Oxidation of branched chain amino acids by HOCl: Kinetics and mechanism.

The kinetics of the chlorination of leucine, isoleucine, and valine (BCAAs) was studied in excess HOCl by stopped-flow and spectrophotometric methods (25 ◦C, I = 1.0 M NaClO4). The intermediates and products were identified and monitored by 1H NMR spectroscopy. It was established that these reactions are fully analogous and proceed according to distinct mechanisms under alkaline and neutral conditions. At high pH, the formation and subsequent rate determining decomposition of N-monochloroamino acid control the process. The decomposition occurs via competing pH-independent and OH--assisted reaction paths and the sequence of chlorination, dichlorination and decarboxylation steps leads to the formation of N-chloroimines and their carbanionic forms, which are in fast acid - base equilibria. The dechlorination of the carbanions yields nitriles as the main products. The hydration of the N-chloro imines produces chloramine and aldehydes which are involved in further oxidation reactions with HOCl. The formation of chloroform and chloroacetaldehyde was confirmed in each system. At pH 7.0, the N-chloro derivatives of BCAAs form immediately and are converted into the corresponding N,N-dichloro species within a few seconds after mixing the reactants. In this reaction, the reactive form of the oxidant is Cl2O. The first-order decomposition of the dichloroamino acids occurs on stopped-flow timescale (k = 0.5 - 0.7 s-1) and yields N-chloroimines which slowly decompose with a characteristic first-order rate constant on the order of a few times 10-5 s-1. The main products are the corresponding nitriles that account for about 80% and 60% of the original amounts of amino acids under neutral and alkaline (cOH- = 5.00 × 10-2 M) conditions, respectively. Aldehydes, carboxylic acids, chloroform and NCl3 were also identified as by-products. The results unequivocally confirm that harmful chlorinated species may form from amino acids long after the chlorination step in water treatment technologies that deteriorates the quality of the finished water. ENVIRONMENTAL IMPLICATION: In source waters, amino acids account for about 75% of the total dissolved nitrogen. Therefore, it is an essential issue how the reactions of these compounds with hypochlorite ion can be controlled to avoid the formation of toxic compounds. The compounds formed from BCAAs are considered to be harmful both under alkaline and neutral conditions (chloroacetaldehyde, chloroform, nitriles). However, some of the intermediates have extended lifetime in these systems and they may also react with other components of raw water during water treatment processes.

The role of the terminal cysteine moiety in a metallopeptide mimicking the active site of the NiSOD enzyme.

Superoxide dismutase (SOD) enzymes are pivotal in regulating oxidative stress. In order to model Ni containing SOD enzymes, the results of the thermodynamic, spectroscopic and SOD activity studies on the complexes formed between nickel(II) and a NiSOD related peptide, CysCysAspLeuProCysGlyValTyr-NH2 (wtCC), are reported. Cysteine was introduced to replace the first histidine residue in the amino acid sequence of the active site of the NiSOD enzyme. The novel peptide exhibits 3 times higher metal binding affinity compared to the native NiSOD fragment. This is due to the presence of the first cysteine in the coordination sphere of nickel(II). At physiological pH, the (NH2,S-,S-,S-) coordinated complex is the major species. This coordination mode is altered when one thiolate group is replaced by an amide nitrogen of the peptide backbone above pH 7.5. The nickel complexes of wtCC exhibit similar SOD activity to that of the complex formed with the active site fragment of the native NiSOD. The reaction between the complexes and the superoxide anion was studied by the sequential stopped-flow method. These studies revealed that the nickel(II) complex is always in excess over the nickel(III) complex during the dismutation process. However, the nickel(III) species is also involved in a relatively fast degradation process. This unambiguously proves that a protective mechanism must be operative in the NiSOD enzyme which prevents the oxidation of the sulfur atom of cysteine in the presence of O2-. The results provide new possibilities for the use of NiSOD mimics in bio- and industrial catalytic processes.

