Polymeric foams as the matrix of voltammetric sensors for the detection of catechol, hydroquinone, and their mixtures

Producción CientíficaPorous electrodes based on polymethylmethacrylate and graphite foams (PMMA_G_F) have been developed and characterized. Such devices have been successfully used as voltammetric sensors to analyze catechol, hydroquinone, and their mixtures. The presence of pores induces important changes in the oxidation/reduction mechanism of catechol and hydroquinone with respect to the sensing properties observed in nonfoamed PMMA_graphite electrodes (PMMA_G). The electropolymerization processes of catechol or hydroquinone at the electrode surface observed using PMMA_G do not occur at the surface of the foamed PMM_G_F. In addition, the limits of detection observed in foamed electrodes are one order of magnitude lower than the observed in the nonfoamed electrodes. Moreover, foamed electrodes can be used to detect simultaneously both isomers and a remarkable increase in the electrocatalytic properties shown by the foamed samples, produces a decrease in the oxidation potential peak of catechol in presence of hydroquinone, from +0.7 V to +0.3 V. Peak currents increased linearly with concentration of catechol in presence of hydroquinone over the range of 0.37·10−3 M to 1.69·10−3 M with a limit of detection (LOD) of 0.27 mM. These effects demonstrate the advantages obtained by increasing the active surface by means of porous structures.Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (project AGL2015-67482-R)Junta de Castilla y Leon - Fondo Europeo de Desarrollo Regional (project VA-011U16

The Electrochemical Oxidation of Substituted Catechols

The oxidation of substituted catechols was studied by cyclic voltammetry, chronoamperometry, rotating ring‐disk electrode, and coulometry. The results showed that the quinones that were formed from the oxidation of substituted catechols reacted with the basic forms of the starting material to yield the dimeric product. These products were generally unstable and rapidly polymerized or underwent some other irreversible reaction to form an electroinactive product. For 3,4‐dihydroxyacetophenone and propriophenone, the intermediate was stable long enough to be observed in cyclic voltammetry. The rate of the coupling reaction was found to correlate well with the Hammett ρ‐σ parameters and indicated that there was substantial negative charge in the transition state. Finally, an analysis of the coulometric n‐values along with the iat1/2/C values indicated that the initial coupling product was a diphenyl ether. Analysis of the coulometry products showed extensive polymerization

Transcriptional analysis of pqqD and study of the regulation of pyrroloquinoline quinone biosynthesis in Methylobacterium extorquens AM1

Methanol dehydrogenase, the enzyme that oxidizes methanol to formaldehyde in gram-negative methylotrophs, contains the prosthetic group pyrroloquinoline quinone (PQQ). To begin to analyze how the synthesis of PQQ is coordinated with the production of other methanol dehydrogenase components, the transcription of one of the key PQQ synthesis genes has been studied. This gene (pqqD) encodes a 29-amino- acid peptide that is thought to be the precursor for PQQ biosynthesis. A unique transcription start site was mapped to a guanidine nucleotide 95 bp upstream of the pqqD initiator codon. RNA blot analysis identified two transcripts, a major one of 240 bases encoding pqqD and a minor one of 1,300 bases encoding pqqD and the gene immediately downstream, pqqG. Both transcripts are present at similar levels in cells grown on methanol and on succinate, but the levels of PQQ are about fivefold higher in cells grown on methanol than in cells grown on succinate. These results suggest that PQQ production is regulated at a level different from the transcription of pqqD. The genes mxbM, mxbD, mxcQ, mxcE, and mxaB are required for transcription of the genes encoding the methanol dehydrogenase subunits and were assessed for their role in PQQ production. PQQ levels were measured in mutants defective in each of these regulatory genes and compared with levels of pqqD transcription, measured with a transcriptional fusion between the pqqD promoter and xylE. The results showed that only a subset of these regulatory genes (mxbM, mxbD, and mxaB) is required for transcription of pqqD, and only mxbM and mxbD mutants affected the final levels of PQQ significantly

A Review on the Bulk and Surface Chemistry of Iron in Atmospherically-relevant Systems Containing Humic Like Substances (HULIS)

