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.

Chelation Therapy Associated with Antioxidant Supplementation Can Decrease Oxidative Stress and Inflammation in Multiple Sclerosis: Preliminary Results.

An imbalance of oxy-inflammation status has been involved in axonal damage and demyelination in multiple sclerosis (MS). The aim of this study was to investigate the efficacy of an antioxidant treatment (calcium disodium ethylenediaminetetracetic acid-EDTA) chelation therapy associated with a micronutrient complex in MS patients. A total of 20 MS patients and 20 healthy subjects, enrolled as a control group (CTR), were recruited. We measured the plasma ROS production and total antioxidant capacity (TAC) by a direct assessment using Electron Paramagnetic Resonance; activities of the antioxidant system (thiols' redox status and enzymes); and the urinary presence of biomarkers of oxidative stress by immunoenzymatic assays. We also evaluated the levels of inflammation by plasmatic cytokines (TNFα, IL-1ß, and IL-6) and assessed the sICAM levels, as well as the nitric oxide (NO) catabolism and transthyretin (TTR) concentration. Comparing CTR and MS, in the latter ROS production, oxidative damage, inflammatory biomarkers, and NO metabolite concentrations results were significantly higher, while TAC was significantly lower. Treatment in MS induced significant (p < 0.05) down-regulating of pro-inflammatory sICAM1, TNF-α, IL6, as well as biomarkers of lipid peroxidation and DNA damage production. The protective effect exhibited may occur by decreasing ROS production and increasing antioxidant capacity, turning into a more reduced thiols' status.

NMR and EPR study of the interaction of tris(3-hydroxy-4-pyridinonato) Ga(III) complexes with liposomes that mimic plant membranes.

We performed an NMR and EPR study of the interaction of four [Ga(3,4-HPO)3] chelates with liposomes derived from a soybean extract (SEL) and simpler formulations using POPC (100%) and POPE:POPC (50%). Parent [Fe(3,4-HPO)3] chelates are eligible to prevent Iron Deficiency Chlorosis and we took advantage of the likenesses of the ions Fe (III) and Ga (III), and the fact their metal ion complexes are isostructural, to perform a combined NMR and EPR study to get information about the permeation properties of the complexes. The results demonstrate the presence of liposomes loaded with Ga-chelates and that the distribution of complexes alongside the bilayer is dependent on their structure. Two compounds, [Ga(mpp)3] and [Ga(etpp)3], have a higher affinity for the polar region of the liposome bilayer thus suggesting that their structure facilitates their permanence at the root-rhizosphere interface. Chelates [Ga(dmpp)3] and [Ga(mrb13)3] interact with all types of protons of the lipid bilayer thus implying that they travel all along the bilayer structure indicating their higher permeation properties through soybean membranes. The results obtained for compound, [Ga(mrb13)3], which has been included in this work but was not yet tested in plant supplementation experiments, encourage its testing in in vivo plant studies once this study revealed that it interacts strongly with the model membranes. If the results of the future experiments in plants are positive and consistent with the present membrane-interaction studies the latter could constitute a good screening test for future compounds thus saving reagents and time.

Recent Overview of Potent Antioxidant Activity of Coordination Compounds.

During recent decades, the complexation of organic ligands toward several metal ions of s-p and d-block has been applied as a plan to enhance its antioxidant performance. Due to their wide range of beneficial impacts, coordination compounds are widely used in industries, specifically in the medicinal and pharmaceutical fields. The activity is generally improved by chelation consequently knowing that the characteristics of both ligands and metals can lead to the development of greatly active compounds. Chelation compounds are a substitute for using the traditional synthetic antioxidants, because metal chelates present benefits, including a variety in geometry, oxidation states, and coordination number, that assist and favor the redox methods associated with antioxidant action. As well as understanding the best studied anti-oxidative assets of these compounds, coordination compounds are involved in the free radical scavenging process and protecting human organisms from the opposing effects of these radicals. The antioxidant ability can be assessed by various interrelated systems. The methodological modification offers the most knowledge on the antioxidant property of metal chelates. Colorimetric techniques are the most used, though electron paramagnetic resonance (EPR) is an alternative for metallic compounds, since color does not affect the results. Information about systems, with their benefits, and restrictions, permits a dependable valuation of the antioxidant performance of coordination compounds, as well as assisting application in various states wherever antioxidant drugs are required, such as in food protection, appropriate good-packaged foods, dietary supplements, and others. Because of the new exhaustive analysis of organic ligands, it has become a separate field of research in chemistry. The present investigation will be respected for providing a foundation for the antioxidant properties of organic ligands, future tests on organic ligands, and building high-quality antioxidative compounds.

