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The thermal stability of the oligomers obtained by using 2-chloro-2-propen-1-ol as the monomer has been studied. The oligomers were synthesized using chromium(III) and oxovanadium(IV) complexes as the catalysts after activation by modified methylaluminoxane (MMAO-12). The complexes used as the catalysts were polycarboxylate complex compounds of oxovanadium(IV) and chromium(III). The studies have been conducted by two methods: thermal gravimetry and differential scanning calorimetry. The obtained results allow to determine the glass transition temperatures and thermal stability of the oligomers depending on the central catalyst cation Cr3+ and V4+.

Elevated levels of reactive nitrogen species, alteration in redox balance and deregulated redox signaling are common hallmarks of cancer progression and chemoresistance. However, depending on the cellular context, distinct reactive nitrogen species are also hypothesized to mediate cytotoxic activity and are thus used in anticancer therapies. We present here the dual face of nitric oxide and its derivatives in cancer biology. Main derivatives of nitric oxide, such as nitrogen dioxide and peroxynitrite cause cell death by inducing protein and lipid peroxidation and/or DNA damage. Moreover, they control the activity of important protein players within the pro- and anti-apoptotic signaling pathways. Thus, the control of intracellular reactive nitrogen species may become a sophisticated tool in anticancer strategies.

Oxidative stress plays an important role in the pathogenesis of many serious diseases, including cancer, atherosclerosis, coronary artery disease, Parkinson’s disease, Alzheimer’s disease, stroke and myocardial infarction. In the body’s natural biochemical processes, harmful free radicals are formed, which can be removed with the help of appropriate enzymes, a balanced diet or the supply of synthetic antioxidant substances such as flavonoids, vitamins or anthocyanins to the body. Due to the growing demand for antioxidant substances, new complex compounds of transition metal ions with potential antioxidant activity are constantly being sought. In this study, four oxovanadium(IV) and dioxovanadium(V) dipicolinate (dipic) complexes with 1,10-phenanthroline (phen), 2,2′-bipyridyl (bipy) and the protonated form of 2-phenylpyridine (2-phephyH): (1) [VO(dipic)(H2O)2]·2 H2O, (2) [VO(dipic)(phen)]·3 H2O, (3) [VO(dipic)(bipy)]·H2O and (4) [VOO(dipic)](2-phepyH)·H2O were synthesized including one new complex, so far unknown and not described in the literature, i.e., [VOO(dipic)](2-phepyH)·H2O. The oxovanadium(IV) dipicolinate complexes with 1,10-phenanthroline and 2,2′-bipyridyl have been characterized by several physicochemical methods: NMR, MALDI-TOF-MS, IR, but new complex [VOO(dipic)](2-phepyH)·H2O has been examined by XRD to confirm its structure. The antioxidant activities of four complexes have been examined by the nitrotetrazolium blue (NBT) method towards superoxide anion. All complexes exhibit high reactivity with superoxide anion and [VOO(dipic)](2-phepyH)·H2O has higher antioxidant activity than L-ascorbic acid. Our studies confirmed that high basicity of the auxiliary ligand increases the reactivity of the complex with the superoxide radical.

The contemporary search for new catalysts for olefin oligomerization and polymerization is based on the study of coordinating compounds and/or organometallic compounds as post-metallocene catalysts. However known catalysts are suffered by many flaws, among others unsatisfactory activity, requirement of high pressure or instability at high temperatures. In this paper, we present a new catalyst i.e. the crystalline complex compound possesing high catalytic activity in the oligomerization of olefins, such as 2-chloro-2-propen-1-ol and ethylene under very mild conditions (room temperature, 0.12 bar for ethylene oligomerization, atmospheric pressure for 2-chloro-2-propen-1-ol oligomerization). New material - Cat-CrNP ( [nitrilotriacetato - 1,10–phenanthroline]chromium(III) tetrahydrate) has been obtained as crystalline form of the nitrilotriacetate complex compound of chromium(III) with 1,10-phenanthroline and characterized in terms of its crystal structure by the XRD method and by multi-analytical investigations towards its physicochemical propeties The yield of catalytic oligomerization over Cat-CrNP reached to 213.92 g ∙ mmol-1 ∙ h-1∙ bar-1 and 3232 g ∙ mmol-1 ∙ h-1 ∙ bar-1 for the 2-chloro-2-propen-1-ol and ethylene, respectively. Furthemore, the synthesis of Cat-CrNP is cheap, easy to perform and solvents used during preparation are environmentally friendly.

The kinetics of the aquation reaction of the [VO(ida)(bipy)]·2H2O (VO(ida)(bipy)) complex (where ida = iminodiacetate anion and bipy = 2,2’-bipyridine) promoted by [Fe(H2O)6]3+ ions were investigated in aqueous solutions. Spectrophotometric studies were carried out at different temperatures in the range of 293.15–313.15 K. The concentration of the [Fe(H2O)6]3+ (Fe3+) ions was kept within the range of 2 × 10–4 to 8 × 10–4 mol L–1, and the concentration of VO(ida)(bipy) was 1 × 10–3 mol L–1. The values of the observable reaction rate constants were calculated based on the Glint computer program. Furthermore, the mechanism for the aquation of VO(ida)(bipy), induced by Fe(III) ions, has been proposed.

The report focuses on the new precatalysts for ethylene oligomerization. The five chromium(III) complex compounds containing the following ligands: dipicolinate anion, oxalate anion, 5-aminopyridine-2-carboxylate anion, 2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine have been examined towards catalytic activity for ethylene oligomerization. The chromium(III) complexes have been activated by modified methylaluminoxane. The obtained oligomers have been investigated by MALDI-TOF–MS, thermal analysis and infrared spectroscopy. The results revealed that the examined chromium(III) complexes are highly active catalysts for ethylene oligomerization. The values of catalytic activities of the examined complexes are in the range 1860 – 3798 g∙mmol-1∙h-1∙bar-1.

