Phosphorus doped cyanobacterial biochar catalyzes efficient persulfate oxidation of the antibiotic norfloxacin.

In this study, cyanobacterial biochars (CBs) enriched/doped with non-metallic elements were prepared by pyrolysis of biomass amended with different N, S, and P containing compounds. Their catalytic reactivity was tested for persulfate oxidation of the antibiotic norfloxacin (NOR). N and S doping failed to improve CB catalytic reactivity, while P doping increased reactivity 5 times compared with un-doped biochar. Biochars produced with organic phosphorus dopants showed the highest reactivity. Post-acid-washing improved catalytic reactivity. In particular, 950 ℃ acid-washed triphenyl-phosphate doped CB showed the largest degradation rate and reached 79% NOR mineralization in 2 h. Main attributes for P-doped CBs high reactivity were large specific surface areas (up to 655 m2/g), high adsorption, high C-P-O content, graphitic P and non-radical degradation pathway (electron transfer). This study demonstrates a new way to reuse waste biomass by producing efficient P-doped metal-free biochars and presents a basic framework for designing carbon-based catalysts for organic pollutant degradation.

Temperature affects the kinetics but not the products of the reaction between 4-methylbenzoquinone and lysine.

Quinones are electrophilic compounds that can undergo Michael addition or Schiff base reaction with nucleophilic amines, but the effect of temperature has not been systematically studied. The aim of this study was to characterize how temperature affects the reaction mechanism and kinetics of 4-methylbenzoquinone (4MBQ) with lysine (Lys), Nα-acetyl Lys or Nε-acetyl Lys. The products were identified and characterized by LC-MS/MS, which revealed formation of Michael addition products, Schiff base, and a di-adduct in Lys and Nα-acetyl Lys-containing reaction mixtures. The product profiles were not affected by temperature in the range of 15-100 °C. NMR analysis proved that Michael addition of Nα-acetyl Lys occurred on the C5 position of 4MBQ. Rate constants for the reactions studied by stopped-flow UV-vis spectrophotometry under pseudo-first-order conditions where the amines were present in excess in the range 15 °C to 45 °C showed the α-amino groups of Lys are more reactive than the ε-groups. The kinetics results revealed that the temperature dependence of reaction rates followed the Arrhenius law, with activation energies in the order: Lys < Nε-acetyl Lys < Nα-acetyl Lys. Our results provide detailed knowledge about the temperature dependence of the reaction between Lys residues and quinones under conditions relevant for storage of foods.

Fast peroxydisulfate oxidation of the antibiotic norfloxacin catalyzed by cyanobacterial biochar.

Peroxydisulfate (PDS) is a common oxidant for organic contaminant remediation. PDS is typically activated by metal catalysts to generate reactive radicals. Unfortunately, as radicals are non-selective and metal catalysts may cause secondary contamination, alternative selective non-radical pathways and non-metal catalysts need attention. Here we investigated PDS oxidation of commonly detected antibiotic Norfloxacin (NOR) using cyanobacterial nitrogen rich biochars (CBs) as catalysts. NOR was fully degraded by CB pyrolysed at 950 °C (CB950) within 120 min. CB950 caused threefold faster degradation than low pyrolysis temperature (PT) CBs and achieved a maximum surface area normalized rate constant of 4.38 × 10-2 min-1 m-2 L compared to widely used metal catalysts. CB950 maintained full reactivity after four repeated uses. High defluorination (82%) and mineralization (>82%) were observed for CB950/PDS. CBs were active over a broad pH range (3-10), but with twice as high rates under alkaline compared with neutral conditions. NOR is degraded by organic, •OH and SO4•- radicals in low PT CBs/PDS systems, where the presence of MnII promotes radical generation. Electron transfer reactions with radicals supplemented dominate high PT CBs/PDS systems. This study demonstrates high PT biochars from algal bloom biomass may find use as catalysts for organic contaminant oxidation.

Effect of dry hopping on the oxidative stability of beer.

