scholarly journals Effect of Two Humic Acids on Laccase-Driven 17β-Estradiol Conversion Kinetics and Polymerization Products at Varying pH Levels

Author(s):  
Kai Sun ◽  
Rui Zhu ◽  
Huijie Wei ◽  
Shunyao Li ◽  
Michael Gatheru Waigi ◽  
...  

Abstract Estrogens with tremendous ecological risks are proverbially found in water. Laccase can drive humification of estrogens to reduce their ecotoxicity and removability, but little investigation existed in exploring the effect of humic acids (HAs) on E2 conversion kinetics and polymerization products at different pH conditions. Here, Trametes versicolor laccase (Tvlac) was capable of efficiently converting a representative estrogen, 17β-estradiol (E2) with two different HAs, and the process followed a pseudo-first-order kinetics. The velocity constants were respectively 0.048, 0.022, and 0.020 min− 1 for HA-free, peat-derived HA, and commercial HA at pH 5.0. The changing pH not only impacted E2 coupling kinetics in Tvlac-evoked humification, but altered the aromaticity and humification degrees of HAs. A total of five intermediate species including estrone (E1), E2 dimer, trimer, and tetramer, as well as E1-E2 cross-linked products were tentatively detected, in which the dominating species were E2 self-oligomers resulting from radical-centered carbon-carbon/oxygen stepwise polymerization routes. Yields of dimeric, trimeric, and tetrameric species with increased molecular sizes were the highest at pH 5.0 in the given pH values, and they were readily handled by precipitation and filtration. Especially E2 was able to be covalently incorporated into humic constituents to generate new humified co-polymers, thereby accelerating E2 humification and detoxification. These findings demonstrate that pH exhibits a far-reaching influence on the conversion kinetics, humification degrees, and products distribution of E2 and HAs in Tvlac-reinforced polyreaction. Thus, there is need to reappraise the fate and transport of estrogens with HAs present in natural water at varying pH levels.

2020 ◽  
Vol 3 (1) ◽  
pp. 49
Author(s):  
Vijay Kumar ◽  
Simranjeet Singh

Atrazine is a broad spectrum herbicide of triazine family. It is a chlorine-containing molecule and it can persist in environment. Chemical and biochemical techniques are the main techniques used to decompose the chemicals. In pre-sent study, the dechlorination of atrazine (Atr) via reaction with Sn(II) ion under aqueous media at neutral pH condi-tions was studied. The observed dechlorinated metabolite was 4-Ethylamino-6-isopropylamino-[1,3,5]triazin-2-ol. Identification of dechlorinated product of Atr was performed by using spectroscopic (FTIR) and mass (ESI-MS) spectrometric analysis. The kinetics of the dechlorination of Atr was measured by using pseudo-first order kinetics. The observed reaction constants was, kobs = 6.11x10-2 (at 430 mg/ L of Atr), and kobs = 6.14 x10-2 (at 215 mg/ L of Atr). The calculated half-life (t1/2) period was, t1/2 = 0.204 d (at 430 mg/ L of Atr), and t1/2 = 0.205 d (at 215 mg/ L of Atr).


2022 ◽  
Vol 52 (5) ◽  
Author(s):  
Renata Oliveira Santos ◽  
Laura Monteiro Keller ◽  
Vanessa Sales de Oliveira ◽  
Carlos Alberto Bucher ◽  
José Lucena Barbosa Junior ◽  
...  

ABSTRACT: This study evaluated the effects of temperature on the pH of extracts of ascorbic acid and anthocyanins from petals of butterfly pea, as well as their in vitro digestive stability in model systems at 60, 70, and 80 °C. The pH values significantly decreased with an increase in the temperature (P < 0.05). The findings were similar for the degradation of anthocyanins and ascorbic acid, which followed first-order kinetics in all the systems. The samples heated at 80 °C presented the highest degradation rate (kobs), as well as higher percentages of degradation at the end of digestive stability in vitro.


Pharmaceutics ◽  
2020 ◽  
Vol 12 (6) ◽  
pp. 560
Author(s):  
Anna Gumieniczek ◽  
Anna Berecka-Rycerz ◽  
Urszula Hubicka ◽  
Paweł Żmudzki ◽  
Karolina Lejwoda ◽  
...  