Application of Amino Acids for High-Dosage Measurements with Electron Paramagnetic Resonance Spectroscopy.

A comparative investigation of amino acids (proline, cysteine, and alanine) as dosimetric materials using electron paramagnetic resonance (EPR) spectroscopy in the absorbed dosage range of 1-25 kGy is presented. There were no signals in the EPR spectra of the samples before irradiation. After irradiation, the complex spectra were recorded. These results showed that the investigated amino acids were sensitive to radiation. In the EPR spectrum of cysteine after irradiation, RS• radicals dominated. The effects of the microwave power on the saturation of the EPR signals showed the presence of at least three different types of free radicals in proline. It was also found out that the DL-proline and cysteine had stable free radicals after irradiation and represented a linear dosage response up to 10 kGy. On the other hand, the amino acid alanine has been accepted by the International Atomic Energy Agency as a transfer standard dosimetry system. In view of this, the obtained results of the proline and cysteine studies have been compared with those of the alanine studies. The results showed that the amino acids proline and cysteine could be used as alternative dosimetric materials in lieu of alanine in a dosage range of 1-10 kGy of an absorbed dose of γ-rays using EPR spectroscopy. Regarding the radiation sensitivity, the following order of decreased dosage responses was determined: alanine > DL-proline > cysteine > L-proline.

Self-Organization Effects of Thin ZnO Layers on the Surface of Porous Silicon by Formation of Energetically Stable Nanostructures.

The formation of complex surface morphology of a multilayer structure, the processes of which are based on quantum phenomena, is a promising domain of the research. A hierarchy of pore of various sizes was determined in the initial sample of porous silicon by the atomic force microscopy. After film deposition by spray pyrolysis, ZnO nanoclusters regularly distributed over the sample surface were formed. Using the electron paramagnetic resonance (EPR) method it was determined that the localization of paramagnetic centers occurs more efficiently as a result of the ZnO deposition. An increase in the number of deposited layers, leads to a decrease in the paramagnetic center relaxation time, which is probably connected with the formation of ZnO nanocrystals with energetically stable properties. The nucleation and formation of nanocrystals is associated with the interaction of particles with an uncompensated charge. There is no single approach to determine the mechanism of this process. By the EPR method supplemented with the signal cyclic saturation, spectral manifestations from individual centers were effectively separated. Based on electron paramagnetic resonance and photoluminescence studies it was revealed that the main transitions between energy levels are due to oxygen vacancies and excitons.

Oxidative stress coping capacity (OSC) value: Development and validation of an in vitro measurement method for blood plasma using electron paramagnetic resonance spectroscopy (EPR) and vitamin C.

