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.     

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     

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.     

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.     

Influence of heat transfer on a peristaltic transport of Herschel–Bulkley fluid in a non-uniform inclined tube

Peristaltic transport in a two-dimensional non-uniform tube filled with Herschel–Bulkley fluid is studied under the assumptions of long wavelength and low Reynold number. The fluid flow is investigated in the wave frame of reference moving with the velocity of the peristaltic wave. Exact solution for the velocity field, the temperature profile, the stream functions and the pressure gradient are obtained. The physical behavior of τ, n, α and on the pressure rise versus flow rate are discussed through graphs. At the end of the article trapping phenomena for Herschel–Bulkley and also for Newtonian, Bingham and power law (which are the special cases of Herschel–Bulkley fluid) fluid are discussed.     

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.     

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.     

An alytical 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.