Kinetic Role of Reactive Intermediates in Controlling the Formation of Chlorine Dioxide in the Hypochlorous Acid-Chlorite Ion Reaction.

An advanced experimental protocol is reported for studying the kinetics and mechanism of the complex redox reaction between chlorite ion and hypochlorous acid under acidic condition. The formation of ClO2 is followed directly by the classical two-component stopped-flow method. In sequential stopped-flow experiments, the target reaction is chemically quenched using NaI solution and the concentration of each reactant and product is monitored as a function of time by utilizing the principles of kinetic discrimination. Thus, in contrast to earlier studies, not only the formation of one of the products but the decay of the reactants was also directly followed. This approach provides a firm basis for postulating a detailed mechanism for the interpretation of the experimental results under a variety of conditions. The intimate details of the reaction are explored by simultaneously fitting 78 kinetic traces, i.e., the concentration vs. time profiles of ClO2-, HOCl, and ClO2, to an 11-step kinetic model. The most important reaction steps were identified, and it was shown that two reactive intermediates have a pivotal role in the mechanism. While chlorate ion predominantly forms via the reaction of Cl2O, chlorine dioxide is exclusively produced in reaction steps involving Cl2O2. This study leads to clear conclusions on how to control the stoichiometry of the reaction and achieve optimum conditions to produce chlorine dioxide and to reduce the formation of the toxic chlorate ion in practical applications.

The chlorination of glycine and α-alanine at excess HOCl: Kinetics and mechanism.

The chlorination of the two simplest amino acids at HOCl excess was studied by stopped-flow, conventional spectrophotometric and time resolved 1H NMR kinetic methods at 25 °C. These reactions show distinct characteristics under neutral and alkaline conditions. At high pH, the common feature of the two systems is that the N-dichloroamino carboxylate ion does not form and the overall process is controlled by the initial decomposition of the N-monochloro derivative. Under such conditions, carbanions form in equilibrium acid - base processes and open alternative reaction paths, resulting in enhanced complexity of the corresponding mechanisms. In the case of α-alanine, the formation of acetonitrile and N-chloro acetamide as main products; acetate ion, acetaldehyde, chloroacetaldehyde, chloroform as byproducts; acetamide and N-chloro ethanimine as intermediates was confirmed. In the case of glycine, the final products are formamide and OCN-. Under neutral conditions, monochloroamino acid forms immediately upon mixing the reactants, and subsequently it is converted into dichloroamino acid by Cl2O in a fast process. In considerably slower further reaction steps, acetonitrile and acetate ion form as final products in the α-alanine system, while the chlorination of glycine proceeds to full mineralization. The detailed mechanisms suggested for these reactions postulate the formation of various imines and N-chloro imines which are involved in decarboxylation, dechlorination, hydration and hydrolytic reaction steps.

Controlling the formation of halogenated byproducts in the chlorination of source waters by oxidative pre-treatment with the Fe(II)/Fe(III)-S(IV)-air system.

Breakpoint chlorination is a generally accepted method for removing ammonium ion from source waters in drinking water treatment technologies. This process is often accompanied by the formation of halogenated organic byproducts. The presence of these compounds in potable water is of primary concern. In this paper, we demonstrate that the concentration of the precursors of the halogenated species can sufficiently be decreased by oxidizing the organic pollutants with the Fe(II)/Fe(III) - S(IV) - air system. Pre-oxidative treatment of the source waters results in a substantial reduction of chemical oxygen demand, while the ammonium ion concentration remains unaffected. The breakpoint chlorination produces substantially less trihalomethanes (THMs) and adsorbable halogenated organic compounds (AOXs) in oxidatively pre-treated source waters than in raw waters. These results offer a possibility to improve drinking water treatment technologies for better controlling the formation of antagonistic byproducts. It is demonstrated that reaching the regulated concentration levels of THMs is feasible with this method even in source waters containing organic pollutants at relatively high concentration levels. The main advantage of the procedure is that the reagents used for the oxidative pre-treatment are converted into non-toxic products (Fe(III) and SO42-) by the end of the process.

