Automatic assignment of 1H‐NMR spectra of small molecules

A novel data‐evaluation procedure for the automatic atom to peak or multiplet assignment of ¹H‐NMR spectra of small molecules has been developed using a fast and robust expert system. The applicability and reliability of the method are demonstrated by comparison of a manually assigned database of ¹H‐NMR spectra with the assignments produced by the automatic procedure. The results of this analysis show an excellent success ratio, indicating that this new algorithm can have a major impact as a time saving tool for the organic chemist. A new graphical feature used to illustrate both the stability and quality of the elementary assignments is also introduced. Copyright © 2013 John Wiley & Sons, Ltd.     

Evaluation of deconvolution modelling applied to numerical combustion

A possible modelling approach in the large eddy simulation (LES) of reactive flows is to deconvolve resolved scalars. Indeed, by inverting the LES filter, scalars such as mass fractions are reconstructed. This information can be used to close budget terms of filtered species balance equations, such as the filtered reaction rate. Being ill-posed in the mathematical sense, the problem is very sensitive to any numerical perturbation. The objective of the present study is to assess the ability of this kind of methodology to capture the chemical structure of premixed flames. For that purpose, three deconvolution methods are tested on a one-dimensional filtered laminar premixed flame configuration: the approximate deconvolution method based on Van Cittert iterative deconvolution, a Taylor decomposition-based method, and the regularised deconvolution method based on the minimisation of a quadratic criterion. These methods are then extended to the reconstruction of subgrid scale profiles. Two methodologies are proposed: the first one relies on subgrid scale interpolation of deconvolved profiles and the second uses parametric functions to describe small scales. Conducted tests analyse the ability of the method to capture the chemical filtered flame structure and front propagation speed. Results show that the deconvolution model should include information about small scales in order to regularise the filter inversion. a priori and a posteriori tests showed that the filtered flame propagation speed and structure cannot be captured if the filter size is too large.     

Introducing Alternative Algorithms for the Determination of the Distribution of Relaxation Times

Impedance spectroscopy is a powerful characterization method to evaluate the performance of electrochemical systems. However, overlapping signals in the resulting impedance spectra oftentimes cause misinterpretation of the data. The distribution of relaxation times (DRT) method overcomes this problem by transferring the impedance data from the frequency domain into the time domain, which yields DRT spectra with an increased resolution. Unfortunately, the determination of the DRT is an ill-posed problem, and appropriate mathematical regularizations become inevitable to find suitable solutions. The Tikhonov algorithm is a widespread method for computing DRT data, but it leads to unlikely spectra due to necessary boundaries. Therefore, we introduce the application of three alternative algorithms (Gold, Richardson Lucy, Sparse Spike) for the determination of stable DRT solutions and compare their performances. As the promising Sparse Spike deconvolution has a limited scope when using one single regularization parameter, we furthermore replaced the scalar regularization parameter with a vector. The resulting method is able to calculate well-resolved DRT spectra.     

9Be and 31P NMR analyses on the influence of imino groups on Be2+ complex stabilities of a series of cyclo‐μ‐imido triphosphate anions

The complexation behaviors of Be²⁺ with cyclo‐μ‐imido triphosphate anions, cP₃O_9?n(NH)_n^3? (n = 1, 2), have been investigated by both ⁹Be and ³¹P NMR techniques at ?2.3 °C in order to clarify the coordination structures of the complexes. The spectra showed that cP₃O_9?n(NH)_n (n = 1, 2) ligands form ML, ML₂, and M₂L complexes with Be²⁺ ions, and the formation of complexes coordinating with nitrogen atoms of the cyclic framework in the ligand molecule has been excluded. These complexation trends are very similar to those of Be²⁺‐cP₃O₆(NH)₃^3? system, which has been reported by us. The peak deconvolution of ⁹Be NMR spectra made these beryllium complexes amenable to stability constant determinations. The stability constants of the complexes increase with an increase in the protonation constants of the ligands as the number of imino groups, which constitute the ligand molecules, is ascended. This increase is primarily attributable to the lower electronegativity of nitrogen atoms than oxygen atoms, which are directly bonded to central phosphorus atoms; moreover, tautomerism equilibrium in the entire of the imidopolyphosphate molecule is also responsible to the higher basicity. ³¹P NMR spectra measured concurrently have verified the formation of the complexes estimated by the ⁹Be NMR measurement. Intrinsic ³¹P NMR chemical shift values of the phosphorus atoms belonging to ligand molecules complexed with Be²⁺ cations have been determined. Not only the protonation constants but also the stability constants of all Be²⁺ complexes increase approximately linearly with an increase in the number of imino groups. Copyright © 2013 John Wiley & Sons, Ltd.     