Oxidative stress as a driver of disease is reinforcing the trend towards supplementation with antioxidants. While antioxidants positively influence the redox status when applied at physiological doses, higher concentrations may have pro-oxidative effects. Precise assessment methods for testing the supply of antioxidants are lacking. Using in-situ-irradiation as stressor and electron paramagnetic resonance (EPR) spectroscopy as readout system for formed radicals, a stress response assessment method was developed, using protein solutions and plasma samples from transfusion medicine. The method was validated in a double-blind placebo-controlled in vivo cross-over pilot study in blood plasma samples of individuals before and after vitamin C supplementation. Reference measurements were performed for the exogenous antioxidants ß-carotene and vitamin C, and glutathione as an endogenous representative. Malondialdehyde was studied for oxidative stress indication. Protein solutions without antioxidants showed a linear increase in radical concentration during irradiation. The in-vitro-addition of vitamin C or plasma samples from subjects displayed two slopes (m1, m2) for radical production, whereby m1 represented the amount of antioxidants and proteins, m2 only the protein content. These two slopes in combination with the intervening transition area (T) were used to calculate the oxidative stress coping capacity (OSC), which correlated positively with vitamin C concentration in blood plasma, while oxidative stress biomarkers showed only fluctuations within their reference ranges. Furthermore, a selective radical quenching mechanism for vitamin C was observed: the proportion of reactive oxygen species (ROS) in the plasma samples was degraded in dependence to the vitamin C concentration ingested. The proportion of lipid oxygen species (LOS) remained stable while the ascorbyl radical increased with higher vitamin C intake. OSC may represent a sensitive method to detect treatment effects on the redox status in vivo in future validation and treatment studies, and potentially in clinical routine.

Extensive Characterization of Polysorbate 80 Oxidative Degradation Under Stainless Steel Conditions.

Polysorbate-80 (PS-80) is a common surfactant used in biologics formulations. However, the tendency of oxidation to PS-80 when exposed to stainless steel surfaces brings various challenges during manufacturing processes, such as inconsistent shelf-life of PS-80 solutions, which can further impact the biologics and vaccines production. In this work, the root causes of PS-80 oxidation when in contact with stainless steel conditions were thoroughly investigated through the use of various complementary analytical techniques including U/HPLC-CAD, LC-MS, ICP-MS, peroxide assay, and EPR spectroscopy. The analytical tool kit used in this work successfully revealed a PS-80 degradation mechanism from the perspective of PS-80 content, PS-80 profile, iron content, peroxide production, and radical species. The combined datasets reveal that PS-80 oxidative degradation occurs in the presence of histidine and iron in addition to being combined with the hydroperoxides in PS-80 material. The oxidative pathway and potential degradants were identified by LC-MS. The PS-80 profile based on the U/HPLC-CAD assay provided an effective way to identify early-signs of PS-80 degradation. The results from a peroxide assay observed increased hydroperoxide along with PS-80 degradation. EPR spectra confirmed the presence of histidine-related radicals during PS-80 oxidation identifying how histidine is involved in the oxidation. All assays and findings introduced in this work will provide insight into how PS-80 oxidative degradation can be avoided, controlled, or detected. It will also provide valuable evaluations on techniques that can be used to identify PS-80 degradation related events that occur during the manufacturing process.

New TEMPO-Appended 2,2'-Bipyridine-Based Eu(III), Tb(III), Gd(III) and Sm(III) Complexes: Synthesis, Photophysical Studies and Testing Photoluminescence-Based Bioimaging Abilities.

Linked to Alzheimer's disease (AD), amyloids and tau-protein are known to contain a large number of cysteine (Cys) residues. In addition, certain levels of some common biogenic thiols (cysteine (Cys), homocysteine (Hcy), glutathione (GSH), etc.) in biological fluids are closely related to AD as well as other diseases. Therefore, probes with a selective interaction with the above-mentioned thiols can be used for the monitoring and visualizing changes of (bio)thiols in the biological fluids as well as in the brain of animal models of Alzheimer's disease. In this study, new Eu(III), Tb(III), Gd(III) and Sm(III) complexes of 2,2'-bipyridine ligands containing TEMPO fragments as receptor units for (bio)thiols are reported. The presence of free radical fragments of the ligand in the complexes was proved by using the electronic paramagnetic resonance (EPR) method. Among all the complexes, the Eu(III) complex turned out to be the most promising one as luminescence- and spin-probe for the detection of biogenic thiols. The EPR and fluorescent titration methods showed the interaction of the resulting complex with free Cys and GSH in solution. To study the practical applicability of the probes for the monitoring of AD in-vivo, by using the above-mentioned Eu(III)-based probe, the staining of the brain of mice with amyloidosis and Vero cell cultures supplemented with the cysteine-enriched medium was studied as well as the fluorescence titration of Bovine Serum Albumin, BSA (as the model for the thiol moieties containing protein), was carried out. Based on the results of fluorescence titration, the formation of a non-covalent inclusion complex between the above-mentioned Eu(III) complex and BSA was suggested.

