Experimental and modeling study on the pyrolysis and oxidation of n-decane and n-dodecane

High pressure n-decane and n-dodecane shock tube experiments were conducted to assist in the development of a Jet A surrogate kinetic model. Jet A is a kerosene based jet fuel composed of hundreds of hydrocarbons consisting of paraffins, olefins, aromatics and naphthenes. In the formulation of the surrogate mixture, n-decane or n-dodecane represent the normal paraffin class of hydrocarbons present in aviation fuels like Jet A. The experimental work on both n-alkanes was performed in a heated high pressure single pulse shock tube. The mole fractions of the stable species were determined using gas chromatography and mass spectroscopy. Experimental data on both n-decane and n-dodecane oxidation and pyrolysis were obtained for temperatures from 867 to 1739 K, pressures from 19 to 74 atm, reaction times from 1.15 to 3.47 ms, and equivalence ratios from 0.46 to 2.05, and ∞. Both n-decane and n-dodecane oxidation showed that the fuel decays through thermally driven oxygen free decomposition at the conditions studied. This observation prompted an experimental and modeling study of n-decane and n-dodecane pyrolysis using a recently submitted revised n-decane/iso-octane/toluene surrogate model. The surrogate model was extended to n-dodecane in order to facilitate the study of the species and the 1-olefin species quantified during the pyrolysis of n-dodecane and n-decane were revised with additional reactions and reaction rate constants modified with rate constants taken from literature. When compared against a recently published generalized n-alkane model and the original and revised surrogate models, the revised (based on our experimental work) and extended surrogate model showed improvements in predicting 1-olefin species profiles from pyrolytic and oxidative n-decane and n-dodecane experiments. The revised and extended model when compared to the published generalized n-alkane and surrogate models also showed improvements in predicting species profiles from flow reactor n-decane oxidation experiments, but similarly predicted n-decane and n-dodecane ignition delay times.     

Theoretical determination of the 1H NMR spectrum of ethanol

GIAO calculations of the ¹H NMR chemical shifts for ethanol at the SCF and DFT levels of theory are presented. The importance of molecular geometry and basis set is discussed. Vibrational correction to the hydroxyl proton chemical shift is also considered in calculations for the monomer of ethanol. The final theoretical results for the monomer obtained at the optimized DFT/B3LYP/6-311G(d,p) geometry with the 6-311G++ (d,p) basis set for NMR are in very good agreement with gas phase experimental data. For the liquid phase ethanol the hydrogen bonding effects are taken into account by performing calculations on various clusters of ethanol. It is shown that inaccuracy due to molecular geometry and basis set in the monomer of ethanol is magnified significantly in calculations for its clusters. In this context the structure of liquid ethanol as predicted recently by quantum cluster equilibrium (QCE) theory is discussed.     

On integrable rational potentials of the Dirac equation

The one-dimensional Dirac equation with a rational potential is reducible to an ordinary differential equation with a Riccati-like coefficient. Its integrability can be studied with the help of differential Galois theory, although the results have to be stated with recursive relations, because in general the equation is of Heun type. The inverse problem of finding integrable rational potentials based on the properties of the singular points is also presented; in particular, a general class of integrable potentials leading to the Whittaker equation is found.     

Boundary Behavior of α-Harmonic Functions on the Complement of the Sphere and Hyperplane

We study α-harmonic functions on the complement of the sphere and on the complement of the hyperplane in Euclidean spaces of dimension bigger than one, for α?∈?(1,2). We describe the corresponding Hardy spaces and prove the Fatou theorem for α-harmonic functions. We also give explicit formulas for the Martin kernel of the complement of the sphere and for the harmonic measure, Green function and Martin kernel of the complement of the hyperplane for the symmetric α-stable Lévy processes. Some extensions for the relativistic α-stable processes are discussed.     

Synchronous states of slowly rotating pendula

Coupled systems that contain rotating elements are typical in physical, biological and engineering applications and for years have been the subject of intensive studies. One problem of scientific interest, which among others occurs in such systems is the phenomenon of synchronization of different rotating parts. Despite different initial conditions, after a sufficiently long transient, the rotating parts move in the same way — complete synchronization, or a permanent constant shift is established between their displacements, i.e., the angles of rotation — phase synchronization. Synchronization occurs due to dependence of the periods of rotating elements motion and the displacement of the base on which these elements are mounted.     

