Chemical details on nucleolipid supramolecular architecture: molecular modeling and physicochemical studies

Nucleolipids are currently under investigation as vectors for oligonucleotides (ON) delivery thanks to their supramolecular organization properties and their ability to develop specific interactions (i.e., stacking and potential Watson and Crick hydrogen bonds) for lipoplexes formation. To investigate the factors that govern the interaction events at a molecular level and optimize nucleolipid chemical structures, physicochemical experiments (tensiometry, AFM, BAM, and ellipsometry) combined with molecular dynamics simulation were performed on a series of zwitterionic nucleolipids (PUPC, DPUPC, PAPC) featuring a phosphocholine chain (PC). After construction and initial equilibration, simulations of pure nucleolipid bilayers were run for 100 ns at constant temperature and pressure, and their properties were compared to experimental data and to natural dipalmitoylphosphatidylcholine (DPPC) bilayers. Nucleolipid-based membranes are significantly more ordered and compact than DPPC bilayers mainly due to the presence of many intermolecular interactions between nucleoside polar heads. The hydrophilic phosphocholine moieties connected to the 5' hydroxyls are located above the bilayers, penalizing nucleic bases accessibility for further interactions with ON. Hence, a neutral nucleolipid (PUOH) without hydrophilic phosphocholine was inserted in the membranes. Simulations and experimental analysis of nucleolipid membranes in interaction with a single strand RNA structure indicate that PUOH interacts with ON in the subphase. This study demonstrates that molecular modeling can be used to determine the interactions between oligonucleotide and nucleolipids.     

Recent progress in diagnosing the reliability of electrical equipment by using infrared thermography

Infrared thermography (IRT) has gained more attention and become an interesting method in electrical preventive maintenance due to its high precision and sensitivity imaging characteristics. This paper provides a review of the application of IRT for diagnosing electrical equipment, including their thermal anomalies and methods of measurement. Improvement of the inspection techniques is highlighted in order to investigate the reliability of electrical equipments due to the effect of the environmental factors and equipment condition. Factors related to the target equipment and the inspection tool together with their characteristics is also presented. Due to the complex analysis, various automatic diagnostic systems are proposed for faster and more accurate analysis. Typical engineering solutions using recent technologies are reviewed which could be used to improve the quality of IRT inspection.     

Modified enzymes for reactions in organic solvents

Recent studies on biocatalysis in water—organic solvent biphasic systems have shown that many enzymes retain their catalytic activities in the presence of high concentrations of organic solvents. However, not all enzymes are organic solvent tolerant, and most have limited and selective tolerance to particular organic solvents. Protein modification or protein tailoring is an approach to alter the characteristics of enzymes, including solubility in organic solvents. Particular amino acids may play pivotal roles in the catalytic ability of the protein. Attaching soluble modifiers to the protein molecule may alter its conformation and the overall polarity of the molecule. Enzymes, in particular lipases, have been chemically modified by attachment of aldehydes, polyethylene glycols, and imidoesters. These modifications alter the hydrophobicity and conformation of the enzymes, resulting in changes in the microenvironment of the enzymes. By these modifications, newly acquired properties such as enhancement of activity and stability and changes in specificity and solubility in organic solvents are obtained. Modified lipases were found to be more active and stable in organic solvents. The optimum water activity (a _w ) for reaction was also shifted by using modified enzymes. Changes in enantioselective behavior were also observed.     

Real time imaging of supramolecular assembly formation via programmed nucleolipid recognition

Supramolecular assembly formation resulting from molecular recognition between complementary nucleolipids has been visualized in real time at the micrometer scale.     

The structure of the high-pressure gas jet from a spark plug fuel injector for direct fuel injection

Abstract  

A spark plug fuel injector (SPFI), which is a combination of a fuel injector and a spark plug was developed with the aim to convert any gasoline port injection spark ignition engine to gaseous fuel direct injection (Mohamad in Development of a spark plug fuel injector for direct injection of methane in spark ignition engine. PhD thesis, Cranfield University, 2006). A direct fuel injector is combined with a spark plug using specially fabricated bracket connected to a fuel pipe and a fuel path running along the periphery of a spark plug body to deliver the injected fuel to the combustion chamber. The injection nozzle of SPFI is significantly bigger than normal direct fuel injector nozzles. Therefore, it is important to understand the effect of such a configuration on the injection process and subsequently the air–fuel mixing behaviour inside the combustion chamber. The flow was visualized using the planar laser-induced fluorescent technique. For safety reasons, nitrogen was used as fuel substitute. Nitrogen at 50, 60 and 80 bar pressure was seeded with acetone as a flow tracer and injected into a bomb containing pressurised nitrogen. Bomb pressure was varied to simulate the pressure inside combustion cylinder during the compression stroke where actual injections in engine experiments will take place. The shape and depth of tip penetration of the gas jet were measured. Results show that the gas jet follows the behaviour suggested by vortex ball model (Turner in Mechanics 13:356–369, 1962). The cone angle and the maximum jet width of the fully developed gas jets from the SPFI injection are 23° and 25 mm, respectively regardless of the injection pressures. The penetration lengths of the fully developed jets are between 90 and 100 mm at 8–14 ms after the start of injection, depending on the bomb and injection pressure. Jet penetration is directly proportional to the injection pressure but inversely proportional to the cylinder or bomb pressure. The penetration lengths indicate that sufficient distance should be travelled by the gas jet for satisfactory air–fuel mixing in the engine.     

