Solvent Effects in the Homogeneous Catalytic Reduction of Propionaldehyde with Aluminium Isopropoxide Catalyst: New Insights from PFG NMR and NMR Relaxation Studies

Solvent effects in homogeneous catalysis are known to affect catalytic activity. Whilst these effects are often described using qualitative features, such as Kamlet-Taft parameters, experimental tools able to quantify and reveal in more depth such effects have remained unexplored. In this work, PFG NMR diffusion and T₁ relaxation measurements have been carried out to probe solvent effects in the homogeneous catalytic reduction of propionaldehyde to 1-propanol in the presence of aluminium isopropoxide catalyst. Using data on diffusion coefficients it was possible to estimate trends in aggregation of different solvents. The results show that solvents with a high hydrogen-bond accepting ability, such as ethers, tend to form larger aggregates, which slow down the molecular dynamics of aldehyde molecules, as also suggested by T₁ measurements, and preventing their access to the catalytic sites, which results in the observed decrease of catalytic activity. Conversely, weakly interacting solvents, such as alkanes, do not lead to the formation of such aggregates, hence allowing easy access of the aldehyde molecules to the catalytic sites, resulting in higher catalytic activity. The work reported here is a clear example on how combining traditional catalyst screening in homogeneous catalysis with NMR diffusion and relaxation time measurements can lead to new physico-chemical insights into such systems by providing data able to quantify aggregation phenomena and molecular dynamics.     

Rapid Learning-Based and Geologically Consistent History Matching

Various types of data become available at different stages of a reservoir’s life. The production data are integrated into the flow simulation models through a process referred to as history matching. The history-matching process is iterative, and it usually involves a large number of simulation runs. Hence, this process requires significant computational time. In most history-matching methods, the initial geological assumptions in the reservoir model are destroyed or significantly altered in the process. Furthermore, they do not account for the information obtained during the previous trials, and lack learning from the previous failures. In this paper, we introduce a new methodology that maintains the geological realism. The candidate realizations are selected through a learning-based history-matching (LHM) algorithm by which all the previously successful patterns are preserved and used to assist the construction of the next realizations. The various pieces of matching regions are assembled together to make a pool of the successful candidates. Such regions are then utilized for making an auxiliary dataset in a multiscale framework by which the next model is generated. To prevent from trapping in local minima, ideas from the genetic algorithm is adapted. The LHM algorithm can be applied to both categorical and continuous distributions. The LHM provides a conditional map by which the new production data are immediately incorporated into the existing reservoir models. We apply the LHM algorithm to various 2D and 3D examples with very complex binary and continuous properties. The algorithm is shown to produce history-matched models with significantly smaller CPU times.     

Fixed-Point Iterations for Asymptotically Nonexpansive Mappings in Banach Spaces

In this paper, we suggest and analyze a three-step iterative scheme for asymptotically nonexpansive mappings in Banach spaces. The new iterative scheme includes Ishikawa-type and Mann-type interations as special cases. The results obtained in this paper represent an extension as well as refinement of previous known results.     

Three-step iterations for nonlinear accretive operator equations

In this paper, we suggest and analyze a three-step iterative scheme for solving nonlinear strongly accretive operator equation Tx=f without continuous condition in a uniformly smooth Banach space. Our results include the Ishikawa, Mann and Noor iterations as special cases. The results presented in this paper improve and extend almost all the current results in the more general setting.     

Quantum Information of the Aharanov–Bohm Ring with Yukawa Interaction in the Presence of Disclination

We investigate quantum information by a theoretical measurement approach of an Aharanov–Bohm (AB) ring with Yukawa interaction in curved space with disclination. We obtained the so-called Shannon entropy through the eigenfunctions of the system. The quantum states considered come from Schrödinger theory with the AB field in the background of curved space. With this entropy, we can explore the quantum information at the position space and reciprocal space. Furthermore, we discussed how the magnetic field, the AB flux, and the topological defect influence the quantum states and the information entropy.     

