improved prediction of retention over a broad mobile phase range, under isocratic and gradient elution conditions. The model does not imply any assumptions concerning either adsorption or partition distribution mechanism, but allows estimating retention in pure strong and in pure weak mobile phase components. The experimental retention data for phenolic acids and flavones on several core-shell columns with different types of stationary phases agree with the theory. Many polar columns with important structural hydrophobic moieties show dual retention mechanism, (Reversed Phase in water rich mobile phases and Hydrophilic Interaction at high acetonitrile concentrations). It is possible to select the mobile phase compositions in each of the two modes for separations of samples containing compounds largely differing in polarity. The three-parameter model describes the retention in each mode, with separately determined best-fit parameters. We applied the two-mode model to the retention data of sulfonamides and benzoic acid related compounds on a new polymethacrylate zwitterionic monolithic micro-column., (Copyright © 2018 Elsevier B.V. All rights reserved.)

DNA is a major target for a number of anticancer substances. Interaction studies between small molecules and DNA are essential for rational drug designing to influence main biological processes and also introducing new probes for the assay of DNA. Tschimgine (TMG) is a monoterpene derivative with anticancer properties. In the present study we tried to elucidate the interaction of TMG with calf thymus DNA (CT-DNA) using different spectroscopic methods. UV-visible absorption spectrophotometry, fluorescence and circular dichroism (CD) spectroscopies as well as molecular docking study revealed formation of complex between TMG and CT-DNA. Binding constant (K b ) between TMG and DNA was 2.27×10 4 M -1 , that is comparable to groove binding agents. The fluorescence spectroscopic data revealed that the quenching mechanism of fluorescence of TMG by CT-DNA is static quenching. Thermodynamic parameters (ΔH<0 and ΔS<0) at different temperatures indicated that van der Waals forces and hydrogen bonds were involved in the binding process of TMG with CT-DNA. Competitive binding assay with methylene blue (MB) and Hoechst 33258 using fluorescence spectroscopy displayed that TMG possibly binds to the minor groove of CT-DNA. These observations were further confirmed by CD spectral analysis, viscosity measurements and molecular docking., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Phenolic compounds have received great attention among the health promoting phytochemicals in common wheat (Triticum aestivum L.), mainly because of their strong antioxidant properties. In the present study a simple Capillary Zone Electrophoresis (CZE) method with UV detection was optimized and validated for the quantitation of six of the most important phenolic acids in whole grain i.e., sinapic, ferulic, syringic, p-coumaric, vanillic and p-hydroxybenzoic acid. The separation was achieved in a running buffer composed of sodium phosphate solution (50 mM) in water/methanol 80:20 (v/v) at pH 6.0 and using a fused-silica capillary at the temperature of 30 °C under application of 27 kV. By means of diode array detector, and made possible by the favorable characteristic UV spectra, the quantitation of the solutes was carried out at 200, 220 and 300 nm, in the complex matrices represented by the soluble and bound fractions of wheat flours. The validation parameters of the method i.e., linearity, sensitivity, precision, accuracy and robustness were in line with those obtained by consolidated separation techniques applied for the same purposes (e.g., HPLC-UV), with a significant advantage in term of analysis time (less than 12 min). Ten varieties of soft wheat (five modern Italian and five old Italian genotypes) were analysed and the data were subjected to Principal Components Analysis (PCA). Interestingly, significant differences of the quantitative phenolic acids profile were observed between the modern and the ancient genotypes, with the latter showing higher amount of the main represented phenolic acids., (Copyright © 2017 Elsevier B.V. All rights reserved.)

