Theoretical study of hydrogen bonding in homodimers and heterodimers of amide, boronic acid, and carboxylic acid, free and in encapsulation complexes

The homodimers and the heterodimers of two amides, two boronic acids, and two carboxylic acids have been calculated in the gas phase and in N,N-dimethylformamide (DMF) and CCl(4) solvents using the DFT (M06-2X and M06-L) and the MP2 methods in conjunction with the 6-31G(d,p) and 6-311+G(d,p) basis sets. Furthermore, their pairwise coencapsulation was studied to examine its effect on the calculated properties of the hydrogen bonds at the ONIOM[M06-2X/6-31G(d,p);PM6], ONIOM[MP2/6-31G(d,p); PM6], and M06-2X/6-31G(d,p) levels of theory. The present work is directed toward the theoretical rationalization and interpretation of recent experimental results on hydrogen bonding in encaptulation complexes [D. Ajami et al. J. Am. Chem. Soc. 2011, 133, 9689-9691]. The calculated dimerization energy (ΔE) values range from 0.74 to 0.35 eV for the different dimers in the gas phase, with the ordering carboxylic homodimers > amide-carboxylic dimers > amide homodimers > boronic-carboxylic dimers > amide-boronic dimers > boronic homodimers. In solvents, generally smaller ΔE values are calculated with only small variations in the ordering. In the capsule, the ΔE values range between 0.67 and 0.33 eV with practically the same ordering as in the gas phase. The calculated % distributions of the encapsulated dimers, taking into account statistical factors, are in agreement with the experimental distribution, where the occurrence of boronic homodimer dominates, even though it is calculated to have the smallest ΔE.     

Estimation and control for linear,partially observable systems with non-gaussian initial distribution

The nonlinear filtering problem of estimating the state of a linear stochastic system from noisy observations is solved for a broad class of probability distributions of the initial state. It is shown that the conditional density of the present state, given the past observations, is a mixture of Gaussian distributions, and is parametrically determined by two sets of sufficient statistics which satisfy stochastic DEs; this result leads to a generalization of the Kalman–Bucy filter to a structure with a conditional mean vector, and additional sufficient statistics that obey nonlinear equations, and determine a generalized (random) Kalman gain. The theory is used to solve explicitly a control problem with quadratic running and terminal costs, and bounded controls.     

An improved unifying convergence analysis of Newton’s method in Riemannian manifolds

Using more precise majorizing sequences we provide a finer convergence analysis than before [1], [7] of Newton’s method in Riemannian manifolds with the following advantages: weaker hypotheses, finer error bounds on the distances involved and a more precise information on the location of the singularity of the vector field.     

Design of cellular manufacturing systems using Latent Semantic Indexing and Self Organizing Maps

A new, efficient clustering method for solving the cellular manufacturing problem is presented in this paper. The method uses the part-machine incidence matrix of the manufacturing system to form machine cells, each of which processes a family of parts. By doing so, the system is decomposed into smaller semi-independent subsystems that are managed more effectively improving overall performance. The proposed method uses Self Organizing Maps (SOMs), a class of unsupervised learning neural networks, to perform direct clustering of machines into cells, without first resorting to grouping parts into families as done by previous approaches. In addition, Latent Semantic Indexing (LSI) is employed to significantly reduce the complexity of the problem resulting in more effective training of the network, significantly improved computational efficiency, and, in many cases, improved solution quality. The robustness of the method and its computational efficiency has been investigated with respect to the dimension of the problem and the degree of dimensionality reduction. The effectiveness of grouping has been evaluated by comparing the results obtained with those of the k-means classical clustering algorithm.AMS classification: 62H30     

Combined use of β-cyclodextrin and ionic liquid as electrolyte additives in EKC for separation and determination of carob's phenolics—A study of the synergistic effect

In this work, a simple, reliable, and fast capillary electrophoretic method was developed and validated for the simultaneous determination of 12 polyphenolic compounds, the most frequently found in carob's pulp and seeds. The present work deals with the development of a novel dual electrophoretic system based on the combined use of β-CD and ionic liquid (IL) as buffer additives. A baseline separation of the target analytes was achieved in less than 10 min by using a BGE consisting of 35 mM borate along with 15 mM β-CD and 3 mM l -alanine tert butyl ester lactate (l -AlaC₄Lac) IL as buffer additives at pH 9.5, a temperature of 25°C, and an applied voltage of 30 kV. The application of the developed electrophoretic method to real samples enabled the identification and quantification of the main phenolic constituents of both ripe and unripe carob pulp extracts. The results revealed the predominance of gallic acid in both ripe (183.92 μg/g carob pulp) and unripe (205.10 μg/g carob pulp) carob pulp and highlighted the great influence of the ripening stage on carobs polyphenolic composition, with unripe pods being more enriched in polyphenols (total phenolics detected: 912.58 and 283.13 μg/g unripe and ripe carob pulp).     

On the assessment of electrocatalysts for nitrate reduction

The electrochemical reduction of nitrate is attracting attention in the context of producing ammonia, besides the traditional removal to harmless N₂. To make progress in this complex reaction and facilitate the search for active and selective catalysts, we need to establish generalized testing protocols which will enable to compare and complement data from different laboratories. The purpose of this article is to raise awareness on the importance of (i) solution processes that involve products of the electrode reaction, (ii) determination of products with appropriate, product-specific quantitative methods, (iii) the strong sensitivity of the reaction on experimental parameters, (iv) the cell design for the separation of anode from cathode processes, and (v) the increase in the interfacial and solution pH that occurs during the electrolysis at high current densities.