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The political and environmental problems related to the massive use of fossil fuels prompted researchers to develop alternative strategies to obtain green and renewable fuels such as hydrogen. The light-driven water splitting process (i.e., the photochemical decomposition of water into hydrogen and oxygen) is one of the most investigated strategies to achieve this goal. However, the water oxidation reaction still constitutes a formidable challenge because of its kinetic and thermodynamic requirements. Recent research efforts have been focused on the exploration of alternative and more favorable oxidation processes, such as the oxidation of organic substrates, to obtain value-added products in addition to solar fuels. In this mini-review, some of the most intriguing and recent results are presented. In particular, attention is directed on hybrid photoanodes comprising molecular light-absorbing moieties (sensitizers) and catalysts grafted onto either mesoporous semiconductors or conductors. Such systems have been exploited so far for the photoelectrochemical oxidation of alcohols to aldehydes in the presence of suitable co-catalysts. Challenges and future perspectives are also briefly discussed, with special focus on the application of such hybrid molecular-based systems to more challenging reactions, such as the activation of C–H bonds.

Plasma membrane function requires distinct leaflet lipid compositions. Two of the P-type ATPases (flippases) in yeast, Dnf1 and Dnf2, translocate aminoglycerophospholipids from the outer to the inner leaflet, stimulated via phosphorylation by cortically localized protein kinase Fpk1. By monitoring Fpk1 activity in vivo, we found that Fpk1 was hyperactive in cells lacking Gin4, a protein kinase previously implicated in septin collar assembly. Gin4 colocalized with Fpk1 at the cortical site of future bud emergence and phosphorylated Fpk1 at multiple sites, which we mapped. As judged by biochemical and phenotypic criteria, a mutant (Fpk1(11A)), in which 11 sites were mutated to Ala, was hyperactive, causing increased inward transport of phosphatidylethanolamine. Thus, Gin4 is a negative regulator of Fpk1 and therefore an indirect negative regulator of flippase function. Moreover, we found that decreasing flippase function rescued the growth deficiency of four different cytokinesis mutants, which suggests that the primary function of Gin4 is highly localized control of membrane lipid asymmetry and is necessary for optimal cytokinesis.

The class 4 P-type ATPases ("flippases") maintain membrane asymmetry by translocating phosphatidylethanolamine and phosphatidylserine from the outer leaflet to the cytosolic leaflet of the plasma membrane. In Saccharomyces cerevisiae, five related gene products (Dnf1, Dnf2, Dnf3, Drs2, and Neo1) are implicated in flipping of phosphatidylethanolamine, phosphatidylserine, and phosphatidylcholine. In MAT A: cells responding to α-factor, we found that Dnf1, Dnf2, and Dnf3, as well as the flippase-activating protein kinase Fpk1, localize at the projection ("shmoo") tip where polarized growth is occurring and where Ste5 (the central scaffold protein of the pheromone-initiated MAPK cascade) is recruited. Although viable, a MAT A: dnf1∆ dnf2∆ dnf3∆ triple mutant exhibited a marked decrease in its ability to respond to α-factor, which we could attribute to pronounced reduction in Ste5 stability resulting from an elevated rate of its Cln2⋅Cdc28-initiated degradation. Similarly, a MAT A: dnf1∆ dnf3∆ drs2∆ triple mutant also displayed marked reduction in its ability to respond to α-factor, which we could attribute to inefficient recruitment of Ste5 to the plasma membrane due to severe mislocalization of the cellular phosphatidylinositol 4-phosphate and phosphatidylinositol 4,5-bisphosphate pools. Thus proper remodeling of plasma membrane aminoglycerolipids and phosphoinositides is necessary for efficient recruitment, stability, and function of the pheromone signaling apparatus.

The utilization of carbon dioxide as a raw material represents nowadays an appealing strategy in the renewable energy, organic synthesis, and green chemistry fields. Besides reduction strategies, carbon dioxide can be exploited as a single-carbon-atom building block through its fixation into organic scaffolds with the formation of new C-C bonds (carboxylation processes). In this case, activation of the organic substrate is commonly required, upon formation of a carbanion C−, being sufficiently reactive toward the addition of CO2. However, the prediction of the reactivity of C− with CO2 is often problematic with the process being possibly associated with unfavorable thermodynamics. In this contribution, we present a thermodynamic analysis combined with density functional theory calculations on 50 organic molecules enabling the achievement of a linear correlation of the standard free energy (ΔG0) of the carboxylation reaction with the basicity of the carbanion C−, expressed as the pKa of the CH/C− couple. The analysis identifies a threshold pKa of ca 36 (in CH3CN) for the CH/C− couple, above which the ΔG0 of the carboxylation reaction is negative and indicative of a favorable process. We then apply the model to a real case involving electrochemical carboxylation of flavone and chalcone as model compounds of α,β-unsaturated ketones. Carboxylation occurs in the β-position from the doubly reduced dianion intermediates of flavone and chalcone (calculated ΔG0 of carboxylation in β = −12.8 and −20.0 Kcalmol-1 for flavone and chalcone, respectively, associated with pKa values for the conjugate acids of 50.6 and 51.8, respectively). Conversely, the one-electron reduced radical anions are not reactive toward carboxylation (ΔG0 > +20 Kcalmol-1 for both substrates, in either α or β position, consistent with pKa of the conjugate acids < 18.5). For all the possible intermediates, the plot of calculated ΔG0 of carboxylation vs. pKa is consistent with the linear correlation model developed. The application of the ΔG0 vs. pKa correlation is finally discussed for alternative reaction mechanisms and for carboxylation of other C=C and C=O double bonds. These results offer a new mechanistic tool for the interpretation of the reactivity of CO2 with organic intermediates.

