Bernardo A. Frontana-Uribe

Electrochemistry of conducting polymers--persistent models and new concepts.

2.2. Cathodic Electropolymerization 4732 2.2.1. Electropolymerization of PPXs and PPVs 4732 3. Charging-Discharging of Conducting Polymers 4733 3.1. Redox Properties of Oligomers and Polymers 4733 3.2. Specific Phenomena of n-Doping 4739 3.3. Conductivity in Charged Systems 4740 4. Controlling the Electropolymerization Process 4742 4.1. Influence of the Polymerization Technique 4742 4.2. Influence of Experimental Conditions 4743 4.3. Electropolymerization in Novel Electrolytic Media 4745

Organic electrosynthesis: a promising green methodology in organic chemistry

Over the last decade, organic electrosynthesis has become recognized as one of the methodologies that can fulfill several important criteria that are needed if society is to develop environmentally compatible processes. It can be used to replace toxic or dangerous oxidizing or reducing reagents, reduce energy consumption, and can be used for the in situ production of unstable and hazardous reagents. These are just a few of the most important attributes that render electrochemistry environmentally useful. In this review the main characteristics of electrochemistry as a promising green methodology for organic synthesis are described and exemplified. Herein we provide basic information concerning the nature of electrosynthetic processes, paired electrochemical reactions, electrocatalytic reactions, reactions carried out in ionic liquids, electrogeneration of reactants, electrochemical reactions that use renewable starting materials (biomass), green organic electrosynthesis in micro- and nano-emulsions, the synthesis of complex molecules using an electrosynthetic key step, and conclude with some insights concerning the future. Throughout the review the “green aspects” of these topics are highlighted and their relationship with the twelve green chemistry principles is described.

Polyisoprenylated Benzophenones In Cuban Propolis; Biological Activity Of Nemorosone §

The Copey tree (Clusia rosea) has a large distribution in Cuba and its floral resin is a rich source of polyisoprenylated benzophenones. To determine the presence of these natural products, we carried out a study by HPLC of 21 propolis samples produced by honey bees (Apis mellifera) from different provinces of Cuba. Nemorosone resulted to be the most abundant polyisoprenylated benzophenone and the mixture of xanthochymol and guttiferone E was also observed, but in minor proportion. We studied the biological activity of the pure natural product nemorosone and its methyl derivatives. We found that nemorosone has cytotoxic activity against epitheloid carcinoma (HeLa), epidermoid carcinoma (Hep-2), prostate cancer (PC-3) and central nervous system cancer (U251). It also exhibited antioxidant capacity. Methylated nemorosone exhibited less biological activity than the natural product

Nemorosone, the major constituent of floral resins of Clusia rosea

Nemorosone, the major constituent of the floral resin of Clusia rosea was isolated after exhaustive chromatography. This compound was fully characterized as it is in the nature, without methylation as reported before. A keto-enol equilibrium was observed and both isomers were totally characterized by NMR spectroscopic techniques. The previously announced structure for methylnemorosone was corrected on the basis of application of chemical methylation, high field 2D NMR techniques and NOE difference spectroscopy experiments on the natural product. Our studies concluded that an interchange occurred in the assignment of the benzoyl moiety position with an isoprenyl group in that structure.

Characterization and detoxification of a mature landfill leachate using a combined coagulation-flocculation/photo Fenton treatment.

The aim of the present work was to characterize and treat a mature landfill leachate using a coagulation/flocculation process followed by a photo-Fenton oxidation treatment. The leachate was obtained from a landfill in Tetlama, Morelos (Mexico) during the drought season and was characterized in terms of its major pollutants. Considerable levels of chemical oxygen demand (COD), total carbon (TC) and NH4+ were identified, as well as high concentrations of Hg, Pb, and As. Other heavy metals such as Ni, Co, Zn, Cd, and Mn were detected at trace levels. The lethal concentration (LC50) of the leachate, evaluated on Artemia salina, was 12,161±11 mg/L of COD, demonstrating an antagonistic interaction among the leachates components. The treatment of this effluent consisted of a coagulation-flocculation process using an optimal dose of FeCl3 · 6H2O of 300 mg/L. The supernatant was treated using a photo-Fenton process mediated with FeCl2 · 4H2O and H2O2 in a compound parabolic concentrator (CPC) photo-reactor operating in batch mode using an R ratio (R=[H2O2]/[Fe2+]) of 114. The global removal efficiencies after treatment were 56% for the COD, 95% for TC, and 64% for NH4+. The removal efficiencies for As, Hg, and Pb were 46%, 9%, and 85%, respectively.

