α-Fe2O3/, Co3O4/, and CoFe2O4/MWCNTs/Ionic Liquid Nanocomposites as High-Performance Electrocatalysts for the Electrocatalytic Hydrogen Evolution Reaction in a Neutral Medium.

Transition metal oxides are a great alternative to less expensive hydrogen evolution reaction (HER) catalysts. However, the lack of conductivity of these materials requires a conductor material to support them and improve the activity toward HER. On the other hand, carbon paste electrodes result in a versatile and cheap electrode with good activity and conductivity in electrocatalytic hydrogen production, especially when the carbonaceous material is agglomerated with ionic liquids. In the present work, an electrode composed of multi-walled carbon nanotubes (MWCNTs) and cobalt ferrite oxide (CoFe2O4) was prepared. These compounds were included on an electrode agglomerated with the ionic liquid N-octylpyridinium hexafluorophosphate (IL) to obtain the modified CoFe2O4/MWCNTs/IL nanocomposite electrode. To evaluate the behavior of each metal of the bimetallic oxide, this compound was compared to the behavior of MWCNTs/IL where a single monometallic iron or cobalt oxides were included (i.e., α-Fe2O3/MWCNTs/IL and Co3O4/MWCNTs/IL). The synthesis of the oxides has been characterized by X-ray diffraction (XRD), RAMAN spectroscopy, and field emission scanning electronic microscopy (FE-SEM), corroborating the nanometric character and the structure of the compounds. The CoFe2O4/MWCNTs/IL nanocomposite system presents excellent electrocatalytic activity toward HER with an onset potential of -270 mV vs. RHE, evidencing an increase in activity compared to monometallic oxides and exhibiting onset potentials of -530 mV and -540 mV for α-Fe2O3/MWCNTs/IL and Co3O4/MWCNTs/IL, respectively. Finally, the system studied presents excellent stability during the 5 h of electrolysis, producing 132 µmol cm-2 h-1 of hydrogen gas.

Electrical and Electrochemical Behavior of Carbon Paste Electrodes Modified with Ionic Liquids Based in N-Octylpyridinium Bis(Trifluoromethylsulfonyl)Imide. A Theoretical and Experimental Study.

In this work, we studied carbon paste electrodes (CPEs) with two kinds of binders: mineral oil or ionic liquids (IL) derived from N-substituted octyl pyridinium bis(trifluoromethylsulfonyl)imide with the substituents H-, CH3-, CN- and CF3-. The work aims to study this series of IL and determine a possible effect of the substituent of the cation in the behavior of the IL as a binder of graphite for obtaining IL-CPEs. The electrochemical response and the electrical behavior were measured by cyclic voltammetry and electrochemical impedance spectroscopy, respectively. Surprisingly, the substituent does not affect the cyclic voltammetry response because in all the cases, high resistance and high capacitive currents were obtained. The best response in terms of conductivity is obtained by CPE. In the case of impedance measurements, the substituent does not cause differences, and in all the cases, the IL-CPEs show nearly the same responses. CPE shows lower capacitance and higher resistance for diffusion compared to the IL-CPEs due to his lower porosity. The high resistance showed by the IL-CPEs by cyclic voltammetry can be attributed to poorly intermolecular forces among graphite, water, electrolyte, and ILs as demonstrated by theoretical calculations.

Recent progress, trends, and new challenges in the electrochemical production of green hydrogen coupled to selective electrooxidation of 5-hydroxymethylfurfural (HMF).

The production of clean electrical energy and the correct use of waste materials are two topics that currently concern humanity. In order to face both problems, extensive work has been done on the electrolytic production of green H2 coupled with the electrooxidative upgrading of biomass platform molecules. 5-Hydroxymethylfurfural (HMF) is obtained from forest waste biomass and can be selectively oxidized to 2,5-furandicarboxylic acid (FDCA) by electrochemical pathways. FDCA is an attractive precursor to polyethylene furanoate (PEF), with the potential to replace petroleum-based polyethylene terephthalate (PET). An integrated electrochemical system can simultaneously produce H2 and FDCA at a lower energy cost than that required for electrolytic water splitting. Here, the benefits of the electrochemical production of H2 and FDCA over other production methods are presented, as well as the innovative applications of each reaction product and the advantages of carrying out both reactions in a coupled system. The recently reported progress is disclosed, through an exploration of electrocatalyst materials used in simultaneous production, including the use of nickel foams (NF) as modification substrates, noble and non-noble metals, metal non-oxides, metal oxides, spinel oxides and the introduction of oxygen vacancies. Based on the latest trends, the next challenges associated with its large-scale production are proposed for its implementation in the industrial world. This work can offer a guideline for the detailed understanding of the electrooxidation of HMF towards FDCA with the production of H2, as well as the design of advanced electrocatalysts for the sustainable use of renewable resources.