Electron spin resonance (ESR) spectroscopy was used todeterminethe effect of dry hopping on the oxidative stability and antioxidative potential of beer.Commercial beerwasdry-hopped at 5 °C and 20 °Cwith six hop varieties (Polish and American). The rate of radical formation and lag time were found to depend on the variety of hop used. An increase in the lag time and a decrease in the rate of radical formation occurred when dry-hopping was performed at 20 °C for all hop varieties (at 5 °C in some varieties). The lag time had a strong correlation with the TPC (total polyphenols content) in beer. The rate of radical formation was correlated with the iron content of the beer. A decrease in iron concentration was observed after dry-hopping at 20 °C. Overall, the evaluation of free radical formation using ESR is useful for predicting oxidative changes in beer during storage.

Wheat Gluten Peptides Enhance Ethanol Stress Tolerance by Regulating the Membrane Lipid Composition in Yeast.

Wheat gluten peptides (WGPs), identified as Leu-Leu (LL), Leu-Leu-Leu (LLL), and Leu-Met-Leu (LML), were tested for their impacts on cell growth, membrane lipid composition, and membrane homeostasis of yeast under ethanol stress. The results showed that WGP supplementation could strengthen cell growth and viability and enhance the ethanol stress tolerance of yeast. WGP supplementation increased the expressions of OLE1 and ERG1 and enhanced the levels of oleic acid (C18:1) and ergosterol in yeast cell membranes. Moreover, LLL and LML exhibited a better protective effect for yeast under ethanol stress compared to LL. LLL and LML supplementation led to 20.3 ± 1.5% and 18.9 ± 1.7% enhancement in cell membrane fluidity, 21.8 ± 1.6% and 30.5 ± 1.1% increase in membrane integrity, and 26.3 ± 4.8% and 27.6 ± 4.6% decrease in membrane permeability in yeast under ethanol stress, respectively. The results from scanning electron microscopy (SEM) elucidated that WGP supplementation is favorable for the maintenance of yeast cell morphology under ethanol stress. All of these results revealed that WGP is an efficient enhancer for improving the ethanol stress tolerance of yeast by regulating the membrane lipid composition.

Measurement of hydrogen peroxide vapor in powders with potassium titanium oxide oxalate loaded cellulose pellets as probes.

An image-based method for determining H2O2 vapor pressures in powder systems was developed based on cellulose pellets loaded with potassium titanium oxide oxalate (PTO Pellets) as probe particles. Solid titanyl salts change color after exposure to hydrogen peroxide vapor and the quantitative response of PTO pellets to H2O2 has been established by comparing reactions with H2O2 in liquid and solid states. Analysis of pictures of the color changes of PTO Pellets mixed into powders can be used to monitor the presence of ppm levels of H2O2 vapor inside powder systems such as bleach containing dry detergent powders.•H2O2 vapor quantification in dry systems with titanyl loaded cellulose particles.•Simple fabrication of H2O2 probe particles.•High sensitivity with LOD 0.190 ppm H2O2 .

Copper Binding in Sweet Worts Made from Specialty Malts.

Trace levels of copper can impact the flavor stability of beer. The main source of copper is malt, and the wort copper levels are established during mashing and lautering. This study focuses on sweet worts made from experimental roasted and caramel malts. Potentiometric titrations using ion-selective electrodes combined with electron paramagnetic resonance spectroscopy have been used to investigate Cu(II) binding in worts as well as the impact of Cu(II) ions on the wort oxidative stability. High-temperature treatment during malting decreased Cu(II) binding affinities in the worts, with roasted malt worts having lower affinities than caramel malt worts of similar color and pH. Electron paramagnetic resonance spectra indicated dipeptides as the main Cu(II) chelators. A positive correlation between Cu and free amino nitrogen levels in worts is demonstrated. In dark worts with high rates of radical formation, Cu(II) had pronounced antioxidative effects. In contrast, moderate prooxidative effects were observed when adding Cu(II) to pale worts with inherently low rates of oxidation.

ESR spin trapping for in situ detection of radicals involved in the early stages of lipid oxidation of dried microencapsulated oils.

