Search

Cohumulone and colupulone are representatives of α- and β-acids, respectively. These compounds are important antimicrobial hop (Humulus lupulus) constituents, where cohumulone is an important source of the bitter taste of beer. In this study, we examined the pH dependence of UV/Vis spectra of both compounds while CD spectra of cohumulone were also measured at various wavelengths. This facilitated the examination of the protolytic equilibrium of both compounds, where the second pK a value of cohumulone was determined for the first time. Additionally, comparing experimental spectra with spectra calculated using time-dependent density functional theory (TD-DFT) enabled the determination of the most likely deprotonation positions and corresponding species most likely present in the aqueous solution at various pH values. Last but not least, comparing calculated and experimental CD spectra of cohumulone facilitated the determination of the absolute stereoconfiguration of cohumulone., 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 The Author(s). Published by Elsevier B.V. All rights reserved.)

This study explores the antioxidative activities of xanthohumol (XN) and isoxanthohumol (IXN), prenylated flavonoids from Humulus lupulus (family Cannabaceae), utilizing the oxygen radical absorption capacity (ORAC) and ferric reducing antioxidant power (FRAP) assays along with computational Density Functional Theory methods. Experimentally, XN demonstrated significantly higher antioxidative capacities than IXN. Moreover, we determined IXN pKa values using the UV/Vis spectrophotometric method for the first time, facilitating its accurate computational modeling under physiological conditions. Through a thermodynamic approach, XN was found to efficiently scavenge HOO• and CH 3 O• radicals via Hydrogen Atom Transfer (HAT) and Radical Adduct Formation (RAF) mechanisms, while CH 3 OO• scavenging was feasible only through the HAT pathway. IXN exhibited its best antioxidative activity against CH 3 O• via both HAT and RAF mechanisms and could also scavenge HOO• through RAF. Both Single Electron Transfer (SET) and Sequential Proton Loss-Electron Transfer (SPLET) mechanisms were thermodynamically unfavorable for all radicals and both compounds., 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 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Tannins represent secondary plant metabolites that are used to control bacterial populations by chelation of essential metal ions. Their presence in food also affects the bioavailability of iron. This study investigates the influence of ellagitannins (vescalin, castalin, vescalagin, castalagin) structure and pH on the stoichiometry and formation constants of ellagitannin-Fe(II) coordination compounds. We demonstrated that ellagitannins are stable for at least one hour at pH values lower than 7.25. The spectra of neutral compounds were measured and explained with the help of TDDFT calculations. Furthermore, the pH-dependence of the ellagitannins UV-Vis spectra was examined to obtain insight into their protolytic equilibrium. Using Job's method in the pH range 3.50-5.51, the stoichiometry of the formed ellagitannin-Fe(II) ions complexes was determined. A model explaining interactions between ellagitannins and Fe(II) ions, that took into account the protolytic equilibrium of ellagitannins, was fitted globally to all four Job plots, whereby the corresponding formation constants were obtained., 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 The Author(s). Published by Elsevier B.V. All rights reserved.)

This study aimed to measure and compare the osmolality and tonicity of isotonic beverages that can be bought on the Slovenian market. The main goal was to examine how good is the agreement between the measured osmolalities of the beverages and the requirements for isotonic beverages set up by EFSA. Osmolalities were measured with an osmometer using the freezing point depression method. Afterwards, two complementary methods for the observation of tonicity were developed. Erythrocytes were exposed to standard NaCl solutions of different osmolalities to observe their influence on the volume and shape of cells following the turbidity of the solution and the morphology of erythrocytes. These two methods enabled us to determine whether standard solutions were hypo-, iso-, or hypertonic. In this way, we found that the osmolality of 12 out of the 18 investigated isotonic beverages was in the range of 270-330 mOsm/kg, as required by EFSA. However, six samples did not meet this criterion and should therefore not have the label "isotonic" or be described as such. The measurements of turbidity of solutions indicated that most isotonic beverages exhibit a lower tonicity than standard NaCl solutions of identical osmolality. However, examination of the erythrocytes in isotonic beverages showed that the measurements were additionally complicated by the low pH values of these beverages. Finally, by demonstrating how different components of isotonic beverages pass through the erythrocyte membranes, we found that even isoosmolal beverages are often not isotonic, as the concentration of actively transported sugars in these beverages is relatively high.

