Ashis K. Satpati

Photophysical Properties of Coumarin-7 Dye: Role of Twisted Intramolecular Charge Transfer State in High Polarity Protic Solvents

Photophysical studies on coumarin‐7 (C7) dye in different protic solvents reveal interesting changes in the properties of the dye on increasing the solvent polarity (Δf; Lippert–Mataga solvent polarity parameter) beyond a critical value. Up to Δf∼0.31, the photophysical properties of the dye follow good linear correlations with Δf. For Δf >∼0.31, however, the photophysical properties, especially the fluorescence quantum yields (Φf), fluorescence lifetimes (τf) and nonradiative rate constants (knr), undergo large deviations from the above linearity, suggesting an unusual enhancement in the nonradiative decay rate for the excited dye in these high polarity protic solvents. The effect of temperature on the τf values of the dye has also been investigated to reveal the mechanistic details of the deexcitation mechanism for the excited dye. Studies have also been carried out in deuterated solvents to understand the role of solute–solvent hydrogen bonding interactions on the photophysical properties of the dye. Observed results suggest that the fluorescence of the dye originates from the planar intramolecular charge transfer (ICT) state in all the solvents studied and the deviations in the properties in high polarity solvents (Δf >∼0.31) arise due to the participation of a new deexcitation channel associated with the formation of a nonfluorescent twisted intramolecular charge transfer (TICT) state of the dye. Comparing present results with those of a homologous dye coumarin 30 (C30; Photochem. Photobiol., 2004, 80, 104), it is indicated that unlike in C30, the TICT state of the C7 dye does not experience any extra stability in protic solvents compared to that in aprotic solvents. This has been attributed to the presence of intramolecular hydrogen bonding between the NH group (in the 3‐benzimidazole substituent) of the C7 dye and its carbonyl group, which renders an extra stability to the planar ICT state, making the TICT state formation relatively difficult. Qualitative potential energy diagrams have been proposed to rationalize the differences observed in the results with C7 and C30 dyes in high polarity protic solvents.

Iron nanoparticles decorated multi-wall carbon nanotubes modified carbon paste electrode as an electrochemical sensor for the simultaneous determination of uric acid in the presence of ascorbic acid, dopamine and L-tyrosine.

Iron nanoparticles decorated multi-wall carbon nanotubes modified carbon paste electrode (Fe-MWCNTs/MCPE) was prepared by bulk-modification method. The electrochemical impedance spectroscopy (EIS) suggests least charge transfer resistance at the modified electrode. The electrochemical behavior of UA was studied in 0.1M phosphate buffer solution (PBS) of pH3.0 using cyclic voltammetry (CV) while differential pulse voltammetry (DPV) was used for quantification. The spectroelectrochemial study of oxidation of UA at Fe-MWCNTs/MCPE showed a decrease in the absorbance of two peaks with time, which are ascribed to π to π(⁎) and n to π(⁎) transitions. Under optimum condition, the DPV response offered two linear dynamic ranges for UA in the concentration range 7.0×10(-8)M-1.0×10(-6)M and 2.0×10(-6)M-1.0×10(-5)M with detection limit (4.80±0.35)×10(-8)M (S/N=3). The practical analytical application of this sensor was successfully evaluated by determination of spiked UA in clinical samples, such as human blood serum and urine with good percentage recovery. The proposed electrochemical sensor offers a simple, reliable, rapid, reproducible and cost effective analysis of a quaternary mixture of biomolecules containing AA, DA, UA and Tyr which was free from mutual interferences.

Ultrafast Electron Transfer Dynamics in Micellar Media Using Surfactant as the Intrinsic Electron Acceptor

Ultrafast photoinduced intermolecular electron transfer (ET) dynamics involving 7-aminocoumarin derivatives as electron donor and pyridinium moiety of surfactant molecules in cetylpyridinium chloride (CPC) micelle as electron acceptor has been investigated to understand the role of separation and orientation of reactants on micellar ET reactions. Unlike in noninteracting micelles (like Triton-X-100, sodium dodecyl sulfate, dodecyltrimethylammonium bromide, etc.), where surfactant-separated donor-acceptor pairs are understood to give the ultrafast ET component with the shortest time constant in the range of approximately 4 ps, in CPC micelles with pyridinium moiety as the intrinsic acceptor the ultrafast ET component is found to be in the subpicosecond time scale (of around 240 fs). This time scale is very similar to the values reported in the cases of ultrafast ET reactions involving coumarin dyes in electron-donating solvents. The ultrafast ET times in CPC micelles are significantly faster than the diffusive solvation dynamics in the micellar media. Correlation of the observed ET rates in the present cases with the free-energy changes of the reactions shows the inverse-bell-shaped correlation, predicted by Marcus ET theory. Interestingly, the onset of the Marcus inversion appears at a relatively lower exergonicity, which is attributed to the nonequilibrium solvent configuration during the ultrafast ET reaction, as envisaged from two-dimensional ET (2DET) model. Along with the ultrafast ET component, there are also slower ET components in these systems, which are attributed to those close-contact donor-acceptor populations in the micelles that have relatively weaker electronic coupling due to improper orientation of the interacting donor-acceptor pairs. The present results suggest that, along with the shifting of Marcus inversion at lower exergonicity, the ET rates can also be maximized in a micellar media by using surfactant molecule as an intrinsic reactant.