Different studies have shown that detection of free radicals by ESR spin trapping provides useful information on the susceptibility to oxidation of bulk oils and accordingly on the oxidative stability of different samples for comparative purposes. With the same goal, ESR spin trapping was evaluated in this work for in situ detection of radicals in dried microencapsulated oils (DMOs). By testing different oils, encapsulation matrices and oxidation conditions, results showed that ESR spin trapping can be useful to evaluate the oxidative susceptibility of DMOs, but ESR data should be interpreted cautiously, as the great complexity of the reactions involved may lead to data misinterpretations. Conditions for oxygen availability can have important impacts on the rates of both spin trapping and spin-adduct quenching affecting the levels of radicals observed. The kinetics of oxidation, spin trapping and spin-adduct decay should be known first in bulk oils for correct data interpretation in DMOs.

Trapping of Carbonyl Compounds by Epicatechin: Reaction Kinetics and Identification of Epicatechin Adducts in Stored UHT Milk.

The kinetics of the reaction between epicatechin and various carbonyl compounds typically formed in cooked and stored foods were evaluated in model systems at pH 7.4 and 37 °C, and the corresponding reaction products in stored ultrahigh temperature (UHT) milk-added epicatechin were identified by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The rate constants for the reactions of carbonyl compounds with epicatechin decreased in the following the order: methylglyoxal; 1.6 ± 0.2 M-1 s-1 > glyoxal; (5.9 ± 0.3) × 10-2 M-1 s-1 ≥ 5-(hydroxymethyl)furfural; (4.0 ± 0.2) × 10-2 M-1 s-1 ≥ acetaldehyde; (2.6 ± 0.3) × 10-2 M-1 s-1 ≥ phenylacetaldehyde; (2.1 ± 0.2) × 10-2 M-1 s-1 ≥ furfural; (4.3 ± 0.1) × 10-3 M-1 s-1 > 2-methylbutanal and 3-methylbutanal; ∼0 M-1 s-1. Reaction products generated by epicatechin and methylglyoxal, glyoxal, 5-(hydroxymethyl)furfural, and acetaldehyde were detected in UHT milk samples by incubating milk samples with epicatechin at 37 °C for 24 h. The lack of reaction between epicatechin and phenylacetaldehyde, furfural, 2-methylbutanal, and 3-methylbutanal in stored UHT milk may be due to their slow reaction rates or low concentration in stored UHT milk. It is demonstrated that epicatechin traps 5-(hydroxymethyl)furfural, acetaldehyde, glyoxal, and methylglyoxal and may thereby reduce off-flavor formation in UHT milk during storage both by trapping of precursors (methylglyoxal and glyoxal) for off-flavor formation and by direct trapping of off-flavors.

Modulation of gastrointestinal digestion of ß-lactoglobulin and micellar casein following binding by (-)-epigallocatechin-3-gallate (EGCG) and green tea flavanols.

The effect of binding of flavonoids, (-)-epigallocatechin-3-gallate (EGCG) and green tea extract (GTE), to beta-lactoglobulin (ß-Lg) and micellar casein (micellar casein isolate, MCI) on protein digestibility was investigated. ß-Lg resisted digestion by pepsin, but in the presence of EGCG the digestion of ß-Lg was enhanced. Binding of EGCG to ß-Lg was identified by nitro blue tetrazolium (NBT) staining and found, by isothermal titration calorimetry, to be an enthalpy-driven exothermic process, with a binding constant of 19 950 L mol-1. Binding promoted a more rapid digestion of ß-Lg during simulated upper duodenal digestion. NBT staining indicated a loss of binding of EGCG to ß-Lg during combined gastric and distal small intestinal digestion and correlated with the cleavage of ß-Lg. However, increased ß-Lg heteromer formation and reduced ß-Lg monomer digestibility were observed for the ß-Lg-GTE complex. MCI was more digestible than ß-Lg during pepsin digestion, but reduced digestibility was observed for both MCI-EGCG and MCI-GTE complexes, with loss of binding during intestinal digestion. The free radical scavenging capacity (FRSC) of EGCG remained stable for the ß-Lg-EGCG complex throughout the gastric and intestinal phases of digestion, but this was significantly lowered for the MCI-EGCG complex. These results indicated that polyphenols bind to milk proteins modulating the in vitro digestibility and FRSC of ß-Lg and MCI as a result of the formation of complexes.