Increasing antimicrobial resistance has caused a great interest in natural products as alternatives or potentiators of antibiotics. The objective of this study was to isolate individual tannins from crude chestnut extract as well as to determine the influence of both crude extracts (tannic acid extract, chestnut extract) and individual pure tannins (gallic acid, vescalin, vescalagin, castalin, castalagin) on the growth of Gram-positive Staphylococcus aureus bacteria. Their antibacterial activity was monitored by measuring the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) as well as the duration of the lag phase, growth rate and generation time. The effect of growth medium strength on the MIC of different tannins was also investigated. Bacterial growth was followed spectrophotometrically, and MIC values were determined by the microdilution method. The MIC values of various isolated compounds allowed us to determine the bioactive compounds and their contribution to antimicrobial activity. It was found that MIC values increase with increasing growth medium strength and that the lag phase lengthens with increasing tannin concentrations, while the growth rates decrease. Comparing the results of the two studies, the antimicrobial activity of tannins against S. aureus was not as pronounced as in the case of E. coli , which may indicate that a different mechanism of action is responsible for the antimicrobial effects of tannins on Gram-positive than on Gram-negative bacteria, or that a different mechanism is more pronounced.

The antimicrobial activity of hop extracts obtained from different hop genotypes were investigated against Staphylococcus aureus and Lactobacillus acidophilus . In this study the pure xanthohumol, purified β-acids rich fraction, as well as α-acids with β-acids rich fraction were used to test antimicrobial activity against Staphylococcus aureus and Lactobacillus acidophilus ; whereby, the antimicrobial activity of different hop extracts against Lactobacillus acidophilus was studied for the first time. Microbial susceptibility to purified hydroacetonic extracts from different hop varieties was investigated by the broth microdilution assay to determine the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC). The hop hydroacetonic extracts were more effective against Staphylococcus aureus than against Lactobacillus acidophilus . Strong inverse correlations of MIC and MBC values were obtained with xanthohumol, cohumulone, n+adhumulone, colupulone and n+adlupulone contents, suggesting that the identified chemical hop compounds are directly responsible for antimicrobial effects. Moreover, the effect of the growth medium strength on the MIC values of hop extracts against Staphylococcus aureus was systematically investigated for the first time. The current study also reveals the effect of different hop extracts on Staphylococcus aureus , which responds to their presence by lag phase extension and generation time prolongation.

The pH dependence of the UV/Vis spectrum of gallic and ellagic acid was measured in a buffer-free solution to obtain reliable data at wavelengths bellow 230 nm. UV/Vis absorption spectra were also calculated for all possible ionised species of gallic and ellagic acid using time dependent density functional theory (TD-DFT). From pK a values of gallic and ellagic acid the molar fraction of different ionised species was calculated for each pH value. Finally, the simulated spectra at different pH values were obtained as a weighted average of spectra of neutral, once, twice, three-times, and four-times deprotonated species. The calculated spectra were then compared to the experimental spectra, and the peaks in the experimental spectrum were explained in the terms of main electronic transitions that results in the observed absorption bands. At low pH values the agreement between the experimental and calculated spectra was excellent. At near-neutral pH values the majority of the experimental spectra features were well reproduced in the calculated spectra. A satisfactory agreement between experimental and calculated spectrum at high pH values was also achieved by incorporating the calculated spectra of the oxidised species of gallic acid as well as ellagic acid spectra with one lactone ring open., 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 © 2021 Elsevier B.V. All rights reserved.)

One important property of tannins involves their ability to form coordination compounds with metal ions, which is vital for the bioavailability of these ions, as well as for the antibacterial and antioxidative activities of tannins. In this study, the pH dependence of interactions between gallic acid, one of the basic building blocks of tannins, and Fe(II) ions, was investigated using UV/Vis spectroscopy, in conjunction with density functional theory (DFT) calculations. Moreover, two models were developed to explain the processes taking place in the solution. The first model treated the reaction as a simple bimolecular process while the second also considered the protolytic equilibrium, which was proven very successful in discerning the pH dependence of formation constants, and whose assumptions were well supported by DFT calculations. We showed that the two-time deprotonated gallic acid species forms the coordination compound with Fe(II) ions in a 1:1 molar ratio. To gain better insight into the process, the coordination compound formation was also studied using various DFT functionals, which further supported the model results. Furthermore, due to the relatively low sample amounts needed, the methodology developed here will be useful to study compounds that are more difficult to isolate.

