Electrografting of Carbon Surfaces with Aliphatic Chains and its Effect on the Rectification of Ferrocene as Redox Probe in Solution.

The mediated oxidation of acetate and octanoate ions in acetonitrile was used to covalently modify carbon surfaces with films bearing saturated aliphatic chains of different length. Film thickness increases proportionally with the length of the aliphatic chain within the carboxylate precursor. The thickest film was obtained from octanoate oxidation and rectification occurs when ferrocene is used as redox probe in acetonitrile solution. This effect increases with the bulky and hydrophobic nature of the supporting electrolyte cations; n-Hx4 N+ >n-Bu4 N+ >Me4 N+ . The combination of the bulky and hydrophobic properties of the supporting electrolyte ions as well as the hydrophobic properties of the electrografted films is the basis of rectification of ferrocene in cyclic voltammetry experiments. This phenomenon was simulated through a CEC mechanism in solution, where the mass transport inside the film channels was emulated through single chemical equilibria.

Competition between Hydrogen Bonding and Proton Transfer during Specific Anion Recognition by Dihomooxacalix[4]arene Bidentate Ureas.

Competition between hydrogen bonding and proton transfer reactions was studied for systems composed of electrogenerated dianionic species from dinitrobenzene isomers and substituted dihomooxacalix[4]arene bidentate urea derivatives. To analyze this competition, a second-order ErCrCi mechanism was considered where the binding process is succeeded by proton transfer and the voltammetric responses depend on two dimensionless parameters: the first related to hydrogen bonding reactions, and the second one to proton transfer processes. Experimental results indicated that, upon an increase in the concentration of phenyl-substituted dihomooxacalix[4]arene bidentate urea, voltammetric responses evolve from diffusion-controlled waves (where the binding process is at chemical equilibrium) into irreversible kinetic responses associated with proton transfer. In particular, the 1,3-dinitrobenzene isomer showed a higher proton transfer rate constant (∼25 M(-1) s(-1)) compared to that of the 1,2-dinitrobenzene (∼5 M(-1) s(-1)), whereas the 1,4-dinitrobenzene did not show any proton transfer effect in the experimental conditions employed.

Site-Specific Description of the Enhanced Recognition Between Electrogenerated Nitrobenzene Anions and Dihomooxacalix[4]arene Bidentate Ureas.

Electron transfer controlled hydrogen bonding was studied for a series of nitrobenzene derivative radical anions, working as large guest anions, and substituted ureas, including dihomooxacalix[4]arene bidentate urea derivatives, in order to estimate binding constants (Kb) for the hydrogen-bonding process. Results showed enhanced Kb values for the interaction with phenyl-substituted bidentate urea, which is significantly larger than for the remaining compounds, e.g., in the case of 4-methoxynitrobenzene a 28-fold larger Kb value was obtained for the urea bearing a phenyl (Kb ∼ 6888) vs tert-butyl (Kb ∼ 247) moieties. The respective nucleophilic and electrophilic characters of the participant anion radical and urea hosts were parametrized with global and local electrodonating (ω(-)) and electroaccepting (ω(+)) powers, derived from DFT calculations. ω(-) data were useful for describing trends in structure­activity relationships when comparing nitrobenzene radical anions. However, ω(+) for the host urea structures lead to unreliable explanations of the experimental data. For the latter case, local descriptors ωk(+)(r) were estimated for the atoms within the urea region in the hosts [∑kωk(+)(r)]. By compiling all the theoretical and experimental data, a Kb-predictive contour plot was built considering ω(-) for the studied anion radicals and ∑kωk(+)(r) which affords good estimations.

Upflow fixed bed bioelectrochemical reactor for wastewater treatment applications.

A cylindrical Upflow Fixed Bed Reactor (UFB-BER) with granular activated carbon, steel mesh electrodes and anaerobic microorganisms, was constructed for analyzing how hydrodynamic parameters affect the reactions involved during wastewater treatment processes for azo dye degradation. Dye removal percentage was not compromised by decreasing HRTm (99-90% upon changing HRTm from 4 to 1h in single pass mode). Using the residence time distribution method for hydrodynamic characterization, it was found that a higher dispersion in the reactor occurs for HRTm=1h, than for HRTm=4h. A kinetic analysis suggests that this dispersion effect could be associated to a higher specific reaction rate dependent on the azo dye concentration.

