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In a previous report on the enzymatic synthesis of the conductive emeraldine salt form of polyaniline (PANI-ES) in aqueous solution using PADPA ( p -aminodiphenylamine) as monomer, horseradish peroxidase isoenzyme C (HRPC) was applied as a catalyst at pH = 4.3 with H 2 O 2 as a terminal oxidant. In that work, anionic vesicles were added to the reaction mixture for (i) guiding the reaction to obtain poly(PADPA) products that resemble PANI-ES, and for (ii) preventing product precipitation (known as the "template effect"). In the work now presented, instead of native HRPC, only its prosthetic group ferric heme b (= hemin) was utilized as a catalyst, and micelles formed from SDBS (sodium dodecylbenzenesulfonate) served as templates. For the elaborated optimal reaction conditions, complementary UV/vis/NIR, EPR, and Raman spectroscopy measurements clearly showed that the reaction mixture obtained after completion of the reaction contained PANI-ES-like products as dominating species, very similar to the products formed with HRPC as catalyst. HEPES (4-(2-hydroxyethyl)-1-piperazineethanesulfonate) was found to have a positive effect on the reaction rate as compared to dihydrogenphosphate. This work is the first on the template-assisted formation of PANI-ES type products under mild, environmentally friendly conditions using hemin as a cost-effective catalyst., Competing Interests: There is no conflict of interest to declare., (This journal is © The Royal Society of Chemistry.)

This communication presents a novel truncated Ni II -containing metbalamin and describes its reversible one electron reduction to a catalytically active Ni I species, that features cofactor F430 model character. Our results strikingly demonstrate that stabilization of Ni I is not restricted to the related hydroporhyrinoid ligands and is of relevance to the application of metallocorrins in (biomimetic) catalysis.

In biology, the reaction of ONOO - with CO 2 is the main sink for ONOO - . This reaction yields CO 3 •- , NO 2 • , NO 3 - , and CO 2 . There is a long-standing debate with respect to the yield of the radicals relative to ONOO - . The reaction of ONOO - with CO 2 results at first in ONOOCO 2 - . According to one hypothesis, ONOOCO 2 - is extremely short-lived and devolves into a solvent cage that contains CO 3 •- and NO 2 • . Of these solvent cages, approximately two/thirds result in NO 3 - and CO 2 , and approximately one/third release CO 3 •- and NO 2 • that oxidize the substrate. According to our hypothesis, ONOOCO 2 - is formed much faster, is relatively long-lived, and may also be an oxidant; the limited yield is the result of ONOOCO 2 - being scavenged by a second CO 2 under conditions of a high CO 2 concentration. We disagree with the first hypothesis for three reasons: First, it is based on an estimated K for the reaction of ONOO - with CO 2 to form ONOOCO 2 - of ∼1 M -1 , while experiments yield a value of 4.5 × 10 3 M -1 . Second, we argue that the solvent cage as proposed is physically not realistic. Given the less than diffusion-controlled rate constant of CO 3 •- with NO 2 • , all radicals would escape from the solvent cage. Third, the reported ∼33% radical is not supported by an experiment where mass balance was established. We propose here a hybrid mechanism. After formation of ONOOCO 2 - , it undergoes homolysis to yield CO 3 •- with NO 2 • , or, depending on [CO 2 ], it is scavenged by a second CO 2 ; CO 3 •- oxidizes ONOO - , if present. These reactions allow us to successfully simulate the reaction of ONOO - with CO 2 over a wide range of ONOO - /CO 2 ratios. At lower ratios, fewer radicals are formed, while at higher ratios, radical yields between 30% and 40% are predicted. The differences in radical yields reported may thus be traced to the experimental ONOO - /CO 2 ratios. Given a physiological [CO 2 ] of 1.3 mM, the yield of CO 3 •- and NO 2 • is 19%, and lower if ONOOCO 2 - has a significant reactivity of its own.

