Electrospinning of poly(lactic acid): Theoretical approach for the solvent selection to produce defect‐free nanofibers

In this study an integrated methodology was proposed for the selection of solvent systems to produce electrospinnable solutions that form defect‐free poly(lactic acid) (PLA) fibers with narrow diameter distributions. The solvent systems were chosen using a thermodynamic approach, combined with electrical and rheological property criteria. More specifically, the three step methodology includes (1) initial choice of solvent by solubility evaluation to meet thermodynamic criteria, (2) electrical properties, that is, conductivity and dielectric constant adjustment by using solvent mixtures to meet electrical property criteria, and (3) critical entanglement concentration (C_e) determination by viscosity measurements, supported by elastic and plastic moduli measurements, followed by concentration adjustment to meet rheological criteria. All three criteria need to be met to ensure defect‐free nanofiber morphology. The methodology was demonstrated using PLA solutions that were characterized in terms of thermodynamic properties, conductivity, surface tension, and viscosity measurements. These data were analyzed and related to the nanofiber morphology and diameter as determined from scanning electron microscopy (SEM). Measurements of the elastic (G′) and the plastic (G″) moduli of PLA solutions showed a sharp increase of G′ at the chain entanglement concentration. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1483–1498     

Tuning the Triplet Excited State of Bis(dipyrrin) Zinc(II) Complexes: Symmetry Breaking Charge Transfer Architecture with Exceptionally Long Lived Triplet State for Upconversion

Zinc(II) bis(dipyrrin) complexes, which feature intense visible absorption and efficient symmetry breaking charge transfer (SBCT) are outstanding candidates for photovoltaics but their short lived triplet states limit applications in several areas. Herein we demonstrate that triplet excited state dynamics of bis(dipyrrin) complexes can be efficiently tuned by attaching electron donating aryl moieties at the 5,5′-position of the complexes. For the first time, a long lived triplet excited state (τ_T=296 μs) along with efficient ISC ability (Φ_Δ=71 %) was observed for zinc(II) bis(dipyrrin) complexes, formed via SBCT. The results revealed that molecular geometry and energy gap between the charge transfer (CT) state and triplet energy levels strongly control the triplet excited state properties of the complexes. An efficient triplet–triplet annihilation upconversion system was devised for the first time using a SBCT architecture as triplet photosensitizer, reaching a high upconversion quantum yield of 6.2 %. Our findings provide a blueprint for the development of triplet photosensitizers based on earth abundant metal complexes with long lived triplet state for revolutionary photochemical applications.     

Interaction of Point Defects with Twin Boundaries in Copper

The interaction between small vacancy clusters and twin boundaries in copper is studied by using many-body potential developed by Ackland et aL for fcc metals. The interaction energies of single-, di- and tri-vacancy clusters with （111） and （112） twin boundaries are computed using well established simulation techniques. For （111） twins the vacancy clusters are highly repelled when they are on the adjacent planes, and are attracted when they are away from the boundary. In the case of （112） twins, vacancy clusters are more attracted to the boundary when they are near the boundary as compared to away from it. Vacancy clusters on both the sides of the boundary are also investigated, and it is observed that the clusters energetically prefer to lie on the off-mirror sites as compared to the mirror position across the twin.     

Numerical solutions of peristaltic flow of Williamson fluid with radially varying MHD in an endoscope

In this article we have studied the peristaltic motion of an incompressible Williamson fluid with constant and radially varying magnetohydrodynamics (MHD) in an endoscope. Using the low Reynolds and long wavelength assumptions, the equations of Williamson fluid model in simplified form are solved using (i) the HAM method and (ii) the Shooting method. The comparisons of both solutions have been found a very good agreement. Graphical results have been presented for various emerging parameters. © British Crown Copyright 2010/MOD. Reproduced with permission. Published by John Wiley & Sons, Ltd.     

