Polarographic determination of acids by means of the reduction wave of quinones in methyl cellosolve solution

Methyl-p-benzoquinone (MQ) gives a single polarographic wave in methyl cellosolve media containing perchlorate as supporting electrolyte, but a prewave corresponding to the reaction Q + 2HA + 2e ái H₂Q + 2A^-, is found when an acid is added. The height of the prewave is proportional to the concentration of added acid. Traces (ca. 0.2%) of free perchloric acid can be determined in crude lithium perchlorate.The half-wave potential of the prewave depends on the pK_a value of the acid; if the dissociation constants of acids differ sufficiently, two prewaves are found and each acid species can be determined simultaneously. This method was applied to the MQ-HClO₄-CH₃COOH, MQ-CCl₃COOH-CH₃COOH and MQ-CHCl₂COOH- CH₃COOH systems.     

Radical-scavenging activity of glutathione,chitin derivatives and their combination

Since chitosan and its amino-, cinnamo- or cinnamo-amino- derivatives are acid-soluble, the effect of acetic acid on hyaluronan (HA) macromolecules degraded by Cu(II) ions and ascorbate was examined to produce reactive oxygen species (ROS). Further, the effects of glutathione (GSH), chitosan and its derivatives, added individually or in combination, on the quenching of ROS and ABTS^˙+ cation radical were examined using rotational viscometry and ABTS assay, respectively. The results of the rotational viscometry indicated a rapid degradation of HA by ROS after the addition of acetic acid. Chitosan and its derivatives moderately decreased the rate of HA degradation, while GSH decreased the rate of HA degradation more significantly. Moreover, GSH enhanced the protection of HA macromolecules against their degradation in the presence of chitosan or its derivatives. The results of the ABTS assay confirmed the results of the rotational viscometry. The GSH in the combination with chitosan and its derivatives reduced ABTS^˙+ more intensively than when added individually.     

Effect of Fusarium oxysporum f. sp. lycopersici on the degradation of humic acid associated with Cu, Pb, and Ni: an in vitro study

The intent of this work was to gain further insight on the fungus-assisted degradation/solubilization of humic acid and the related changes in metal-binding profiles. In the experimental design, Aldrich reagent humic acid (HA) or HA enriched with Cu, Pb, and Ni (HA(Me)) was added to Fusarium oxysporum f. sp. lycopersici cultures in vitro. The cultures were supplied by different carbon- and nitrogen-containing nutrients (glucose, Glc, or glutamate, Glu and ammonium, NH₄⁺, or nitrate, NO₃⁻, ions, respectively) in order to examine their possible effect on HA and HA(Me) decomposition. During the first 48 h of fungus growth, gradual acidification to pH 2 was observed in medium containing Glc + NH₄⁺, while for other cultures, alkalinization to pH 9 occurred and then, the above conditions were stable up to at least 200 h. Size exclusion chromatography (SEC) with UV/Vis detection showed progressive degradation and solubilization of both HA and HA(Me) with the increasing time of fungus growth. However, the molecular mass distributions of HA-related soluble species were different in the presence of metals (HA(Me)) as referred to HA and were also influenced by the composition of growth medium. The solubilization of Pb, Cu, and Ni and their association with HA molecular mass fractions were studied using inductively coupled plasma mass spectrometry (ICP-MS) detection. Under acidic conditions, relatively high concentrations of low-molecular-mass metallic species were found in culture supernatants, while in alkaline media, metal solubilization was generally poorer. In contrast to low pH culture, SEC-ICP-MS results obtained in alkaline supernatants indicated metal binding to degradation products of humic substances of MM > 5 kDa. In summary, the results of this study suggest that fungus-assisted degradation of HA and HA(Me) might be controlled using appropriate N- and C- sources required for fungus growth, which in turn would affect molecular mass distribution of soluble metallic species thus potentially influencing their actual bioaccessibility. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Antioxidative properties of <Emphasis Type="Italic">Sambucus nigra</Emphasis> extracts

Potential protective effects of elderberry (Sambucus nigra) extracts against oxidative degradation of hyaluronan (HA) were detected in vitro. To induce free-radical-mediated HA degradation, Weissberger’s biogenic oxidative system, which mimics the situation of acute inflammation, was applied. Time- and dose-dependent changes of dynamic viscosity of the HA solutions in the presence and absence of two elderberry extracts produced in 2006 and 2012 were recorded by rotational viscometry (RV). Radical scavenging capacity of both extracts was investigated by the spectrocolorimetric ABTS [2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt] assay and the “inverted” ABTS assay. Oxygen consumption of the system oxidizing HA either in the absence or presence of the elderberry extracts was determined. The results of RV revealed that an addition of the newer extract (2012) promoted the inhibition of HA degradation more markedly compared to the older extract (2006). The same effect of both extracts on ABTS^·+ scavenging was observed. Inverted ABTS assay demonstrated that colorful substances were not responsible for the radical-scavenging activity. Results of oximetry demonstrated that the effect of the extract from 2006 was more significant than that of the extract from 2012.     