Horseradish peroxidase isoenzyme C (HRPC) is often used as catalyst for the preparation of the conductive emeraldine salt form of polyaniline (PANI-ES) from aniline and hydrogen peroxide (H 2 O 2 ) in the presence of anionic templates in aqueous solution. Here, a direct comparison of three types of soft templates was made, (i) the sodium salt of sulfonated polystyrene (SPS), (ii) micelles from sodium dodecylbenzenesulfonate (SDBS), and (iii) vesicles from either a 1 : 1 molar mixture of SDBS and decanoic acid or from AOT (sodium bis(2-ethylhexyl)sulfosuccinate). Based on UV/vis/NIR, EPR and Raman spectroscopy measurements all three types of templates are similarly suitable, with advantages of the two vesicle systems in terms of aniline conversion degree and radical content in the final PANI-ES product. First experiments with sulfated cellulose nanocrystals (CNCs) indicate that they are promising rigid templates for the preparation of electroconductive PANI-ES-coated cellulose materials or devices., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We present a comprehensive investigation of main-chain scission processes affecting peripherally charged and neutral members of a class of dendronized polymers (DPs) studied in our laboratory. In these thick, sterically highly congested macromolecules, scission occurs by exposure to solvents, in some cases at room temperature, in others requiring modest heating. Our investigations rely on gel permeation chromatography and atomic force microscopy and are supported by molecular dynamics simulations as well as by electron paramagnetic resonance spectroscopy. Strikingly, DP main-chain scission depends strongly on two factors: first the solvent, which must be highly polar to induce scission of the DPs, and second the dendritic generation g . In DPs of generations 1 ≤ g ≤ 8, scission occurs readily only for g = 5, no matter whether the polymer is charged or neutral. Much more forcing conditions are required to induce degradation in DPs of g ≠ 5. We propose solvent swelling as the cause for the main-chain scission in these individual polymer molecules, explaining in particular the strong dependence on g : g < 5 DPs resemble classical polymers and are accessible to the strongly interacting, polar solvents, whereas g > 5 DPs are essentially closed off to solvent due to their more closely colloidal character. g = 5 DPs mark the transition between these two regimes, bearing strongly sterically congested side chains which are still solvent accessible to some degree. Our results suggest that, even in the absence of structural elements which favour scission such as cross-links, solvent swelling may be a generally applicable mechanochemical trigger. This may be relevant not only for DPs, but also for other types of sterically strongly congested macromolecules.

Many previous studies have shown that (i) the oxidation of aniline or the aniline dimer p -aminodiphenylamine (PADPA) in a slightly acidic aqueous solution can be catalyzed with heme peroxidases or multicopper laccases and that (ii) subsequent reactions lead to oligomeric or polymeric products, which resemble chemically synthesized polyaniline in its conductive emeraldine salt form (PANI-ES), provided that (iii) an anionic "template" is present in the reaction medium. Good templates are anionic polyelectrolytes, micelles, or vesicles. Under optimal conditions, their presence directs the reactions in a positive way toward the desired formation of PANI-ES-type products. The effect of four different types of anionic templates on the formation of PANI-ES-like products from PADPA was investigated and compared by using Trametes versicolor laccase (TvL) as a catalyst in an aqueous pH 3.5 solution at room temperature. All four templates contain sulfonate groups: the sodium salt of the polyelectrolyte sulfonated polystyrene (SPS), micelles from sodium dodecylbenzenesulfonate (SDBS), vesicles from a 1:1 molar mixture of SDBS and decanoic acid, and vesicles from sodium bis(2-ethylhexyl)sulfosuccinate (AOT). Although with all four templates, stable, inkjet-printable solutions or suspensions consisting of PANI-ES-type products were obtained under optimized conditions, considerably higher amounts of TvL were required with SDBS micelles to achieve comparable monomer conversion to PANI-ES-like products during the same time period when compared to those with SPS or the two types of vesicles. This makes SDBS micelles less attractive as templates for the investigated reaction. In situ UV/vis/near-infrared, electron paramagnetic resonance (EPR), and Raman spectroscopy measurements in combination with an high-performance liquid chromatography analysis of extracted reaction products, which were deprotonated and chemically reduced, showed seemingly small but significant differences in the composition of the mixtures obtained when reaching reaction equilibrium after 24 h. With the two vesicle systems, the content of unwanted substituted phenazine units was lower than in the case of SPS polyelectrolyte and SDBS micelles. The EPR spectra indicate a more localized, narrower distribution of electronic states of the paramagnetic centers of the PANI-ES-type products synthesized in the presence of the two vesicle systems when compared to that of the similar products obtained with the SPS polyelectrolyte and SDBS micelles as templates. Overall, the data obtained from the different complementary methods indicate that with the two vesicle systems structurally more uniform (regular) PANI-ES-type products formed. Among the two investigated vesicle systems, for the investigated reaction (oxidation of PADPA with TvL and O 2 ), AOT appears a somewhat better choice as it leads to a higher content of the PANI-ES polaron form., Competing Interests: The authors declare no competing financial interest.