Electrochemical and theoretical analysis of the reactivity of shikonin derivatives: dissociative electron transfer in esterified compounds.

An electrochemical and theoretical analysis of a series of shikonin derivatives in aprotic media is presented. Results showed that the first electrochemical reduction signal is a reversible monoelectronic transfer, generating a stable semiquinone intermediate; the corresponding E(I)° values were correlated with calculated values of electroaccepting power (ω(+)) and adiabatic electron affinities (A(Ad)), obtained with BH and HLYP/6-311++G(2d,2p) and considering the solvent effect, revealing the influence of intramolecular hydrogen bonding and the substituting group at position C-2 in the experimental reduction potential. For the second reduction step, esterified compounds isobutyryl and isovalerylshikonin presented a coupled chemical reaction following dianion formation. Analysis of the variation of the dimensionless cathodic peak potential values (ξ(p)) as a function of the scan rate (v) functions and complementary experiments in benzonitrile suggested that this process follows a dissociative electron transfer, in which the rate of heterogeneous electron transfer is slow (~0.2 cm s(-1)), and the rate constant of the chemical process is at least 10(5) larger.

Nature of electrogenerated intermediates in nitro-substituted nor-ß-lapachones: the structure of radical species during successive electron transfer in multiredox centers.

Electrochemical, spectroelectrochemical, and theoretical studies of the reduction reactions in nor-ß-lapachone derivatives including a nitro redox center showed that reduction of the compounds involves the formation of several radical intermediates, including a biradical dianion resultant from the separate reduction of the quinone and nitro groups in the molecules. Theoretical descriptions of the corresponding Fukui functions f(αα)⁺ and f(ßß)⁺(r) and LUMO densities considering finite differences and frozen core approximations for describing the changes in electron and spin densities of the system allowed us to confirm these results. A description of the potential relationship with the obtained results and biological activity selectivity indexes suggests that both the formation of stable biradical dianion species and the stability of the semiquinone intermediates during further reduction are determining factors in the description of their biological activity.

Inner reorganization limiting electron transfer controlled hydrogen bonding: intra- vs. intermolecular effects.

In this work, experimental evidence of the influence of the electron transfer kinetics during electron transfer controlled hydrogen bonding between anion radicals of metronidazole and ornidazole, derivatives of 5-nitro-imidazole, and 1,3-diethylurea as the hydrogen bond donor, is presented. Analysis of the variations of voltammetric EpIcvs. log KB[DH], where KB is the binding constant, allowed us to determine the values of the binding constant and also the electron transfer rate k, confirmed by experiments obtained at different scan rates. Electronic structure calculations at the BHandHLYP/6-311++G(2d,2p) level for metronidazole, including the solvent effect by the Cramer/Truhlar model, suggested that the minimum energy conformer is stabilized by intramolecular hydrogen bonding. In this structure, the inner reorganization energy, λi,j, contributes significantly (0.5 eV) to the total reorganization energy of electron transfer, thus leading to a diminishment of the experimental k.

Employment of electrodonating capacity as an index of reactive modulation by substituent effects: application for electron-transfer-controlled hydrogen bonding.

Evaluation of the substituent effect in reaction series is an issue of interest, as it is fundamental for controlling chemical reactivity in molecules. Within the framework of density functional theory, employment of the chemical potential, µ, and the chemical hardness, η, leads to the calculation of properties of common use, such as the electrodonating (ω(-)) and electroaccepting (ω(+)) powers, in many chemical systems. In order to examine the predictive character of the substituent effect by these indexes, a comparison between these and experimental binding constants (Kb) for binding of a series of radical anions from para- and ortho-substituted nitrobenzenes with 1,3-diethylurea in acetonitrile was performed, and fair correlations were obtained; furthermore, this strategy was suitable for all of the studied compounds, even those for which empirical approximations, such as Hammett's model, are not valid. Visual representations of substituent effects are presented by considering the local electrodonating power ω(-)(r).

Development of an activated carbon-packed microbial bioelectrochemical system for azo dye degradation.