2-methoxyestradiol (2-ME) is a physiological anticancer compound, metabolite of 17β-estradiol. Previously, our group evidenced that from mechanistic point of view one of anticancer mechanisms of action of 2-ME is specific induction and nuclear hijacking of neuronal nitric oxide synthase (nNOS), resulting in local generation of nitro-oxidative stress and finally, cancer cell death. The current study aims to establish the substantial mechanism of generation of reactive nitrogen species by 2-ME. We further achieved to identify the specific reactive nitrogen species involved in DNA-damaging mechanism of 2-ME. The study was performed using metastatic osteosarcoma 143B cells. We detected the release of biologically active (free) nitric oxide (•NO) with concurrent measurements of peroxynitrite (ONOO−) in real time in a single cell of 143B cell line by using •NO/ONOO− sensitive microsensors after stimulation with calcium ionophore. Detection of nitrogen dioxide (•NO2) and determination of chemical rate constants were carried out by a stopped-flow technique. The affinity of reactive nitrogen species toward the guanine base of DNA was evaluated by density functional theory calculations. Expression and localization of nuclear factor NF-kB was determined using imaging cytometry, while cell viability assay was evaluated by MTT assay. Herein, we presented that 2-ME triggers pro-apoptotic signalling cascade by increasing cellular reactive nitrogen species overproduction – a result of enzymatic uncoupling of increased nNOS protein levels. In particular, we proved that ONOO− and •NO2 directly formed from peroxynitrous acid (ONOOH) and/or by auto-oxidation of •NO, are inducers of DNA damage in anticancer mechanism of 2-ME. Specifically, the affinity of reactive nitrogen species toward the guanine base of DNA, evaluated by density functional theory calculations, decreased in the order: ONOOH > ONOO− > •NO2 > •NO. Therefore, we propose to consider the specific inducers of nNOS as an effective tool in the field of chemotherapy.

Environmental contaminants, such as heavy metals, nanomaterials, and pesticides, induce the formation of reactive oxygen and nitrogen species (RONS). Plants interact closely with the atmosphere, water, and soil, and consequently RONS intensely affect their biochemistry. For the past 30 years researchers have thoroughly examined the role of RONS in plant organisms and oxidative modifications to cellular components. Hydrogen peroxide, superoxide anion, nitrogen(II) oxide, and hydroxyl radicals have been found to take part in many metabolic pathways. In this review the various aspects of the oxidative stress induced by environmental contamination are described based on an analysis of literature. The review reinforces the contention that RONS play a dual role, that is, both a deleterious and a beneficial one, in plants. Environmental contamination affects human health, also, and so we have additionally described the impact of RONS on the coupled human – environment system.

The oxydiacetate complexes of copper(II) with 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) have been investigated towards their kinetic and thermodynamic stability. The kinetics of the substitution reactions of the oxydiacetate complex of Cu2+ with bipy and phen have been studied in two types of surfactant solutions - anionic dodecyl sulfate sodium (SDS) and cationic hexadecyl trimethyl-ammonium bromide (CTAB). The values of the observable rate constants for the studied reactions have been determined using the “Glint” program. Moreover, the thermodynamic stability of the copper(II) complexes with oda, phen and bipy in aqueous solutions has been investigated using potentiometric titration method (PT). The concentration distributions of the studied complexes as a function of pH calculated based on the values of log βpqrs have been determined. Additionally, the antioxidant activities of the oxydiacetate complexes of copper(II) with bipy and phen have been studied by the nitro blue tetrazolium (NBT) test and the cyclic voltammetry (CV) technique.

Breast cancer is the most common cancer of women—it affects more than 2 million women worldwide. PTP1B phosphatase can be one of the possible targets for new drugs in breast cancer therapy. In this paper, we present new curcumin derivatives featuring a 4-piperidone ring as PTP1B inhibitors and ROS inducers. We performed cytotoxicity analysis for twelve curcumin derivatives against breast cancer MCF-7 and MDA-MB-231 cell lines and the human keratinocyte HaCaT cell line. Furthermore, because curcumin is a known antioxidant, we assessed antioxidant effects in its derivatives. For the most potent cytotoxic compounds, we determined intracellular ROS and PTP1B phosphatase levels. Moreover, for curcumin and its derivatives, we performed real-time microscopy to observe the photosensitizing effect. Finally, computational analysis was performed for the curcumin derivatives with an inhibitory effect against PTP1B phosphatase to assess the potential binding mode of new inhibitors within the allosteric site of the enzyme. We observed that two tested compounds are better anticancer agents than curcumin. Moreover, we suggest that blocking the -OH group in phenolic compounds causes an increase in the cytotoxicity effect, even at a low concentration. Furthermore, due to this modification, a higher level of ROS is induced, which correlates with a lower level of PTP1B.

The kinetics and thermodynamics have been studied for the reactions of the copper(II) complexes with iminodiacetate (ida), 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) as ligands. The kinetics of substitution reactions of two aqua ligands for bipy and phen in the [Cu(ida)(H2O)2] coordination compound has been studied in water and three type of aqueous solutions of the following surfactants: anionic sodium dodecyl sulfate (SDS), cationic hexadecyl trimethyl-ammonium bromide (CTAB) and nonionic t-octylphenoxypolyetoxyethanol (Triton X-100). The progress of the substitution reactions in the studied solutions was monitored spectrophotometrically using the stopped-flow method. The studies have allowed the determination of the effect of the type of surfactant solutions on the rate of the substitution reaction. Moreover, the order of studied reactions has been determined. The research performed has also allowed us to propose the reaction mechanism of the [Cu(ida)(H2O)2] binary complex with chelate ligands (bipy or phen). In addition, the thermodynamic stability of complexes under study in aqueous solutions has been examined using the potentiometric titration method. Moreover, the potential scavenging activity of the copper(II) complexes has been investigated towards the superoxide radical.