The Trametes versicolor laccase (TvL)-catalysed oligomerisation of the aniline dimer p -aminodiphenylamine (PADPA) was investigated in an aqueous medium of pH = 3.5, containing 80-100 nm-sized anionic vesicles formed from AOT, the sodium salt of bis(2-ethylhexyl)sulfosuccinic acid. If run under optimal conditions, the reaction yields oligomeric products which resemble the emeraldine salt form of polyaniline (PANI-ES) in its polaron state, known to be the only oxidation state of linear PANI which is electrically conductive. The vesicles serve as "templates" for obtaining products with the desired PANI-ES-like features. For this complex, heterogeneous, vesicle-assisted, and enzyme-mediated reaction, in which dissolved dioxygen also takes part as a re-oxidant for TvL, small changes in the composition of the reaction mixture can have significant effects. Initial conditions may not only affect the kinetics of the reaction, but also the outcome, i.e. , the product distribution once the reaction reaches its equilibrium state. While a change in the reaction temperature from T ≈ 25 to 5 °C mainly influenced the rate of reaction, increase in enzyme concentration and the presence of millimolar concentrations of chloride ions were found to have significant undesired effects on the outcome of the reaction. Chloride ions, which may originate from the preparation of the pH = 3.5 solution, inhibit TvL, such that higher TvL concentrations are required than without chloride to yield the same product distribution for the same reaction runtime as in the absence of chloride. With TvL concentrations much higher than the elaborated value, the products obtained clearly were different and over-oxidised. Thus, a change in the activity of the enzyme was found to have influence not only on kinetics but also led to a change in the final product distribution, molecular structure and electrical properties, which was a surprising find. The complementary analytical methods which we used in this work were in situ UV/vis/NIR, EPR, and Raman spectroscopy measurements, in combination with a detailed ex situ HPLC analysis and molecular dynamics simulations. With the results obtained, we would like to recall the often neglected or ignored fact that it is important to describe and pay attention to the experimental details, since this matters for being able to perform experiments in a reproducible way., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

With CO 2 present in excess, ONOO - reacts to form an adduct in solution and in the solid state, most likely ONOOCO 2 - . In solution, the adduct appears within 2 ms and absorbs at 300 with an extinction coefficient, which is either 50% or 100% (preferred) of that of ONOO - , 1.70 × 10 3 M -1 cm -1 , and at 685 nm with an extinction coefficient of 85 M -1 cm -1 . When solid [(CH 3 ) 4 N][ONOO] is treated with CO 2 , these two maxima are red-shifted by 30-50 nm. The equilibrium constant for adduct formation in solution is (4.5 ± 0.5) × 10 3 M. The adduct reacts further with another CO 2 at a rate of (2.6 ± 0.8) × 10 4 M -1 s -1 and produces 2 CO 2 and NO 3 - . Thermochemical calculations show that ΟΝΟΟCO 2 - is a strong two-electron oxidizing agent, E°(ONOOCO 2 - , H + /NO 2 - , HCO 3 - ) = +1.28 V at pH 7 and an even stronger one-electron oxidizing agent E°'(ONOOCO 2 - , H + /NO 2 • , HCO 3 - ) = +1.51 V at pH 7. The extent of homolysis, that is formation of NO 2 • and CO 3 •- , is small, slightly less than 1% relative to ONOO - at the physiological concentration of CO 2 of 1.3 mM in plasma. Thus, ONOOCO 2 - is more relevant than CO 3 •- under in vivo conditions.

Oligoanilines with characteristic properties of the electrically conductive emeraldine salt form of polyaniline (PANI-ES) are promising molecules for various applications. A mixture of such oligoanilines can be obtained, for example, enzymatically under mild conditions from the linear aniline dimer p-aminodiphenylamine (PADPA) with hydrogen peroxide (H 2 O 2 ) and low amounts of horseradish peroxidase (HRP) in an aqueous pH = 4.3 suspension of anionic vesicles formed from AOT, the sodium salt of bis(2-ethylhexyl)sulfosuccinate. However, the simultaneous formation of undesired side products containing phenazine-type units or oxygen atoms is unsatisfactory. We have found that this situation can be improved considerably by using a mixture of PADPA and aniline instead of PADPA only but otherwise nearly identical conditions. The PANI-ES-like oligoaniline products that are obtained from the PADPA and aniline mixture were not only found to have much lower contents of phenazine-type units and not contain oxygen atoms but also were shown to be more electroactive in cyclic voltammetry measurements than the PANI-ES-like products obtained from PADPA only. The AOT vesicle suspension remained stable without product precipitation during and after the entire reaction so that it could be analyzed by in situ UV/visible/near-infrared, in situ electron paramagnetic resonance, and in situ Raman spectroscopy measurements. These measurements were complemented with ex situ high-performance liquid chromatography analyses of the deprotonated and reduced products formed from mixtures of PADPA and either fully or partially deuterated aniline. On the basis of the results obtained, a reaction mechanism is proposed for explaining this improved HRP-triggered, vesicle-assisted synthesis of electroactive PANI-ES-like products. The oligomeric products obtained can be further used, without additional special workup, for example, to coat electrodes for their possible application in biosensor devices.