An environmental friendly sorbent of polymeric ionic liquids modified graphene oxide-grafted silica (PILs@GO@Sil) was synthesized for solid-phase extraction (SPE) of phenolic acids. The sorbent was prepared via a chemical layer-to-layer fabrication including amidation reaction, surface radical chain-transfer polymerization and in situ anion exchange. After modification with PILs, the silica surface had higher positive potential so that it would exhibit stronger electrostatic interaction for acidic compounds compared with GO@Sil. The adsorption performance of phenolic acids was investigated through the theoretical calculation and static, kinetic state adsorption experiments. Under the optimized conditions, wide linear ranges were obtained with correlation coefficients ranging from 0.9912 to 0.9998, and limits of detection were in the range of 0.20-0.50μgL -1 . Compared with other reported methods, the proposed PILs@GO@Sil-SPE-HPLC showed higher extraction efficiency. Finally, the black wolfberry yogurt and urine were analyzed as real samples and good recoveries spiked with standard solution were obtained., (Copyright © 2017. Published by Elsevier B.V.)

Guan-Xin-Shu-Tong capsules are one of the well-known and first-line Chinese traditional herbal formula for treating coronary heart disease. A validated and sensitive method via ultra fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS) was established to simultaneously determinate five phenolic acids and four diterpenoids in rats in order to investigate their pharmacokinetic profiles firstly. Analytes were extracted by ethyl acetate and determined via multiple reaction monitoring mode in both positive and negative ion modes. The values for limit of quantification were in range of 0.025-1.250ng/ml. Inter- and intra-day precisions were no more than 10.9% with accuracy of -11.0%-10.6%, meanwhile the stable and suitable extraction recoveries were also obtained. And finally such excellent method was used to compare the pharmacokinetics of nine compounds in normal and acute blood stasis rats after oral administration of Guan-Xin-Shu-Tong capsules., (Copyright © 2017 Elsevier B.V. All rights reserved.)

To overcome the problem on the relationship of antioxidative effect with the branch number in a tetramer, we herein designed a series of antioxidants with pentaerythritol, glycerol, and ethylene glycol as the cores, and gallic, ferulic, caffeic, and p-hydroxybenzoic acids as the antioxidative moieties. In the case of DNA oxidation mediated by 2,2'-azobis(2-amidinopropane hydrochloride, AAPH), it was found that the stoichiometric factor (n) of a carboxylic acid increased rapidly when the acid was esterified with ethylene glycol, glycerol, and pentaerythritol to form a dimer, trimer, and tetramer, respectively. Interestingly, the coefficient in the equation of n∼{branch} ({branch} referred to the number of branches) was higher than one, indicating that the antioxidative effect was enhanced more promptly than the increase of the number of branches. Meanwhile, tetramer exhibited high intercalation effect with DNA strand. Therefore, additionally antioxidative effect was ascribed to the tethering effect resulting from tetrameric structure and strong intercalation with DNA strand generated by tetramer., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The wide usage of acetaminophen as human medicine has resulted in its ubiquitous occurrence in various environmental compartments. However, the information for the transformation of acetaminophen in soil is still limited. In this study, oxidative coupling of acetaminophen in bulk solution mediated by Fe 3+ -saturated montmorillonite was observed under different environmental conditions. In the absence of natural phenolic acids, acetaminophen could be fully eliminated from the solution within 72h at pH3.5, acetaminophen dimer was identified as the major reaction product. Reduction of montmorillonite associated Fe 3+ coupled with the oxidation of acetaminophen was considered as the main mechanism for acetaminophen transformation on Fe 3+ -saturated montmorillonite. The clay associated Fe 3+ showed higher reactivity than Fe 3+ in solution due to the strong complexation between surface Fe 3+ and acetaminophen. The cross-coupling reaction between acetaminophen and phenolic acids was also observed when phenolic acids were present in the system. While with the increase of phenolic acid concentration, the competition for the reactive sites between acetaminophen and phenolic acids significantly suppressed acetaminophen removal. These results demonstrated the importance of transition metal saturated clay minerals for the abiotic transformation of anthropogenic micropollutants., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The bioactive substance investigation of Balanophora involucrata obtained 15 phenolic acids, including 5 new compounds (1-3, 8, 9), which were determined by various spectroscopic data analyses. Most isolated compounds displayed inhibitory effects on α-Glucosidase in vitro. For the potential inhibitors 8 (1.95μM) and 10 (9.02μM), the inhibition kinetics have been studied, which gave the K i values as 0.68, 3.15μM respectively. And, in silico docking analyses have been performed to investigate the inhibitory mechanism of compounds 8 and 10. Additionally, most isolated compounds showed anti-oxidant activities in the DPPH scavenging assay. New compound 8 also could inhibit the acetyl transfer activity of GlmU moderately with the IC 50 value of 18.21μM, which was a new antibacterial target., (Copyright © 2017. Published by Elsevier B.V.)