Bioreactor as the root cause of the "manganese effect" during Aspergillus niger citric acid fermentations.

High-yield citric acid production by the filamentous Ascomycete fungus Aspergillus niger requires a combination of extreme nutritional conditions, of which maintaining a low manganese (II) ion concentration (<5 µg L-1) is a key feature. Technical-scale production of citric acid predominantly uses stainless-steel tank fermenters, but glass bioreactors used for strain improvement and manufacturing process development also contain stainless steel components, in which manganese is an essential alloying element. We show here that during citric acid fermentations manganese (II) ions were leaching from the bioreactor into the growth media, resulting in altered fungal physiology and morphology, and significant reduction of citric acid yields. The leaching of manganese (II) ions was dependent on the fermentation time, the acidity of the culture broth and the sterilization protocol applied. Manganese (II) ion leaching was partially mitigated by electrochemical polishing of stainless steel components of the bioreactor. High concentrations of manganese (II) ions during early cultivation led to a reduction in citric acid yield. However, the effect of manganese (II) ions on the reduction of citric acid yield diminished towards the second half of the fermentation. Since maintaining low concentrations of manganese (II) ions is costly, the results of this study can potentially be used to modify protocols to reduce the cost of citric acid production.

Environment-Friendly Catalytic Mineralization of Phenol and Chlorophenols with Cu- and Fe- Tetrakis(4-aminophenyl)-porphyrin-Silica Hybrid Aerogels.

Fenton reactions with metal complexes of substituted porphyrins and hydrogen peroxide are useful tools for the mineralization of environmentally dangerous substances. In the homogeneous phase, autooxidation of the prophyrin ring may also occur. Covalent binding of porphyrins to a solid support may increase the lifetime of the catalysts and might change its activity. In this study, highly water-insoluble copper and iron complexes of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin were synthesized and bonded covalently to a very hydrophilic silica aerogel matrix prepared by co-gelation of the propyl triethoxysilyl-functionalized porphyrin complex precursors with tetramethoxysilane, followed by a supercritical carbon dioxide drying. In contrast to the insoluble nature of the porphyrin complexes, the as-prepared aerogel catalysts were highly compatible with the aqueous phase. Their catalytic activities were tested in the mineralization reaction of phenol, 3-chlorophenol, and 2,4-dichlorophenol with hydrogen peroxide. The results show that both aerogels catalyzed the oxidation of phenol and chlorophenols to harmless short-chained carboxylic acids under neutral conditions. In batch experiments, and also in a miniature continuous-flow tubular reactor, the aerogel catalysts gradually reduced their activity, due to the slow oxidation of the porphyrin ring. However, the rate and extent of the degradation was moderate and did not exclude the possibility that the as-prepared catalysts, as well as their more stable derivatives, might find practical applications in environment protection.

Interaction of Aqueous Bovine Serum Albumin with Silica Aerogel Microparticles: Sorption Induced Aggregation.

Mesoporous silica aerogels have a wide range of potential applications in biotechnology, the food industry, pharmacy and medicine. Understanding the nature of the interactions of biomolecules with these porous nanostructured materials is essential for achieving optimum performance in the targeted applications. In this study, the well-characterized bovine serum albumin (BSA) was chosen as a model protein to probe protein-aerogel interactions in the solution phase. Aqueous BSA was mixed with suspended silica aerogel microparticles, and the colloid system was monitored on-line by UV-vis spectrophotometry and turbidimetry. The global mathematical analysis of the time-resolved data reveals that the fast sorption of the protein on the aerogel microparticles follows a multistep binding mechanism. The extensive sorption of the protein eventually induces the aggregation of the covered aerogel due to the alteration of the electrical double layer of the particles. The interaction of BSA and silica aerogel is the strongest between pH = 4 and 5, because their native surface charges are the opposite in this pH range, as indicated by their respective zeta potentials.