Determination of a representative formal redox potential of the Fe(II)/Fe(III) redox couple in cyanhaemoglobin, at pH=7 and related to the state in solution, was the objective of this work. It was achieved at low concentrations of the protein (5μM) to circumvent undesired adsorption. Square-wave voltammetry instead of classical cyclic voltammetry was applied because this method is more sensitive and provides information on the formal redox potential and reversibility, even for rapid processes. We obtained E°'=-0.12±0.01V for cyanhaemoglobin and E°'=-0.10±0.01V, vs. SHE, for myoglobin in comparison. These values differ by only 20mV because the two Fe(II)/Fe(III) redox centres are embedded in closely resembling chemical environments. The small difference is probably owed to the additional axially coordinating cyanide ligand in cyanmethaemoglobin which slightly favours the Fe(III) state in the haem macrocycle., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The autoxidation of NO • was studied in glass-like matrices of 2-methylbutane at 110 K and in a 8:3 v/v mixture of 2,2-dimethylbutane and n-pentane (rigisolve) at 80-90 K, by letting gaseous NO • diffuse into these solvents that were saturated with O 2 . In 2-methyllbutane, we observed a red compound. However, in rigisolve at 85-90 K, a bright yellow color appears that turns red when the sample is warmed by 10-20 K. The new yellow compound is a precursor of the red one and also diamagnetic. The UV-vis spectrum of the yellow compound contains a band which resembles that present in ONOO - . Because the red and yellow intermediates are not paramagnetic, we postulate that O═N-O-O • is in close contact with NO • , or with another O═N-O-O • . Diffusion of gaseous O 2 into rigisolve saturated with NO • does not produce a color; however, a weak EPR signal (g = 2.010) is observed. This signal most likely indicates the presence of ONOO • . These findings complement our earlier observation of a red color at low temperatures and the presence of ONOO • in the gas phase (Galliker, B.; Kissner, R.; Nauser, T.; Koppenol, W. H. Chem. Eur. J. 2009, 15, 6161-6168), and they indicate that the termolecular autoxidation of nitrogen monoxide proceeds via the intermediate ONOO • and not via N 2 O 2 .

We report about the first Raman spectroscopy study of a vesicle-assisted enzyme-catalyzed oligomerization reaction. The aniline dimer N-phenyl-1,4-phenylenediamine (= p-aminodiphenylamine, PADPA) was oxidized and oligomerized with Trametes versicolor laccase and dissolved O2 in the presence of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) vesicles (80-100 nm diameter) as templates. The conversion of PADPA into oligomeric products, poly(PADPA), was monitored during the reaction by in situ Raman spectroscopy. The results obtained are compared with UV/vis/NIR and EPR measurements. All three complementary methods indicate that at least some of the poly(PADPA) products, formed in the presence of AOT vesicles, resemble the conductive emeraldine salt form of polyaniline (PANI-ES). The Raman measurements also show that structural units different from those of "ordinary" PANI-ES are present too. Without vesicles PANI-ES-like products are not obtained. For the first time, the as-prepared stable poly(PADPA)-AOT vesicle suspension was used directly to coat electrodes (without product isolation) for investigating redox activities of poly(PADPA) by cyclic voltammetry (CV). CV showed that poly(PADPA) produced with vesicles is redox active not only at pH 1.1-as expected for PANI-ES-but also at pH 6.0, unlike PANI-ES and poly(PADPA) synthesized without vesicles. This extended pH range of the redox activity of poly(PADPA) is important for applications.

Electrode potentials for aromatic amino acid radical/amino acid couples were deduced from cyclic voltammograms and pulse radiolysis experiments. The amino acids investigated were l-tryptophan, l-tyrosine, N-acetyl-l-tyrosine methyl ester, N-acetyl-3-nitro-l-tyrosine ethyl ester, N-acetyl-2,3-difluoro-l-tyrosine methyl ester, and N-acetyl-2,3,5-trifluoro-l-tyrosine methyl ester. Conditional potentials were determined at pH 7.4 for all compounds listed; furthermore, Pourbaix diagrams for l-tryptophan, l-tyrosine, and N-acetyl-3-nitro-l-tyrosine ethyl ester were obtained. Electron transfer accompanied by proton transfer is reversible, as confirmed by detailed analysis of the current waves, and because the slopes of the Pourbaix diagrams obey Nernst's law. E°'(Trp(•),H(+)/TrpH) and E°'(TyrO(•),H(+)/TyrOH) at pH 7 are 0.99 ± 0.01 and 0.97 ± 0.01 V, respectively. Pulse radiolysis studies of two dipeptides that contain both amino acids indicate a difference in E°' of approximately 0.06 V. Thus, in small peptides, we recommend values of 1.00 and 0.96 V for E°'(Trp(•),H(+)/TrpH) and E°'(TyrO(•),H(+)/TyrOH), respectively. The electrode potential of N-acetyl-3-nitro-l-tyrosine ethyl ester is higher, while because of mesomeric stabilization of the radical, those of N-acetyl-2,3-difluoro-l-tyrosine methyl ester and N-acetyl-2,3,5-trifluoro-l-tyrosine methyl ester are lower than that of tyrosine. Given that the electrode potentials at pH 7 of E°'(Trp(•),H(+)/TrpH) and E°'(TyrO(•),H(+)/TyrOH) are nearly equal, they would be, in principle, interchangeable. Proton-coupled electron transfer pathways in proteins that use TrpH and TyrOH are thus nearly thermoneutral.