The effect of molecular structure of polyphenols on the kinetics of the trapping reactions with methylglyoxal.

Reaction kinetics for the reactions between four polyphenols (trans-resveratrol, apigenin, kaempferol and fisetin) and methylglyoxal (MGO) were determined at pH 7.4 and 37 °C, and the effect of functional groups of polyphenols on MGO trapping ability was examined. Reaction products of polyphenols with MGO were characterized by HPLC-MS/MS. The apparent second order rate constants for the reaction of MGO with trans-resveratrol, apigenin, kaempferol and fisetin were (2.7 ± 0.2) × 10-2 M-1 s-1, (4.4 ± 0.4) × 10-3 M-1 s-1, (6.3 ± 0.2) × 10-2 M-1 s-1, and (3.6 ± 0.1) × 10-3 M-1 s-1, respectively. The rate constants were used to evaluate the possible competition between MGO with nucleophilic sites on proteins and polyphenols at concentrations relevant to UHT milk. Combining this information with solubility and flavour of the polyphenols, it was concluded that kaempferol could effectively trap MGO and hereby inhibit Maillard reactions in UHT milk.

Quantitation of Protein Cysteine-Phenol Adducts in Minced Beef Containing 4-Methyl Catechol.

Thiol groups of cysteine (Cys) residues in proteins react with quinones, oxidation products of polyphenols, to form protein-polyphenol adducts. The aim of the present work was to quantify the amount of adduct formed between Cys residues and 4-methylcatechol (4MC) in minced beef. A Cys-4MC adduct standard was electrochemically synthesized and characterized by liquid chromatography-mass spectrometry (LC-MS) as well as NMR spectroscopy. Cys-4MC adducts were quantified after acidic hydrolysis of myofibrillar protein isolates (MPIs) and LC-MS/MS analysis of meat containing either 500 or 1500 ppm 4MC and stored at 4 °C for 7 days under a nitrogen or oxygen atmosphere. The concentrations of Cys-4MC were found to be 2.2 ± 0.3 nmol/mg MPI and 8.1 ± 0.9 nmol/mg MPI in meat containing 500 and 1500 ppm 4MC, respectively, and stored for 7 days under oxygen. The formation of the Cys-4MC adduct resulted in protein thiol loss, and ca. 62% of the thiol loss was estimated to account for the formation of the Cys-4MC adduct for meat containing 1500 ppm 4MC. Furthermore, protein polymerization increased in samples containing 4MC as evaluated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), and the polymerization was found to originate from protein-polyphenol interactions as evaluated by a blotting assay with staining by nitroblue tetrazolium.

Identification of emulsifier potato peptides by bioinformatics: application to omega-3 delivery emulsions and release from potato industry side streams.

In this work, we developed a novel approach combining bioinformatics, testing of functionality and bottom-up proteomics to obtain peptide emulsifiers from potato side-streams. This is a significant advancement in the process to obtain emulsifier peptides and it is applicable to any type of protein. Our results indicated that structure at the interface is the major determining factor of the emulsifying activity of peptide emulsifiers. Fish oil-in-water emulsions with high physical stability were stabilized with peptides to be predicted to have facial amphiphilicity: (i) peptides with predominantly α-helix conformation at the interface and having 18-29 amino acids, and (ii) peptides with predominantly ß-strand conformation at the interface and having 13-15 amino acids. In addition, high physically stable emulsions were obtained with peptides that were predicted to have axial hydrophobic/hydrophilic regions. Peptides containing the sequence FCLKVGV showed high in vitro antioxidant activity and led to emulsions with high oxidative stability. Peptide-level proteomics data and sequence analysis revealed the feasibility to obtain the potent emulsifier peptides found in this study (e.g. γ-1) by trypsin-based hydrolysis of different side streams in the potato industry.

Multiresponse Kinetic Modeling of Heat-Induced Equilibrium of ß-Carotene cis-trans Isomerization in Medium-Chain Triglyceride Oil.