In this study, important H1 antihistaminic drugs, i.e., emedastine (EME), epinastine (EPI), and ketotifen (KET), were irradiated with UV/Vis light (300–800 nm) in solutions of different pH values. Next, they were analyzed by new high performance liquid chromatography (HPLC) methods, in order to estimate the percentage of degradation and respective kinetics. Subsequently, ultra-performance liquid chromatography tandem-mass spectrometry (UPLC-MS/MS) was used to identify their photodegradation products and to propose degradation pathways. In addition, the peroxidation of linoleic acid and generation of singlet oxygen (SO) and superoxide anion (SA) were examined, together with the molar extinction coefficient (MEC) evaluation, to estimate their phototoxic risk. The photodegradation of all EME, EPI, and KET followed pseudo first-order kinetics. At pH values of 7.0 and 10.0, EPI was shown to be rather stable. However, its photostability was lower at pH 3.0. EME was shown to be photolabile in the whole range of pH values. In turn, KET was shown to be moderately labile at pH 3.0 and 7.0. However, it degraded completely in the buffer of pH 10.0. As a result, several photodegradation products were separated and identified using the UPLC-MS/MS method. Finally, our ROS assays showed a potent phototoxic risk in the following drug order: EPI < EME < KET. All of these results may be helpful for manufacturing, storing, and applying these substantial drugs, especially in their ocular formulations.


1985 ◽  
Vol 40 (9-10) ◽  
pp. 721-725 ◽  
Author(s):  
María D . Ortega ◽  
Alonso Rodríguez-Navarro

Abstract In growing cells, K+ and Rb+ effluxes followed first order kinetics, took place with slight differences between K+ and Rb+ and were stimulated at acidic pH values. In uncoupled cells and ATP-depleted cells, K+ efflux was higher than Rb+ efflux. In ATP-depleted cells, the effluxes were not stimulated at acidic pH values. Two different K+ effluxes are proposed: (i) the normal efflux, which may be a K+/H+ antiport and does not function in ATP-depleted cells, and (ii) the backward reaction of the uptake system, which can be high in depolarized cells. The role of the normal efflux system in K+ content and pH regulation is discussed.


2014 ◽  
Vol 18 (1) ◽  
pp. 36-49 ◽  
Author(s):  
A.G. Hassabo ◽  
A. Mendrek ◽  
C. Popescu ◽  
H. Keul ◽  
M. Möller

Functionalized polyethylenimine–dye (FPEI) is prepared by mixing branched polyethyleneimine (PEI), in which its primary amine groups are modified at different ratios with a quaternary ammonium coupler (QI), and reactive dyestuff (RD) (QI/RD = 0/100, 20/80, 40/60, 60/40 and 80/20 mole/mole %). The deposition of FPEI from an aqueous solution onto the surface of cotton and wool fibres is studied. The adsorption of a charged polymer from an aqueous medium by cotton and wool fibres is investigated at different pH values, and the uptake of colour on fibres is measured by Datacolor and UVVIS spectrophotometers. The study of the kinetics of adsorption shows that pseudo-first-order kinetics provide the best correlation of the experimental data. The equilibrium data indicate that the deposition process onto both cotton and wool follows the Langmuir isotherm. In terms of colour strength (K/S value) the coated fibres compare well with those dyed with a commercial dyestuff, C.I. Basic Red 51, which suggests that the coating is a good alternative to classical dyeing.


TAPPI Journal ◽  
2018 ◽  
Vol 17 (03) ◽  
pp. 167-178 ◽  
Author(s):  
Xin Tong ◽  
Jiao Li ◽  
Jun Ma ◽  
Xiaoquan Chen ◽  
Wenhao Shen

Studies were undertaken to evaluate gaseous pollutants in workplace air within pulp and paper mills and to consider the effectiveness of photo-catalytic treatment of this air. Ambient air at 30 sampling sites in five pulp and paper mills of southern China were sampled and analyzed. The results revealed that formaldehyde and various benzene-based molecules were the main gaseous pollutants at these five mills. A photo-catalytic reactor system with titanium dioxide (TiO2) was developed and evaluated for degradation of formaldehyde, benzene and their mixtures. The experimental results demonstrated that both formaldehyde and benzene in their pure forms could be completely photo-catalytic degraded, though the degradation of benzene was much more difficult than that for formaldehyde. Study of the photo-catalytic degradation kinetics revealed that the degradation rate of formaldehyde increased with initial concentration fitting a first-order kinetics reaction. In contrast, the degradation rate of benzene had no relationship with initial concentration and degradation did not conform to first-order kinetics. The photo-catalytic degradation of formaldehyde-benzene mixtures indicated that formaldehyde behaved differently than when treated in its pure form. The degradation time was two times longer and the kinetics did not reflect a first-order reaction. The degradation of benzene was similar in both pure form and when mixed with formaldehyde.