Phenolic Profile, EPR Determination, and Antiproliferative Activity against Human Cancer Cell Lines of Anthyllis vulneraria Extracts.

In the current work, the leaf and flower extracts of Anthyllis vulneraria were evaluated for their chemical characterization using HPLC-MS and for their radical scavenging capacity toward methoxy radicals produced by a Fenton-type reaction using an electron paramagnetic resonance (EPR) spectroscopy assay. The in vitro antiproliferative activity of these extracts against several human-derived cancer cells (breast: MCF-7; cervical: HeLa; hepatocellular: HepG2) was also evaluated. The results showed that the Anthyllis vulneraria leaf extract was characterized by 17 different phenolic compounds, among which phenolic acids were the most abundant, while its flower extract exhibited higher contents of flavonoids. Furthermore, Anthyllis vulneraria extracts demonstrated a potent radical scavenging activity against methoxy radicals. Both extracts also significantly reduced the viability of the different cancer cell lines. The results of the current study suggested that Anthyllis vulneraria extracts are a promising source of antioxidant compounds with health benefits and pointed to their potential use for treating cancer and developing novel therapeutic agents.

Extracellular matrix degrading enzyme with stroma-targeting peptides enhance the penetration of liposomes into tumors.

Various anti-tumor nanomedicines have been developed based on the enhanced permeability and retention effect. However, the dense extracellular matrix (ECM) in tumors remains a major barrier for the delivery and accumulation of nanoparticles into tumors. While ECM-degrading enzymes, such as collagenase, hyaluronidase, and bromelain, have been used to facilitate the accumulation of nanoparticles, serious side effects arising from the current non-tumor-specific delivery methods limit their clinical applications. Here, we report targeted delivery of bromelain into tumor tissues through its covalent attachment to a hyaluronic acid (HA)-peptide conjugate with tumor ECM targeting ability. The ECM targeting peptide, collagen type IV-binding peptide (C4BP), was chosen from six candidate-peptides based on their ability to bind to frozen sections of triple-negative breast cancer, 4T1 tumor ex vivo. The HA- C4BP conjugate showed a significant increase in tumor accumulation in 4T1-bearing mice after intravenous administration compared to unmodified HA. We further demonstrated that the systemic administration of bromelain conjugated C4BP-HA (C4BP-HA-Bro) potentiates the anti-tumor efficacy of liposomal doxorubicin. C4BP-HA-Bro decreased the number and length of collagen fibers and improved the distribution of doxorubicin within the tumor. No infusion reaction was noted after delivery of C4BP-HA-Bro. C4BP-HA thus offers a potential for effective and safe delivery of bromelain for improved intratumoral delivery of therapeutics.

Heating of consumer cannabis oils can lead to free radical initiated degradation, causing CBD and THC depletion.