The characterization of competent intermediates of metal complexes, involved in catalytic transformations for the activation of small molecules, is an important target for mechanistic comprehension and catalyst design. Iron complexes deserve particular attention, due to the rich chemistry of iron that allows their application both in oxidation and reduction processes. In particular, iron complexes with tetradentate Schiff base ligands show the possibility to electrochemically generate FeI intermediates, capable of reacting with carbon dioxide. In this work, we investigate the electronic and spectroscopic features of FeI intermediates in five Fe(LN2O2) complexes, and evaluate the electrocatalytic reduction of CO2 in the presence of phenol (PhOH) or trifluoroethanol (TFE) as proton donors. The main findings include: (i) a correlation of the potentials of the FeII/I couples with the electronic character of the LN2O2 ligand and the energy of the metal-to-ligand charge transfer absorption of FeI species (determined by spectroelectrochemistry, SEC-UV/Vis); (ii) the reactivity of FeI species with CO2, as proven by cyclic voltammetry and SEC-UV/Vis; (iii) the identification of Fe(salen) as a competent homogeneous electrocatalyst for CO2 reduction to CO, in the presence of phenol or trifluoroethanol proton donors (an overpotential of 0.91 V, a catalytic rate constant estimated at 5 × 104 s−1, and a turnover number of 4); and (iv) the identification of sudden, ligand-assisted decomposition routes for complexes bearing a ketylacetoneimine pendant, likely associated with the protonation under cathodic conditions of the ligands.

O crescimento da população, não só nacional como mundial, aliado aos novos padrões de vida de uma população consumista tem ocasionado um aumento significativo na geração de resíduos sólidos e tem por consequência a preocupação com saúde pública e ambiental. Este estudo objetiva caracterizar gravimetricamente os resíduos sólidos urbanos gerados no município de Iomerê, em Santa Catarina, com a perspectiva de influenciar as autoridades do município a aprimorar a gestão dos resíduos sólidos urbanos, através da implantação de um sistema de coleta seletiva. Foi realizado um sorteio intercalado e aleatório de 45 residências do município, no período entre 11/03/2014 e 16/04/2014, totalizando 13,6% das residências do município, em seguida o material foi coletado e submetido sob a técnica de caracterização gravimétrica com análises qualitativas e quantitativas dos resíduos sólidos urbanos. Foi determinado a geração de 194,00 kg.mês-1 de rejeitos, 47,40 kg.mês-1 de plástico, 66,40 kg.mês-1 de papel, 16,80 kg.mês-1 de vidro, 4,20 kg.mês-1de alumínio, 497,20 kg.mês-1 de orgânicos e 27,27 kg.mês-1 de outros resíduos, totalizando 853,70 kg.mês-1 de resíduos gerados nas residências analisadas. Assim, com o levantamento dos resíduos é possível obter as diretrizes para a implantação do sistema de coleta seletiva, visto que o município possui a necessidade da implantação desse sistema.

This paper describes the preparation and the photoelectrochemical performances of visible light driven photoanodes based on novel r-GO/β-Cu2V2O7/TiO2 nanorods/composites. β-Cu2V2O7 was deposited on both fluorine doped tin oxide (FTO) and TiO2 nanorods (NRs)/FTO by a fast and convenient Aerosol Assisted Spray Pyrolysis (AASP) procedure. Ethylenediamine (EN), ammonia and citric acid (CA) were tested as ligands for Cu2+ ions in the aerosol precursors solution. The best-performing deposits, in terms of photocurrent density, were obtained when NH3 was used as ligand. When β-Cu2V2O7 was deposited on the TiO2 NRs a good improvement in the durability of the photoanode was obtained, compared with pure β-Cu2V2O7 on FTO. A further remarkable improvement in durability and photocurrent density was obtained upon addition, by electrophoretic deposition, of reduced graphene oxide (r-GO) flakes on the β-Cu2V2O7/TiO2 composite material. The samples were characterized by X-ray Photoelectron Spectroscopy (XPS), Raman, High Resolution Transmission Electron Microscopy (HR-TEM), Scanning Electron Microscopy (SEM), Wide Angle X-ray Diffraction (WAXD) and UV-Vis spectroscopies. The photoelectrochemical (PEC) performances of β-Cu2V2O7 on FTO, β-Cu2V2O7/TiO2 and r-GO/β-Cu2V2O7/TiO2 were tested in visible light by linear voltammetry and Electrochemical Impedance Spectroscopy (EIS) measurements.