A ferrous oxalate mediated photo-Fenton system: Toward an increased biodegradability of indigo dyed wastewaters

This study assessed the applicability of a ferrous oxalate mediated photo-Fenton pretreatment for indigo-dyed wastewaters as to produce a biodegradable enough effluent, likely of being derived to conventional biological processes. The photochemical treatment was performed with ferrous oxalate and hydrogen peroxide in a Compound Parabolic Concentrator (CPC) under batch operation conditions. The reaction was studied at natural pH conditions (5-6) with indigo concentrations in the range of 6.67-33.33 mg L(-1), using a fixed oxalate-to-iron mass ratio (C(2)O(4)(2-)/Fe(2+)=35) and assessing the systems biodegradability at low (257 mg L(-1)) and high (1280 mg L(-1)) H(2)O(2) concentrations. In order to seek the optimal conditions for the treatment of indigo dyed wastewaters, an experimental design consisting in a statistical surface response approach was carried out. This analysis revealed that the best removal efficiencies for Total Organic Carbon (TOC) were obtained for low peroxide doses. In general it was observed that after 20 kJ L(-1), almost every treated effluent increased its biodegradability from a BOD(5)/COD value of 0.4. This increase in the biodegradability was confirmed by the presence of short chain carboxylic acids as intermediate products and by the mineralization of organic nitrogen into nitrate. Finally, an overall decrease in the LC(50) for Artemia salina indicated a successful detoxification of the effluent.

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.

Comparative study of the N-isobutyl-(2E,6Z)-dodecadienamide chemical and electrochemical syntheses

In order to show the advantages and limitations of organic electrosynthesis in the total synthesis of a natural product, one of the promising green chemistry techniques in organic chemistry, the synthesis of N-isobutyl-(2E,6Z)-dodecadienamide (3) was undertaken. Chemical and electrochemical routes that use the same intermediates were used to carry out the syntheses. Four reactions were compared from a green chemistry point of view in the synthesis of 3: (a) alcohol to aldehyde oxidation, (b) the Horner–Emmons reaction, (c) carboxylic acid amidation with triphenylphosphonium ions and (d) the Wittig reaction. All the electrolyses were carried out in non-divided cells at a constant current. The electrochemical method in the oxidation reaction of alcohols and the carboxylic acid amidation gave better yields (95% and 67%, respectively) than the corresponding chemical reactions. The Horner–Emmons reaction gave the same yields in both techniques (80–85%); however, the electrochemical method was more environmentally friendly, due to the fact that the base used was electrogenerated, avoiding corrosive and sensitive base manipulation. Finally, the electrochemical Wittig reaction was unsuccessful in the different experimental conditions attempted, and only the chemical method produced the target product. This study demonstrated that organic electrochemistry can be a reliable method for the synthesis of important intermediates, but not all electrochemical reactions can compete with the already well-established methods of organic chemistry.

Conducting Polymers in the Fields of Energy, Environmental Remediation, and Chemical–Chiral Sensors

Conducting polymers (CPs), thanks to their unique properties, structures made on-demand, new composite mixtures, and possibility of deposit on a surface by chemical, physical, or electrochemical methodologies, have shown in the last years a renaissance and have been widely used in important fields of chemistry and materials science. Due to the extent of the literature on CPs, this review, after a concise introduction about the interrelationship between electrochemistry and conducting polymers, is focused exclusively on the following applications: energy (energy storage devices and solar cells), use in environmental remediation (anion and cation trapping, electrocatalytic reduction/oxidation of pollutants on CP based electrodes, and adsorption of pollutants) and finally electroanalysis as chemical sensors in solution, gas phase, and chiral molecules. This review is expected to be comprehensive, authoritative, and useful to the chemical community interested in CPs and their applications.

Reduction of pollutants and disinfection of industrial wastewater by an integrated system of copper electrocoagulation and electrochemically generated hydrogen peroxide

The objective of this study was to evaluate the effect of copper electrocoagulation and hydrogen peroxide on COD, color, turbidity, and bacterial activity in a mixed industry wastewater. The integrated system of copper electrocoagulation and hydrogen peroxide is effective at reducing the organic and bacterial content of industrial wastewater. The copper electrocoagulation alone reduces COD by 56% in 30 min at pH 2.8, but the combined system reduces COD by 78%, biochemical oxygen demand (BOD5) by 81%, and color by 97% under the same conditions. Colloidal particles are flocculated effectively, as shown by the reduction of zeta potential and the 84% reduction in turbidity and 99% reduction in total solids. Additionally, the total coliforms, fecal coliforms, and bacteria are all reduced by 99%. The integrated system is effective and practical for the reduction of both organic and bacterial content in industrial wastewater.