The Effect of Heat Treatment of ß-Tricalcium Phosphate-Containing Silica-Based Bioactive Aerogels on the Cellular Metabolism and Proliferation of MG63 Cells.

ß-Tricalcium phosphate was combined with silica aerogel in composites prepared using the sol-gel technique and supercritical drying. The materials were used in this study to check their biological activity and bone regeneration potential with MG63 cell experiments. The composites were sintered in 100 °C steps in the range of 500-1000 °C. Their mechanical properties, porosities, and solubility were determined as a function of sintering temperature. Dissolution studies revealed that the released Ca-/P molar ratios appeared to be in the optimal range to support bone tissue induction. Cell viability, ALP activity, and type I collagen gene expression results all suggested that the sintering of the compound at approximately 700-800 °C as a scaffold could be more powerful in vivo to facilitate bone formation within a bone defect, compared to that documented previously by our research team. We did not observe any detrimental effect on cell viability. Both the alkaline phosphatase enzyme activity and the type I collagen gene expression were significantly higher compared with the control and the other aerogels heat-treated at different temperatures. The mesoporous silica-based aerogel composites containing ß-tricalcium phosphate particles treated at temperatures lower than 1000 °C produced a positive effect on the osteoblastic activity of MG63 cells. An in vivo 6 month-long follow-up study of the mechanically strongest 1000 °C sample in rat calvaria experiments provided proof of a complete remodeling of the bone.

Copper(II) Complexes of Pyridine-2,6-dicarboxamide Ligands with High SOD Activity.

Copper(II) complexes of pyridine-based ligands functionalized with alanine (PydiAla) and tyrosine (PydiTyr) moieties have been synthesized as novel superoxide dismutase mimics. The complexes were characterized by pH-potentiometric, spectroscopic (UV-vis, circular dichroism, mass spectrometry, electron paramagnetic resonance spectroscopy), computational (DFT), and X-ray diffraction methods. Both ligands form high stability copper(II) complexes via the (Npy,N-,N-) donor set supported by the binding of the carboxylate pendant arms. Although the coordination mode is the same for the two systems, the tyrosine containing counterpart exhibits increased copper(II) binding affinity, which is most likely due to the presence of the aromatic moiety of the side chains. Both copper(II) complexes are capable of binding N-methylimidazole, and the formation of the corresponding ternary species was observed at physiological pH. The binary and ternary copper(II) complexes exhibit high SOD activity. The PydiTyr complex exhibits about 1 order of magnitude higher activity than the PydiAla complex. This is probably due to the presence of the phenolic OH group in the former species, which promotes the binding of the superoxide anion radical to the metal center. The results serve as a basis for designing highly efficient copper(II) mimics for medical and practical applications.

Sulfur(IV) assisted oxidative removal of organic pollutants from source water.

The removal of organic pollutants presents a major challenge for drinking water treatment plants. The chemical oxygen demand (COD) is essentially the measure of oxidizable organic matter in source waters. In this study, we report that COD can efficiently be decreased by adding Fe(II)/Fe(III) and sulfite ion to the source water while purging it with air. In this process, oxygen is activated to oxidize the main constituents of COD, i.e. organic substrates, via the generation of reactive inorganic oxysulfur radical ions. In the end, the total amount of sulfur(IV) is converted to the non-toxic sulfate ion. It has been explored how the COD removal efficiency depends on the concentration of S(IV), the total concentration of iron species, the concentration ratio of Fe(II) and Fe(III), the purging rate and the contact time by using source water from a specific location (Királyhegyes, Hungary). The process has been optimized by applying the Response Surface Methodology (RSM). Under optimum conditions, the predicted and experimentally found COD removal efficiencies are in excellent agreement: 85.4% and 87.5%, respectively. The robustness of the process was tested by varying the optimum values of the parameters by ± 20%. It was demonstrated that the method is universally applicable because a remarkable decrease was achieved in COD, 62.0-88.5%, with source waters of various compositions acquired from 9 wells at other locations using the same conditions as in the case of Királyhegyes.