A microbial bioelectrochemical reactor (BER) was employed for the degradation of azo dyes without the use of an external electron donor, using activated carbon (GAC) as a redox mediator. Contribution of pH values, open circuit potential (OCP), dye concentration and applied current were individually studied. A batch system and an upflow fixed bed bioreactor were built for analyzing the effect of the applied current on biodegradation of the azo dye Reactive Red 272. The presence of GAC (20% w/v) regulated both pH and OCP values in solution and led to a removal efficiency of 98%. Cyclic voltammetry results indicate a dependence of the electron transfer mechanism with the concentration of the azo compound. With these results, a continuous flow reactor operating with J=0.045 mA cm(-2), led to removal rates of 95% (± 3.5%) in a half-residence time of 1 hour.

Tacticity influence on the electrochemical reactivity of group transfer polymerization-synthesized PTMA.

Spectroscopic, thermal, and electrochemical characterization results are presented for the redox active polymer poly(2,2,6,6-tetramethyl-1-piperinidyloxy-4-yl methacrylate) or PTMA, synthesized by group transfer polymerization (GTP), and its precursors 4-hydroxy-tetramethylpiperidine-N-oxyl (HO-TEMPO) and 4-methacryloyloxy-tetramethylpiperidine-N-oxyl (MO-TEMPO). DSC analysis of synthesized PTMA showed that the glass transition temperature (T(g)) of the polymer structure occurs at 155 °C, corroborated by dynamic mechanical analysis (DMA), which is higher when compared with T(g) data for PTMA synthesized by other methods. Also, the amount of radical species present in PTMA synthesized by GTP reactions (100%) is higher than the values typically upon synthesizing PTMA by radical polymerization. Electrochemical and spectroelectrochemical-electron spin resonance studies in acetonitrile revealed two redox events in the PTMA polymer, one of which is reversible, accounting for ca. 80% of the spins in the polymer and giving rise to the battery behavior. The other redox event is irreversible, accounting for the remaining ca. 20% of spins, which has not previously been reported. These two redox events are linked to a structural property associated with the tacticity of the polymer, where the reversible feature (responsible for cathode behavior) is the dominant species. This corresponds to a number of isotactic domains of the polymer (determined by high temperature (1)H NMR). The second feature accounts for the three-line impurity observed in the ESR, which has been reported previously but poorly explained, associated to the number of heterotactic/syndiotactic triads.

Towards a molecular-level understanding of the reactivity differences for radical anions of juglone and plumbagin: an electrochemical and spectroelectrochemical approach.

An electrochemical and spectroelectrochemical strategy is presented for evaluating reactivity differences in the semiquinone anions from naturally occurring quinones juglone (5-hydroxy-1,4-naphthoquinone) and plumbagin (2-methyl-5-hydroxy-1,4-naphthoquinone). By employing cyclic voltammetry and in situ spectroelectrochemical electron spin resonance measurements, it was found that while semiquinone species generated from plumbagin are stable radical anions in DMSO solution, the species generated from juglone are more reactive. These latter species are involved in a self-protonation process involving a slow rate of protonation (1.8-2.1 mol L(-1)) due to the mild acidity of the OH group at the C-5 position. This result is important when considering observed differences in biochemical reactivity for these quinones, particularly in cases where mediated cytotoxic action is provoked by these agents, as is discussed in this work.

Inner reorganization during the radical-biradical transition in a nor-beta-lapachone derivative possessing two redox centers.

In this work, the electrochemical behaviour of an antitumoral nitro o-quinone derivative obtained from 3-bromo-nor-beta-lapachone was studied. Cyclic voltammetric experiments, in acetonitrile solution, revealed that both quinone and nitro functions are reduced independently as quasi-reversible one-electron transfer processes in this order. Depending on the reduction potential, a radical anion or a biradical dianion is obtained. The formation of these paramagnetic species was confirmed by performing in situ Electrochemical-Electron Spin Resonance (E-ESR) experiments. Analysis of the kinetics of electron transfer associated to those electron uptake processes, in terms of the Marcus-Hush-Levich model, revealed differences in the reorganization energy (lambda((k))) for both steps (lambda((I)): 1.07-1.11 eV; lambda((II)): 1.21-1.30 eV). By evaluating the conformations of the radical and biradical systems by calculations at the BLYP//TZVP level of theory, it was found that the inner component, for the second reduction process (lambda((II))) was approximately 72% of lambda((II)), reflecting modifications in the molecular structure during the radical anion-biradical dianion transition. This change is also reflected in the differences presented by line widths of the ESR signals of both electrogenerated radical and diradical species.