Tuning of intermolecular electron transfer reaction by modulating the microenvironment inside copolymer-surfactant supramolecular assemblies.

Photoinduced intermolecular electron transfer (ET) dynamics between various 7-aminocoumarin acceptors and N,N-dimethylaniline (DMAN) donor has been studied in copolymer-surfactant supramolecular assemblies prepared in aqueous 1% P123 triblock copolymer micellar solution with varying concentration of surfactants (sodium dodecyl sulfate (SDS), cetyl trimethyl ammonium chloride (CTAC), and triton-X-100 (TX100)). The aim of the present study is to modulate the reaction environment, especially the degree of micellar hydration inside the P123 micelle by the addition of the surfactants, which can modulate the ET reaction through the changes in the ET rates and the reaction exergonicity. Within the limited surfactant to copolymer molar ratios (n) used in the present study, fluorescence spectroscopy, dynamic light scattering (DLS), and small-angle neutron scattering (SANS) investigations indicate that the copolymer-surfactant supramolecular assemblies retain their micellar structure, although the micellar size gradually decreases with n. The redox potentials of the electron donor and acceptors are also found to change with n, although the extent of the effect is different for SDS, CTAC, and TX100 cosurfactants. In the presence of CTAC, the estimated exergonicity (-ΔG(0)) of the ET reaction is found to increase with an increase in n compared with that in pure P123, whereas it decreases marginally with SDS and remains almost the same for TX100. Substantial quenching of coumarin fluorescence is observed in the presence of DMAN in all copolymer-surfactant micellar aggregates because of ET reaction. The ET rate is seen to increase gradually with an increase in SDS and CTAC concentration in the supramolecular assembly, although it remains unaffected on the addition of TX100. The increased ionic strength in the Corona region of the copolymer-surfactant supramolecular aggregates due to the addition of the ionic surfactants has been envisaged for the increase in the ET rates. A correlation of the quenching rate constants with the free-energy changes (ΔG(0)) of the ET reactions shows the typical bell-shaped curve as predicted by Marcus outersphere ET theory. A substantial shift along the exergonicity axis (~0.3 eV) for the appearance of the Marcus correlation is observed in some cases, although the extent of such shift depends on both the nature of the cosurfactant and the amount of cosurfactant used in the copolymer-surfactant supramolecular assembly. Therefore, these preliminary results suggest a possibility of not only modulating the ET rates but also tuning the appearance of Marcus inversion along the exergonicity scale by suitably tuning the reaction environment inside the copolymer-surfactant supramolecular assemblies with a relatively more hydrophilic cosurfactant.

An electrochemical method for the preparation of 63Ni source for the calibration of thermoluminescence dosimeter (TLD)

A novel electrochemical approach for preparation of (63)Ni sources for their application as check-light source for the calibration of thermo luminescence dosimeters (TLD) is described here. Required amount of (63)Ni on a copper substrate could be deposited by optimizing the experimental parameters such as current density, time of deposition, pH of the electrolyte and nickel ion concentration in the bath. (63)Ni sources of strength approximately 3.7 MBq could be prepared by electrodeposition at constant current on the copper matrix. Quality assurance tests to ensure nonleachability, uniform distribution of activity and stability of the sources that are necessary before application were performed.

A nanoreactor for tuning the chemical reactivity of a solute.

Present results demonstrate that the redox potential and hence the chemical reactivity of a solute dissolved in a polymer-surfactant supramolecular assembly, considered as a nanoreactor, can be tuned substantially by changing the composition of the supramolecular assembly. It is understood from detailed study that, on changing the polymer-surfactant composition of the supramolecular assembly, the probe undergoes a change in its location in these nanoreactors and accordingly its physical and chemical properties can be modulated.