Mesoporous Aerogel Microparticles Injected into the Abdominal Cavity of Mice Accumulate in Parathymic Lymph Nodes.

Mesoporous aerogel microparticles are promising drug delivery systems. However, their in vivo biodistribution pathways and health effects are unknown. Suspensions of fluorescein-labeled silica-gelatin hybrid aerogel microparticles were injected into the peritoneum (abdominal cavity) of healthy mice in concentrations of 52 and 104 mg kg-1 in a 3-week-long acute toxicity experiment. No physiological dysfunctions were detected, and all mice were healthy. An autopsy revealed that the aerogel microparticles were not present at the site of injection in the abdominal cavity at the end of the experiment. The histological study of the liver, spleen, kidneys, thymus and lymphatic tissues showed no signs of toxicity. The localization of the aerogel microparticles in the organs was studied by fluorescence microscopy. Aerogel microparticles were not detected in any of the abdominal organs, but they were clearly visible in the cortical part of the parathymic lymph nodes, where they accumulated. The accumulation of aerogel microparticles in parathymic lymph nodes in combination with their absence in the reticuloendothelial system organs, such as the liver or spleen, suggests that the microparticles entered the lymphatic circulation. This biodistribution pathway could be exploited to design passive targeting drug delivery systems for flooding metastatic pathways of abdominal cancers that spread via the lymphatic circulation.

Synthesis and Characterization of 1,10-Phenanthroline-mono-N-oxides.

N-oxides of N-heteroaromatic compounds find widespread applications in various fields of chemistry. Although the strictly planar aromatic structure of 1,10-phenanthroline (phen) is expected to induce unique features of the corresponding N-oxides, so far the potential of these compounds has not been explored. In fact, appropriate procedure has not been reported for synthesizing these derivatives of phen. Now, we provide a straightforward method for the synthesis of a series of mono-N-oxides of 1,10-phenanthrolines. The parent compounds were oxidized by a green oxidant, peroxomonosulfate ion in acidic aqueous solution. The products were obtained in high quality and at good to excellent yields. A systematic study reveals a clear-cut correlation between the basicity of the compounds and the electronic effects of the substituents on the aromatic ring. The UV spectra of these compounds were predicted by DFT calculations at the TD-DFT/TPSSh/def2-TZVP level of theory.

False Morphology of Aerogels Caused by Gold Coating for SEM Imaging.

The imaging of non-conducting materials by scanning electron microscopy (SEM) is most often performed after depositing few nanometers thick conductive layers on the samples. It is shown in this work, that even a 5 nm thick sputtered gold layer can dramatically alter the morphology and the surface structure of many different types of aerogels. Silica, polyimide, polyamide, calcium-alginate and cellulose aerogels were imaged in their pristine forms and after gold sputtering utilizing low voltage scanning electron microscopy (LVSEM) in order to reduce charging effects. The morphological features seen in the SEM images of the pristine samples are in excellent agreement with the structural parameters of the aerogels measured by nitrogen adsorption-desorption porosimetry. In contrast, the morphologies of the sputter coated samples are significantly distorted and feature nanostructured gold. These findings point out that extra care should be taken in order to ensure that gold sputtering does not cause morphological artifacts. Otherwise, the application of low voltage scanning electron microscopy even yields high resolution images of pristine non-conducting aerogels.

In situ remediation efficacy of hybrid aerogel adsorbent in model aquatic culture of Paramecium caudatum exposed to Hg(II).