Preparation and properties of redox responsive modified hyaluronic acid hydrogels for drug release

A series of oxidized hyaluronic acid (oxi‐HA)/3,3′‐dithiobis (propionohydrazide) (DTP) redox responsive hydrogels by Schiff base reaction under physiological conditions were designed and prepared. The influence of the concentration of oxi‐HA and DTP on rheological properties, equilibrium swelling ratio, and degradation rate were investigated. All oxi‐HA/DTP hydrogels exhibited good rheological properties, high equilibrium swelling ratio, low degradation rate, and sustainable drug release properties, and the comprehensive performance of oxi‐HA5/DTP6 hydrogel was better than that of others. The redox responsiveness was evaluated by means of degradation and in vitro bovine serum albumin release behavior investigation with the stimulus of different concentration of dithiothreitol as reducing agent. The intelligent hydrogels could be potentially applied in the fields of drug delivery system, tissue engineering, or cell scaffold materials. Copyright © 2017 John Wiley & Sons, Ltd.     

Degradation of pesticide Cartap in Padan 95SP by combined advanced oxidation and electro-Fenton process

The electro-Fenton process combined with a boron-doped diamond-positive electrode in a one-compartment cell has shown efficient degradation of Cartap (95% in Padan 95SP) by hydroxyl radicals (•OH) generated in the electro-Fenton and the electrochemical oxidation processes. The influence of added NaOCl in a pretreatment step, effects of H₂O₂ concentration, Fe²⁺-ion addition, presence of further metals acting as co-catalysts, and solution pH on the efficiency of Cartap degradation were studied. The concentration of Cartap was determined by UV-vis spectroscopy according to the 5,5-dithiobis-(2-nitrobenzoic acid) procedure. The efficiency reaches approximately 80% when measured as total carbon concentration decrease, even with increased concentrations of H₂O₂, Fe²⁺, or metal ions added as co-catalyst. This limitation is presumably due to recalcitrant intermediates, which cannot be destroyed by •OH.

     

Automatic potentiometric two-phase titration in pharmaceutical analysis : Part 3. Titrimetric Identification of Drugs

The conditional acidity constant in a liquid-liquid two-phase system (pK^*_HA + value) can be used as an identity parameter for drug compounds. The pK^*_HA + value can be calculated if the phase ratio and the acidity and distribution constants are known. Selectivity is obtained mainly by the choice of the organic phase. An excess of hydrochloric acid is first added to the sample in the two-phase system. The hydrochloric acid and the sample are then titrated sequentially with sodium hydroxide. The proposed titration procedure makes it possible to calibrat the electrodes, determine the pK^*_HA + value(s), quantify one or more compounds, and check the performance of the electrodes in one and the same experimental run. Lidocaine was “identified” and assayed in different dosage forms such as ointment and solution for injection. The results were in agreement with those obtained by liquid chromatography.     

Amplification effects of magnetic field on hydroxylamine-promoted ZVI/H2O2 near-neutral Fenton like system

This study has demonstrated an interesting amplification effect of magnetic field（MF） on the hydroxylamine（HA）-promoted zero valent iron（ZVI）/H2 O₂ Fenton-like system.Sulfamethoxazole（SMX） could be efficiently degraded at near neutral pH.Conditional parameters affecting the SMX degradation in the ZVI/H₂ O₂/HA/MF system,e.g.,pH and the dosages of ZVI,HA and H₂ O₂,were investigated.Unlike the acid-favorable ZVI/H₂ O₂ and ...     