Rationale: Hemolysis occurs not only in conditions such as sickle cell disease and malaria but also during transfusion of stored blood, extracorporeal circulation, and sepsis. Cell-free Hb depletes nitric oxide (NO) in the vasculature, causing vasoconstriction and eventually cardiovascular complications. We hypothesize that Hb-binding proteins may preserve vascular NO signaling during hemolysis., Objectives: Characterization of an archetypical function by which Hb scavenger proteins could preserve NO signaling during hemolysis., Methods: We investigated NO reaction kinetics, effects on arterial NO signaling, and tissue distribution of cell-free Hb and its scavenger protein complexes., Measurements and Main Results: Extravascular translocation of cell-free Hb into interstitial spaces, including the vascular smooth muscle cell layer of rat and pig coronary arteries, promotes vascular NO resistance. This critical disease process is blocked by haptoglobin. Haptoglobin does not change NO dioxygenation rates of Hb; rather, the large size of the Hb:haptoglobin complex prevents Hb extravasation, which uncouples NO/Hb interaction and vasoconstriction. Size-selective compartmentalization of Hb functions as a substitute for red blood cells after hemolysis and preserves NO signaling in the vasculature. We found that evolutionarily and structurally unrelated Hb-binding proteins, such as PIT54 found in avian species, functionally converged with haptoglobin to protect NO signaling by sequestering cell-free Hb in large protein complexes., Conclusions: Sequential compartmentalization of Hb by erythrocytes and scavenger protein complexes is an archetypical mechanism, which may have supported coevolution of hemolysis and normal vascular function. Therapeutic supplementation of Hb scavengers may restore vascular NO signaling and attenuate disease complications in patients with hemolysis.

Iron in iron overload disease is present as non-transferrin-bound iron, consisting of iron, citrate, and albumin. We investigated the redox properties of iron citrate by electrochemistry, by the kinetics of its reaction with ascorbate, by ESR, and by analyzing the products of reactions of ascorbate with iron citrate complexes in the presence of H2O2 with 4-hydroxybenzoic acid as a reporter molecule for hydroxylation. We report -0.03 V < E°' > +0.01 V for the (Fe(3+)-cit/Fe(2+)-cit) couple. The first step in the reaction of iron citrate with ascorbate is the rapid formation of mixed complexes of iron with citrate and ascorbate, followed by slow reduction to Fe(2+)-citrate with k = ca. 3 M(-1) s(-1). The ascorbyl radical is formed by iron citrate oxidation of Hasc(-) with k = ca. 0.02 M(-1) s(-1); the majority of the ascorbyl radical formed is sequestered by complexation with iron and remains EPR silent. The hydroxylation of 4-hydroxybenzoic acid driven by the Fenton reduction of iron citrate by ascorbate in the presence of H2O2 proceeds in three phases: the first phase, which is independent of the presence of O2, is revealed as a nonzero intercept that reflects the rapid reaction of accumulated Fe(2+) with H2O2; the intermediate oxygen-dependent phase fits a first-order accumulation of product with k = 5 M(-1) s(-1) under aerobic and k = 13 M(-1) s(-1) under anaerobic conditions; the slope of the final linear phase is ca. k = 5 × 10(-2) M(-1) s(-1) under both aerobic and anaerobic conditions. Product yields under aerobic conditions are greater than predicted from the initial concentration of iron, but they are less than predicted for continuous redox cycling in the presence of excess ascorbate. The ongoing formation of hydroxylated product supports slow redox cycling by iron citrate. Thus, when H2O2 is available, iron-citrate complexes may contribute to pathophysiological manifestations of iron overload diseases.

Small-sized FeO(OH) colloids stabilised by sugars, commercially available for the clinical treatment of iron deficiency, show two waves during cathodic polarographic sweeps, or two current maxima with stationary electrodes, in neutral to slightly alkaline aqueous medium. Similar signals are observed with Fe(III) in alkaline media, pH > 12, containing citrate in excess. Voltammetric and polarographic responses reveal a strong influence of fast adsorption processes on gold and mercury. Visible spontaneous accumulation was also observed on platinum. The voltammetric signal at more positive potential is caused by Fe(III)→Fe(II) reduction, while the one at more negative potential has previously been assigned to Fe(II)→Fe(0) reduction. However, the involvement of adsorption phenomena leads us to the conclusion that the second cathodic current is caused again by Fe(III)→Fe(II), of species deeper inside the particles than those causing the first wave. This is further supported by X-ray photoelectron spectra obtained after FeO(OH) particle adsorption and reduction on a gold electrode surface. The same analysis suggests that sucrose stabilising the colloid is still bound to the adsorbed material, despite dilution and rinsing.