Synthesis and characterisation of luminescent rhenium tricarbonyl complexes with axially coordinated 1,2,3-triazole ligands

A series of 1-alkyl-4-aryl-1,2,3-triazoles (1-methyl-4-phenyl-1,2,3-triazole (1a); 1-propyl-4-phenyl-1,2,3-triazole (1b); 1-benzyl-4-phenyl-1,2,3-triazole (1c); 1-propyl-4-p-tolyl-1,2,3-triazole (1d)) have been prepared through a one-pot procedure involving in situ generation of the alkyl azide from a halide precursor followed by copper catalysed alkyne/azide cycloaddition (CuAAC) with the appropriate aryl alkyne. Cationic Re(I) complexes [Re(bpy)(CO)(3)(1a-d)]PF(6) (2a-d) were then prepared by stirring [Re(bpy)(CO)(3)Cl] with AgPF(6) in dichloromethane in the presence of ligands 1a-d. X-ray crystal structures were obtained for 2a and 2b. In the solid state, 2a adopts a highly distorted geometry, which is not seen for 2b, in which the plane of the triazole ligand tilts by 13° with respect to the Re-N bond as a result of a π-stacking interaction between the Ph substituent and one of the rings of the bpy ligand. This π-stacking interaction also results in severe twisting of the bpy ligand. Infrared spectra of 2a-d exhibit ν(CO) bands at ～2035 and ～1926 cm(-1) suggesting that these ligands are marginally better donors than pyridine (ν(CO) = 2037, 1932 cm(-1)). The complexes are luminescent in aerated dichloromethane at room temperature with emission maxima at 542 to 552 nm comparable to that of the pyridine analogue (549 nm) and blue shifted relative to the parent chloride complex. Long luminescent lifetimes are observed for the triazole complexes (475 to 513 ns) in aerated dichloromethane solutions at room temperature.     

Power law fluid model for blood flow through a tapered artery with a stenosis

In the present paper, blood flow through a tapered artery with a stenosis is analyzed, assuming the flow is steady and blood is treated as non-Newtonian power law fluid model. Exact solution has been evaluated for velocity, resistance impedance, wall shear stress and shearing stress at the stenosis throat. The graphical results of different types of tapered arteries (i.e. converging tapering, diverging tapering, non-tapered artery) have been examined for different parameters of interest. Some special cases of the problem are also presented.     

An analytical and numerical study of peristaltic transport of a Johnson-Segalman fluid in an endoscope

In the present study, we discuss the peristaltic flow of a Johnson-Segalman fluid in an endoscope. Perturbation, homotopy, and numerical solutions are found for the non-linear differential equation. The comparative study is also made to check the validity of the solutions. The expressions for pressure rise frictional forces, pressure gradient, and stream lines are presented to interpret the behavior of various physical quantities of the Johnson-Segalman fluid.     

Synthesis and crystal structures of polynuclear complexes of Cu with 1-methyl-1,3-imidazoline-2-thione

Reactions of equimolar solutions of copper(I) halides with 1-methyl-1,3-imidazoline-2-thione (SC₄H₆N₂) in acetonitrile have yielded a trinuclear complex, {Cu₃(η¹-Br)₃(μ-SC₄H₆N₂)₃} · CH₃CN 1, and 1D polymer, {Cu₂(μ-I)₂(μ-SC₄H₆N₂)₂}_n2. The thio-ligands/halogens adopt μ-S, η¹-X or μ-X modes. There is weak interaction between trinuclear units {Cu···Br, 3.025 Å} and Cu···Cu contacts lie in the range, 2.974(2)–3.650(2) Å. Polymer 2 has alternating Cu₂I₂ and Cu₂S₂ cores involving sulfur/iodine bridging in a twisted ribbon type arrangement with short Cu···Cu distances {2.6912(9) and 2.785(9) Å}, respectively. The polynuclear complexes in dimethyl sulfoxide exhibit intense fluorescent bands {λ_em = 319 (1) and 322 (2)}.