A UPLC-DAD-Based Bio-Screening Assay for the Evaluation of the Angiotensin Converting Enzyme Inhibitory Potential of Plant Extracts and Compounds: Pyrroquinazoline Alkaloids from Adhatoda vasica as a Case Study

Angiotensin converting enzyme (ACE) plays a crucial role in regulating blood pressure in the human body. Identification of potential ACE inhibitors from medicinal plants supported the idea of repurposing these medicinal plants against hypertension. A method based on ultra-performance liquid chromatography (UPLC) coupled with a diode array detector (DAD) was used for the rapid screening of plant extracts and purified compounds to determine their ACE inhibitory activity. Hippuryl-histidiyl-leucine (HHL) was used as a substrate, which is converted into hippuric acid (HA) by the action of ACE. A calibration curve of the substrate HHL was developed with the linear regression 0.999. The limits of detection and quantification of this method were found to be 0.134 and 0.4061 mM, respectively. Different parameters of ACE inhibitory assay were optimized, including concentration, incubation time and temperature. The ACE inhibition potential of Adhatoda vasica (methanolic-aqueous extract) and its isolated pyrroquinazoline alkaloids, vasicinol (1), vasicine (2) and vasicinone (3) was evaluated. Compounds 1–3 were characterized by various spectroscopic techniques. The IC₅₀ values of vasicinol (1), vasicine (2) and vasicinone (3) were found to be 6.45, 2.60 and 13.49 mM, respectively. Molecular docking studies of compounds 1–3 were also performed. Among these compounds, vasicinol (1) binds as effectively as captopril, a standard drug of ACE inhibition.     

Comparative analysis of commercial dermal fillers based on crosslinked hyaluronan: Physical characterization and in vitro enzymatic degradation

The cosmetic market for hyaluronic acid (HA)-based dermal fillers is in continuous and rapid growth and, simultaneously, the development of more effective and safer products is strongly intensifying. In order to highlight the differences among the currently available fillers, in terms of their physical characteristics and on the relation of such properties with product effectiveness, an in vitro evaluation of eight marketed HA-based gels was performed.Filler swelling properties, soluble HA fraction and rheological behaviour were investigated. Furthermore the relative stability to enzymatic hydrolysis was tested. The presence of soluble HA in the formulations varied from 7 ± 1(%) to 33 ± 5(%) with respect to the total HA concentration. Chromatographic analyses showed that the soluble fractions consist of low molecular weight chains (M_w: 260-480 kDa) presenting large distributions (M_w/M_n: 1.6-2.5). The investigated fillers were found to be non-equilibrium gels in their commercial formulation also showing different swelling capacities. Rheological measurements indicated a shear thinning behaviour for all the products and elastic modulus values varied over a wide range (100-1800 Pa). Fillers proved differently sensitive to enzymatic degradation. Swelling capacity and enzymatic stability were found consistently dependent on the total HA concentration, insoluble/soluble HA ratio and on the crosslinking extent.     

Highly sensitive determination of hydroxylamine using fused gold nanoparticles immobilized on sol-gel film modified gold electrode

We are reporting the highly sensitive determination of hydroxylamine (HA) using 2-mercapto-4-methyl-5-thiazoleacetic acid (TAA) capped fused spherical gold nanoparticles (AuNPs) modified Au electrode. The fused TAA-AuNPs were immobilized on (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film, which was pre-assembled on Au electrode. The immobilization of fused TAA-AuNPs on MPTS sol-gel film was confirmed by UV-vis absorption spectroscopy and atomic force microscopy (AFM). The AFM image showed that the AuNPs retained the fused spherical morphology after immobilized on sol-gel film. The fused TAA-AuNPs on MPTS modified Au electrode were used for the determination of HA in phosphate buffer (PB) solution (pH = 7.2). When compared to bare Au electrode, the fused AuNPs modified electrode not only shifted the oxidation potential of HA towards less positive potential but also enhanced its oxidation peak current. Further, the oxidation of HA was highly stable at fused AuNPs modified electrode. Using amperometric method, determination of 17.5 nM HA was achieved for the first time. Further, the current response of HA increases linearly while increasing its concentration from 17.5 nM to 22 mM and a detection limit was found to be 0.39 nM (S/N = 3). The present modified electrode was also successfully used for the determination of 17.5 nM HA in the presence of 200-fold excess of common interferents such as urea, NO₂⁻, NH₄⁺, oxalate, Mn²⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Ba²⁺ and Cu²⁺. The practical application of the present modified electrode was demonstrated by measuring the concentration of HA in ground water samples.     