Experimental and Theoretical Studies on Extract of Date Palm Seed as a Green Anti-Corrosion Agent in Hydrochloric Acid Solution

Extracts from plant materials have great potential as alternatives to inorganic corrosion inhibitors, which typically have harmful consequences. Experimental and theoretical methodologies studied the effectiveness of agricultural waste, namely, date palm seed extract as a green anti-corrosive agent in 0.5 M hydrochloric acid. Experimental results showed that immersion time and temperature are closely related to the effectivity of date palm seed as a corrosion inhibitor. The inhibition efficiency reduced from 95% to 91% at 1400 ppm when the immersion time was increased from 72 h to 168 h. The experimental results also indicated that the inhibition efficiency decreased as the temperature increased. The presence of a protective layer of organic matter was corroborated by scanning electron microscopy. The adsorption studies indicated that date palm seed obeyed Langmuir adsorption isotherm on the carbon steel surface, and Gibbs free energy values were in the range of −33.45 to −38.41 kJ·mol⁻¹. These results suggested that the date palm seed molecules interacted with the carbon steel surface through mixture adsorption. Theoretical calculations using density functional theory showed that the capability to donate and accept electrons between the alloy surface and the date palm seed inhibitor molecules is critical for adsorption effectiveness. The HOMO and LUMO result indicated that the carboxyl (COOH) group and C=C bond were the most active sites for the electron donation-acceptance type of interaction and most auxiliary to the adsorption process over the Fe surface.     

Thermal fragmentation and rearrangement of some N-phenylbenzamide oxime dervatives II. Synthesis of benzimidazoles

Thermolysis of N-phenylbenzamide oximes I, II and III (R = Cl, NO₂ and OCH₃) under nitrogen gives rise to benzimidazoles as the major products (45-52%), in addition to benzonitrile, arylamines, benzoic acid, phenols, benzanilides, 2-phenyl benzoxazoles and carbazoles. In the presence of naphthalene, I gave α- and β-naphthols beside the previous products. Also heating of I under reflux boiling tetralin lead to the formation of 1-hydroxytetralin, α-tetralone and 1,1′-bitetralyl as the major products. The isolated products have been interpreted in the terms of a free radical mechanism involving the homolysis of N-O and/or C-N bonds.     

First-principles study on structural and electronic properties of Prussian blue cathode material for sodium-ion battery

Abstract

Prussian blue, Fe[Fe(CN)₆] currently attracts a huge attention as a promising material in the application of large-scale energy storage because of its cost-effective and environmental friendly material. Besides, open framework structure and stability are the main causes for PB performance. In this study, effects of sodium cation insertion/deinsertion toward the structural and electronic properties were analyzed. The use of Hubbard U method successfully delivered a good approximation on electronic properties of the transition-metal ions in PB. The calculated band gap of 1.84?eV was in good agreement with theoretical and experimental results. Upon the insertion of the sodium cation, volume of the cathode material expanded between 2% and 4% showing that this cathode material has good cycle retention. From partial density of states, Fe 3d dominated the conduction and valence band. Furthermore, the redox reaction mechanism of Prussian blue can also be depicted. The voltage obtained from energy calculation for the first and second insertion of cation was 3.32 and 3.42?V, respectively.     

Volumetric Properties and Refractive Indices for Binary Mixtures of 1-Propyronitrile-3-hexylimidazolium Bromide + Ethanol at Temperatures from 293.15 to 323.15 K

Densities and refractive indices have been measured for binary mixtures of 1-propyronitrile-3-hexylimidazolium bromide + ethanol in the temperature range 293.15–323.15 K. From the experimental data the excess molar volume V ^E, refractive index deviation Δn _D, and the coefficient of thermal expansion α were calculated and fitted to fifth- and third-order Redlich–Kister type equations, respectively. Using the measured densities, the apparent molar volumes (V _ϕ ), limiting apparent molar volumes (V_f⁰V_{\phi}^{0}) and limiting apparent molar expansivities (E_f ⁰E_{\phi} ^{0}) were also determined and the details are discussed.