Circadian Rhythm Dysregulation and Leukemia Development: The Role of Clock Genes as Promising Biomarkers

The circadian clock (CC) is a daily system that regulates the oscillations of physiological processes and can respond to the external environment in order to maintain internal homeostasis. For the functioning of the CC, the clock genes (CG) act in different metabolic pathways through the clock-controlled genes (CCG), providing cellular regulation. The CC’s interruption can result in the development of different diseases, such as neurodegenerative and metabolic disorders, as well as cancer. Leukemias correspond to a group of malignancies of the blood and bone marrow that occur when alterations in normal cellular regulatory processes cause the uncontrolled proliferation of hematopoietic stem cells. This review aimed to associate a deregulated CC with the manifestation of leukemia, looking for possible pathways involving CG and their possible role as leukemic biomarkers.     

The adsorption of methyl nitrite on the Au(111) surface

The interaction of the methyl nitrite molecule (CH₃ONO) with the gold(111) surface has been studied by means of density functional calculations. The perfect Au(111) surface has been represented by a rather large cluster model, Au₂₂, that was in turn used to extract information about the preferred adsorption geometry of the CH₃ONO species. Vibrational frequencies and adsorption energy are also reported. The calculated adsorption energies are 31.2 kJ/mol with respect to gas phase cis-conformer and 35.1 kJ/mol with respect to trans-methyl nitrite, very close to the experimental adsorption energy of 33.5 kJ/mol. From the analysis of vibrational frequencies of gas phase and adsorbed species it is concluded that only the cis-conformer is present at the Au(111) surface.     

Catalytic Amyloids as Novel Synthetic Hydrolases

Amyloids are supramolecular assemblies composed of polypeptides stabilized by an intermolecular beta-sheet core. These misfolded conformations have been traditionally associated with pathological conditions such as Alzheimer’s and Parkinson´s diseases. However, this classical paradigm has changed in the last decade since the discovery that the amyloid state represents a universal alternative fold accessible to virtually any polypeptide chain. Moreover, recent findings have demonstrated that the amyloid fold can serve as catalytic scaffolds, creating new opportunities for the design of novel active bionanomaterials. Here, we review the latest advances in this area, with particular emphasis on the design and development of catalytic amyloids that exhibit hydrolytic activities. To date, three different types of activities have been demonstrated: esterase, phosphoesterase and di-phosphohydrolase. These artificial hydrolases emerge upon the self-assembly of small peptides into amyloids, giving rise to catalytically active surfaces. The highly stable nature of the amyloid fold can provide an attractive alternative for the design of future synthetic hydrolases with diverse applications in the industry, such as the in situ decontamination of xenobiotics.     

Strongly Photosensitive and Fluorescent F8T2 Electrospun Fibers

Electrospun fibers of poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐bithiophene] (F8T2) with exceptional electro‐optical performance are obtained. The I/T characteristics measured in fibers with 7–15 µm diameter and 1 mm length show a semiconductor behavior; their thermal activation energy is 0.5 eV and the dark conductivity at RT is 5 × 10^?9 (Ω cm)^?1. Besides exhibiting a photosensitivity of about 60 under white light illumination with a light power intensity of 25 mW · cm^?2, the fibers also attain RT photoluminescence in the cyan, yellow, and red wavelength range under ultraviolet, blue, and green light excitation, respectively. Optical microscope images of F8T2 reveal homogeneous electrospun fibers, which are in good agreement with the uniformly radial fluorescence observed.

     

N-acryloxysuccinimide: Synthesis, characterization, and incorporation in dental adhesives

In an attempt to enrich the world of dentistry through the development of new materials, this study proposes to synthesize and incorporate a monomer containing the N-hydroxysuccinimide (NHS) ester reactive group to a dental adhesive. As such, this study developed a simple method to obtain NHS esters by employing acrylic acid (AA) and NHS in the presence of EDC (N-ethyl-N′-(3-dimethylaminopropyl)carbodiimide), from an aprotic medium. The experimental N-acryloxysuccinimide (NSA) monomer was analyzed by infrared spectroscopy (FTIR) and nuclear magnetic resonance of hydrogen (¹H NMR). This monomer was then incorporated within a prepared dental adhesive, in a 5% proportion. The modified adhesive, containing NSA, was applied to the dental surface of bovine teeth to obtain an adhesive/dentin interface in vitro. The characterization of this interface by Raman spectroscopy presented the formation of new amide bonds. Moreover, through scanning electron microscopy (SEM), it became possible to observe an intense penetration of this modified adhesive on the dental surface. Considering the outcome, it can be concluded that the synthesized NSA monomer provided a favorable condition for the dental adhesives to interact chemically with the dentin collagen fibers.     

Electrochemical oxidation of several chlorophenols on diamond electrodes Part I. Reaction mechanism

The electrochemical oxidation of 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol aqueous wastes using boron-doped diamond electrodes was studied. This treatment led to complete mineralization of the wastes regardless of the operating conditions. A simple mechanistic model is consistent with the voltammetric and electrolysis results. According to this model, the electrochemical treatment of chlorophenol aqueous wastes involves the anodic and cathodic release of chlorine followed by the formation of non-chlorinated aromatic intermediates. Subsequent cleavage of the aromatic ring gives rise to non-chlorinated carboxylic acids. Chlorine atoms arising from the hydrodehalogenation of the chlorophenols are converted into more oxidized molecules at the anode. These molecules react with unsaturated C₄ carboxylic acid to finally yield trichloroacetic acid through a haloform reaction. The non-chlorinated organic acids are ultimately oxidized to carbon dioxide and the trichloroacetic acid into carbon dioxide and volatile organo-chlorinated molecules. Both direct and mediated electrochemical oxidation processes are involved in the electrochemical treatment of chlorophenols.     