Principal eigenvalue of the fractional Laplacian with a large incompressible drift

We study the principal Dirichlet eigenvalue of the operator \({L_A=\Delta^{\alpha/2}+Ab(x)\cdot\nabla}\) , on a bounded C ^1,1 regular domain D. Here \({\alpha\in(1,2)}\) , \({\Delta^{\alpha/2}}\) is the fractional Laplacian, \({A\in\mathbb{R}}\) , and b is a bounded d-dimensional divergence-free vector field in the Sobolev space W ^1,2d/(d+α)(D). We prove that the eigenvalue remains bounded, as A→ + ∞, if and only if b has non-trivial first integrals in the domain of the quadratic form of \({\Delta^{\alpha/2}}\) for the Dirichlet condition.     

Magnetostructural transformations in Ni<Subscript>51</Subscript>Mn<Subscript>36</Subscript>Sn<Subscript>13</Subscript> Heusler alloy thin films

In this paper we report structural, magnetic and transport properties of strongly textured Ni₅₁Mn₃₆Sn₁₃ thin films. The off-stoichiometric Heusler alloy films with 200 nm thickness were sputter-deposited on a MgO(100) substrate at 500 K and after annealed at 1000 K in UHV conditions. The textured growth was confirmed by x-ray diffraction in Bragg-Brentano geometry. The temperature dependence of the magnetic properties was measured by VSM and FMR methods. The electron transport measurements were carried out in function of temperature in 0 Oe and 50 kOe fields. All measurements corroborate the existence of the martensitic transformation in the film. Furthermore, transport measurements reveal an influence of the magnetic field on the transition temperature.     

On a new class of functional equations satisfied by polynomial functions

Aequationes mathematicae - The classical result of L. Székelyhidi states that (under some assumptions) every solution of a general linear equation must be a polynomial function. It is known...     

Revealing the Bonding Pattern from the Molecular Electron Density Using Single Exponential Decay Detector: An Orbital‐Free Alternative to the Electron Localization Function

We introduce a new tool (single exponential decay detector: SEDD) to extract information about bonding and localization in atoms, molecules, or molecular assemblies. The practical evaluation of SEDD does not require any explicit information about the orbitals. The only quantity needed is the electron density (calculated or experimental) and its derivatives up to the second order.     

Application of HPLC-DAD for In Vitro Investigation of Acetylcholinesterase Inhibition Activity of Selected Isoquinoline Alkaloids from Sanguinaria canadensis Extracts

Isoquinoline alkaloids may have a wide range of pharmacological activities. Some of them have acetylcholinesterase activity inhibition. Nowadays, neurodegenerative disorders such as Alzheimer’s disease have become a serious public health problem. Searching for new effective compounds with inhibited acetylcholinesterase activity is one of the most significant challenges of modern scientific research. The aim of this study was the in vitro investigation of acetylcholinesterase activity inhibition of extracts obtained from Sanguinaria canadensis collected before, during and after flowering. The acetylcholinesterase activity inhibition of these extracts has not been previously tested. The aim was also to quantify selected alkaloids in the investigated extracts by high performance liquid chromatography (HPLC). The analyses of alkaloid content were performed using HPLC in reversed phase (RP) mode using Polar RP column and mobile phase containing acetonitrile, water and ionic liquid (IL). The acetylcholinesterase activity inhibition of the tested plant extracts and respective alkaloid standards were examined using high performance liquid chromatography with diode-array detector (HPLC-DAD) for the quantification of 5-thio-2-nitro-benzoic acid, which is the product of the reaction between the thiocholine (product of the hydrolysis of acetylthiocholine reaction) with Ellman reagent. The application of the HPLC method allowed for elimination of absorption of interfering components, for example, alkaloids such as sanguinarine and berberine. It is revealed that the HPLC method can be successfully used for the evaluation of the acetylcholinesterase inhibitory activity in samples such as plant extracts, especially those containing colored components adsorbing at wavelength in the range 405–412 nm. The acetylcholinesterase inhibition activity synergy of pairs of alkaloid standards and mixture of all investigated alkaloids was also determined. Most investigated alkaloids and all Sanguinaria canadensis extracts exhibited very high acetylcholinesterase activity inhibition. IC₅₀ values obtained for alkaloid standards were from 0.36 for berberine to 23.13 µg/mL for protopine and from 61.24 to 89.14 µg/mL for Sanguinaria canadensis extracts. Our investigations demonstrated that these plant extracts can be recommended for further in vivo experiments to confirm their acetylcholinesterase activity inhibition.