S.R. Inamdar

Large-scale advection of continental aerosols during INDOEX

In this paper, we present passive and active remote sensing measurements of atmospheric aerosols over the North Indian Ocean (NIO) during the Intensive Field Phase (IFP, January to March 1999) of the Indian Ocean Experiment. The variability of the aerosol load over NIO is discussed based on three-dimentional numerical simulations made at a local scale by use of Regional Atmospheric Modeling System (RAMS) and at a regional scale using the zoomed Laboratoire de Meteorologie Dynamique global circulation model (LMD-Z version 3.3). Ground-based measurements of the columnar aerosol optical thickness (AOT) and of surface black carbon (BC) concentration were carried out at two different sites in India: Goa University on the NIO coast and Dharwar 150 km inland. Local-scale investigations point out that the trend in BC concentration at the ground is not correlated with AOT. Lidar profiles obtained both from the surface at Goa and in the NIO from the Mystere-20 research aircraft indicate that a significant contribution to the total AOT (more than 50%) is due to a turbid monsoon layer located between 1 and 3 km height. RAMS simulation shows that the advection of aerosols in the monsoon layer is due to the conjunction of land-sea breeze and topography. We present the regional-scale extent of the aerosol plume in terms of AOT derived from the visible channel of Meteosat-5. During March, most of the Bay of Bengal is overcast by a haze with a monthly average AOT of 0.61±0.18, and a spatially well-defined aerosol plume is spreading from the Indian west coast to the Intertropical Convergence Zone with an average AOT of 0.49±0.08. Those values are bigger than in February with AOT at 0.35±0.18 and 0.37±0.09 for the Bay of Bengal and the Arabian Sea, respectively. One of the principal findings of this paper is that a significant contribution to the aerosol load over the NIO is due to the advection of continental aerosols from India in a well-identified monsoon layer above the marine boundary layer. Moreover, it is suggested that the increase in biomass burning plays a significant role in the increasing trend in AOT during the winter dry monsoon season.

Interaction between an 8-methoxypyrimido[4′,5′:4,5] thieno (2,3-b)quinoline-4(3H)one antitumour drug and deoxyribonucleic acid

The interaction of 8-methoxypyrimido[4′,5′:4,5]thieno(2,3-b)quinoline-4(3H)one (MPTQ) with DNA was studied by UV-Vis and fluorescence spectrophotometry as well as by hydrodynamic methods. On binding to DNA, the absorption spectrum underwent bathochromic and hypochromic shifts and the fluorescence was quenched. Binding parameters, determined from spectrophotometric measurements by Scatchard analysis, indicated a binding constant of 3.56 × 106 M−1 for calf thymus DNA at ionic strength 0.01 M. Binding to the GC-rich DNA ofMicrococcus lysodeikticus was stronger than the binding to calf thymus DNA at ionic strength 0.01 M. The MPTQ increased the viscosity of sonicated rod-like DNA fragments, producing a calculated length of 2.4Å/bound MPTQ molecule. The binding of MPTQ to DNA increased the melting temperature by about 4 °C. This research offers a new intercalation functional group to DNA targetted drug design.

Determination of ground and excited state dipole moments of dipolar laser dyes by solvatochromic shift method

The absorption and fluorescence spectra of three medium sized dipolar laser dyes: coumarin 478 (C478), coumarin 519 (C519) and coumarin 523 (C523) have been recorded and studied comprehensively in various solvents at room temperature. The absorption and fluorescence spectra of C478, C519 and C523 show a bathochromic and hypsochromic shifts with increasing solvent polarity indicate that the transitions involved are π→π(∗) and n→π(∗). Onsager radii determined from ab initio calculations were used in the determination of dipole moments. The ground and excited state dipole moments were evaluated by using solvatochromic correlations. It is observed that the dipole moment values of excited states (μe) are higher than corresponding ground state values (μg) for the solvents studied. The ground and excited state dipole moments of these probes computed from ab initio calculations and those determined experimentally are compared and the results are discussed.

Solvents effect on the absorption and fluorescence spectra of 7-diethylamino-3-thenoylcoumarin: Evaluation and correlation between solvatochromism and solvent polarity parameters

Effect of solvents of varying polarities on absorption and fluorescence spectra and dipole moment of laser dye: 7-diethylamino-3-thenoylcoumarin (DETC) has been investigated. A small band shift is obtained in the absorption spectra compared to emission spectra. The spectral shifts were correlated with Catalans parameters using linear solvation energy relationship. It reveals that non-specific interaction measured by solvent polarity has more influence on absorption and solvent dipolarity contribution is significant in case of fluorescence. A bathochromic shift observed in absorption and emission spectra with increasing solvent polarity, which implied that the transition involved is π→π(∗). The solvatochromic correlations were used to estimate the excited state dipole moment using experimentally determined ground state dipole moment. The observed single-state excited state dipole moment is found to be greater than the ground state.