The current study examines the effect of tannins and tannin extracts on the lag phase duration, growth rate, and generation time of Escherichia coli . Effects of castalagin, vescalagin, gallic acid, Colistizer, tannic acid as well as chestnut, mimosa, and quebracho extracts were determined on E. coli 's growth phases using the broth microdilution method and obtained by turbidimetric measurements. E. coli responds to the stress caused by the investigated antimicrobial agents with reduced growth rates, longer generation times, and extended lag phases. Prolongation of the lag phase was relatively small at low tannin concentrations, while it became more pronounced at concentrations above half the MIC. Moreover, for the first time, it was observed that lag time extensions follow a strict exponential relationship with increasing tannin concentrations. This feature is very likely a direct consequence of the tannin complexation of certain essential ions from the growth medium, making them unavailable to E. coli for its growth.

In this study the effect of growth medium strength on the minimum inhibitory concentration (MIC) of different tannins and tannin extracts against Escherichia coli was systematically investigated for the first time. Three pure compounds (vescalagin, castalagin and gallic acid) and five extracts (chestnut, quebracho, mimosa, Colistizer and tannic acid) were studied. Broth microdilution was assayed and bacteria were grown using different growth medium strengths varying from half to double the concentration recommended by the producer. MICs were determined using the iodonitrotetrazolium chloride (INT) dye or turbidity measurements. It was observed that MIC values depend on the growth medium strength. With an increase in the growth medium concentration MIC values rose roughly linearly for all samples, while their relative order remained unchanged, indicating that a direct interaction of tannins with growth medium nutrients represents the likely source of their antimicrobial activity. Understanding the effect of growth medium strength can finally yield a plausible explanation for the observed variation in MIC values reported in the scientific literature as well as provide help in planning proper applications of tannins in the livestock production.

Poly(thiophen-3-ylacetic acid) (PTAA) is a representative of conjugated polyelectrolytes which are used in many optoelectronics devices. The performance of these devices is affected by the polymer conformation, which, among others, depends on the nature of the counterion. In this study, the binding of tetrabutylammonium counterions (TBA + ) on PTAA was determined using a combination of nuclear Overhauser effect spectroscopy (NOESY) and molecular dynamics (MD) simulation. It was found that TBA + ions specifically bind on the hydrophobic main chain of PTAA, while, according to MD simulations, alkali counterions predominantly bind in the vicinity of negatively charged carboxylic groups located on side chains. The MD trajectories were used to compute the relaxation matrices and the NOESY spectra. With the help of these latter calculations, the changes of intensities in experimental NOESY spectra upon binding of TBA + ions to PTAA were interpreted., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Tannins are natural compounds that have historically been used in the tanning of leather. In the scientific literature, one finds many reports of their possible beneficial health effects, although these are not always unequivocally confirmed. In order to gain a better insight into their proposed anticancer potential, we studied the scavenging capacity of the basic tannin building blocks against various chemical carcinogens of the epoxy type. The reactivity of gallic acid, ellagic acid, and epicathechin was examined using quantum mechanical calculations at the Hartree-Fock level of theory in conjunction with flexible basis sets and implicit solvation models. The monomeric tannin building blocks exhibited significant scavenging potential, with epicatechin presenting the best scavenger, thus encouraging and guiding future experimental studies of their anticarcinogenic properties.

The addition of simple salt to a solution of conjugated polyelectrolyte can lead to substantial changes in its optical properties caused by the conformational change of the polymer chain. The effect of the addition of alkali metal and tetraalkylammonium chlorides to solutions of lithium salt of poly(thiophen-3-ylacetic acid) is investigated by NMR. The fractions of free alkali metal counterions are in agreement with predictions of the cylindrical Poisson-Boltzmann cell model. On the other hand, the fractions of free tetraalkylammonium counterions deviate from the prediction of this model and diminish with increasing size of these counterions. This trend is consistent with observed ultraviolet-visible absorption spectra and measured self-diffusion coefficients of the polyion in mixtures with tetraalkylammonium salts. A transition to more constricted conformation of the polyion chain becomes more pronounced with the lengthening of alkyl groups in the added tetraalkylammonium cation. Taking into account the obtained fractions of free counterions, existing thermodynamic data are reanalysed in order to determine thermodynamic parameters for binding of different counterions to the polyion. This analysis shows that standard enthalpies of binding of alkali metal counterions are distinctively different, which is most probably related to differences in hydration shells of counterions. On the other hand, such an analysis fails in the case of tetraalkylammonium chlorides where obviously more complex changes take place.