The crystal and molecular structures of a new dinuclear oxidovanadium(IV) complex with the N-(phosphonomethyl)iminodiacetate (pmida) ligand and the 4-amino-2-methylquinolinium ([amqH]+) cation of the molecular formula [amqH]4[V2O2(pmida)2]6H2O have been determined. The phosphonate groups in the two pmida4− ligands form two bridges between adjacent V4+ atoms, resulting in the formation of a [V2O2(pmida)2]4− dimer with a V2O4P2 eight-membered ring. This is the first example of a quinoline derivative complex containing the [V2O2(pmida)2]4− ion. The susceptibility curve for the complex exhibits a maximum at approximately 10 K, indicating the presence of antiferromagnetic interactions transmitted in the crystal lattice. Furthermore, the biological properties of the complex in the concentration range 1–100 μM were investigated in relation to its cytoprotective activity against oxidative damage generated exogenously using hydrogen peroxide in the hippocampal neuronal HT22 cell line (MTT tests). The obtained results were subsequently referred to the [amqH][VO(nta)(H2O)]H2O analogue as well as trolox and ascorbic acid, used as known antioxidants. It has been established that the title compound effectively protects HT22 from oxidative damage and is a potentially good candidate for further evaluation of the mechanism of its action.

1,3-Diphenylisobenzofuran (DPBF) has been developed as a selective probe for the detection and quantitative determination of hydrogen peroxide in samples containing different reactive nitrogen and oxygen species (RNOS). DPBF is a fluorescent probe which, for almost 20 years, was believed to react in a highly specific manner toward some reactive oxygen species (ROS) such as singlet oxygen and hydroxy, alkyloxy or alkylperoxy radicals. Under the action of these individuals DPBF has been rapidly transformed to 1,2-dibenzoylbenzene (DBB). In order to check if DPBF can act as a unique indicator of the total amount of different RNOS, as well as oxidative stress caused by an overproduction of these individuals, a series of experiments was carried out, in which DPBF reacted with peroxynitrite anion, superoxide anion, hydrogen peroxide, hypochlorite anion, and anions commonly present under biological conditions, namely nitrite and nitrate. In all cases, except for hydrogen peroxide, the product of the reaction is DBB. Only under the action of H

The influence of the oxydiacetate (ODA) and thiodiacetate (TDA) ligands on the physicochemical and biological properties of the oxidovanadium(IV) ternary complexes of the VO(L)(B) type, where L denotes ODA or TDA and B denotes 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen), has been investigated. The stability of the complexes in aqueous solutions, assessed based on the potentiometric titration method, increases in the following direction: VO(TDA)(bipy)

This publication presents a new chromium(III) complex with 5-aminopyridine-2-carboxylate anions. The title compound was characterized by single-crystal X-ray diffraction analysis, potentiometric and conductometric titrations. The oligomerization reaction of the 2-chloro-2-propen-1-ol alcohol was carried out using the title complex as a catalyst for the reaction. The resulting product was examined by MALDI-TOF MS and infrared spectroscopy. The catalytic activity of the complex in the oligomerization reaction of 2-chloro-2-propen-1-ol was determined.

This publication presents the new trends and opportunities for further development of coordination compounds used in the chemical industry. The review describes the influence of various physicochemical factors regarding the coordination relationship (for example, steric hindrance, electron density, complex geometry, ligand), which condition technological processes. Coordination compounds are catalysts in technological processes used during organic synthesis, for example: Oxidation reactions, hydroformylation process, hydrogenation reaction, hydrocyanation process. In this article, we pointed out the possibilities of using complex compounds in catalysis, and we noticed what further research should be undertaken for this purpose.

A coordination complex, [Co(ida)(H2O)2] where ida denotes iminodiacetate, as a potential highly active catalyst was designed and obtained. To obtain a full structural characteristic, i.e. to determine the crystallographic details and the spatial structure of the crystals of the studied complex, X-ray analysis was carried out. [Co(ida)(H2O)2] was investigated also by elementary analysis, IR spectrophotometry and MALDI-TOF-MS to get a full physicochemical characteristics. The stoichiometry of [Co(ida)(H2O)2] in aqueous solutions was determined using the conductometric titrations. Consequently, the potentiometric titrations were performed to determine the thermodynamic stability of the title compound in aqueous solutions. Moreover, the antioxidant activity of [Co(ida)(H2O)2] against superoxide anion radical has been examined by NBT test. The catalytic properties of the cobalt(II) complex, [Co(ida)(H2O)2], were examined. It turned out that complex studied is a highly active catalyst for the 2-chloro-2-propen-1-ol oligomerization. It catalyzes the reaction of oligomerization in mild conditions: under normal pressure and at room temperature. The oligomerization reaction products were fully characterized by the following spectroscopic methods: IR, NMR, MALDI-TOF-MS. Furthermore, to investigate the thermal behavior of the obtained oligomer, the product of the oligomerization obtained using [Co(ida)(H2O)2] as the catalyst was studied with the use of thermal analysis methods, i.e. DSC and TG. The catalytic activity of the title complex has also been calculated.

The new 2-pyridinecarboxylate (2-pic) complex of chromium(III) has been designed and synthesized as a new highly active and selective oligomerization catalyst. The crystal structure of the new compound has been determined by X-ray diffraction. The composition and purity of [Cr(2-pic)2(OH2)2]NO3 have been confirmed by several spectroscopic methods and the elemental analysis. Furthermore, the new complex has been investigated towards its catalytic activity for the oligomerization of 2-chloro-2-propen-1-ol under the atmospheric pressure and at room temperature. It has turned out that the novel catalyst exhibits a very high catalytic activity. Consequently, [Cr(2-pic)2(OH2)2]NO3 belongs to a new generation of non-metallocene catalysts.

