Enzymatically synthesized polyaniline film deposition studied by simultaneous open circuit potential and electrochemical quartz crystal microbalance measurements

The chemical and enzymatic deposition of polyaniline (PANI) films by in situ polymerization was studied and the resulting films were characterized. The film formation and polymerization processes were simultaneously monitored by the evolution of the open circuit potential and quartz-crystal microbalance measurements. Different substrates, such as Indium-Tin oxide electrodes and gold-coated quartz-crystal electrodes were used as substrates for PANI deposition. Electroactive PANI films were successfully deposited by in situ enzymatic polymerization at low oxidation potential. The electrogravimetric response of the enzymatically deposited PANI film was studied by cyclic voltammetry in monomer-free acidic medium. The morphology of the films was observed by scanning electron microscopy, revealing a granular structure in enzymatically deposited PANI. The PANI films were also characterized by thermogravimetric analysis, electrochemical impedance spectroscopy, and X-ray photoelectron and Fourier-transformed infrared spectroscopy. The simultaneous use of quartz crystal microbalance and open circuit potential is presented as a very useful technique to monitor enzymatic reactions involving oxidoreductases.     

Organocatalytic enantioselective synthesis of 2,3-dihydropyridazines

We have developed an efficient procedure for the easy and straightforward preparation of functionalized dihydropyridazines as highly enantiopure materials by reaction of pyruvaldehyde 2-tosyl hydrazone with a variety of α,β-unsaturated aldehydes using a chiral secondary amine as catalyst. The overall process consists of a cascade reaction involving an initial aza-Michael reaction, in which the stereocentre is installed, followed by an intramolecular aldol reaction/dehydration step.     

Stabilization of graphene sheets by a structured benzene/hexafluorobenzene mixed solvent

Applications requiring pristine graphene derived from graphite demand a solution stabilization method that utilizes an easily removable media. Using a combination of molecular dynamics simulations and experimental techniques, we investigate the solublization/suspension of pristine graphene sheets by an equimolar mixture of benzene and hexafluorobenzene (C(6)H(6)/C(6)F(6)) that is known to form an ordered structure solidifying at 23.7 °C. Our simulations show that the graphene surface templates the self-assembly of the mixture into periodic layers extending up to 30 ? from both sides of the graphene sheet. The solvent structuring is driven by quadrupolar interactions and consists of stacks of alternating C(6)H(6)/C(6)F(6) molecules rising from the surface of the graphene. These stacks result in density oscillations with a period of about 3.4 ?. The high affinity of the 1:1 C(6)H(6)/C(6)F(6) mixture with graphene is consistent with observed hysteresis in Wilhelmy plate measurements using highly ordered pyrolytic graphite (HOPG). AFM, SEM, and TEM techniques verify the state of the suspended material after sonication. As an example of the utility of this mixture, graphene suspensions are freeze-dried at room temperature to produce a sponge-like morphology that reflects the structure of the graphene sheets in solution.     

Capillary flooding of wood with microemulsions from Winsor I systems

A new approach based on microemulsions formulated with at least 85% water and minority components consisting of oil (limonene) and surfactant (anionic and nonionic) is demonstrated for the first time to be effective for flooding wood's complex capillary structure. The formulation of the microemulsion was based on phase behavior scans of Surfactant-Oil-Water systems (SOWs) and the construction of pseudo-ternary diagrams to localize thermodynamically stable one-phase emulsion systems with different composition, salinity and water-to-oil ratios. Wicking and fluid penetration isotherms followed different kinetic regimes and indicated enhanced performance relative to that of the base fluids (water, oil or surfactant solutions). The key properties of microemulsions to effectively penetrate the solid structure are discussed; microemulsion formulation and resultant viscosity are found to have a determining effect in the extent of fluid uptake. The solubilization of cell wall components is observed after microemulsion impregnation. Thus, the microemulsion can be tuned not only to effectively penetrate the void spaces but also to solubilize hydrophobic and hydrophilic components. The concept proposed in this research is expected to open opportunities in fluid sorption in fiber systems for biomass pretreatment, and delivery of hydrophilic or lipophilic moieties in porous, lignocellulosics.     

