Solvent effects on the intramolecular charge transfer character of N,N-diaryl dihydrophenazine catalysts for organocatalyzed atom transfer radical polymerization

The nature of intramolecular charge transfer (CT) of N,N-diaryl dihydrophenazine photocatalysts (PCs) in different solvents is explored in context of their performance in organocatalyzed atom transfer radical polymerization (O-ATRP). PCs having a computationally predicted lowest energy excited state exhibiting CT character can operate a highly controlled O-ATRP in a wide range of solvent polarities, from non-polar hexanes to highly polar N,N-dimethylacetamide. For PCs having a computationally predicted lowest energy excited state not possessing CT character, their ability to operate a controlled O-ATRP is decreased. This study confirms the importance of CT character in the excited state for N,N-diaryl dihydrophenazine PCs, and a deeper understanding of the activity of CT PCs has enabled the synthesis of polymers of low dispersity (<1.10) in a controlled fashion. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3017–3027     

Synthesis and antimicrobial activity of some novel benzofuran based 1,2,3-triazoles

In the present study, a series of novel {6-[(1H-1,2,3-triazol-4-yl)methoxy]-3-methylbenzofuran-2-yl}(phenyl)methanones (7a–7o) have been synthesized using click chemistry approach. The structures of all newly synthesized compounds were characterized by FT-IR, ¹H and ¹³C NMR, and MASS spectral data. Most of products demonstrated high antimicrobial activity.

     

Experimental and theoretical determination of frequencies of elastic toroids

Experiments are described which determine natural frequencies of five toroidal models whose major diameters are of 10 in. and whose minor diameters vary from 0.25 to 2 in. The experimentally determined frequencies are compared with the theoretical frequencies derived using the elementary theories for the in-plane and out-of-plane vibrations of circular rings of R. Hoppe and J. H. Michell, as well as the method of internal constraints. The comparative results for the frequencies are presented in tabular form.     

A Sedimentological Approach to Upscaling

Optimised upscaling in reservoir simulations requires the construction of realistic petrophysical properties that are representative of the heterogeneity in the sedimentary deposits. Reservoir heterogeneities are controlled by the arrangement of various hierarchies of sedimentary facies and their internal bounding surfaces. The conventional sedimentological approach to reservoir upscaling involves subdivision and ranking of various hierarchies of architectural units and associated bounding surfaces of the reservoir sequence according to their geological significance. This global upscaling approach produces realistic scaled up models that retain both the structural and non-structural heterogeneities of the original sedimentological models. Analyses of sedimentary sequences from various depositional environments indicate that the fractional Levy model can adequately describe the heterogeneity and scaling characteristics of individual genetic sediment sequences in the clastic sedimentary system without further subdividing and ranking of the heterogeneous sequences. The heterogeneous nature of each sedimentary system can be quantified by the Levy index parameter, whereas the maximum upscaling magnitude (or upscaling index) for a particular sequence can be determined from the Levy width parameter plot. Depositional modelling mimics the sedimentary processes in a range of scales and honours hierarchies of sedimentary facies and their bounding surfaces. It can be used effectively for upgridding and upscaling in accordance with the stratigraphic framework and sedimentological models. Both the fractional Levy model and the depositional modelling provide quantitative alternatives to the conventional global sedimentological upscaling approach.     

Numerical-Asymptotic Expansion Matching for Computing a Viscous Flow Around a Sharp Expansion Corner

A computational technique which is based on a numerical-asymptotic expansion matching for computing the local singular behavior of a viscous flow around a sharp right-angle expansion corner is presented. Moffatt's (1964) asymptotic solution is extended and a matching with a time-marching finite-difference scheme of the Navier--Stokes equations is formulated. Local mesh refinement around the corner is required to meet the validity of the asymptotic solution. Flows in an expanding channel with expansion ratio D/d=3 at various Reynolds numbers 1≤Re≤700 are simulated. The results are compared with those from a standard finite-difference scheme that uses second-order forward/backward differences near the corner. It is found that the results of the standard scheme converge toward those of the present technique as the level of local refinement near the corner is increased. The time-dependent parameters of the first two terms of the asymptotic solution at the steady-state solution are also described for various cases of Re and D/d. It is demonstrated that the present method enhances the accuracy of the simulations and requires less refinements near the corners to achieve converged numerical results. Received 14 August 2000 and accepted 25 October 2001     