As the fourth most abundant element by mass in the Earth’s crust, iron is ubiquitous and its chemistry is rich and interdisciplinary in nature. This review synthesizes the current state of knowledge of iron chemistry in multicomponent atmospheric aerosols, which is also applicable to other atmospherically-relevant systems that include iron-containing anthropogenic nanodust, ocean surfaces and buildings. Because of the abundance of humic-like substances (HULIS) in these systems, studies on their chemistry with iron and those used as models for HULIS are the focus of this review. Findings from field measurements and laboratory studies are summarized to highlight major themes in iron chemical reactivity that varies depending on the solubility, redox conditions, absence and presence of UV-visible light and reactive oxygen species, pH, and temperature. The review also highlights key differences between bulk and surface chemistry of iron-containing materials, which varies considerably because of the structure of interfacial water and solvent cage effect. Additional laboratory, field, and modeling studies are needed to better understand the contributions of transition metals chemistry to secondary organic aerosol formation and chemistry, uptake, and release of trace gas phase species. This information will improve the predictive power of models that incorporate aerosols chemistry and physics

Isolation and characterization of Alicycliphilus denitrificans strain BC, which grows on benzene with chlorate as the electron acceptor

A bacterium, strain BC, was isolated from a benzene-degrading chlorate-reducing enrichment culture. Strain BC degrades benzene in conjunction with chlorate reduction. Cells of strain BC are short rods that are 0.6 microm wide and 1 to 2 microm long, are motile, and stain gram negative. Strain BC grows on benzene and some other aromatic compounds with oxygen or in the absence of oxygen with chlorate as the electron acceptor. Strain BC is a denitrifying bacterium, but it is not able to grow on benzene with nitrate. The closest cultured relative is Alicycliphilus denitrificans type strain K601, a cyclohexanol-degrading nitrate-reducing betaproteobacterium. Chlorate reductase (0.4 U/mg protein) and chlorite dismutase (5.7 U/mg protein) activities in cell extracts of strain BC were determined. Gene sequences encoding a known chlorite dismutase (cld) were not detected in strain BC by using the PCR primers described in previous studies. As physiological and biochemical data indicated that there was oxygenation of benzene during growth with chlorate, a strategy was developed to detect genes encoding monooxygenase and dioxygenase enzymes potentially involved in benzene degradation in strain BC. Using primer sets designed to amplify members of distinct evolutionary branches in the catabolic families involved in benzene biodegradation, two oxygenase genes putatively encoding the enzymes performing the initial successive monooxygenations (BC-BMOa) and the cleavage of catechol (BC-C23O) were detected. Our findings suggest that oxygen formed by dismutation of chlorite can be used to attack organic molecules by means of oxygenases, as exemplified with benzene. Thus, aerobic pathways can be employed under conditions in which no external oxygen is supplie

Physiological and genetic description of dissimilatory perchlorate reduction by the novel marine bacterium Arcobacter sp. strain CAB.

A novel dissimilatory perchlorate-reducing bacterium (DPRB), Arcobacter sp. strain CAB, was isolated from a marina in Berkeley, CA. Phylogenetically, this halophile was most closely related to Arcobacter defluvii strain SW30-2 and Arcobacter ellisii. With acetate as the electron donor, strain CAB completely reduced perchlorate (ClO4(-)) or chlorate (ClO3(-)) [collectively designated (per)chlorate] to innocuous chloride (Cl(-)), likely using the perchlorate reductase (Pcr) and chlorite dismutase (Cld) enzymes. When grown with perchlorate, optimum growth was observed at 25 to 30°C, pH 7, and 3% NaCl. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) preparations were dominated by free-swimming straight rods with 1 to 2 polar flagella per cell. Strain CAB utilized a variety of organic acids, fructose, and hydrogen as electron donors coupled to (per)chlorate reduction. Further, under anoxic growth conditions strain CAB utilized the biogenic oxygen produced as a result of chlorite dismutation to oxidize catechol via the meta-cleavage pathway of aerobic catechol degradation and the catechol 2,3-dioxygenase enzyme. In addition to (per)chlorate, oxygen and nitrate were alternatively used as electron acceptors. The 3.48-Mb draft genome encoded a distinct perchlorate reduction island (PRI) containing several transposases. The genome lacks the pcrC gene, which was previously thought to be essential for (per)chlorate reduction, and appears to use an unrelated Arcobacter c-type cytochrome to perform the same function. IMPORTANCE The study of dissimilatory perchlorate-reducing bacteria (DPRB) has largely focused on freshwater, mesophilic, neutral-pH environments. This study identifies a novel marine DPRB in the genus Arcobacter that represents the first description of a DPRB associated with the Campylobacteraceae. Strain CAB is currently the only epsilonproteobacterial DPRB in pure culture. The genome of strain CAB lacks the pcrC gene found in all other DPRB tested, demonstrating a new variation on the (per)chlorate reduction pathway. The ability of strain CAB to oxidize catechol via the oxygenase-dependent meta-cleavage pathway in the absence of external oxygen by using the biogenic oxygen produced from the dismutation of chlorite provides a valuable model for understanding the anaerobic degradation of a broad diversity of xenobiotics which are recalcitrant to anaerobic metabolism but labile to oxygenase-dependent mechanisms