Interparticle Potentials in Nonaqueous Silicon Nitride Suspensions

The rheological properties of nonaqueous silicon nitride suspensions are studied. Suspensions were prepared to volume fractions of solids of 0.21, 0.25, 0.29, and 0.33, and dispersed with phosphate ester in a mixture of solvents (methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone). Expanded viscosity curves were obtained by measuring under controlled rate and stress conditions, and the experimental data were fitted to the Cross model that provides the high shear limiting viscosity (η_∞). The evolution of viscosity with volume fraction of solids was fitted to the Krieger-Dougherty equation, to predict the maximum packing fraction (φ_m). The electrostatic pair potential was calculated based on the DLVO theory by evaluating the dielectric constant of the three-component solvent and the Hamaker constant of the Si₃N₄–solvent system. The surface potential was calculated by measuring the elastic modulus through dynamic rheological measurements. The steric potential was also evaluated from the available models. It has been observed that phosphate ester provides a purely steric stabilization at short separation distances (up to 9 nm), while electrostatic forces dominate at larger separation distances.     

Controlling the phase stability of polymer blends through the introduction of impenetrable interfaces

In this work, the effect of the introduction of modified solid surfaces into polymer blends on the phase‐separation process was investigated. Glass fibers with surfaces having different chemistries were introduced into polystyrene–poly(methyl methacrylate) blends. The glass fibers used either had fully hydrated surfaces or had surfaces covered with a random copolymer, poly(styrene‐co‐methyl methacrylate). The copolymer was synthesized by free‐radical polymerization of styrene and methyl methacrylate in the presence of previously vinyl silane‐treated glass fibers. The copolymerization and grafting procedures were investigated by FTIR and thermal analysis. Blends containing the fibers were studied using FTIR microscopy and optical microscopy. FTIR microscopy results showed that the composition of the phases in the blends was shifted by using fibers with different surface chemistries. Fibers with grafted copolymers were capable of narrowing the immiscibility region in the phase diagram, while fully hydrated fibers were able to expand the gap. It was proposed that interfacial interactions regulated by a hydrophilic–hydrophobic type of forces were responsible for guiding the described phase‐separation process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1619–1627, 2003     

Hot-erosion of nano-bonded refractory castables for petrochemical industries

Cold-erosion tests are usually applied for refractory castable evaluation in petrochemical industries, mainly for materials used in cyclones and risers of fluidized catalytic cracking units (FCCU). Due to the fact that in the operation, the refractory material is subjected to high temperature, at first, hot-erosion tests could be more representative. Erosion wear has a great influence on the FCCU refractory working life and the lost income associated with a production halt can reach values close to US$500,000 per day. These aspects are strong enough to justify hot-erosion resistance characterization. The test viability, which could result in selecting better material for the application, was evaluated using commercial products and nano-bonded castables from 200 up to 815 °C. At this temperature range, a significant difference between the cold and hot-erosion loss was not observed. Therefore, it indicates that the cold-erosion test is suitable and sufficient for selecting refractory castables for FCCU applications. The cold-erosion test also presented a higher data correlation with the splitting tensile strength and the hot modulus of rupture. Regarding the different evaluated materials, the nano-bonded castables showed a higher erosion resistance and were less susceptible to the temperature effect than the calcium aluminate cement bonded commercial products.     

Experimental design of the kinetic resolution of a key precursor of high‐value bioactive myo‐inositols by an immobilized lipase

BACKGROUND: The response surface methodology was successfully applied to the optimization of the reaction variables for the kinetic resolution of a precursor of high‐value myo‐inositols, ( ± )‐1,2‐O‐isopropylidene‐3,6‐di‐O‐benzyl‐myo‐inositol (( ± )‐1), by Novozym 435. The resolutions were run separately, with two acylating agents, ethyl acetate and vinyl acetate, in a solvent‐free system. The variables analyzed were reaction temperature, substrate concentration, water concentration and enzyme activity. A statistical model was employed for the evaluation of the influence of the variables on conversion and enantiomeric excess (ee). RESULTS: The optimal conditions for this resolution using vinyl acetate as acylating agent were 45 °C, 5 mg mL^?1 of substrate, 71 U of enzyme activity and 0%w/w of water concentration. The high conversion (49.2 %) and ee (>99%) reached in the chemoenzymatic synthesis of acylated product, L‐(?)‐5‐O‐Acetyl‐3,6‐di‐O‐benzyl‐1,2‐O‐isopropylidene‐myo‐inositol, secure the efficient synthesis of the D enantiomorph present in the original racemic mixture (( ± )‐1) as well. CONCLUSIONS: The use of the experimental design strategy was productive, leading to a 14‐fold increase in the productivity of the reaction compared with the non‐optimized conditions. Both derivative L‐(?)‐2 and remaining substrate D‐(+)‐1 were obtained at high ee. © 2012 Society of Chemical Industry