H2 has been suggested to act as an antioxidant when administered just before the reperfusion phase of induced oxidative stress. These effects have been reported, for example, for the heart, brain, and liver. It is hypothesized that this beneficial effect may be due to selective scavenging of HO(⋅) and ONOOH by H2. The reaction of H2 with HO(⋅) has been studied by pulse radiolysis in the past and is too slow to be physiologically relevant, not to mention that the reaction yields the reactive H(⋅) radical. We therefore investigated whether H2 reacts with ONOOH and whether the presence of H2 influences the yield of nitration of tyrosine by ONOOH. With only negative results, we entertained the notion that H2 may possibly exert its beneficial effects by reducing Fe(III) centers, oxidized during oxidative stress. However, neither hemes nor iron-sulfur clusters were reduced., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Reactions of ferrate(VI) during water treatment generate perferryl(V) or ferryl(IV) as primary intermediates. To better understand the fate of perferryl(V) or ferryl(IV) during ferrate(VI) oxidation, this study investigates the kinetics, products, and mechanisms for the reaction of ferrate(VI) with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) and self-decay of ferrate(VI) in phosphate-buffered solutions. The oxidation of ABTS by ferrate(VI) via a one-electron transfer process produces ABTS(•+) and perferryl(V) (k = 1.2 × 10(6) M(-1) s(-1) at pH 7). The perferryl(V) mainly self-decays into H2O2 and Fe(III) in acidic solution while with increasing pH the reaction of perferryl(V) with H2O2 can compete with the perferryl(V) self-decay and produces Fe(III) and O2 as final products. The ferrate(VI) self-decay generates ferryl(IV) and H2O2 via a two-electron transfer with the initial step being rate-limiting (k = 26 M(-1) s(-1) at pH 7). Ferryl(IV) reacts with H2O2 generating Fe(II) and O2 and Fe(II) is oxidized by ferrate(VI) producing Fe(III) and perferryl(V) (k = ∼10(7) M(-1) s(-1)). Due to these facile transformations of reactive ferrate(VI), perferryl(V), and ferryl(IV) to the much less reactive Fe(III), H2O2, or O2, the observed oxidation capacity of ferrate(VI) is typically much lower than expected from theoretical considerations (i.e., three or four electron equivalents per ferrate(VI)). This should be considered for optimizing water treatment processes using ferrate(VI).

The enzymatic polymerization of aniline to polyaniline (PANI) with Trametes versicolor laccase (TvL) as catalyst and dioxygen (O₂) as oxidant was investigated in an aqueous medium containing unilamellar vesicles with an average diameter of about 80 nm formed from AOT (=sodium bis(2-ethylhexyl) sulfosuccinate). Compared to the same reaction carried out with horseradish peroxidase isoenzyme C (HRPC) as catalyst and hydrogen peroxide (H₂O₂) as oxidant, notable differences were found in the kinetics of the reaction, as well as in the characteristics of the PANI obtained. Under comparable optimal conditions, which are pH 3.5 for TvL/O₂ and pH 4.3 for HRPC/H₂O₂, the reaction with TvL/O₂ was much slower than with HRPC/H₂O₂, i.e. ≈27 days vs. 1 day reaction time to reach equilibrium with >90% yield at 25 °C. Although in both cases, aniline monomer coupling occurred mainly via the carbon atom in para position of aniline, UV-vis-NIR absorption and EPR measurements indicate that the reaction with TvL/O₂ yielded mainly overoxidized products (with λ(max)=730 nm). These products had a lower amount of unpaired electrons if compared with the products obtained with HRPC/H₂O₂ (with λ(max)≈1000 nm, which is characteristic for the polaron state of PANI-ES, the emeraldine salt form of PANI). Similarly to previous findings with HRPC/H₂O₂, enzyme inactivation occurred during the polymerization also in the case of TvL/O₂. Since the aqueous PANI-vesicle suspensions obtained are of high colloidal stability, they can be used directly as ink in a conventional thermal inkjet printer for printing on paper or on surface treated polyimide films. Printed PANI-ES patterns on paper changed colour from green (emeraldine salt) to blue (emeraldine base) upon exposure to ammonia gas, demonstrating the expected ammonia sensing properties., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Lipid bilayer permeation is considered the major route for in vivo barrier passage of drugs. Despite this fact, no technique is currently available to measure the kinetics of permeation across a single lipid bilayer of structurally unrelated drug-like solutes. We developed a liposomal fluorescence assay capable to determine permeation kinetics of basic drug-like solutes across lipid bilayers. The assay is based on the hypothesis that permeation of a weak base along a concentration gradient results in net proton release at the cis-side and net proton capture at the trans-side of the bilayer. The resulting pH changes were monitored with pH-sensitive fluorophores: Test compounds were incubated with liposomes containing a pH-sensitive fluorophore at the bilayer surfaces or in the aqueous lumen and fluorescence changes were monitored with a stopped-flow apparatus in solution or by total internal reflection fluorescence microscopy with surface-captured liposomes on a microfluidic platform. Incubation with lipophilic basic drugs resulted in the expected fluorescence changes while incubation with compounds without basic functionality or high polarity did not affect fluorescence. Kinetics of fluorescence changes followed bi-exponential functions. Logarithmic permeation coefficients (logPermapp) determined in solution and by microfluidics technology showed a good correlation (r(2)=0.94, n=7) and logPermapp increased with increasing lipophilicity. Neither diffusion in the aqueous phase nor partitioning into the bilayer was rate-limiting. PEGylation of 2% of the liposomal lipids reduced Permapp by a factor ~300. In conclusion, the presented liposomal fluorescence assay is capable to determine permeation kinetics of weak basic drug-like solutes across lipid bilayers. The method is adaptable to microfluidics technology for high-throughput measurements and can potentially be modified to work for weak acid solutes., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The synthesis of 5-nitro-1-(trifluoromethyl)-3H-1λ(3),2-benziodaoxol-3-one (3), a hypervalent-iodine-based electrophilic trifluoromethylating reagent, is described. Whereas considerations based on cyclic voltammetry and X-ray structural properties would predict an inferior reactivity when compared to the non-nitrated derivative 2, (19)F NMR kinetic studies showed that this new derivative is almost one order of magnitude more reactive. Furthermore, differential scanning calorimetry measurements indicated that, in addition, it is also safer to handle.