Effect of reactive and non-reactive counterion micelles upon the alkaline degradation of indomethacin

In the present paper, kinetics of alkaline degradation of well known drug, indomethacin (2-[1-(4-chlorobenzoyl)-5-methoxy-2-methylindol-3-yl]acetic acid), was studied in presence of excess [NaOH]. The rate of hydrolysis of substrate was independent of the [indomethacin] though it increased linearly with increasing the hydroxide ion concentration with a positive slope, suggesting the following rate law: k_obs = k₁[OH⁻]. Cationic surfactants having non-reactive ions (cetyltrimethylammonium bromide, CTAB and cetyltrimethylammonium sulfate (CTA)₂SO₄) first increased the rate constants at lower concentrations and then decreased it at higher concentrations while in case of the surfactant with reactive counterions (cetyltrimethylammonium hydroxide, CTAOH) the rate increases sharply at lower concentrations of surfactant until it reaches to a plateau in contrast to the appearance of maxima in case of CTAB and (CTA)₂SO₄. Anionic surfactant, sodium dodecyl sulfate (SDS), inhibited the reaction rate at all concentrations used in the study. Pseudophase ion-exchange model was used for analyzing the effect of cationic micelles while the inhibition by SDS micelles was fitted using the Menger–Portnoy model. The effect of salts (NaCl, NaBr and (CH₃)₄NBr) was also seen on the hydrolysis of indomethacin and it was found that all salts inhibited the rate of reaction. The inhibition followed the trend NaCl < NaBr < (CH₃)₄NBr.     

Influences of levofloxacin salts on the metabolism of Escherichia coli by microcalorimetry

A microcalorimetric technique was used to evaluate the influence of both Levofloxacin lactate in sodium chloride injection (drug A) and Levofloxacin hydrochloride in sodium chloride injection (drug B) on the metabolism of Escherichia coli. By means of an isothermal calorimeter and ampoule method at 37 °C, the power-time curves of E. coli growth were obtained under different conditions. The parameters such as the growth rate constant k, maximum power output P _m, time t _m corresponding to the maximum power output and inhibitory ratio I of these two drugs were obtained. The results reveal that the inhibitory abilities enhance with increasing concentrations of the two drugs. The critical growth concentration and the half-inhibitory concentration IC₅₀ were 0.15 and 0.079 μg mL^?1 (for drug A), 0.13 and 0.061 μg mL^?1 (for drug B), respectively. These results show the drug A has slightly better inhibitory effect on E. coli than that of drug B.     

Full factorial experimental design applied to oxalic acid photocatalytic degradation in TiO2 aqueous suspension

Full factorial experimental design technique was used to study the main effects and the interaction effects between operational parameters in the photocatalytic degradation of oxalic acid in a batch photo-reactor using TiO₂ aqueous suspension. The important parameters which affect the removal efficiency of oxalic acid such as agitation, initial concentration, volume of the solution and TiO₂ dosage were investigated. The parameters were coded as X₁, X₂, X₃ and X₄, consecutively, and were investigated at two levels (−1 and +1). The effects of individual variables and their interaction effects for dependent variables, namely, photocatalytic degradation efficiency (%) were determined. From the statistical analysis, the most effective parameters in the photocatalytic degradation efficiency were initial concentration and volume of solution. The interaction between initial concentration, volume of solution and TiO₂ dosage was the most influencing interaction. However, the interaction between agitation, initial concentration and volume of solution was the least influencing parameter.     

Effect of inorganic ions on the photocatalytic degradation of humic acid

The article studies on the effects of six inorganic ions (Ca²⁺, Mg²⁺, Cl^?, SO ₄ ^2? , H₂PO ₄ ^? , and HCO ₃ ^? ) on titanium dioxide (TiO₂)-based photocatalytic degradation of humic acid (HA). We focus on the effects of the inorganic ions on HA characters, adsorption of HA on TiO₂ and photocatalytic degradation of HA. The results indicate that Ca²⁺ and Mg²⁺ with HA can form complexes which can decrease the solubility of HA, and then increase the HA adsorbed on TiO₂. However, the complex is more difficult to be degraded than HA. The effects of Cl^? and SO ₄ ^2? are closely related to their influences on HA solubility. The solubility changes of HA to some extent can enhance the adsorption of HA on TiO₂, and promote the photocatalytic degradation. Nevertheless, great solubility decreasing of HA can weaken the photocatalytic degradation. HCO ₃ ^? and H₂PO ₄ ^? can inhibit the photocatalytic degradation process seriously, because HCO ₃ ^? and H₂PO ₄ ^? are the strong scavengers of hydroxyl radicals, and can weaken the adsorption of HA on TiO₂ due to adsorption competition.     