Silica-gelatin hybrid aerogel of 24 wt% gelatin content is an advanced functional material suitable for the high performance selective adsorption of aqueous Hg(II). The remediation efficacy of this adsorbent was tested under realistic aquatic conditions by exposing cultures of Paramecium caudatum to Hg(II) and monitoring the model cultures by time-lapse video microscopy. The viability of Paramecium was quantified by analyzing the pixel differences of the sequential images caused by the persistent movement (motility) of the cells. The viability of Paramecium displays a clear exposure-response relationship with Hg(II) concentration. Viability decreases with increasing Hg(II) concentration when the latter is higher than 125 µg L-1. In the presence of 0.1 mg mL-1 aerogel adsorbent, the viability of the cells decreases only at Hg(II) concentrations higher than 500 µg L-1, and 220 min survival time was measured even at 1000 µg L-1 Hg(II). The effective toxicity of Hg(II) is lower in the presence of the aerogel, because the equilibrium concentration of aqueous Hg(II) is low due to adsorption, thus Paramecium cells do not uptake as much Hg(II) as in the un-remediated cultures. Video imaging of Paramecium cultures offers a simple, robust and flexible method for providing quantitative information on the effectiveness of advanced materials used in adsorption processes for water treatment.

Mechanism of Hydration and Hydration Induced Structural Changes of Calcium Alginate Aerogel.

The most relevant properties of polysaccharide aerogels in practical applications are determined by their microstructures. Hydration has a dominant role in altering the microstructures of these hydrophilic porous materials. To understand the hydration induced structural changes of monolithic Ca-alginate aerogel, produced by drying fully cross-linked gels with supercritical CO2, the aerogel was gradually hydrated and characterized at different states of hydration by small-angle neutron scattering (SANS), liquid-state nuclear magnetic resonance (NMR) spectroscopy, and magic angle spinning (MAS) NMR spectroscopy. First, the incorporation of structural water and the formation of an extensive hydration sphere mobilize the Ca-alginate macromolecules and induce the rearrangement of the dry-state tertiary and quaternary structures. The primary fibrils of the original aerogel backbone form hydrated fibers and fascicles, resulting in the significant increase of pore size, the smoothing of the nanostructured surface, and the increase of the fractal dimension of the matrix. Because of the formation of these new superstructures in the hydrated backbone, the stiffness and the compressive strength of the aerogel significantly increase compared to its dry-state properties. Further elevation of the water content of the aerogel results in a critical hydration state. The Ca-alginate fibers of the backbone disintegrate into well-hydrated chains, which eventually form a quasi-homogeneous hydrogel-like network. Consequently, the porous structure collapses and the well-defined solid backbone ceases to exist. Even in this hydrogel-like state, the macroscopic integrity of the Ca-alginate monolith is intact. The postulated mechanism accounts for the modification of the macroscopic properties of Ca-alginate aerogel in relation to both humid and aqueous environments.

Iron and Manganese Retention of Juvenile Zebrafish (Danio rerio) Exposed to Contaminated Dietary Zooplankton (Daphnia pulex)-a Model Experiment.

In present study the effect of iron (Fe) and manganese (Mn) contamination was assessed by modeling a freshwater food web of water, zooplankton (Daphnia pulex), and zebrafish (Danio rerio) under laboratory conditions. Metals were added to the rearing media of D. pulex, and enriched zooplankton was fed to zebrafish in a feeding trial. The elemental analysis of rearing water, zooplankton, and fish revealed significant difference in the treatments compared to the control. In D. pulex the Mn level increased almost in parallel with the dose of supplementation, as well as the Fe level differed statistically. A negative influence of the supplementation on the fish growth was observed: specific growth rate (SGR%) and weight gain (WG) decreased in Fe and Mn containing treatments. The redundancy analysis (RDA) of concentration data showed strong correlation between the rearing water and D. pulex, as well as the prey organism of Fe- and Mn-enriched D. pulex and the predator organism of D. rerio. The bioconcentration factors (BCF) calculated for water to zooplankton further proved the relationship between the Fe and Mn dosage applied in the treatments and measured in D. pulex. Trophic transfer factor (TTF) results also indicate that significant retention of the metals occurred in D. rerio individuals, however, in a much lower extent than in the water to zooplankton stage. Our study suggests that Fe and Mn significantly accumulate in the lower part of the trophic chain and retention is effective through the digestive track of zebrafish, yet no biomagnification occurs. Graphical abstract.