Distinguishing and quantification of the human visual pathways using high-spatial-resolution diffusion tensor tractography

Quantification of the living human visual system using MRI methods has been challenging, but several applications demand a reliable and time-efficient data acquisition protocol. In this study, we demonstrate the utility of high-spatial-resolution diffusion tensor fiber tractography (DTT) in reconstructing and quantifying the human visual pathways. Five healthy males, age range 24–37 years, were studied after approval of the institutional review board (IRB) at The University of Texas Health Science Center at Houston. We acquired diffusion tensor imaging (DTI) data with 1-mm slice thickness on a 3.0-Tesla clinical MRI scanner and analyzed the data using DTT with the fiber assignment by continuous tractography (FACT) algorithm. By utilizing the high-spatial-resolution DTI protocol with FACT algorithm, we were able to reconstruct and quantify bilateral optic pathways including the optic chiasm, optic tract, optic radiations free of contamination from neighboring white matter tracts.     

Synthesis and Antibacterial Evaluation of Benzofuran Based Di-1,2,3-triazoles

Russian Journal of General Chemistry - A series of novel benzofuran-1,2,3-triazole hybrid molecules are synthesized using the click chemistry approach. Structures of the synthesized compounds were...     

Bridging Ligand Length Controls AT Selectivity and Enantioselectivity of Binuclear Ruthenium Threading Intercalators

The slow dissociation of DNA threading intercalators makes them interesting as model compounds in the search for new DNA targeting drugs, as there appears to be a correlation between slow dissociation and biological activity. Thus, it would be of great value to understand the mechanisms controlling threading intercalation, and for this purpose we have investigated how the length of the bridging ligand of binuclear ruthenium threading intercalators affects their DNA binding properties. We have synthesised a new binuclear ruthenium threading intercalator with slower dissociation kinetics from ct‐DNA than has ever been observed for any ruthenium complex with any type of DNA, a property that we attribute to the increased distance between the ruthenium centres of the new complex. By comparison with previously studied ruthenium complexes, we further conclude that elongation of the bridging ligand reduces the sensitivity of the threading interaction to DNA flexibility, resulting in a decreased AT selectivity for the new complex. We also find that the length of the bridging ligand affects the enantioselectivity with increasing preference for the ΔΔ enantiomer as the bridging ligand becomes longer.     

PHI: A powerful new program for the analysis of anisotropic monomeric and exchange‐coupled polynuclear d‐ and f‐block complexes

A new program, PHI, with the ability to calculate the magnetic properties of large spin systems and complex orbitally degenerate systems, such as clusters of d‐block and f‐block ions, is presented. The program can intuitively fit experimental data from multiple sources, such as magnetic and spectroscopic data, simultaneously. PHI is extensively parallelized and can operate under the symmetric multiprocessing, single process multiple data, or GPU paradigms using a threaded, MPI or GPU model, respectively. For a given problem PHI is been shown to be almost 12 times faster than the well‐known program MAGPACK, limited only by available hardware. © 2013 Wiley Periodicals, Inc.     

A Cyclodextrin Molecular Reactor for the Regioselective Synthesis of 1,5-disubstituted-1,2,3-triazoles

6^A-Deoxy-6^A-propynamido-β-cyclodextrin reacts with 4-tert-butylphenyl azide in aqueous solution, to form the 5-(aminocarbonyl)-substituted triazole in preference to the 4-(aminocarbonyl)-substituted analogue, in a ratio of 25:1. The cyclodextrin moiety templates the reaction through the formation of a host-guest complex of the dipole with the dipolarophile, controlling the regioselectivity of cycloaddition. In a control reaction under similar conditions, with propiolamide instead of the cyclodextrin derivative, 5- and 4-(aminocarbonyl)-1-(4-tert-butylphenyl)-1,2,3-triazole were formed in a ratio of 1:4. As well as reversing the regioselectivity, the cyclodextrin substituent increases the rate of cycloaddition, by at least two orders of magnitude for the reaction to give the 5-substituted cycloadduct. Even the rate of formation of the 4-substituted cycloadduct is increased by a factor of two. Less marked effects are observed with phenyl azide and 4-tert-butylbenzyl azide as dipoles.