Phloroglucinol Derivatives from Dryopteris crassirhizoma as Potent Xanthine Oxidase Inhibitors

Dryopteris crassirhizoma rhizomes are used as a traditional medicine in Asia. The EtOAc extract of these roots has shown potent xanthine oxidase (XO) inhibitory activity. However, the main phloroglucinols in D. crassirhizoma rhizomes have not been analyzed. Thus, we investigated the major constituents responsible for this effect. Bioassay-guided purification isolated four compounds: flavaspidic acid AP (1), flavaspidic acid AB (2), flavaspidic acid PB (3), and flavaspidic acid BB (4). Among these, 1 showed the most potent inhibitory activity with a half-maximal inhibitory concentration (IC₅₀) value of 6.3 µM, similar to that of allopurinol (IC₅₀ = 5.7 µM) and better than that of oxypurinol (IC₅₀ = 43.1 µM), which are XO inhibitors. A comparative activity screen indicated that the acetyl group at C3 and C3′ is crucial for XO inhibition. For example, 1 showed nearly 4-fold higher efficacy than 4 (IC₅₀ = 20.9 µM). Representative inhibitors (1–4) in the rhizomes of D. crassirhizoma showed reversible and noncompetitive inhibition toward XO. Furthermore, the potent inhibitors were shown to be present in high quantities in the rhizomes by a UPLC-QTOF-MS analysis. Therefore, the rhizomes of D. crassirhizoma could be used to develop nutraceuticals and medicines for the treatment of gout.     

The effects of copper ions on the catalytic degradation of azo dye acid chrome dark blue

The effect of Cu²⁺ on the catalytic degradation of Acid chrome dark blue (ACDB) in UV-TiO₂ process and Fenton process was studied. In these two processes, Cu²⁺ markedly inhibited the degradation of ACDB. These inhibition effects had an obvious relationship with the concentration of Cu²⁺. The experimental results indicated that in pH 5.0 buffer solution, ACDB reacted with Cu²⁺ with the formation of new complex Cu(ACDB)₂. This interaction was favorable to protect some groups in ACDB from the oxidation of reactive oxygen species generated in UV-TiO₂ process and Fenton process, and consequently had suppressing effects on degradation of ACDB.     

Unrecognized role of humic acid as a reductant in accelerating fluoroquinolones oxidation by aqueous permanganate

A great concern has been raised regarding the issue of fluoroquinolones（FQs） in the environment. In this work, the transformation of FQs by commonly used oxidant permanganate(Mn（VII）) in the absence and presence of humic acid（HA）, ubiquitously existing in aquatic environments, was systematically investigated. Here, the catalytic role of in-situ formed MnO₂ on Mn（VII） oxidation of FQs depending on solution pH and co-existing substrates was firstly reported. It was interestingly found t...     

Synthesis and physicochemical properties of calcium hydroxylapatite/multi-walled carbon nanotubes nanocomposites

Calcium hydroxylapatite/carbon nanotubes (HA/CNT) composites with various CNT contents have been synthesized by coprecipitation from aqueous solutions in the CaCl₂-(NH₄)₂HPO₄-NH₃-CNT-H₂O system (25°C) under conditions modeling the interaction between HA (Ca₁₀(PO₄)₆(OH)₂), which is an inorganic component of osseous tissue, and multi-walled CNTs. The empirical formula of the composites is Ca₁₀(PO₄)₆(OH)₂ · nCNT · 6H₂O, where n = 0.2?C5.0. The synthesis products have been identified by the solubility (Tananaev??s residual concentration) method, pH measurements, chemical analysis, X-ray diffraction, IR spectroscopy, electron spectroscopy for chemical analysis, and scanning and transmission electron microscopy. The effect of the CNT concentration in aqueous solution on the composition of the HA/CNT composites and on the crystallographic and morphological characteristics of HA nanocrystals in HA/CNT has been investigated.     

The kinetics of radical polymerization—XXVII. Investigation of the radical reactivity of 3,3′- and 4,4′-disubstituted azobenzenes in the polymerization of vinylacetate

A study was made on the inhibition by some 3,3′- and 4,4′-disubstituted azobenzenes of the polymerization of vinylacetate initiated by azoisobutyronitrile at 50°. The inhibitory effects of these substances can be attributed to their ability to engage in radical addition giving a less reactive hydrazyl type radical. The mechanism of the inhibition has been established by ESR and kinetic (stoichiometric) measurements. The value of k₅/k₂ (characteristic of the reactivity of an inhibitor) was determined for 9 substituents. The radical reactivity of the aromatic azo group was decreased by electron donor substituents and increased by electron acceptors. The substituent effect can be well interpreted by the Hammett equation; the value of the reaction constant was ? = +0.53.