105 research outputs found

    Preferential solvation and bimolecular quenching reactions of boronic acid dye at very low quencher concentrations studied by fluorescence spectrum in toluene and butanol binary mixtures

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    168-177Inferable from the significance of solvent mixtures in practical chemistry, toluene (TL) and butanol (BL) mixtures are used to studyfluorescence behavior of boronic acid dye 2-methoxy-5-fluoro-phenyl boronic acid (2MEFPBA). At the inception, preferential solvation is examined in TL-BL, to understand specific and nonspecific interactions. Suppan’s dielectric enrichment model is further used to understand the nonideality and dielectric enrichment in TL-BL mixtures for preferential solvation. Bimolecular quenching reaction studies of 2MEFPBA with aniline as quencher are made in mixtures of TL–BLto know the effect of viscosity and dielectric constant variation at room temperature.  The quenching process is studied in all solvent mixtures by steady state and transient state method. Quenching is characterized by S-V plots having upward curvature. Analysis of modified S-V equations which accounts both static and dynamic quenching allows calculating bimolecular quenching rate constant. The bimolecular quenching reactions are found to be significantly larger. Further finite sink approximation model is invoked so as to check whether reactions are diffusion limited. The extents of these rate parameters demonstrate that positive deviations in the Stern-Volmer (S-V) plot are because of the presence of apparent static and dynamic quenching process

    Preferential solvation and bimolecular quenching reactions of boronic acid dye at very low quencher concentrations studied by fluorescence spectrum in toluene and butanol binary mixtures

    Get PDF
    Inferable from the significance of solvent mixtures in practical chemistry, toluene (TL) and butanol (BL) mixtures are used to studyfluorescence behavior of boronic acid dye 2-methoxy-5-fluoro-phenyl boronic acid (2MEFPBA). At the inception, preferential solvation is examined in TL-BL, to understand specific and nonspecific interactions. Suppan’s dielectric enrichment model is further used to understand the nonideality and dielectric enrichment in TL-BL mixtures for preferential solvation. Bimolecular quenching reaction studies of 2MEFPBA with aniline as quencher are made in mixtures of TL–BLto know the effect of viscosity and dielectric constant variation at room temperature. The quenching process is studied in all solvent mixtures by steady state and transient state method. Quenching is characterized by S-V plots having upward curvature. Analysis of modified S-V equations which accounts both static and dynamic quenching allows calculating bimolecular quenching rate constant. The bimolecular quenching reactions are found to be significantly larger. Further finite sink approximation model is invoked so as to check whether reactions are diffusion limited. The extents of these rate parameters demonstrate that positive deviations in the Stern-Volmer (S-V) plot are because of the presence of apparent static and dynamic quenching process

    Effect of hydrogen bonding and solvent polarity on the fluorescence quenching and dipole moment of 2-methoxypyridin-3-yl-3-boronic acid

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    Two photophysical properties namely, fluorescence quenching and dipole moment (both ground state and excited state) of 2-methoxypyridin-3-yl-3-boronic acid (2MPBA) have been investigated in alcohol environment using steady state fluorescence technique at 300 K. In quenching studies, a rare but not unusual observation; negative Stern-Volmer (S-V) deviation has been noticed. It has been explained using the concept of solute’s conformational changes in the ground state due to inter-molecular and intra-molecular hydrogen bonding in alcohol environment. The spectroscopic data has been processed using Lehrer equation and thereby Stern-Volmer constant (KSV) has been evaluated. It has been found to be above 100 for most of the solvents used. The data related to dipole moment has been examined using different solvent polarity functions. Theoretical calculation of dipole moment in the ground state has been done using Gaussian software. The general solute–solvent interactions and hydrogen bond interactions have been found to be operative. An appreciable red shift of about 25 nm in the emission spectra has been identified with the rise in solvent polarity and decrease in molar mass of alcohols. It confirms the π→π* transition as well as the possibility of intra-molecular charge transfer (ICT) character in the emitting singlet state of 2MPBA

    Modified Newton-Raphson Method to Tune Feedback Gains of Control System for Standing by Functional Neuromuscular Stimulation Following Spinal Cord Injury

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    Background: Functional neuromuscular stimulation (FNS) can restore standing capabilities following spinal cord injury. Feedback control of these systems can optimize performance by reducing the required upper extremity support. However, tuning these control systems can be intensive and clinically inconvenient

    Artificial Inclusion Environments—Replicating Industry in the Laboratory

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    The authors present a series of complementary test methods which were developed and used to investigate reactions between high aluminium steel and silica rich inclusions. Non-metallic inclusions (NMIs) cause many defects in the final steel product, therefore the ability to track their size, morphology and composition and correlate this with fundamental reaction kinetics provides important knowledge to support the production of clean quality steel products. Novel steel grades such as TRIP, TWIP and low-density steels have high aluminium contents; aluminium is a readily oxidisable species presenting the potential for instability and excessive reaction with commonly used mould powders that contain silica. A novel combination of techniques including HT-CLSM (High-Temperature Confocal Laser Scanning Microscope), XCT (X-ray computed tomography) and SEM/EDS (scanning electron microscopy/electron dispersive spectroscopy) have been used to study the interaction of entrained mould powder inclusions with steel at high temperatures simulating industrial conditions. This report presents a discussion on the development of techniques and samples to achieve representative and repeatable results that can provide information on the complex chemical and physical interaction phenomena with confidence. Each experimental technique had its own learning points and consequent results. Outcomes presented include possible confirmation of the chemical reaction rate controlling step being aluminium mass transfer; heterogeneous local environmental conditions including fluidity and chemical composition; and occurrence of spontaneous emulsification where the mould powder inclusion breaks apart into a cloud of smaller fragments
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