Dangling and hydrolyzed ligand arms in [Mn3] and [Mn6] coordination assemblies: synthesis, characterization, and functional activity

Two flexible, branched, and sterically constrained di- and tripodal side arms around a phenol backbone were utilized in ligands H3L1 and H5L2 to isolate {Mn6} and {Mn3} coordination aggregates. 2,6-Bis{(1-hydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol (H3L1) gave trinuclear complex [Mn3(μ-H2L1)2(μ1,3-O2CCH3)4(CH3OH)2](ClO4)2·4CH3OH (1), whereas 2,6-bis[{1-hydroxy-2-(hydroxymethyl)butan-2-ylimino}methyl]-4-methylphenol (H5L2) provided hexanuclear complex [Mn6(μ4-H2L2)2(μ-HL3)2(μ3-OH)2(μ1,3-O2CC2H5)4](ClO4)2·2H2O (2). Binding of acetates and coordination of {H2L1}− provided a linear MnIIIMnIIMnIII arrangement in 1. A MnIII6 fused diadamantane-type assembly was obtained in 2 from propionate bridges, coordination of {H2L2}3–, and in situ generated {HL3}2–. The magnetic characterization of 1 and 2 revealed the properties dominated by intramolecular anti-ferromagnetic exchange interactions, and this was confirmed using density functional theory calculations. Complex 1 exhibited field-induced slow magnetic relaxation at 2 K due to the axial anisotropy of MnIII centers. Both the complexes show effective solvent-dependent catechol oxidation toward 3,5-di-tert-butylcatechol in air. The catechol oxidation abilities are comparable from two complexes of different nuclearity and structure

Differential Cyclic Voltammetry - a Novel Technique for Selective and Simultaneous Detection using Redox Cycling Based Sensors

Redox cycling (RC) is an effect that is used to amplify electrochemical signals. However, traditional techniques such as cyclic voltammetry (CV) do not provide clear insight for a mixture of multiple redox couples while RC is applied. Thus, we have developed a new measurement technique which delivers electrochemical spectra of all reversible redox couples present based on concentrations and standard potentials. This technique has been named differential cyclic voltammetry (DCV). We have fabricated micrometer-sized interdigitated electrode (IDE) sensors to conduct DCV measurements in mixtures of 1mM catechol and 4mM [Ru(NH3)6]Cl3. To simulate the electrochemical behavior of these sensors we have also developed a finite element model (FEM) in Comsol®. The\ud experimental data corresponds to the calculated spectra obtained from simulations. Additionally, the measured spectra can be used to easily derive standard potentials and concentrations simultaneously and selectively.\u

Robust and Biocompatible Functionalization of ZnS Nanoparticles by Catechol-Bearing Poly(2-Methyl-2-Oxazoline)s.

Zinc sulfide (ZnS) nanoparticles (NPs) are particularly interesting materials for their electronic and luminescent properties. Unfortunately, their robust and stable functionalization and stabilization, especially in aqueous media, has represented a challenging and not yet completely accomplished task. In this work, we report the synthesis of colloidally stable, photoluminescent and biocompatible core\u2013polymer shell ZnS and ZnS:Tb NPs by employing a water-in-oil miniemulsion (ME) process combined with surface functionalization via catechol-bearing poly-2-methyl-2-oxazoline (PMOXA) of various molar masses. The strong binding of catechol anchors to the metal cations of the ZnS surface, coupled with the high stability of PMOXA against chemical degradation, enable the formation of suspensions presenting excellent colloidal stability. This feature, combined with the assessed photoluminescence and biocompatibility, make these hybrid NPs suitable for optical bioimaging