Rare earth element sequestration by Aspergillus oryzae biomass.

The fungus Aspergillus oryzae could be shown to be a viable alternative for biosorption of valuable metals from solution. Fungal biomass can be obtained easily in high quantities as a waste of biofermentation processes, and used in a complex, multi-phase solution mimicking naturally occurring, mining-affected water samples. With test solution formulated after natural conditions, formation of secondary Al and Fe phases co-precipitating Ce was recorded in addition to specific biosorption of rare earth elements. Remarkably, the latter were removed from the solution despite the presence of high concentrations of interfering Fe and Al. The biomass was viable even after prolonged incubation in the metal solution, and minimal inhibitory concentrations for single metals were higher than those in the test solution. While precipitation/biosorption of Ce (maximal biosorption efficiency was 58.0 ± 22.3% after 6 h of incubation) coincided with the gross removal of Fe from the metal solution, Y (81.5 ± 11.3% efficiency, 24 h incubation) and Nd (87.4 ± 9.1% efficiency, 24 h incubation) were sequestered later, similarly to Ni and Zn. The biphasic binding pattern specific to single metals could be connected to dynamically changing pH and NH4+ concentrations, which were attributed to the physiological changes taking place in starving A. oryzae biomass. The metals were found extracellularly in minerals associated with the cell wall, and intracellularly precipitated in the vacuoles. The latter process was explained with intracellular metal detoxification resulting in metal resistance.

High Enzyme Activity of a Binuclear Nickel Complex Formed with the Binding Loops of the NiSOD Enzyme*.

Detailed equilibrium, spectroscopic and superoxide dismutase (SOD) activity studies are reported on a nickel complex formed with a new metallopeptide bearing two nickel binding loops of NiSOD. The metallopeptide exhibits unique nickel binding ability and the binuclear complex is a major species with 2×(NH2 ,Namide ,S- ,S- ) donor set even in an equimolar solution of the metal ion and the ligand. Nickel(III) species were generated by oxidizing the NiII complexes with KO2 and the coordination modes were identified by EPR spectroscopy. The binuclear complex formed with the binding motifs exhibits superior SOD activity, in this respect it is an excellent model of the native NiSOD enzyme. A detailed kinetic model is postulated that incorporates spontaneous decomposition of the superoxide ion, the dismutation cycle and fast redox degradation of the binuclear complex. The latter process leads to the elimination of the SOD activity. A unique feature of this system is that the NiIII form of the catalyst rapidly accumulates in the dismutation cycle and simultaneously the NiII form becomes a minor species.

The Chlorination of N-Methyl Amino Acids with Hypochlorous Acid: Kinetics and Mechanisms.

The formation and decomposition kinetics of N-chloro-N-methyl amino acids were studied to predict the fate and impact of these compounds in water treatment technologies and biological systems. These compounds form in fast second-order reactions between N-methyl amino acids and hypochlorous acid. The comparison of the activation parameters for the reactions of N-methyl substituted and nonsubstituted branched-chain amino acids reveals the transition-state features less organized structure and stronger bonds between the reactants in the reactions with the N-methyl derivatives. This is due to a combined positive inductive effect of the N-methyl group and the alkyl side chain as well as to the steric effects of the substituents. N-Methyl-N-chloro amino acids decompose much faster than the nonsubstituted compounds. The reaction rates do not depend on the pH, and the same final product is formed in the entire pH range. N-Chlorosarcosine is an exception, as it decomposes via competing paths, kdobs = kd + kdOH[OH-], yielding different final products. This feature is most likely due to the lack of an alkyl substituent on the α-carbon atom. Under physiological pH, aldehydes and methylamine form in these reactions, which are not particularly toxic.