Steady‐State and Time‐Resolved Emission Studies of 6‐Methoxy Quinoline

Abstract Steady‐state absorption, fluorescence excitation, and emission spectra of 6‐methoxy quinoline (6‐MQ) were measured at room temperature in cyclohexane, dioxane, ethanol, acetonitrile, water, and water–dioxane solvents. Absorption spectra of cyclohexane, n‐hexane, and isopentane solutions show resolved vibronic structure at room temperature. However, the excitation spectrum of cyclohexane solution is structureless and is found to be emission wavelength dependent, indicating the formation of at least two distinct species in the ground state. Similar behavior was observed in dioxane and water–dioxane solutions. For all other solutions, the fluorescence excitation spectrum of 6‐MQ was found to be the same for different emissions. Emission of 6‐MQ in all solvents consisted of two bands with their maxima around 355 nm (I) and 430 nm (II), the actual positions and the relative intensities being dependent on the solvent used. The bands I and II were respectively attributed to normal and protonated/H‐bonded species of either 1La or 1Lb states or mixed (1La/1Lb) state of ππ* character. Fluorescence decay of this dye in all solvents monitored over each emission maximum showed biexponential behavior, and the analysis yielded two different lifetime components for each emission band. The short and long fluorescence decay components were respectively in the range of 0.30–3.00 ns and 18–20 ns. The observed emission characteristics coupled with the nature of the fluorescence polarization spectra and two different decay components for each emission suggest the existence of two different conformers having two different excited electronic states.

Fluorescence Quenching of UVITEX‐OB by Aniline in Alcohols and Alkanes

Abstract Fluorescence quenching of UVITEX‐OB [2,5‐thiophenediylbis(5‐tert‐butyl‐1,3‐benzoxazole)] by aniline in different polar and nonpolar solvents was examined at room temperature by steady‐state fluorescence measurements. Positive deviations from the nonlinear Stern–Volmer plots were observed in most of the solvents indicating the extent of quenching to be large. The quencher concentration dependence data were analyzed using ground‐state complex and sphere of action static quenching models in order to interpret the results. The magnitudes of the quenching rate parameters suggest that a sphere of action static quenching model is expected to describe the data most accurately. Also, the results are suggestive of both static and dynamic quenching processes being responsible for the observed positive deviation in the Stern–Volmer plot. Experimental results are described by an equation derived using the finite sink approximation model, which allows the evaluation of diffusion‐limited interaction and the estimation of encounter distance and mutual diffusion coefficient independently.

Rotational Diffusion of Coumarins in Alcohols: A Dielectric Friction Study

The rotational dynamics of three structurally similar polar molecules viz., coumarin 440, coumarin 151 and coumarin 450 has been studied in alcohols at room temperature using steady-state fluorescence depolarization method and time correlated single photon counting technique. The observed reorientation times of all the three probes are found to be longer than those predicted by Stokes–Einstein–Debye (SED) hydrodynamic theory with stick boundary condition and a deviation towards super-stick behavior is noted. Dielectric friction theories of Nee–Zwanzig and van der Zwan–Hynes, which treat the solute as a point dipole, overestimate the dielectric friction contribution exhibited by all the three coumarins in alcohols. Results are discussed in the light of theoretical models and the possibility of hydrogen bonding between the amino group of the probe molecules and the hydroxyl group of the alcohols.

Rotational Diffusion of Coumarins: A Dielectric Friction Study

The rotational diffusion of three probes: coumarin 522B (C522B), coumarin 307 (C307) and coumarin 138 (C138) with nearly identical size was studied at room temperature employing steady-state and time-resolved fluorescence anisotropy techniques in series of alcohols and alkanes. Experimental observations indicate faster rotation of C138 compared to the other two dyes in alcohols and a faster rotation of C522B than C307 in alkanes. The dielectric friction theories of Nee-Zwanzig (NZ) and van der Zwan-Hynes (ZH) were employed to estimate the friction experienced by the probes in alcohols, in addition to the mechanical friction calculated using Stokes-Einstein-Debye (SED) hydrodynamic with slip boundary condition and Dote-Kivelson-Schwartz (DKS) quasihydrodynamic theories. The observed reorientation times for the three probes do not follow the trend predicted by dielectric friction theories of NZ and ZH. The dipole moments determined from solvatochromic techniques were found to be different for the three probes.

Rotational Diffusion of Coumarins in Aqueous DMSO

The rotational dynamics of four structurally similar polar molecules viz., coumarin 440, coumarin 450, coumarin 466 and coumarin 151 has been studied in binary mixtures comprising of dimethyl sulphoxide and water at room temperature using the steady state fluorescence depolarization method and time correlated single photon counting technique. The binary mixtures are characterized by the fact that at a particular composition the viscosity (η) of the solution reaches a maximum value that is higher than the viscosities of either of the two co-solvents. The dielectric properties of the solution change across the composition range and the qualitative features of the solvent relaxation dynamics in complex systems are known to differ from those in simple solutions. A hook type profile of rotational reorientation time (τr) vs viscosity (η) is obtained for all the solutes in dipolar aprotic mixture of dimethyl sulphoxide-water, with the rotational reorientation times being longer in organic solvent-rich zone, compared to the corresponding isoviscous point in water-rich zone due to strong hydrogen bonding. Fluorescence lifetimes as well as rotational reorientation times are sensitive to the composition of the binary solvent system under study than to the viscosity suggesting the importance of local structure. The results are discussed in the light of hydrodynamic and dielectric friction models.

Energy-transfer dye lasers

A brief review of energy-transfer dye lasers is presented along with an experimental study of a Coumarin 102 (donor)+ fluorescein (acceptor) laser system and its fluorescence when pumped by N2 laser and Hg-lamp, respectively. The results indicate the dominance of resonance energy transfer at high concentrations for pulsed excitation.