Analysis of the substituent effect on the reactivity modulation during self-protonation processes in 2-nitrophenols.

A voltammetric and spectroelectrochemical ESR study of the reduction processes of five substituted 4-R-2-nitrophenols (R = -H, -OCH(3), -CH(3), -CN, -CF(3)) in acetonitrile was performed. In the potential range considered here (-0.2 to -2.5 V vs Fc+/Fc), two reduction signals (Ic and IIc) were detected; the first one was associated with the formation of the corresponding hydroxylamine via a self-protonation pathway. The voltammetric analysis at the first reduction signal showed that there are differences in the reduction pathway for each substituted 4-R-2-nitrophenol, being the E1/2 values determined by the inductive effect of the substituent in the meta position with respect to the nitro group, while the electron-transfer kinetics was determined by the protonation rate (k(1)+ ) of the anion radical electrogenerated. However, at potential values near the first reduction peak, no ESR signal was recorded from stable radical species, indicating the instability of the radical species in solution. Nevertheless, an intense ESR spectrum generated at the second reduction peak was detected for all compounds, indicating the monoelectronic reduction of the corresponding deprotonated 4-R-2-nitrophenols. The spin-coupling hyperfine structures revealed differences in the chemical nature of the electrogenerated radical; meanwhile, the -CF(3) and -CN substituents induced the formation of a dianion radical structure, and the -H, -CH(3), and -OCH(3) substituents provoked the formation of an anion radical structure due to protonation by acetonitrile molecules of the initially electrogenerated dianion radical. This behavior was confirmed by analyzing the ESR spectra in deuterated acetonitrile and by performing quantum chemical calculations of the spin densities at each site of the electrogenerated anionic radicals.

Remote position substituents as modulators of conformational and reactive properties of quinones. Relevance of the pi/pi intramolecular interaction.

Several studies have described that quinoid rings with electron-rich olefins at remote position experience changes in their redox potential. Since the original description of these changes, different approaches have been developed to describe the properties of the binding sites of ubiquinones. The origin of this phenomenon has been attributed to lateral chain flexibility and its effect on the recognition between proteins and substrates associated with their important biological activity. The use of electrochemical-electron spin resonance (EC-ESR) assays and theoretical calculations at MP2/6-31G(d,p) and MP2/6-31++G(d,p)//MP2/6-31G(d,p) levels of several conformers of perezone [(2-(1,5-dimethyl-4-hexenyl)-3-hydroxy-5-methyl-1,4-benzoquinone] established that a weak pi-pi interaction controls not only the molecular conformation but also its diffusion coefficient and electrochemical properties. An analogous interaction can be suggested as the origin of similar properties of ubiquinone Q10. The use of nuclear magnetic resonance rendered, for the first time, direct evidence of the participation of different perezone conformers in solution and explained the cycloaddition process observed when the aforementioned quinone is heated to form pipitzols, sesquiterpenes with a cedrene skeleton. The fact that biological systems can modulate the redox potential of this type of quinones depending on the conformer recognized by an enzyme during a biological transformation is of great relevance.

Substituent effect on a family of quinones in aprotic solvents: an experimental and theoretical approach.

In this work a comparison between redox potentials, obtained by constructing current-potential plots from chronoamperometric measurements, and the parameter sigma(x), as proposed by Zuman in terms of the Hammett substituent parameters, was performed for several quinone compounds. This study shows the limitations of this approach and proves that methods based on quantum chemistry can be used to study the substituent effect in quinone systems. By using the Density Functional Theory, in the Kohn-Sham context with three exchange-correlation functionals, BLYP, B3LYP, and BHLYP, it was found that the electron affinity is good enough to give a useful relationship with experimental redox potentials of quinone systems. This conclusion is reached when the basis set functions involve diffuse functions, and also when the Hartree-Fock exchange energy is included in the exchange-correlation functional. The Fukui function, to describe preferential sites involved at initial stages of a system that bind an electron, is analyzed when electron donor and electron acceptor groups are present as substituents in quinone systems. The methods applied in this work are valid for any kind of quinone compound and will be used in further analysis of the electron reorganization in semiquinone species.