Pancreatic ductal adenocarcinoma is one of the most aggressive human malignancies, where the 5-year survival rate is less than 4% worldwide. Successful treatment of pancreatic cancer is a challenge for today’s oncology. Several studies showed that increased levels of oxidative stress may cause cancer cells damage and death. Therefore, we hypothesized that oxidative as well as nitro-oxidative stress is one of the mechanisms inducing pancreatic cancer programmed cell death. We decided to use silver nanoparticles (AgNPs) (2.6 and 18 nm) as a key factor triggering the reactive oxygen species (ROS) and reactive nitrogen species (RNS) in pancreatic ductal adenocarcinoma cells (PANC-1). Previously, we have found that AgNPs induced PANC-1 cells death. Furthermore, it is known that AgNPs may induce an accumulation of ROS and alteration of antioxidant systems in different type of tumors, and they are indicated as promising agents for cancer therapy. Then, the aim of our study was to evaluate the implication of oxidative and nitro-oxidative stress in this cytotoxic effect of AgNPs against PANC-1 cells. We determined AgNP-induced increase of ROS level in PANC-1 cells and pancreatic noncancer cell (hTERT-HPNE) for comparison purposes. We found that the increase was lower in noncancer cells. Reduction of mitochondrial membrane potential and changes in the cell cycle were also observed. Additionally, we determined the increase in RNS level: nitric oxide (NO) and nitric dioxide (NO2) in PANC-1 cells, together with increase in family of nitric oxide synthases (iNOS, eNOS, and nNOS) at protein and mRNA level. Disturbance of antioxidant enzymes: superoxide dismutase (SOD1, SOD2, and SOD3), glutathione peroxidase (GPX-4) and catalase (CAT) were proved at protein and mRNA level. Moreover, we showed cells ultrastructural changes, characteristic for oxidative damage. Summarizing, oxidative and nitro-oxidative stress and mitochondrial disruption are implicated in AgNPs-mediated death in human pancreatic ductal adenocarcinoma cells.

The new type of catalysts designed for the olefin derivatives polymerization has been synthetized. The novel catalysts are chromium(III) salt type complexes composed of both organic cation and anion, i.e. [Cr(dipic)2][Cr(bipy)(dipic)H2O]∙2H2O and [Cr(dipic)2]Hdmbipy∙2.5 H2O. The compositions of these complexes have been confirmed by a number of instrumental methods including NMR, IR, UV-Vis, MS and elemental analysis ones. Moreover, the crystal structures of these novel catalysts were determined and reported. Furthermore, the [Cr(dipic)2][Cr(bipy)(dipic)H2O]∙2H2O and [Cr(dipic)2]Hdmbipy∙2.5H2O complexes have been studied towards their catalytic activity, after the activation by MMAO (modified methylaluminoxane), in the case of 2-chloro-2-propen-1-ol polymerization at 21 °C and atmospheric pressure. It has been found that novel catalysts, [Cr(dipic)2][Cr(bipy)(dipic)H2O]∙2H2O and [Cr(dipic)2]Hdmbipy∙2.5 H2O, exhibit a very high catalytic activity in the process of the polymerization of the beta-olefin derivatives. The products of a such catalyzed polymerization are the poly(allyl alcohol) derivatives.

The antioxidant properties of oxydiacetate complexes of cobalt(II) and nickel(II) with 1,10-phenantroline and 2,2′-bipyridine have been investigated towards the superoxide radical using the nitro blue tetrazolium chloride (NBT) test and the cyclic voltammetry (CV). Moreover, the biological activity of the complexes under study has been investigated in the Human Dermal Fibroblasts adult (HDFa) cell line. In the first step, the cytotoxic and the antiproliferative activities of the complexes were examined. Subsequently, the cytoprotective properties of the complexes have been investigated in an oxidative stress conditions induced by H2O2.

The crystal structure of 2,2′-bipyridyl(iminodiacetato)oxidovanadium(IV) dihydrate of [VO(IDA)bipy]·2H2O molecular formula was redetermined. The vanadium atom has an octahedral coordination. The IDA ligand adopts the facial conformation in VO(IDA)bipy. The stability of title compound in aqueous solutions was investigated by using the potentiometric titration method. Furthermore, the kinetics of substitution reactions of the [VO(IDA)H2O]H2O binary complex with 2,2′-bipyridine was investigated in aqueous solutions. These reactions were monitored spectrophotometrically using the stopped-flow method at 260 nm. The kinetic measurements were performed in the 293–308 K temperature range, at different concentrations in the 0.1–0.5 mM range of the binary complex and at the constant concentration of bipy (0.05 mmol/L). The antioxidant properties of [VO(IDA)bipy]·2H2O and [VO(IDA)H2O]H2O complexes have been studied. The antioxidant activity of these complexes against the superoxide radical as well as stable organic radicals, namely 1,1-diphenyl-2-picrylhydrazyl radical (DPPH ) and 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) radical was investigated. The evaluation of [VO(IDA)bipy]·2H2O as a potential antioxidant agent shows that the titled complex exhibit the antioxidant activity against the superoxide anion and organic radicals.