A novel, simple and accurate on-line green methodology for Se(IV) monitoring by molecular fluorescence has been developed. Because the analyte does not exhibit fluorescence, the organic dye Chrome azurol S (CAS) has been chosen to allow detection. The effect of metal-quenching on CAS excitation and emission conditions (λex=300nm; λem=407nm) was used as criterion for analyte quantification in presence of sodium cholate bile salt (NaC). The quenching mechanism was explored, and it can be classified as a collisional type with a Stern-Volmer constant value of 3.0×10 7 molL -1 . To improve the sampling rate, minimize the reagent consumption and generated wastes, an on-line configuration was designed. Experimental variables that affect the fluorimetric sensitivity were optimized using uni-variation assays. Under optimal experimental conditions, the limit of detection was 0.27µgL -1 with a lineal range for Se(IV) concentration from 0.84 to 6.00µgL -1 . The developed methodology is low cost and fast sampling, allowing Se(IV) quantification in the presence of other common ions. Bulbous vegetables and biological samples were successfully analyzed with an average recovery close to 100%., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The present study explores the preparation, characterization and the role of phenolic acid tethered fibrous protein in the management of induced oxidative stress studied under in vitro conditions. In brief, the biomaterial is prepared by engineering the fibrous protein with dihydroxy and trihydroxy phenolic acid moieties and subjected to characterization to ensure the tethering. The resultant biomaterial studied for its efficacy as a free radical scavenger using polymorphonuclear (PMN) cells with induced oxidative stress and also as an agent for cell migration using fibroblasts cells. Results revealed that induced oxidative stress in PMN cells after exposure to UVB radiation managed well with the prepared biomaterial by reducing the levels of superoxide anion, oxygen and hydroxyl radicals. Further, the protein and the phenolic acid interaction supports the cell migration as evidenced from the scratch assay. In conclusion, though phenolic acids are well known for their antimicrobial and antioxidant potential, indenting these acids directly to the wounds is not sensible, but tethering to protein explored the scavenging activity as expected. The present study infers that phenolic acid engineered protein has a significant role in managing the imbalance in the redox state prevailing in wounds and supports the healing at appreciable level., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A rapid, sensitive and specific ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed and validated to simultaneously determine the twelve major bioactive ingredients (neochlorogenic acid, chlorogenic acid, caffeic acid, cynarin, scopoletin, scutellarin, isochlorogenic acid A, apigenin-7-o-glucuronide, isochlorogenic acid C, scutellarein, luteolin, and apigenin) in rat plasma. Gallic acid and wogonoside were used as internal standards (IS1 and IS2). The plasma samples were pretreated and extracted by liquid-liquid extraction and protein precipitation with ethyl acetate-acetonitrile (95:5, v/v). Chromatographic separation was accomplished on Agilent ZORBAX RRHD Eclipse Plus C18 column (2.1mm×50mm, 1.8μm) utilizing 0.1% formic acid aqueous solution and acetonitrile as mobile phase under gradient conditions at a flow rate of 0.3mL·min -1 . Mass spectrometric detection was performed in multiple reaction monitoring (MRM) mode using electrospray ionization (ESI) in positive and negative mode. The whole intra- and inter-day precision (as relative standard deviation) of all analytes were less than 11.03%, and the accuracy (as relative error) were in the range from -10.43% to 9.76% and from -10.14% to 10.33%. The lower limits of quantification (LLOQ) were 20, 3.0, 100, 7.0, 0.30, 2.0, 70, 1.0, 20, 30, 10, and 2.0ngmL -1 for neochlorogenic acid, chlorogenic acid, caffeic acid, cynarin, scopoletin, scutellarin, isochlorogenic acid A, apigenin-7-o-glucuronide, isochlorogenic acid C, scutellarein, luteolin, and apigenin, respectively. Extraction recovery, matrix effect and stability were found to be the required limits. This method was selective and sensitive