A Mg2+-induced conformational switch rendering a competent DNA polymerase catalytic complex.

The structural and dynamical changes occurring before nucleotide addition were studied using molecular dynamics (MD) simulations of human immunodeficiency virus type 1 (HIV-1) reverse transcriptase (RT) complexes containing one or two Mg2+ ions in the presence of dNTP. Our models revealed that the formation of a catalytically competent DNA polymerase complex required subtle rearrangements at the catalytic site A, which occurred only when an Mg2+ ion was bound. This model has been validated using pre-steady-state kinetics to show that free Mg2+ is necessary to obtain a catalytically competent polymerase. Kinetic studies carried out with Be2+ as a cofactor permitted the functional discrimination between metal sites A and B. At low concentrations, Be2+ increased the catalytic efficiency of the polymerase, while at higher concentrations, it competed with Mg2+ for binding to site A, and inhibited DNA polymerization. In agreement with experimental data, MD simulations revealed that the catalytic attack distance between the 3-OH of the primer and the phosphorus in complexes containing Be2+ instead of Mg2+ at site A was above 4.5 A. Our findings provide a detailed description of the mechanism of DNA polymerization and should be helpful to understand the molecular basis of DNA replication fidelity.

Spatial and Temporal Patterns of Neurogenesis in the Chick Retina.

Chick embryo retinas were labelled in ovo by single injections of [3H]thymidine at selected times between days 2 and 12 of incubation. Embryos were later removed, at different stages of development, and the retinas processed for autoradiography of either serial sections or dissociated cell preparations. Analysis of unlabelled cells shows that neurogenesis starts, on day 2 of incubation, in a dorsotemporal area of the central retina, close to the posterior pole and to the optic nerve head. A gradient of neurogenesis spreads from this central area to the periphery, where neurogenesis ends, shortly after day 12, when the last few bipolar cells withdraw from the cell cycle. Additional dorsal-to-ventral and temporal-to-nasal gradients can be discerned in our autoradiographs. In all retinal sectors, ganglion cells start first to withdraw from the cell cycle, followed, with substantial overlapping, by amacrine, horizontal, photoreceptor plus Müller, and bipolar neuroblasts. Ganglion cells are also the first to reach the 50% level of unlabelled cells, followed this time by horizontal, photoreceptor, amacrine, Müller and bipolar cells. Finally, 100% levels of unlabelled cell populations are attained simultaneously by ganglion, horizontal and photoreceptor cells, followed by amacrine, then by Müller, and last by bipolar cells. Although all classes of neurons, in varying proportions, are being produced most of the time, our results also demonstrate that, in any given retinal area, the first cells leaving the cycle are determined to become ganglion cells, and the last ones bipolar cells, and not other types.

Kainate-triggered currents in Xenopus oocytes injected with chick retinal membrane fragments: effect of guanine nucleotides.

PURPOSE: To electrophysiologically characterize alpha-amino-3-hydroxy-5-methyl-4-isoxazolepropionate (AMPA)/kainate receptors in chick retinal membrane fragments, incorporated into Xenopus oocytes by direct microinjection. METHODS: A 6-day retinal membrane suspension was injected into Xenopus oocytes by use of an electronic nanoliter injector. Fifteen to 40 hours after injection, the oocytes were assayed for kainate-elicited inward currents, under voltage-clamp conditions (membrane potential held at -70 mV). The structural incorporation of the retinal membrane fragments into the oocyte membrane was verified by specific immunofluorescent staining. RESULTS: Chick retinal membrane fragments were efficiently grafted onto Xenopus oocytes after microinjection, with 22.9% +/- 7.6% of the oocyte membrane being stained with anti-chick retina antibody. Part of the retinal material was seen as patches of relatively uniform size (292.1 +/- 72.3 microm(2)). Bath-applied kainate induced dose-dependent (EC(50): 64 +/- 7 microM), nondesensitizing inward currents (15-90 nA) in the chimeric Xenopus oocytes. Sham-injected oocytes did not respond to kainate. Kainate-driven currents were blocked by 6,7-dinitroquinoxaline-2,3-dione (DNQX) and 1-(4-aminopropyl)-4-methyl-7,8-methylenedioxy-5H-2,3-benzodiazepine hydrochloride (GYKI 52466), but not by gamma-D-glutamylaminomethyl sulfonic acid (GAMS) or aminophosphonoheptanoate (AP7), suggesting the involvement of AMPA receptors in the observed responses. Guanine nucleotides (GNs) also blocked kainate currents in a concentration-dependent manner. CONCLUSIONS: An alternative oocyte microinjection technique to analyze the electrophysiological properties of glutamate receptors in chick retinal membranes is described. The results show the functional activity of putative AMPA-preferring receptors from chick retina and confirm, in the chick retinal model, the antagonistic behavior of guanine nucleotides toward glutamate receptors and their potential role as neuroprotective agents under excitotoxic conditions.