2019 ◽  
Author(s):  
Chem Int

The kinetics of oxidation of methyl orange by vanadium(V) {V(V)} has been investigated in the pH range 2.3-3.79. In this pH range V(V) exists both in the form of decavanadates and VO2+. The kinetic results are distinctly different from the results obtained for the same reaction in highly acidic solution (pH &lt; 1) where V(V) exists only in the form of VO2+. The reaction obeys first order kinetics with respect to methyl orange but the rate has very little dependence on total vanadium concentration. The reaction is accelerated by H+ ion but the dependence of rate on [H+] is less than that corresponding to first order dependence. The equilibrium between decavanadates and VO2+ explains the different kinetic pattern observed in this pH range. The reaction is markedly accelerated by Triton X-100 micelles. The rate-[surfactant] profile shows a limiting behavior indicative of a unimolecular pathway in the micellar pseudophase.


1995 ◽  
Vol 31 (1) ◽  
pp. 117-128 ◽  
Author(s):  
Jean-Pierre Arcangeli ◽  
Erik Arvin

This study has shown that microorganisms can adapt to degrade mixtures of aromatic pollutants at relatively high rates in the μg/l concentration range. The biodegradation rates of the following compounds were investigated in biofilm systems: aromatic hydrocarbons, phenol, methylphenols, chlorophenols, nitrophenol, chlorobenzenes and aromatic nitrogen-, sulphur- or oxygen-containing heterocyclic compounds (NSO-compounds). Furthermore, a comparison with degradation rates observed for easily degradable organics is also presented. At concentrations below 20-100 μg/l the degradation of the aromatic compounds was typically controlled by first order kinetics. The first-order surface removal rate constants were surprisingly similar, ranging from 2 to 4 m/d. It appears that NSO-compounds inhibit the degradation of aromatic hydrocarbons, even at very low concentrations of NSO-compounds. Under nitrate-reducing conditions, toluene was easily biodegraded. The xylenes and ethylbenzene were degraded cometabolically if toluene was used as a primary carbon source; their removal was influenced by competitive inhibition with toluene. These interaction phenomena are discussed in this paper and a kinetic model taking into account cometabolism and competitive inhibition is proposed.


2020 ◽  
Vol 16 ◽  
Author(s):  
M. Alarjah

Background: Prodrugs principle is widely used to improve the pharmacological and pharmacokinetic properties of some active drugs. Much effort was made to develop metronidazole prodrugs to enhance antibacterial activity and or to improve pharmacokinetic properties of the molecule or to lower the adverse effects of metronidazole. Objective: In this work, the pharmacokinetic properties of some of monoterpenes and eugenol pro metronidazole molecules that were developed earlier were evaluated in-vitro. The kinetic hydrolysis rate constants and half-life time estimation of the new metronidazole derivatives were calculated using the validated RP-HPLC method. Method: Chromatographic analysis was done using Zorbbax Eclipse eXtra Dense Bonding (XDB)-C18 column of dimensions (250 mm, 4.6 mm, 5 μm), at ambient column temperature. The mobile phase was a mixture of sodium dihydrogen phosphate buffer of pH 4.5 and methanol in gradient elution, at 1ml/min flow rate. The method was fully validated according to the International Council for Harmonization (ICH) guidelines. The hydrolysis process carried out in an acidic buffer pH 1.2 and in an alkaline buffer pH 7.4 in a thermostatic bath at 37ºC. Results: The results followed pseudo-first-order kinetics. All metronidazole prodrugs were stable in the acidic pH, while they were hydrolysed in the alkaline buffer within a few hours (6-8 hr). The rate constant and half-life values were calculated, and their values were found to be 0.082- 0.117 hr-1 and 5.9- 8.5 hr., respectively. Conclusion: The developed method was accurate, sensitive, and selective for the prodrugs. For most of the prodrugs, the hydrolysis followed pseudo-first-order kinetics; the method might be utilised to conduct an in-vivo study for the metronidazole derivatives with monoterpenes and eugenol.


1984 ◽  
Vol 67 (4) ◽  
pp. 844-845
Author(s):  
Naomi Richfield-Fratz

Abstract 4,4'-(Diazoamino)-bis(5-methoxy-2-methylbenzenesuIfonic acid), when present as a reaction by-product in FD&C Red No. 40, is shown to decompose rapidly in aqueous solutions of the color additive. The decomposition is halted by the addition of sodium borate buffer. Quantitationly liquid chromatography shows that decomposition is nonlinear with time and follows approximate first order kinetics.


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