for the investigation of the pharmacokinetics of twelve constituents following oral administration to research study about in Erigeron breviscapus of clinical practices for separately analytes on rats., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Secondary metabolites present in lichens, which comprise aliphatic, cycloaliphatic, aromatic and terpenic compounds, are unique with respect to those of higher plants and show interesting biological and pharmacological activities. However, only a few of these compounds, have been assessed for their effectiveness against various in vitro cancer models. In the present study, we investigated the cytotoxicity of three lichen secondary metabolites (atranorin, gyrophoric acid and physodic acid) on A375 melanoma cancer cell line. The tested compounds arise from different lichen species collected in different areas of Continental and Antarctic Chile. The obtained results confirm the major efficiency of depsidones. In fact, depsides atranorin and gyrophoric acid, showed a lower activity inhibiting the melanoma cancer cells only at more high concentrations. Whereas the depsidone physodic acid, showed a dose-response relationship in the range of 6.25-50 μM concentrations in A375 cells, activating an apoptotic process, that probably involves the reduction of Hsp70 expression. Although the molecular mechanism, by which apoptosis is induced by physodic acid remains unclear, and of course further studies are needed, the results here reported confirm the promising biological properties of depsidone compounds, and may offer a further impulse to the development of analogues with more powerful efficiency against melanoma cells., (Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.)

In this pioneer study, 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) was used to improve the solubility of the diffractaic acid (DA) via inclusion complex (DA:HP-β-CD). Subsequently, DA:HP-β-CD was incorporated into poly-ε-caprolactone (PCL) microspheres (DA:HP-β-CD-MS). Microspheres containing DA (DA-MS) or DA:HP-β-CD (DA:HP-β-CD-MS) were prepared using the multiple W/O/W emulsion-solvent evaporation technique. The phase-solubility diagram of DA in HP-β-CD (10-50mM) showed an A L type curve with a stability constant K 1:1 =821M -1 . 1 H NMR, FTIR, X-ray diffraction and thermal analysis showed changes in the molecular environment of DA in DA:HP-β-CD. The molecular modeling approach suggests a guest-host complex formation between the carboxylic moiety of both DA and the host (HP-β-CD). The mean particle size of the microspheres were ∅ DA-MS =5.23±1.65μm and ∅ DA:HP-β-CD-MS =4.11±1.39μm, respectively. The zeta potential values of the microspheres were ζ DA-MS =-7.85±0.32mV and ζ DA:HP-β-CD-MS =-6.93±0.46mV. Moreover, the encapsulation of DA:HP-β-CD into microspheres resulted in a more slower release (k 2 =0.042±0.001; r 2 =0.996) when compared with DA-MS (k 2 =0.183±0.005; r 2 =0.996). The encapsulation of DA or DA:HP-β-CD into microspheres reduced the cytotoxicity of DA (IC 50 =43.29μM) against Vero cells (IC 50 of DA-MS=108.48μM and IC 50 of DA:HP-β-CD-MS=142.63μM)., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Thrombin was immobilized on dynabeads ® M-270 epoxy by direct covalent binding method for the first time. The enzyme coated magnetic beads were combined with ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry technique to establish a simple, rapid and reliable approach for screening thrombin inhibitors from Danshen preparation. The conjugation of thrombin to the magnetic beads was characterized using scanning electron microscope, transmission electron microscope and infrared spectroscopy, and the enzyme activity was determined by the analysis of enzyme-bead ratio and peak areas of target compounds. Several factors including amount of magnetic beads, type of elution solvent, incubation temperature and time were optimized. Additionally, two thrombin-bound compounds (protocatechuic aldehyde and salvianolic acid C) in Danshen injection were validated by conventional inhibitory assay and the IC 50 values were 286.11 and 66.09μg/mL, respectively. Our findings suggested that the proposed method was efficient in screening active compounds from medicinal plants., (Copyright © 2016 Elsevier B.V. All rights reserved.)