The decay of ONOOH near neutral pH has been examined as a function of isomerization to H(+) and NO3(-), and decomposition to NO2(-) and O2via O2NOO(-). We find that in phosphate buffer k(isomerization) = 1.11 ± 0.01 s(-1) and k(disproportionation) = (1.3 ± 0.1) × 10(3) M(-1) s(-1) at 25 °C and I = 0.2 M. In the presence of 0.1 M tris(hydroxymethyl)aminomethane (Tris), the decay proceeds more rapidly: k(disproportionation) = 9 × 10(3) M(-1) s(-1). The measured first half-life of the absorbance of peroxynitrite correlates with [Tris]0·([ONOO(-)]0 + [ONOOH]0)(2), where the subscript 0 indicates initial concentrations; if this function exceeds 6.3 × 10(-12) M(3), then Tris significantly accelerates the decomposition of peroxynitrite.

The isomerisation of ONOOH to NO(3)(-) and H(+), some oxidations and all hydroxylations and nitrations of aromatic compounds are first-order in ONOOH and zero-order in the compounds that are modified. These reactions are widely believed to proceed via homolysis of ONOOH into HO˙ and NO(2)˙ to an extent of ca. 30%. We review the evidence pro and contra homolysis in studies that involve (1) thermochemical considerations, (2) isomerisation to NO(3)(-) and H(+), (3) decomposition to NO(2)(-) and O(2), (4) HO˙ scavenger studies, (5) deuterium isotope effects, (6) (18)O-scrambling studies, (7) electrochemistry, (8) CIDNP NMR, and (9) photolysis. Our conclusion is that homolysis may be involved to a minor extent of ca. 5%. The initiation of ONOOH isomerisation may be visualised as an out-of-plane vibration of the terminal HO-group relative to the nitrogen. At ONOO(-) concentrations exceeding 0.1 mM and near neutral pH, disproportionation to NO(2)(-) and O(2) occurs; such disproportionations are typical for peroxy acids. For oxidation and nitration of organic substrates, we favour a mechanism involving initial formation of an adduct between the compound to be oxidised or nitrated and ONOOH.