The kinetics of substitution reactions of the CuODA and CuTDA binary complexes (ODA = oxydiacetate, TDA = thiodiacetate) with 1,10-phenanthroline (phen) and 2,2’-bipyridine (bipy) were studied in aqueous and DMSO solutions. These reactions were monitored spectrometrically using the stopped-flow method in the UV range. The studies were carried out at three temperatures - 298.15, 303.15 and 308.15 K. The concentrations of the binary complexes were kept within the range of 0.2–0.5 mmol L−1, whereas the concentration of phen or bipy was constant = 0.05 mmol L−1. The values of the reaction rate constants were calculated based on the A → B reaction model. A linear relationship of the rate of the substitution reaction versus the concentration of the binary complex as well as temperature was observed. The impact of the type of the primary (ODA and TDA) and auxiliary ligands (phen and bipy) as well as the effect of solvent on the rate of substitution reaction have been discussed.

A new oxidovanadium(IV) complex was prepared by the reaction of vanadyl acetylacetonate [VO(acac)2], iminodiacetic acid (H2IDA) and 1,10-phenanthroline (phen) in aqueous solutions. The crystal structure of [VO(IDA)phen]·2H2O was determined by X-ray diffraction crystallographic analysis. The stability of the title compound in aqueous solution was investigated by using potentiometric titration methods. Moreover, the kinetics of substitution reactions of the VO(IDA) binary complex with 1,10-phenanthroline were investigated in aqueous solutions. These reactions were monitored spectrophotometrically at 249 nm by using stopped-flow methods. Kinetic measurements were performed in the 293–308 K temperature range, at different concentrations (0.1–0.5 mM) of the binary complex and at a constant concentration of phen (0.05 mmol/L). Moreover, the antioxidant properties of this complex against superoxide radicals were studied by nitrobluetetrazolium (NBT) and cyclic voltammetry (CV) and the antioxidant properties were also investigated against two organic radicals: the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH·) and the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical (ABTS·+) by using spectrophotometric methods. The results of the antioxidant tests show that VO(IDA)phen scavenges superoxide free radicals as well as organic radicals (ABTS·+ and DPPH·).

Detection and quantitative determination in biological media of the hydroxyl radical are of great importance due to the role this radical plays in many physiological and pathological processes. This review focuses on the progress that has been made in recent years in the development of fluorescent and luminescent probes employed to monitor hydroxyl radical concentrations under biological conditions.

Due to the biological significance of 4-hydroxy-TEMPO, its detection in biological systems such as blood serum is of great importance in both research and clinical applications. The following paper reports a novel fluorimetric method for the detection and quantitative determination of 4-hydroxy-TEMPO radicals in an aqueous solution using dihydroxycoumarins as fluorescent probes. Among the 17 coumarin derivatives studied, only some dihydroxycoumarins show high sensitivity, specificity and selectivity for 4-hydroxy-TEMPO. Among them, 6,7-dihydroxycoumarin (esculetin) exhibits the strongest fluorescence enhancement under the action of 4-hydroxy-TEMPO. In this assay, esculetin reacts with 4-hydroxy-TEMPO to exclusively yield a dimer. 6,7-Dihydroxycoumarin responds to 4-hydroxy-TEMPO quickly and shows a 2.5-fold fluorescence enhancement with an estimated detection limit of 285 μM.

We have proposed a new method which can be applied in assessing the intracellular production of hydrogen peroxide. Using this assay we have examined the hydrogen peroxide generation during the L-glutamate induced oxidative stress in the HT22 hippocampal cells. The detection of hydrogen peroxide is based on two crucial reagents cis-[Cr(C2O4)(pm)(OH2)2]+ (pm denotes pyridoxamine) and 2-ketobutyrate. The results obtained indicate that the presented method can be a promising tool to detect hydrogen peroxide in biological samples, particularly in cellular experimental models.

The isothermal titration calorimetry (ITC) technique supported by potentiometric titration data was used to study the interaction of zinc ions with pH buffer substances, namely 2-(N-morpholino)ethanesulfonic acid (Mes), piperazine-N,N'-bis(2-ethanesulfonic acid) (Pipes), and dimethylarsenic acid (Caco). The displacement ITC titration method with nitrilotriacetic acid as a strong, competitive ligand was applied to determine conditional-independent thermodynamic parameters for the binding of Zn(II) to Mes, Pipes, and Caco. Furthermore, the relationship between the proposed coordination mode of the buffers and the binding enthalpy has been discussed.

The purpose of this study was to examine the application of the coordinated cis-[Cr(C2O4)(pm)(OH)2]+ cation where pm denotes pyridoxamine, as a specific sensing ion for the detection of hydrogen peroxide (H2O2). The proposed method for H2O2 detection includes two key steps. The first step is based on the nonenzymatic decarboxylation of pyruvate upon reaction with H2O2, while the second step is based on the interaction of cis-[Cr(C2O4)(pm)(OH2)2]+ with the CO2 released in the previous step. Using this method H2O2 generated during glutamate-induced oxidative stress was detected in HT22 hippocampal cells. The coordination ion cis-[Cr(C2O4)(pm)(OH2)2]+ and the spectrophotometric stopped-flow technique were applied to determine the CO2 concentration in cell lysates, supernatants and cell-free culture medium. Prior to CO2 assessment pyruvate was added to all samples studied. Pyruvate reacts with H2O2 with 1:1 stoichiometry, and consequently the amount of CO2 released in this reaction is equivalent to the amount of H2O2.

Potentiometric (PT) and conductometric (CT) titration methods have been used to determine the stoichiometry and formation constants in water for a series of ternary complexes of Co(II) and Ni(II) involving the oxydiacetate anion (ODA) and 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) ligands, namely [Co(ODA)(phen)(H2O)], [Co(ODA)(bpy)(H2O)], [Ni(ODA)(phen)(H2O)] and [Ni(ODA)(bpy)(H2O)]. The ternary complex formation process was found to take place in a stepwise manner in which the oxydiacetate ligand acts as a primary ligand and the phen or bipy ligands act as auxiliary ones. The stability of the ternary complexes formed is discussed in the relation to the corresponding binary ones. Furthermore, the kinetics of the substitution reactions of the aqua ligands in the coordination sphere of the Ni-ODA and Co-ODA complexes to phen or bipy were studied by the stopped-flow method. The kinetic measurements were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (4–7 mM). The influence of experimental conditions and the kind of the auxiliary ligands (phen/bipy) on the substitution rate was discussed.