Commercial cannabis oil products are widely available in Canada even though there is a significant gap in scientific information regarding them. Oils, such as vegetable oils, are known to undergo oxidative changes through free radical mechanisms when they are heated or aged, but the cannabis oils used in this study did not have expiry dates or best-before usage dates. This led to the question of how these products would be affected with time. We hypothesized that cannabis oils would produce increased concentrations of free radicals in aging-simulated conditions, which would be related to a decrease in cannabidiol (CBD) or Δ9-tetrahydrocannabinol (THC) content. Cannabis oils and their respective vehicles (oils) were heated using two protocols: One (moderate aging method) used a 2-day heating protocol at 50 °C, and the other (enhanced aging method) used a 14-day heating protocol at 70 °C. We used electron paramagnetic resonance (EPR) spectroscopy for free radical analysis using the spin trapping technique using 200 mM PBN and 0.02 mM CuCl2 (for peroxide breakdown to free radicals). For active ingredient analysis (CBD, THC), we used LC/MS. Cannabis oils that contained unsaturated oils as their vehicles, such as olive or sunflower oil, all showed varying degrees of free radical formation. In both aged and unaged oils containing CBD or THC, less free radical formation was detected compared to the vehicle controls. Cannabis oils using medium-chain triglycerides (MCT) showed little or no free radical formation. The most significant decrease in CBD or THC was observed in the products using sunflower oil, to a lesser extent in MCT oil, and THC also decreased in olive oil. These findings are important for consumers and policymakers considering using such products in hot beverages or cooking and highlighting the importance of appropriate storage conditions.

Redox imbalance in COVID-19 pathophysiology.

BACKGROUND: The pathophysiologic significance of redox imbalance is unquestionable as numerous reports and topic reviews indicate alterations in redox parameters during corona virus disease 2019 (COVID-19). However, a more comprehensive understanding of redox-related parameters in the context of COVID-19-mediated inflammation and pathophysiology is required. METHODS: COVID-19 subjects (n = 64) and control subjects (n = 19) were enrolled, and blood was drawn within 72 h of diagnosis. Serum multiplex assays and peripheral blood mRNA sequencing was performed. Oxidant/free radical (electron paramagnetic resonance (EPR) spectroscopy, nitrite-nitrate assay) and antioxidant (ferrous reducing ability of serum assay and high-performance liquid chromatography) were performed. Multivariate analyses were performed to evaluate potential of indicated parameters to predict clinical outcome. RESULTS: Significantly greater levels of multiple inflammatory and vascular markers were quantified in the subjects admitted to the ICU compared to non-ICU subjects. Gene set enrichment analyses indicated significant enhancement of oxidant related pathways and biochemical assays confirmed a significant increase in free radical production and uric acid reduction in COVID-19 subjects. Multivariate analyses confirmed a positive association between serum levels of VCAM-1, ICAM-1 and a negative association between the abundance of one electron oxidants (detected by ascorbate radical formation) and mortality in COVID subjects while IL-17c and TSLP levels predicted need for intensive care in COVID-19 subjects. CONCLUSION: Herein we demonstrate a significant redox imbalance during COVID-19 infection affirming the potential for manipulation of oxidative stress pathways as a new therapeutic strategy COVID-19. However, further work is requisite for detailed identification of oxidants (O2•-, H2O2 and/or circulating transition metals such as Fe or Cu) contributing to this imbalance to avoid the repetition of failures using non-specific antioxidant supplementation.

Temperature-sensitive polymers to promote heat-triggered drug release from liposomes: Towards bypassing EPR.

Heat-triggered drug release from temperature-sensitive nanocarriers upon the application of mild hyperthermia is a promising approach to achieve site-specific delivery of drugs. The combination of mild hyperthermia (41-42 °C) and temperature-sensitive liposomes (TSL) that undergo lipid phase-transition and drug release has been studied extensively and has shown promising therapeutic outcome in a variety of animal tumor models as well as initial indications of success in humans. Sensitization of liposomes to mild hyperthermia by means of exploiting the thermal behavior of temperature-sensitive polymers (TSP) provides novel opportunities. Recently, TSP-modified liposomes (TSPL) have shown potential for enhancing tumor-directed drug delivery, either by triggered drug release or by triggered cell interactions in response to heat. In this review, we describe different classes of TSPL, and analyze and discuss the mechanisms and kinetics of content release from TSPL in response to local heating. In addition, the impact of lipid composition, polymer and copolymer characteristics, serum components and PEGylation on the mechanism of content release and TSPL performance is addressed. This is done from the perspective of rationally designing TSPL, with the overall goal of conceiving efficient strategies to increase the efficacy of TSPL plus hyperthermia to improve the outcome of targeted anticancer therapy.