The kinetics and mechanism of the stepwise cis-trans isomerization reactions of all-trans-ß-carotene dissolved in MCT (medium-chain triglyceride) oil at temperatures in the range of 80-160 °C have been analyzed using multiresponse modeling. Quantitation of the cis-isomers was performed using HPLC-DAD and quantitation at the reaction isosbestic point at 421 nm. Multiresponse kinetic modeling using the Bayesian criterion was initially performed at 120 °C to determine the best model. Subsequently, the reparametrized Arrhenius equation was used to calculate the activation energies of all reactions. The equilibrium constants for the individual isomerization reactions were determined from the rate constants and the final product distributions. The enthalpies and entropies of the isomerization reactions were determined from the temperature dependence of the equilibrium constants. The 13-cis and 13,13'-di-cis isomers were found to be the fastest formed isomers followed by the 9-cis, 9,13-di-cis, and 13,15-di-cis isomers, where the latter was found to be formed from 13-cis and not the 15-cis isomer. The relative free energies of the ß-carotene isomers were determined as all-trans < 13-cis < 9-cis < 13,13'-di-cis < 9,13-di-cis ≈ 15-cis < 13,15-di-cis. The entropic contribution of each reaction was found to play an important role in the ordering. It is concluded that the ß-carotene system is quite labile at temperatures ranging from 80 to 160 °C and resulting in equilibrium distributions of the cis-trans isomers.

Morphology and Structure of Solid Lipid Nanoparticles Loaded with High Concentrations of ß-Carotene.

Solid lipid nanoparticles (SLNs) containing up to 37.5 wt % all-trans ß-carotene in the lipid phase are potential water-dispersible food colorants. SLNs have been made by hot-melt high-pressure homogenization with fully hydrogenated sunflower oil and with polysorbate 80 and sunflower lecithin as stabilizers. Atomic force microscopy revealed the SLNs had thin platelet structures most likely derived from the triglyceride crystal ß-form, as detected by X-ray diffraction. No indications of crystalline ß-carotene were detected. High-performance liquid chromatography analysis showed the extensive isomerization of ß-carotene into more than 10 cis isomers, suggesting that it is present as an amorphous mixture. The high ß-carotene loadings did not affect the triglyceride crystal structure and the morphology of the SLNs. It is suggested the SLNs consist of a platelet core of crystalline triglyceride surrounded by an amorphous ß-carotene-containing layer. The layered structure is suggested to affect the coloring power of the SLNs at ß-carotene loadings above 15 wt % of the lipid phase.

Effect of pH on the reaction between naringenin and methylglyoxal: A kinetic study.

Methylglyoxal (MGO) is a highly reactive ɑ-dicarbonyl compound that may adversely impact food quality and human health by modifying proteins. The kinetics of the reaction of naringenin with MGO was studied at pH 6-8 and 37 °C by UV-Vis spectrophotometry and reaction products were characterized by liquid chromatography-mass spectrometry (LC-MS/MS). The apparent second order rate constant (k2) increased at pH above the lowest pKa value of naringenin, indicating deprotonated naringenin as the main reactant. A Lederer-Manasse type reaction mechanism is suggested, with dehydration of the MGO-dihydrate as a rate determining step. The quantitative data obtained in the present study was used to simulate the competitive reaction between MGO and nucleophilic amino acid residues (Lys, Arg and Cys) and naringenin in milk. It is predicted that naringenin will be able to efficiently trap MGO during storage of milk, although the reversible trapping of MGO by Cys residues is initially kinetically favourable.

Oxygen permeability and oxidative stability of fish oil-loaded electrosprayed capsules measured by Electron Spin Resonance: Effect of dextran and glucose syrup as main encapsulating materials.

The oxygen permeability and oxidative stability of fish oil-loaded electrosprayed capsules were studied by Electron Spin Resonance (ESR). Electrosprayed capsules with dextran as main biopolymer showed a significantly faster broadening (ΔHpp) of 16-doxyl-stearate ESR spectrum when compared to glucose syrup capsules. This finding indicates a higher oxygen permeability of dextran capsules than glucose syrup capsules, which is explained by a reduced average free volume in the glucose syrup matrix than in the dextran shell. Moreover, glucose syrup capsules showed a significantly lower increase in the peak-to-peak amplitude of N-tert-butyl-α-phenylnitrone (PBN) ESR spectrum during storage when compared to dextran capsules. This implies a higher oxidative stability of glucose syrup capsules than dextran capsules, which correlated well with the lower oxygen permeability of the former. These results indicated the importance of the oxygen barrier properties of the wall materials when encapsulating long chain omega-3 polyunsaturated fatty acids by electrospraying.