The impact of oxydiacetate oxidovanadium(IV) complexes on plants is currently unknown. This report demonstrates the influence of these complexes on Arabidopsis thaliana (L.) Heynh. In the presence of 10−6M vanadium(IV) complexes, plants proceeded through their entire life cycle, with the occurrence of proper morphological and cytological organisation of leaf and root tissues. The addition of 10−1M H2O2 caused root damage, leaf necrosis, and plant death at around the seventh day, due to the destruction of the root system. Pretreatment of the plants with 10−6M of vanadium(IV) compounds: VOSO4 and VO(oda), alleviated the effects of H2O2 to some extent. Plants pretreated with 10−6M vanadium(IV) complexes survived longer despite the presence of H2O2. Considering the higher rate of plant survival in the presence of VOSO4, and the relatively high photosynthetic parameters and anthocyanin contents in the cells, we conclude that this vanadium(IV) compound can have positive effects on plants that are grown under stress conditions.

The reactivity of superoxide free radicals (O2·–) generated electrochemically towards the oxydiacetate metal complexes, namely [VO(oda)(H2O)2], [Co(oda)(H2O)2]·H2O, and [Ni(oda)(H2O)3]·1.5H2O (oda = oxydiacetate) was examined by cyclic voltammetry. The measurements were carried out in DMSO solution using a platinum electrode. Based on the height of the anodic peak Ea that corresponds to electrochemical oxidation O2·– O2 + e, in the absence and in the presence of the compounds in the mixture, their O2·– scavenge ability was assessed. The influence of the type of the complex was briefly discussed. H2O2 was used to induce cellular injury in a mouse hippocampal cell line (HT22). The cytoprotection of chemical compounds was tested at the mitochondrial (MTT test) and plasma membrane level (LDH leakage). Dose-dependent effect (10 and 100 μM of the complex) of investigated compounds was observed.

The quenching of fluorescence of four polycyclic aromatic hydrocarbons (anthracene, benzo(a)anthracene, pyrene, and fluoranthene) by 4-OH-TEMPO was investigated in 5% Triton X-100 in the temperature range from 15 to 55°C. No deviations from linearity in the Stern-Volmer plots were observed. The quenching mechanism was found to be entirely dynamic. The quenching rate constants were obtained for all temperatures studied. The findings demonstrate the possibility of developing an analytical method for the quantitative determination of nitrogen dioxide radical scavenger, 4-OH-TEMPO.

1,3-Diphenylisobenzofuran (DPBF) is a fluorescent molecule which is believed to react highly specifically toward reactive oxygen species such as singlet oxygen (1O2), hydroxy (HO·), alkyloxy (RO·), and alkylperoxy (ROO·) radicals. In all cases the reaction product is 1,2-dibenzoylbenzene. In order to prove that DPBF gives the same product in contact with reactive nitrogen species, its reaction with nitrogen dioxide radical has been studied in 2,2,4-trimethylpentane using the steady-state fluorescence method and mass spectrometry. The progress of the studied reaction was measured by observation of changes in fluorescence intensity of DPBF after addition of nitrogen dioxide (NO2). The rate constants of DPBF fluorescence decay affected by NO2 have been determined. Experiments were conducted over the temperature range of 13–37 °C and for NO2 concentrations from 0.02 to 0.14 mmol dm−3. It has been found that the reaction between 1,3-diphenylisobenzofuran and nitrogen dioxide proceeds in two steps. The first step is a very rapid reaction whose rate could not be measured under established experimental conditions. The second step is slower. The reaction product was identified by registration of mass spectra. The probable reaction mechanism is proposed.

The crystal structure of 2-methylpyridinium tetrachloroferrate(III) was determined. The iron cation is tetracoordinated by chloride anions, and it adopts a slightly distorted tetrahedral coordination with three angles smaller, two almost equal and one larger than the tetrahedral. The compound is isostructural with its 3-, and 4-methylpyridinium analogues. The thermal properties of 2-, 3- and 4-methylpyridinium tetrachloroferrates(III) have been studied using TG and DSC techniques. The compounds exhibit a high stability in the melt.

The kinetics of CO(2) uptake by the cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+ complex cation and the acid hydrolysis of the cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]- complex anion (where BaraNH(2) denotes methyl 3-amino-2,3-dideoxy-b-D-arabino-hexopyranoside) were studied using the stopped-flow technique. The reactions under study were investigated in aqueous solution in the 288-308 K temperature range. In the case of the reaction between CO(2) and cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+ cation variable pH values (6.82-8.91) and the constant ionic strength of solution (H+, Na+, ClO(4)- = 1.0) were used. Carbon dioxide was generated by the reaction between sodium pyruvate and hydrogen peroxide. The acid hydrolysis of cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]- was investigated for varying concentrations of H+ ions (0.01-2.7 M). The obtained results enabled the determination of the number of steps of the studied reactions. Based on the kinetic equations, rate constants were determined for each step. Finally, mechanisms for both reactions were proposed and discussed. Based on the obtained results it was concluded that the carboxylation (CO(2) uptake) reactions of cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+ and the decarboxylation (acid hydrolysis) of the cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]- are the opposite of each other.