Chromatographic Chiral Recognition and Computer Aided Deconvolution of the Enantiomeric Secondary Alcohol with a Self‐Packed Chiral Stationary Phase HPLC Column

The γ‐aminopropyl‐derivatized silica was treated with the (R)‐(‐)‐N‐(3,5‐dinitrobenzoyl)‐α‐phenylglycine and was packed into a standard 250 mm × 4.5 mm HPLC column to perform the chiral separation of secondary alcohol. Enantiomers of four homologous series of aryl alkyl substituted alcohol were resolved in different degrees. The chiral recognition mechanism was proposed that could be used to rationalize well the elution order and the resolution between the R‐ and S‐configuration of a secondary alcohol. The unresolved peak of the enantiomers of 1‐phenylethanol and the partially resolved peak of the enantiomers of 1‐(1‐naphthyl)ethanol were deconvoluted by the assistance of computer and a program written in BASIC computer language. Two mathematical models were used for the deconvolution and were based on modified Gaussian functions with a fixed baseline that can take into account the skew of a chromatographic peak. Parameters in the mathematical model were estimated by using a nonlinear regression algorithm. The selected mathematical models were suitable for deconvolving the less skewed overlapping peaks of 1‐phenylethanol.     

XPS study on surface modification of NiTi alloy by acidic solution immersion and subsequent heating in air

Changes in the surface chemical state of a nearly equiatomic nickel–titanium (NiTi) alloy caused by immersion in aqueous solutions of HNO₃ and H₂SO₄ as well as subsequent heating in air at 723 K were analyzed using X-ray photoelectron spectroscopy (XPS). An XPS analysis using angle-resolved technique and a mathematical deconvolution technique revealed that a passive layer formed in an ambient atmosphere contained TiO₂ as a major state and Ni(OH)₂ and NiO as minor states. The Ni(OH)₂ on the alloy remained in the region even when heated in air at 723 K. Therefore, the resulting layer became a Ti-oxide layer with Ni segregated region at the surface, which was NiO formed via dehydration of Ni(OH)₂. However, immersion in an aqueous solution of HNO₃ or H₂SO₄ enables Ni(OH)₂ state to dissolve in the passive layer of a NiTi alloy; thereby, the Ni segregated region rarely appeared in the oxide layer by heating. The Ni segregated region at the surface becomes an obstacle for the inward diffusion of oxygen; thus, the annihilation of such a segregated region results in an increase in the thickness of the oxide layer.     

Atomic resolution imaging of oxygen atoms close to heavy atoms by HRTEM and ED,using the superconductor SmFeAsO0.85F0.15 as an example

Imaging of light atoms has always been a challenge in high-resolution electron microscopy. Image resolution is mainly limited by lens aberrations, especially the spherical aberration of the objective lens. Image deconvolution could correct for the image distortion by lens aberrations and restore the structure projection, the resolution of which is limited by the information limit of the microscope. Electron diffraction unrestricted by lens aberrations could overcome this resolution limit. Here we show a combination of electron diffraction and image deconvolution to reveal simultaneously the atomic columns of O and considerably heavier Sm at a very close distance (1.17 Å) in iron-based superconductor SmFeAsO_0.85F_0.15 using a conventional 200 kV electron microscope. The approach used here, starting from an image and an electron diffraction pattern, has an advantage for those radiation-sensitive samples. Besides, it can be applied to simultaneously imaging light and heavy atoms, even though they have a big difference in atomic number and a much smaller atomic distance than the microscope resolution.     

On the convergence of an approximate deconvolution model to the 3D mean Boussinesq equations

In this paper, we study an LES model for the approximation of large scales of the 3D Boussinesq equations. This model is obtained using the approach first described by Stolz and Adams, based on the Van Cittern approximate deconvolution operators, and applied to the filtered Boussinesq equations. Existence and uniqueness of a regular weak solution are provided. Our main objective is to prove that this solution converges towards a solution of the filtered Boussinesq equations, as the deconvolution parameter goes to zero. Copyright © 2014 John Wiley & Sons, Ltd.     

Energy analysis and improved regularity estimates for multiscale deconvolution models of incompressible flows

This paper presents new analytical results and the first numerical results for a recently proposed multiscale deconvolution model (MDM) recently proposed. The model involves a large‐eddy simulation closure that uses a novel deconvolution approach based on the introduction of two distinct filtering length scales. We establish connections between the MDM and two other models, and, on the basis of one of these connections, we establish an improved regularity estimate for MDM solutions. We also prove that the MDM preserves Taylor‐eddy solutions of the Navier–Stokes equations and therefore does not distort this particular vortex structure. Simulations of the MDM are performed to examine the accuracy of the MDM and the effect of the filtering length scales on energy spectra for three‐dimensional homogeneous and isotropic flows. Numerical evidence for all tests clearly indicates that the MDM gives very accurate coarse‐mesh solutions and that this multiscale approach to deconvolution is effective. Copyright © 2015 John Wiley & Sons, Ltd.     

Automated instrumental method for on-line fraction analysis and peak deconvolution in gradient multicomponent overloaded high performance liquid chromatography

An automated method for deconvolution of overloaded band profiles in gradient elution is described. The instrumental set-up consists of a pseudo-bidimensional HPLC system, where overloaded band profiles generated in the first direction are sampled on the second one. The method, previously employed under isocratic conditions, has been now extended to gradient elution, where one has to face the problem of band compression (and possibly band interference) during gradient, which decreases the time-window available along the first direction for sampling the overloaded profiles. The effect of the gradient steepness on the problem of defining a minimum number of sampling points to reconstruct single component bands from overloaded profiles is investigated. This approach is particularly useful in the framework of using inverse method (IM) to determine adsorption isotherm parameters for preparative gradient elution. In fact, it allows for the gathering of the information necessary to run IM calculations with minimum efford, also in cases where the individual component forming the mixture have different UV spectra.