Facile preparation of poly(methylene blue) modified carbon paste electrode for the detection and quantification of catechin

Free radicals are formed as byproducts of metabolism, and are highly unstable due to the presence of unpaired electrons. They readily react with other important cellular components such as DNA causing them damage. Antioxidants such as (+)-catechin (CAT), neutralize free radicals in the blood stream. Hence there is a need for detection and quantification of catechin concentration in various food sources and beverages. Electro-oxidative properties of catechin were investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). A carbon paste working electrode modified by electropolymerizing methylene blue (MB) was fabricated. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) techniques were used to study the surface morphology of the electrode. Quasi-reversible electron transfer reaction occurred at +0.260V through a diffusion controlled process. In comparison to the bare carbon paste electrode (CPE), there was a significant 5.3 times increment in anodic current sensitivity at the modified electrode at physiological pH. Our findings indicate that for the electro-oxidation of CAT, CPE is a better base material for electropolymerization of MB compared to glassy carbon electrode (GCE). Nyquist plot followed the theoretical shape, indicating low interfacial charge transfer resistance of 0.095kΩ at the modified electrode. Calibration plots obtained by DPV were linear in two ranges of 1.0×10-3 to 1.0×10-6 and 1.0×10-7 to 0.1×10-8M. The limit of detection (LOD) and limit of quantification (LOQ) was 4.9nM and 14nM respectively. Application of the developed electrode was demonstrated by detecting catechin in green tea and spiked fruit juice with satisfactory recoveries. The sensor was stable, sensitive, selective and reproducible.

Electrodeposited Bi-Au nanocomposite modified carbon paste electrode for the simultaneous determination of copper and mercury

Composites of bismuth and gold nanoparticles (Bi–AuNPs) were prepared on a carbon paste electrode (CPE) by an electrochemical deposition method. The electrochemical parameters were optimized for the effective deposition of Bi–AuNP composite materials. Microscopic examination revealed that nanoparticle clusters of gold were embedded well within the bismuth films (Bi films) over the surface of the CPE. An analytical anodic stripping voltammetry method has been developed for the simultaneous determination of copper and mercury at ultratrace levels using the Bi–AuNP modified CPE. It was possible to observe well separated stripping peaks of the two metal ions and the modified electrode was successfully applied for simultaneous determination of Cu and Hg. The limits of detection using the optimized analytical procedure were observed as 0.16 μg L−1 and 0.28 μg L−1 for Cu and Hg respectively. Interference effects of some of the commonly occurring metal ions were investigated and the method was applied for the determination of Cu and Hg in two ground water and two soil samples collected from different places.

On the application of electrochemical techniques for the preparation of 57Co source core, encapsulation and quality evaluation for radiometric assay of nuclear fuel rods

Abstract This paper describes an electrochemical method for the preparation of 57Co source to be used in quality evaluation of nuclear fuel rods. The electrolytic cell, the experimental set up used and the process of deposition are described. The effect of various parameters such as pH of the electrolyte, bath temperature, current density, content of cobalt in the bath, electrolyte volume in the cell and deposition time were investigated and optimized for maximum deposition. The texture and morphology of the electrodeposited samples were examined by X-ray diffraction (XRD), SEM and EDS analyses. Sources containing ∼370 MBq (10 mCi) 57Co on a circular copper foil of 4 mm diameter could be prepared and encapsulated in an aluminum capsule. Quality assurance tests performed to ensure non-leachability, uniform distribution of activity and stability of the sources gave satisfactory results.

Bi-Film on a carbon paste electrode modified with nafion film embedded with multiwall carbon nano tubes for the determination of heavy metals

Bi-film was deposited on the carbon paste electrode and used as the modified electrode in stripping voltammetry. Bi deposition was carried out ex-situ in acetate buffer solution of pH 4.5 under mild stirring conditions. The deposition potential, deposition time and the Bi-concentration in the deposition solution were optimized and the corresponding values are −0.8 V (SCE), 300 s and 0.3 mM Bi-nitrate solution respectively. A substantial enhancement of an order of magnitude in the sensitivity has been observed when carbon paste electrode was modified with nafion coated carbon nano tube on which Bi-film was deposited. This enhanced sensitivity was attributed to the increased active surface area and also the enhanced charge transfer processes which increased the deposition processes and so the stripping current. Effect of different surfactants on the stripping peak of the heavy metal ions is investigated with and without modification by nafion. Detection limits using Bi-film electrode was obtained for Zn, Cd and Pb as 17.3, 16.9, 11.9 μg L−1, respectively, using Bi-film electrode. Analysis result of two water samples and two ayurvedic medicines are reported.