Kinetics of oxalate substitution by water in [Cr(C2O4)2(L–L)]− and [Cr(C2O4)(L–L)(H2O)2]+ (where L–L denote AaraNH2 and BaraNH2, i.e., methyl 3-amino-2,3-dideoxy-α-D-arabino-hexopyranoside and methyl 3-amino-2,3-dideoxy-β-D-arabino-hexopyranoside) induced by Fe3+ ions was studied. The reactions were investigated in aqueous solution from 288 to 308 K with initial concentrations of the substrates at 2 × 10−2 mol L−1, variable concentrations of Fe3+ in the range 0.02–0.08 mol L−1, and constant ionic strength (H+; Na+; = 1.0;) [H3O+] = 0.15 mol L−1. Investigations were carried out using the spectrophotometrical method from 350 to 700 nm. The results allowed determination of the number of steps of the reactions. Based on the kinetic equations (−d[Cr(C2O4)2(L–L)]−/dt = {a + b[Fe(H2O)6]3+}[Cr(C2O4)2(L–L)−]; −d[Cr(C2O4)(H2O)2(L–L)]+/dt = {c + d[Fe(H2O)6]3+}[Cr(C2O4)(H2O)2(L–L)]+, rate constants were determined for each step; activation parameters were also determined. The mechanism of substitution of oxalate ind...

Isothermal titration calorimetry (ITC) and potentiometric titration methods have been used to study the process of proton transfer in the copper(II) ion-gly- cylglycine reaction. The stoichiometry, conditional stabil- ity constants, and thermodynamic parameters (DG, DH, and DS) for the complexation reaction were determined using the ITC method. The measurements were carried out at 298.15 K in solutions with a pH of 6 and the ionic strength maintained with 100 mM NaClO4. Carrying out the measurements in buffer solutions of equal pH but dif- ferent enthalpies of ionization of its components (Mes, Pipes, Cacodylate) enabled determination of the enthalpy of complex formation, independent of the enthalpy of buffer ionization. The number of protons released by gly- cylglycine on account of complexation of the copper(II) ions was determined from calorimetric and potentiometric measurements.

In this paper instrumental methods of carbon dioxide (CO2) detection in biological material were compared. Using cis-[Cr(C2O4)(pm)(OH2)2]+ cation as a specific molecular biosensor and the stopped-flow technique the concentrations of CO2 released from the cell culture medium as one of final products of pyruvate decomposition caused by hydrogen peroxide were determined. To prove the usefulness of our method of CO2 assessment in the case of biological samples we investigated protective properties of exogenous pyruvate in cultured osteosarcoma 143B cells exposed to 1 mM hydrogen peroxide (H2O2) added directly to culture medium. Pyruvic acid is well known scavenger of H2O2 and, moreover, a molecule which is recognized as one of the major mediator of oxidative stress detected in many diseases and pathological situations like ischemia-reperfusion states. The pyruvate's antioxidant activity is described as its rapid reaction with H2O2, which causes nonenzymatic decarboxylation of pyruvate and releases of CO2, water and acetate as final products. In this work for the first time we have correlated the concentration of CO2 dissolved in culture medium with pyruvate's oxidant-scavenging abilities. Moreover, the kinetics of the reaction between aqueous solution of CO2 and coordinate ion, cis-[Cr(C2O4)(pm)(OH2)2]+ was analysed. The results obtained enabled determination of the number of steps of the reaction studied. Based on the kinetic equations, rate constants were determined for each step.

Kinetics of the reaction of [tetraamminediaquacobalt(III)] perchlorate ion with carbon dioxide in aqueous solution was studied at various temperatures (5–25 °C), variable concentration of CO2 (0.005M; 0.01M; 0.015M) and over the pH range 6.04–8.15 at a fixed ionic strength of solution (1 M NaClO4). Investigations were carried out using stopped-flow spectrophotometry in the range of 300 – 700 nm. The results enabled determination of the number of steps of the reaction studied. Based on the kinetic equations, rate constants were determined for each step. Finally, the mechanism of carbon dioxide uptake by [tetraamminediaquacobalt(III)] perchlorate ion was proposed and discussed.

Hydrogen peroxide is a well-established precursor of reactive oxygen and nitrogen species that are known to contribute to oxidative stress—the crucial factor responsible for the course of a wide range of phy-sicochemical processes as well as the genesis of various diseases, such as cancer and neurodegenerative disorders. Thus, the development of sensitive and selective methods for the detection and quantitative determination of hydrogen peroxide is of great importance in monitoring the in vivo production of that species and elucidating its biological functions. This review highlights the progress that has been made in the development of fluorescent and luminescent probes (excluding nanoparticles) employed to monitor hydrogen peroxide under biological conditions. Attention was focused on probes developed in the past 10 years.

A stopped-flow method was used to investigate the kinetics of the acid hydrolysis of a newly synthesised coordination ion of the cis-[Cr(C2O4)(AaraNH2)(O2CO)]− type, where AaraNH2 stands for methyl 3-amino-2,3-dideoxy-α -d-arabino-hexapyranoside, over a range of hydrogen ion concentrations 0.01 < [H+] < 2.7 M and temperatures 5 < T < 25°C. Initiated by perchloric acid (HClO4), the hydrolysis (decarboxylation) of the chromium(III) ion complexed with a bicoordinately linked carbonate ligand turned out to be a two-step process. The kinetic parameters k 1, k 2 were determined of both steps of the hydrolysis of the cis-[Cr(C2O4)(AaraNH2)(O2CO)]− ion, as was the equilibrium constant K of the protonation of this ion, which precedes the actual two-step hydrolysis. From an analysis of the values of the constants obtained, a mechanism is proposed for the acid hydrolysis of the cis-[Cr(C2O4)(AaraNH2)(O2CO)]− coordination ion.