Interactions of dietary fiber bound antioxidants with hydroxycinnamic and hydroxybenzoic acids in aqueous and liposome media.

The interactions between dietary fiber (DF)-bound antioxidants and free antioxidants, with different substitution patterns of -OH and -OCH3 groups on their aromatic rings has been investigated. The activity and efficiency of these interactions were examined with a structural approach. Whole wheat (WW) DF-bound antioxidants and 21 hydroxycinnamic acid/hydroxybenzoic acids (HCA/HBA) were used in the experimental studies. Studies were performed in liposome and aqueous media by monitoring lipid oxidation and scavenging of DPPH radical in the presence of WW-bound antioxidants and HCA/HBA derivatives. Predominantly synergistic interactions were observed in aqueous medium, while both synergistic and antagonistic interactions were seen in liposome medium. Concentrations of HCA/HBA and WW-bound antioxidants in mixtures and their 2-way interactions made significant effect on lipid oxidation and radical scavenging reactions, with some exceptions. HCA/HBA derivatives with 3 ,4 -dihydroxyphenyl substitution acted as strong antioxidants in liposome medium, while the number of -OH groups affected antioxidant activity in aqueous medium.

Influence of mediators on laccase catalyzed radical formation in lignin.

Laccases (EC 1.10.3.2) catalyze oxidation of phenolic groups in lignin to phenoxyl radicals during reduction of O2 to H2O. Here, we examine the influence on this radical formation of mediators which are presumed to act by shuttling electrons between the laccase and the subunits in lignin that the enzyme cannot approach directly. Treatments of three different lignins with laccase-mediator-systems (LMS) including laccases derived from Trametes versicolor and Myceliophthora thermophila, respectively, and four individual mediators, 1-hydroxybenzotriazole (HBT), N-hydroxyphthalimide (HPI), 2,2,6,6-tetramethylpiperidin-1-yloxy (TEMPO), and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) were assessed by real time electron paramagnetic resonance measurements. Radical steady state concentrations and radical formation rates were quantified. LMS treatments with 500 µM N-OH type mediators (HPI or HBT) did not affect the lignin radical formation, but increased doses of those mediators (5 mM) surprisingly led to significantly decreased radical formation rates and lowered steady state radical concentrations. Laccase-TEMPO treatment at a 5 mM mediator dose was the only system that significantly increased steady state radical concentration and rate of radical formation in beech organosolv lignin. The data suggest that electron shuttling by mediators is not a significant general mechanism for enhancing laccase catalyzed oxidation of biorefinery lignin substrates, and the results thus provide a new view on laccase catalyzed lignin modification.

Interactions of coffee and bread crust melanoidins with hydroxycinnamic and hydroxybenzoic acids in aqueous radical environment.

The interactions of coffee and bread crust melanoidins with hydroxycinnamic and hydroxybenzoic acids (HCA/HBA) containing different numbers of -OH and -OCH3 groups localized at different positions on the aromatic ring were investigated. By doing so, mechanism of the interactions was intended to be explained with a structural approach. Experimental studies were carried out in DPPH radical medium. Chemometric methods were used for experimental design and multivariate data analysis. Area under the curve (AUC) values calculated from the plots of time versus inhibition (%) for coffee and bread crust melanoidins and HCA/HBA derivatives were ranged between 6532 ±â€¯97-19,106 ±â€¯85, 3997 ±â€¯102-7565 ±â€¯159 and - 1678 ±â€¯81-22,486 ±â€¯119, respectively. Synergistic interactions were revealed for both coffee and bread crust melanoidins and HCA/HBA derivatives. The significance of the concentrations of coffee and bread crust melanoidins on radical scavenging activity was clearly centered from the scores plots obtained via Principal component analysis (PCA). Phases of radical scavenging reactions were also revealed from the loadings plots.