Study of the molecular-structural composition of alcoholic extracts of radio-induced potato tubers by mass spectrometry and EPR.

This article presents data on electron paramagnetic resonance (EPR) and mass spectrometric analysis of potato tubers, irradiated with gamma rays, in order to examine and identify changes in the molecular composition of organic matter following radiation exposure. The products of the Maillard reaction were compared with the products of intramolecular radiolysis of organic constituents of potatoes. The presence of free radicals was verified using EPR. DDPM (2,3-dihydro-3,5-dihydroxy-6-methyl-4 (H) -pyran-4-one) was among the radiolysis products detected via mass spectrometry, which points to the intramolecular dehydration of potato carbohydrates. EPR signals indicate single-electron transitions of the semidione radical anionic molecular compounds. It has been shown that irradiation with gamma rays significantly destroys the carbohydrate, lipid, keto-carotene and amino acid molecules of potatoes.

Role of the Hydroxyl Radical-Generating System in the Estimation of the Antioxidant Activity of Plant Extracts by Electron Paramagnetic Resonance (EPR).

The scavenging activity of hydroxyl radicals, produced by the Fenton reaction, is commonly used to quantify the antioxidant capacity of plant extracts. In this study, three Fenton systems (Fe/phosphate buffer, Fe/quinolinic acid and Fe/phosphate buffer/quinolinic acid) and the thermal degradation of peroxydisulfate were used to produce hydroxyl radicals; the hydroxyl radical scavenging activity of plant extracts (ginger, blueberry juices and green tea infusion) and chemical compounds (EGCG and GA) was estimated by spin trapping with DMPO (5,5-dimethyl-1-pyrroline N-oxide) and EPR (Electron Paramagnetic Resonance) spectroscopy. Phosphate buffer was used to mimic the physiological pH of cellular systems, while quinolinic acid (pyridine-2,3-dicarboxylic acid) facilitates the experimental procedure by hindering the spontaneous oxidation of Fe(II). The EC50 (the concentration of chemical compounds or plant extracts which halves the intensity of the DMPO-OH adduct) values were determined in all the systems. The results show that, for both the chemical compounds and the plant extracts, there is not a well-defined order for the EC50 values determined in the four hydroxyl radical generating systems. The interactions of phosphate buffer and quinolinic acid with the antioxidants and with potential iron-coordinating ligands present in the plant extracts can justify the observed differences.

Oxidation of ferumoxytol by ionizing radiation releases iron. An electron paramagnetic resonance study.

Ferumoxytol (FMX) is an iron oxide nanoparticle that is FDA approved for the treatment of iron deficiency anemia. FMX contains an Fe3O4 core. Currently, the redox chemistry of Fe3O4 nanoparticles remains relatively unexplored. FMX has recently gained interest as an anti-cancer agent. Ionizing radiation (IR) is a treatment modality employed to treat several types of cancer. Utilizing electron paramagnetic resonance (EPR) spectroscopy, we found that the products produced from the radiolysis of water can oxidize the Fe3O4 core of FMX. Because of the limited diffusion of the HO2• and HO• produced, these highly oxidizing species have little direct effect on FMX oxidation. We have determined that H2O2 is the primary oxidant of FMX. In the presence of labile Fe2+, we found that reducing species generated from the radiolysis of H2O are able to reduce the Fe3+ sites of the Fe3O4 core. Importantly, we also have shown that IR stimulates the release of ferric iron from FMX. Because of its release of iron, FMX may serve as an adjuvant to enhance radiotherapy.

Pure drug nano-assemblies: A facile carrier-free nanoplatform for efficient cancer therapy.