Suzuki cross-coupling of solid-supported chloropyrimidines with arylboronic acids

The utility of the Suzuki cross-coupling to synthesize biaryl compounds is expanded herein to include reactions of resin-supported chloropyrimidines with boronic acids. In particular, an efficient method is described for the synthesis of a library of biaryl compounds from solid-supported chloropyrimidines. The Suzuki reaction was performed in an inert atmosphere using Pd(2)(dba)(3)/P(t-Bu)(3) as catalyst, spray-dried KF as base, and THF as solvent. The reaction was allowed to proceed overnight at 50 degrees C. Upon cleavage with acid, a library of 4-(substituted amino)-6-arylpyrimidines was obtained in moderate yield and high purity.     

Novel extracellular polymeric substances produced by Cupriavidus necator IPT 027 grown on glucose and crude glycerol originated from biodiesel

The aim of this study was to evaluate the production and properties of novel extracellular polymeric substances (EPS) from glucose (EPS 1) and crude glycerol (CG) from castor beans oil (EPS 2). Cupriavidus necator IPT 027 cultivated with glucose and CG (35 °C, 150 rpm, 72 hr, pH 7, shaker) produced approximately 1.60 ± 0.01 and 2.83 ± 0.02 g l^?1 EPS, respectively, with high‐molecular weight (3.89 × 10⁵ and 1.89 × 10⁷ Da) and constituted of different functional groups such as uronic acid, monosaccharides (glucose, mannose, arabinose, and fucose) and primary amine group. The composition of the fermentable substrate influenced the melting temperature (221.11 and 230.18 °C), crystallinity (34.36% and 37.11%), degradation temperature (255.06 and 296.62 °C) and morphology. EPS showed pseudoplastic non‐Newtonian fluid behavior in the aqueous solutions, presenting potential applicability biotechnological and industrial mainly in food industry as emulsifiers and biosurfactants. This is the first study on the production and characterization of EPS obtained by C. necator IPT 027 in culture with glucose and CG. Copyright © 2016 John Wiley & Sons, Ltd.     

222Rn content and234U/238U activity ratio in groundwaters

Geochemical radioanalytical studies of groundwater were performed in the valleys of Villa de Reyes and San Luis Potosi (Mexico). The experiments were designed to measure radon and uranium content and²³⁴U/²³⁸U activity ratio in groundwater samples taken from wells in these sites and at the Nuclear Center of Salazar, Mexico.²²²Rn content varied depending on the sample source, reaching a maximum value of 235 pCi/l; uranium concentration results were less than 1 g/1 and²³⁴U/²³⁸U activity ratios were close to equilibrium.     

Taking Advantage of Hydrophobic Fluorine Interactions for Self‐Assembled Quantum Dots as a Delivery Platform for Enzymes

Self‐assembly of nanoparticles provides unique opportunities as nanoplatforms for controlled delivery. By exploiting the important role of noncovalent hydrophobic interactions in the engineering of stable assemblies, nanoassemblies were formed by the self‐assembly of fluorinated quantum dots in aqueous medium through fluorine–fluorine interactions. These nanoassemblies encapsulated different enzymes (laccase and α‐galactosidase) with encapsulation efficiencies of ≥74 %. Importantly, the encapsulated enzymes maintained their catalytic activity, following Michaelis–Menten kinetics. Under an acidic environment the nanoassemblies were slowly disassembled, thus allowing the release of encapsulated enzymes. The effective release of the assayed enzymes demonstrated the feasibility of this nanoplatform to be used in pH‐mediated enzyme delivery. In addition, the as‐synthesized nanoassemblies, having a diameter of about 50 nm, presented high colloidal stability and fluorescence emission, which make them a promising multifunctional nanoplatform.