Solvatochromism of 2‐(N,N‐dimethylamino)‐7‐nitrofluorene and the natural dye β‐carotene: application for the determination of solvent dipolarity and polarizability

The effects of solvents on chemical phenomena (rate and equilibrium constants, spectroscopic transitions, etc.) are conveniently described by solvation free‐energy relationships that take into account solvent acidity, basicity and dipolarity/polarizability. The latter can be separated into its components by manipulating the UV–vis spectra of two solvatochromic probes, 2‐(N,N‐dimethylamino)‐7‐nitrofluorene (DMANF) and a di‐(tert‐butyl)‐tetramethyl docosanonaen probe (ttbP9) whose synthesis is laborious and expensive. Recently, we have shown that the natural dye β‐carotene can be conveniently employed instead of ttbP9 for the determination of solvent polarizability (SP) of 76 molecular solvents and four ionic liquids. In the present work, we report the polarizabilities of further 24 solvents. Based on the solvatochromism of β‐carotene and DMANF, we have calculated solvent dipolarity (SD) for 103 protic and aprotic molecular solvents, and ionic liquids. The dependence of SD and SP on the number of carbon atoms in the acyl‐ or alkyl group of several homologous series (alcohols; 2‐alkoxyethanols; carboxylic acid‐ anhydrides, and esters, ionic liquids) is calculated and briefly discussed. Copyright © 2013 John Wiley & Sons, Ltd.     

Nonclassicality of two-mode nonorthogonal states

Nonclassical features of Schrödinger cat state with two-mode superposition state based on two coherent states π out of phase by fixing the relative phase equal to average photon number are discussed. Study of two-mode quadrature squeezing, oscillatory and sub-Poissonian photon statistics show that nonclassicality exists for these states. However, it is observed that the considered states do not violates the Cauchy–Schwarz inequality. Furthermore, simultaneously existence of quadrature squeezing and sub-Poissonian photon statistics shows that these states have more nonclassical features than that of famous even and odd coherent states.     

Generalized set-valued mixed nonlinear quasi variational inequalities

In this paper we introduce and study a number of new classes of quasi variational inequalities. Using essentially the projection technique and its variant forms we prove that the generalized set-valued mixed quasivariational inequalities are equivalent to the fixed point problem and the Wiener-Hopf equations (normal maps). This equivalence enables us to suggest a number of iterative algorithms for solving the generalized variational inequalities. As a special case of the generalized set-valued mixed quasi variational inequalities, we obtain a class of quasi variational inequalities studied by Siddiqi, Husain and Kazmi [35], but there are several inaccuracies in their formulation of the problem, the statement and the proofs of their results. We have removed these inaccuracies. The correct formulation of their results can be obtained as special cases from our main results.     

Optical Fiber Excitation of Fano Resonances in a Silicon Microsphere

In this article, Fano lineshape whispering gallery modes were observed in the light scattering spectrum of a silicon microsphere in near-infrared telecommunication wavelengths. A simple model is presented to explain the transition from Lorentzian lineshape to the Fano lineshape resonances with the coupled-mode theory of multiple whispering gallery modes. Polar mode spacing of 0.23 nm is observed in the spectra, which correlates well with the calculated value. The quality factor of the Lorentzian and Fano resonances are on the order of 10⁵. By using an appropriate interface design for the microsphere coupling geometries, Fano lineshape optical resonances herald novel device applications for silicon volumetric lightwave circuits.     

Projection algorithms for solving a system of general variational inequalities

In this paper, we introduce and consider a new system of general variational inequalities involving four different operators. Using the projection operator technique, we suggest and analyze some new explicit iterative methods for this system of variational inequalities. We also study the convergence analysis of the new iterative method under certain mild conditions. Since this new system includes the system of variational inequalities involving three operators, variational inequalities and related optimization problems as special cases, results obtained in this paper continue to hold for these problems. Our results can be viewed as a refinement and improvement of the previously known results for variational inequalities.