Guanine and adenine nucleotidase activities in rat cerebrospinal fluid.

Adenine and guanine nucleotides have been shown to exert multiple roles in central and peripheral nervous systems, and the sequential breakdown of these nucleotides by enzymatic systems is an important step in the modulation of their extracellular effects. The aim of this study was to investigate whether nucleotide hydrolysis also occurs in the cerebrospinal fluid (CSF) of rats. CSF was able to hydrolyze all guanine and adenine nucleotides investigated (2.0 mM): GDPz.Gt;ADP=ATP=GTPz.Gt;AMP=GMP. More detailed studies with the diphosphate nucleotides showed that the hydrolysis of ADP and GDP was linear with incubation time and protein concentration. The apparent K(M) (Henry-Michaelis-Menten constant) and V (maximal velocity) values for ADP and GDP were 164.3+/-54.7 microM and 12.2+/-3.8 nmol P(i)/min per mg protein, and 841.0+/-90.2 microM and 22.8+/-8.0 nmol P(i)/min per mg protein. The sum of ADP, GDP and UDP hydrolysis (2.0 mM) upon individual incubations with CSF was similar to the hydrolysis observed when all three nucleotides were incubated together. This pattern of hydrolysis strongly suggests the involvement of more than one enzyme activity. The higher maximum activity for GDP and UDP compared to ADP is compatible with presence of a soluble NTDPase5.

Binding of 5'-GMP to the GluR2 AMPA receptor: insight from targeted molecular dynamics simulations.

Guanine nucleotides behave as competitive antagonists at ionotropic glutamate receptors and show neuroprotective activity in different experimental excitotoxicity paradigms, both in vivo and in cultured cell preparations. Taking 5'-GMP as the reference nucleotide, we have tried to understand how these molecules interact with the agonist-binding site of the GluR2 alpha-amino-3-hydroxy-5-methyl-4-isoxazolepropionate (AMPA) receptor. Using a crystallographic model of the ligand-binding core of the GluR2 receptor in complex with kainate, we have previously analyzed the structural changes associated to the binding of agonists to the receptor and suggested a mechanism for the coupling of agonist binding to channel gating. In the present investigation we used the structure of the apo form of the receptor to probe the primary interactions between GMP and GluR2 by means of an automated docking program. A targeted molecular dynamics (TMD) simulation procedure was subsequently used to force the closing of the protein and to study the rearrangement of the ligand and surrounding amino acids. The resulting structure provides a plausible model of the nucleotide-receptor complex. Indirect support for the validity of our approach was obtained when the same methodology was shown to yield structures of the kainate-GluR2 and 6,7-dinitroquinoxaline-2,3-dione (DNQX)-GluR2 complexes that were in very good agreement with the published crystallographic structures. Both the stacking interaction between the phenyl ring of Tyr73 and the purine ring of GMP and a salt bridge between the phosphate group of GMP and Arg108 in the S1 domain, together with several hydrogen bonds, are proposed to secure the anchoring of GMP to the agonist-binding site. Unlike conventional competitive antagonists, such as DNQX, occupancy of the site by GMP still allows receptor segments S1 and S2 to close tightly around GMP without interacting with the critical residue Glu209 that triggers channel opening. Thus, GMP appears to be rather a false agonist than a competitive antagonist. This fact and the nature of the energy barriers that stabilize GMP bound to the closed form of the receptor provide an explanation for the unusual behavior of some guanine nucleotides in ligand-displacement experiments.