Nanoparticulate drug delivery systems (Nano-DDSs) have emerged as possible solution to the obstacles of anticancer drug delivery. However, the clinical outcomes and translation are restricted by several drawbacks, such as low drug loading, premature drug leakage and carrier-related toxicity. Recently, pure drug nano-assemblies (PDNAs), fabricated by the self-assembly or co-assembly of pure drug molecules, have attracted considerable attention. Their facile and reproducible preparation technique helps to remove the bottleneck of nanomedicines including quality control, scale-up production and clinical translation. Acting as both carriers and cargos, the carrier-free PDNAs have an ultra-high or even 100% drug loading. In addition, combination therapies based on PDNAs could possibly address the most intractable problems in cancer treatment, such as tumor metastasis and drug resistance. In the present review, the latest development of PDNAs for cancer treatment is overviewed. First, PDNAs are classified according to the composition of drug molecules, and the assembly mechanisms are discussed. Furthermore, the co-delivery of PDNAs for combination therapies is summarized, with special focus on the improvement of therapeutic outcomes. Finally, future prospects and challenges of PDNAs for efficient cancer therapy are spotlighted.

Free Radical Scavenging Activity of Infusions of Different Medicinal Plants for Use in Obstetrics.

An X-band (9.3 GHz) electron paramagnetic resonance (EPR) spectroscopy was used to examine the free radical scavenging activity of the following infusions, which were nonirradiated and exposed to UVA: root of Asparagus racemosus and herbs of Mitchella repens, Cnicus benedictus L., Galega officinalis L., and Eupatorium cannabinum L. The plant materials for obstetrics applications were chosen for analysis. The aims of these studies were to compare the free radical scavenging ability of the tested infusions and to determine the influence of UVA irradiation of the plant materials on interactions of these infusions with free radicals. Both the magnitude and kinetics of the interactions of the infusions with the model DPPH free radicals were examined. The ability to quench the free radicals for the examined plant infusions increases in the following order: Asparagus racemosus (root) < Mitchella repens (herb) < Cnicus benedictus L. (herb) < Galega officinalis L. (herb) < Eupatorium cannabinum L. (herb). The analyzed infusions differ in the kinetics of the interactions with free radicals. The fastest interactions with free radicals characterize the infusions of Galega officinalis L. herb and Eupatorium cannabinum L. herb. The infusion of Mitchella repens herb interacts with free radicals in the slowest way. UVA radiation reduces the antioxidant interactions of all tested infusions, especially the infusion of Eupatorium cannabinum L. herb, which should be protected against UVA radiation during storage. The weakest decrease of free radical scavenging activity was observed for the infusion of the root of Asparagus racemosus exposed to UVA radiation. UVA radiation affected the speed of the free radical interactions of the infusions, depending on the type of plant materials. EPR spectroscopy is useful to examine the free radical scavenging activity of plant infusions, which is helpful to find effective antioxidants for applications in obstetrics and their optimal storage conditions.

Thermodynamic Study of Oxidovanadium(IV) with Kojic Acid Derivatives: A Multi-Technique Approach.

The good chelating properties of hydroxypyrone (HPO) derivatives towards oxidovanadium(IV) cation, VIVO2+, constitute the precondition for the development of new insulin-mimetic and anticancer compounds. In the present work, we examined the VIVO2+ complex formation equilibria of two kojic acid (KA) derivatives, L4 and L9, structurally constituted by two kojic acid units linked in position 6 through methylene diamine and diethyl-ethylenediamine, respectively. These chemical systems have been characterized in solution by the combined use of various complementary techniques, as UV-vis spectrophotometry, potentiometry, NMR and EPR spectroscopy, ESI-MS spectrometry, and DFT calculations. The thermodynamic approach allowed proposing a chemical coordination model and the calculation of the complex formation constants. Both ligands L4 and L9 form 1:1 binuclear complexes at acidic and physiological pHs, with various protonation degrees in which two KA units coordinate each VIVO2+ ion. The joined use of different techniques allowed reaching a coherent vision of the complexation models of the two ligands toward oxidovanadium(IV) ion in aqueous solution. The high stability of the formed species and the binuclear structure may favor their biological action, and represent a good starting point toward the design of new pharmacologically active vanadium species.