A Co-based metal-organic framework (MOF) was investigated as a catalytic material in the aerobic epoxidation of olefins in DMF and exhibited, based on catalyst mass, a remarkably high catalytic activity compared with the Co-doped zeolite catalysts that are typically used in this reaction. The structure of STA-12(Co) is similar to that of STA-12(Ni), as shown by XRD Rietveld refinement and is stable up to 270 °C. For the epoxidation reaction, significantly different selectivities were obtained depending on the substrate. Although styrene was epoxidized with low selectivity due to oligomerization, (E)-stilbene was converted with high selectivities between 80 and 90 %. Leaching of Co was low and the reaction was found to proceed mainly heterogeneously. The catalyst was reusable with only a small loss of activity. The catalytic epoxidation of stilbene with the MOF featured an induction period, which was, interestingly, considerably reduced by styrene/stilbene co-epoxidation. This could be traced back to the formation of benzaldehyde promoting the reaction. Detailed parameter and catalytic studies, including in situ EPR and EXAFS spectroscopy, were performed to obtain an initial insight into the reaction mechanism., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Manganese(III)-meso-tetraphenylporphyrin [Mn(TPP)] and manganese(III)-meso-tetrakis(pentafluorophenyl)porphyrin [Mn(TPFPP)] catalyse the epoxidation of cyclooctene by IO(4)(-) in the presence of excess imidazoles, in both dry CH(2)Cl(2) and CH(2)Cl(2) saturated with H(2)O. The reaction rates of the electron deficient Mn(TPFPP) are a factor 24 less than those of Mn(TPP); however, the former increases 15-30 times in the presence of water, while those of Mn(TPP) do so by a factor of 2-3. The most striking catalytic enhancement caused by the addition of water was observed with 2-methylimidazole and Mn(TPFPP). As deprotonation of imidazoles may play a significant role in the presence of water, we found that manganese(III)-meso-tetrakis(phenyl-4-sulfonato)porphyrin [Mn(TPPS)] decreases the NH proton pK(a) of axially coordinated imidazole from 14.2 to 9.5. We conclude that the imidazole ligand is partially deprotonated in the presence of water. The latter enables the solvation of imidazolium ions that are formed simultaneously. The imidazolate form of the co-catalyst is a much stronger donor than the imidazole itself, providing electron density to Mn(III) and thus promoting oxygen transfer. The failure of N-methylimidazole to increase the reaction rates upon addition of water supports this hypothesis. A functionally related deprotonation has been shown to occur in horseradish peroxidase (J. S. de Ropp, V. Thanabal, G. N. La Mar, J. Am. Chem. Soc. 1985, 107, 8270-8272) and in chlorite dismutase (B. R. Goblirsch, B. R. Streit, J. L. Dubois, C. M. Wilmot, J. Biol. Inorg. Chem. 2010, 15, 879-888). Mn(III)porphyrins in combination with imidazoles and water constitute a functional biomimetic model of peroxidases., (This journal is © The Royal Society of Chemistry 2011)

The feasibility of using surfactant vesicles as soft templates for the peroxidase-triggered polymerization of aniline was investigated. It was found that mixed anionic vesicles (diameter approximately 80 nm) composed of sodium dodecylbenzenesulfonate (SDBS) and decanoic acid (1:1, molar ratio) are promising templates. In the presence of the vesicles and horseradish peroxidase/hydrogen peroxide (H2O2) as initiator system, aniline polymerizes under optimized conditions at pH=4.3 to the desired conductive emeraldine form of polyaniline (PANI). The optimal polymerization conditions were elaborated, and some of the chemical and physicochemical aspects of the reaction system were investigated. After addition of aniline and peroxidase to the vesicles, aniline is only loosely associated with the vesicles, as shown by NOESY-NMR and zeta potential measurements. In contrast, the peroxidase strongly binds to the vesicle surface, as shown by fluorescence measurements using TNS (2-(p-toluidino)naphthalene-6-sulfonate) as vesicle membrane probe. This binding of the enzyme to the vesicle surface indicates that the polymerization reaction is initiated predominantly on the surface of the vesicles. Cryo-transmission electron microscopy indicates that the polymerization product remains associated with the vesicles on their surface. For short reaction times (30 s

The decomposition of peroxynitrite near neutral pH leads ultimately to the formation of dioxygen and nitrite via an intermediate with an absorbance maximum at 284 nm. The intermediate oxidises I(-) with a rate constant of (78 +/- 8) x 10 M(-1) s(-1) and decays near pH 7 with a rate constant of (0.58 +/- 0.02) s(-1) at 22 degrees C, but is longer-lived at lower pH. On the basis of experiments performed with a tandem-quenching flow reactor, we tentatively identify this intermediate as peroxynitric acid, formed during the proposed reaction sequence ONOOH + ONOO(-) --> NO(2)(-) + O(2)NOO(-) + H(+) --> 2 NO(2)(-) + O(2). These products are those expected from a peracid. The rate constant for the first reaction is ca. 3 x 10(4) M(-1) s(-1). Part of the dioxygen formed is in the (1)Delta(g) state (S. Miyamoto, G. E. Ronsein, T. C. Corréa, G. R. Martinez, M. H. G. Medeiros and P. Di Mascio, Dalton Trans., 2009, DOI: 10.1039/b905560f). The decay of peroxynitrous acid at concentrations higher than 0.1 mM near neutral pH is best described by the simultaneous process of isomerisation (k = 1.2 s(-1)) and decomposition to peroxynitrate. The rate of formation and the amount of peroxynitrate formed are much larger than can be accounted for by homolysis reactions.