The enthalpies of dilution ΔHdil of aqueous solutions of a conjugated polyelectrolyte, poly(thiophen-3-ylacetic acid), neutralized by lithium, sodium, cesium, tetramethyl-, tetraethyl-, tetrapropyl-, and tetrabutylammonium hydroxides, were determined in the concentration range from cp = 2 × 10(-3) to 1 × 10(-1) monomol dm(-3) and for T = 278.15, 298.15, and 318.15 K. At low concentrations the dilution of the alkali PTAA salts yields an endothermic effect, which is in part a consequence of the hydrolysis. An exception is PTALi at 278.15 K, where ΔHdil < 0. In the case of tetraalkylammonium salts the enthalpies of dilution increase in the order TBA < TPA < TEA < TMA. Only the TBA salt of PTAA yields an exothermic effect upon dilution in the whole temperature range. In the second part of the study we measured the enthalpies of mixing, ΔHmix, of various salts of poly(thiophen-3-ylacetic acid) with LiCl, NaCl, KCl, and CsCl solutions in water. When lithium salt of PTAA is mixed with LiCl ΔHmix is positive. For mixing experiments with other alkali chlorides the effect is exothermic. In addition, the enthalpies of mixing of PTALi with tetramethyl-, tetraethyl-, tetrapropyl-, and tetrabutylammonium chloride were measured at T = 278.15 K, 298.15 K, and 318.15 K. Popular polyelectrolyte theories, such as Manning's limiting law, predict for the heat to be released upon dilution, and consumed upon mixing; the agreement between this purely electrostatic theory and experiments is at best qualitative. The ΔHmix values are correlated with the enthalpies of hydration of the cations of the low molecular mass salts added to the solution.

The title polymer, PTAA, practically free of ester groups was obtained by oxidative polymerization of methyl thiophen-3-ylacetate and subsequent basic hydrolysis of primary polymer. Poly(thiophen-3-ylacetic acid) has been thoroughly characterized by NMR, IR, Raman, and UV/Vis spectroscopy. The polyacid behavior during neutralization titrations with lithium and sodium hydroxides, carried out under nitrogen atmosphere, has been studied by conductometry and potentiometry. Henderson-Hasselbach plots of potentiometric titration curves show a break point at pH around 6, where the curve slope drops from 1.8 (at lower pH) to a value from 1.05 to 1.3 (at higher pH values). The UV/Vis spectra monitored during back titration show: (i) monotonous decrease of both λmax and εmax as pH decreases, (ii) the presence of the isosbestic point at 401 nm that can be ascribed to conformational transition of PTAA chains, and (iii) absence of the isosbestic point at 392 nm reported previously by other authors.

UV/Vis spectroscopic investigation of aqueous solutions of regio-irregular poly(thiophen-3-ylacetic acid) (PTAA) with and without methyl-ester groups in the presence of sodium and lithium ions as counterions is presented. The samples were carefully purified and characterized with respect to molar mass and the amount of -COOH groups present. We examined how the UV/Vis spectra of solution change with aging of PTAA solution, polymer concentration, addition of low molecular weight salt, temperature, and some other parameters. We show that results crucially depend on whether the spectra are taken for freshly prepared or mature solutions. We demonstrate the validity of the Beer-Lambert law for PTANa, PTAA/Na, and PTAA/Li (aged solution), and violation of this law for PTANa/Me (fresh) solutions in water; the latter system is instead found to exhibit an isosbetic point at 402 nm. We prove that UV/Vis spectra of polythiophene derivatives in water depend on the "age" (time after dissolution) of the solution. The inconsistencies among the spectroscopic data found in literature, as also the discrepancies with our own measurements on PTAA-based systems are discussed.