The cis-[Cr(phen)2(O2CO)]+ ion was prepared through the displacement of two molecules of water from the cis-[Cr(phen)2(OH2)2]3+ by the bidentate carbonate anion. It underwent two-phase hydrolysis reactions under acidic conditions (0.1 < [H+] < 2.7 m) at 5, 10, 15, 20 and 25 °C. Via slow carbonato chelate ring opening (first step k1slow) and a second fast decarboxylation(k2fast value). The first step was preceded by protonation of the coordinate bidentate carbonate ligand. The second step exhibited no pH dependence, while k1slow values increased with acid concentration that suggested the presence of both protonated and deprotonated reactant species. Based on these observations we have proposed a hydrolysis mechanism featuring H2O-induced ring-opening of the coordinate CO32− group in the first step k1slow followed by loss of CO32− from two intermediates, [Cr(phen)2(O2COH)]2+ (k1slow) and [Cr(phen)2(OH2)(O2COH)]2+ (k2fast).

This study demonstrated the direct formation of the nitrogen dioxide ( NO 2 ) radical during the decomposition of 3-morpholinosydnonimine (SIN-1) in biological buffer 4-morpholinoethanosulfone acid solution. Consequently, at approximately pH 4, SIN-1 can be used successfully as a source of NO 2 . This conclusion is drawn from a comparison of the reactions of cis -[Cr(C 2 O 4 )(L– L)(OH 2 ) 2 ] + , where L–L denotes pyridoxamine (Hpm) or histamine (hm), with the gaseous NO 2 radical obtained by two methods: from SIN-1 and from a simple redox reaction. These reactions were investigated using the stopped-flow technique. The measurements were carried out at temperatures ranging from 5 to 25 °C over a pH range from 6.52 to 9.11 for cis -[Cr(C 2 O 4 )(Hpm) (OH 2 ) 2 ] + and from 6.03 to 8.15 for cis -[Cr(C 2 O 4 )(hm)(OH 2 ) 2 ] + . We also determined the thermodynamic activation parameter ( E a ) and the uptake mechanism for each of the coordination compounds studied.

The kinetics of the reaction between gaseous CO2 and the cis-[Cr(phen)2(OH2)2]3+ ion leading to the formation of the carbonato complex ion, have been studied over the pH and temperature ranges: 3 < pH < 6 and 5 < T < 25 °C, respectively, at a constant ionic strength of 1 m (NaClO4). Investigations were carried out using the stopped-flow spectrophotometry technique in the UV–Vis range: 340–700 nm. The major reactant species in the pH range studied was cis-[Cr(phen)2(OH)(OH2)]2+ ion, which underwent reaction with CO2 to form cis-[Cr(phen)2(OH2)(HCO3)]2+ ion. Subsequently, slower ring closure of the latter species to form the bidentate carbonato chelate was observed. The possible mechanism has been discussed and the activation parameters ΔH† and ΔS† were also determined for the reaction studied.

The crystal structure of new 1,10-phenathrolin-1-ium aqua-(nitrilotriacetato-N,O,O',O")-oxidovanadium(IV) semihydrate of molecular formula (phenH)[VO(NTA)(H2O)]∙1/2H2O was determined. This is the first example of structurally characterized compound that comprises a distinctly separated, monomeric [VO(NTA)(H2O)](-) coordination entity. The crystallographic measurements have subsequently been complemented by the IR spectroscopic characterization and thermal analysis. Furthermore, the electrochemical (cyclic voltammetry) as well as spectrophotometric (UV-vis) studies revealed that the compound is capable of scavenging the superoxide free radicals (O2(-)) as well as stable organic radicals i.e. 2,2'-azinobis(3-ethylbenzothiazoline-6 sulfonic acid) cation radical (ABTS(+)) and 2,2-diphenyl-1-picrylhydrazyl radical (DPPH), but its reactivity towards radicals is lower than that of VOSO4. Finally, biological properties of the complex in the range of 1-100 μM were investigated in relation to its cytoprotective activity against the oxidative damage generated exogenously by using hydrogen peroxide in the hippocampal neuronal HT22 cell line (the MTT and LDH tests). It has been established that in contrast to VOSO4 the title compound protects the HT22 from the oxidative damage. The paper presents a new perspective for oxidovanadium(IV) complexes as candidates for novel, low-molecular mass cytoprotective agents.

The mechanism and kinetics of the reaction between an aqueous solution of CO2 and coordinate ions, cis-[Cr(C2O4)(L–L)(OH2)2]+, where L–L denotes histamine (hm) or pyridoxamine (pm), were investigated using the stopped-flow technique. The studies were carried out at 5 to 25 °C over the pH range 6.04–8.15 at a fixed ionic strength solution (1 M NaClO4). The results enabled determination of the number of steps of the reactions studied. Based on the kinetic equations, rate constants were determined for each step. Finally, thermodynamic activation parameter values ΔH‡, were calculated for the reaction studied from temperature relationships.

By employing quantum-mechanical calculations using the semiempirical (AM1) and ab initio methods (RHF, MP2 and PCM), the energetic parameters of protonation and deprotonation for four isomers of methyl 3-azido-2,3-dideoxyhexopyranosides with the α/β- d - arabino ( 1 , 2 ) and β/α- d - ribo ( 3 , 4 ) configurations have been determined. The calculations of the energy and Gibbs free energy of protonation and deprotonation were acomplished by using a Gaussian 6-31G* basis set. Results of calculation carried out for above four isomers under consideration of six plausible protonation centres enabled to conclude that in all of isomers the preferred protonation centre is the nitrogen atom of the azide group situated at the immediate vicinity of the pyranoside ring. Deprotonation reaction of compounds 1 - 3 occur more readily with primary hydroxyl group, whereas a reverse sequence of deprotonation was found for the α- d - ribo compound 4 . Both the protonation and deprotonation reactions are highly dependent on configuration of the anomeric carbon atom, solvent nucleophilicity and steric effects due to mutual relations in space of substituents in the pyranoside ring.