Underlying molecular interaction of bovine serum albumin and linezolid: a biophysical outlook.

Linezolid, one of the reserve antibiotic of oxazolidinone class has wide range of antimicrobial activity. Here we have conducted a fundamental study concerning the dynamics of its interaction with bovine serum albumin (BSA), and the post binding modification of the later by employing different spectroscopic (absorption, fluorescence and circular dichroism (CD) spectroscopy) and molecular docking tools. Gradual quenching of the tryptophan (Trp) fluorescence upon addition of linezolid to BSA confirms their interaction. Analysis of fluorescence quenching at different temperature indicates that the interaction is made by static complex formation and the BSA has one binding site for the drug. The negative Gibbs energy change (ΔG0), and positive values of enthalpy change (ΔH0) and entropy change (ΔS0) strongly suggest that it is an entropy driven spontaneous and endothermic reaction. The reaction involves hydrophobic pocket of the protein, which is further stabilized by hydrogen bonding and electrostatic interactions as evidenced from 8-anilino-1-napthalene sulfonic acid, sucrose and NaCl binding studies. These findings also support the molecular docking study using AutoDock 4.2. The influence of this interaction on the secondary structure of the protein is negligible as evidenced by CD spectroscopy. So, from these findings, we conclude that linezolid interacts with BSA in 1:1 ratio through hydrophobic, hydrogen bonding and ionic interactions, and this may not affect the secondary structure of the protein.

Does excited-state proton-transfer reaction contribute to the emission behaviour of 4-aminophthalimide in aqueous media?

4-Aminophthalimide (AP) is an extensively used molecule both for fundamental studies and applications primarily due to its highly solvent-sensitive fluorescence properties. The fluorescence spectrum of AP in aqueous media was recently shown to be dependent on the excitation wavelength. A time-dependent blue shift of its emission spectrum is also reported. On the basis of these findings, the excited-state solvent-mediated proton-transfer reaction of the molecule, which was proposed once but discarded at a later stage, is reintroduced. We report on the fluorescence behaviour of AP and its imide-H protected derivative, N-BuAP, to prove that a solvent-assisted excited-state keto-enol transformation does not contribute to the steady-state and time-resolved emission behaviour of AP in aqueous media. Our results also reveal that the fluorescence of AP in aqueous media arises from two distinct hydrogen-bonded species. The deuterium isotope effect on the fluorescence quantum yield and lifetime of AP, which was thought to be a reflection of the excited-state proton-transfer reaction in the system, is explained by considering the difference in the influence of H(2)O and D(2)O on the nonradiative rates and ground-state exchange of the proton with the solvent.

Dual fluorescence of ellipticine: excited state proton transfer from solvent versus solvent mediated intramolecular proton transfer.

Photophysical properties of a natural plant alkaloid, ellipticine (5,11-dimethyl-6H-pyrido[4,3-b]carbazole), which comprises both proton donating and accepting sites, have been studied in different solvents using steady state and time-resolved fluorescence techniques primarily to understand the origin of dual fluorescence that this molecule exhibits in some specific alcoholic solvents. Ground and excited state calculations based on density functional theory have also been carried out to help interpretation of the experimental data. It is shown that the long-wavelength emission of the molecule is dependent on the hydrogen bond donating ability of the solvent, and in methanol, this emission band arises solely from an excited state reaction. However, in ethylene glycol, both ground and excited state reactions contribute to the long wavelength emission. The time-resolved fluorescence data of the system in methanol and ethylene glycol indicates the presence of two different hydrogen bonded species of ellipticine of which only one participates in the excited state reaction. The rate constant of the excited state reaction in these solvents is estimated to be around 4.2-8.0 × 10(8) s(-1). It appears that the present results are better understood in terms of solvent-mediated excited state intramolecular proton transfer reaction from the pyrrole nitrogen to the pyridine nitrogen leading to the formation of the tautomeric form of the molecule rather than excited state proton transfer from the solvents leading to the formation of the protonated form of ellipticine.

Fluorescence response of 4-(N,N'-dimethylamino)benzonitrile in room temperature ionic liquids: observation of photobleaching under mild excitation condition and multiphoton confocal microscopic study of the fluorescence recovery dynamics.

The fluorescence behavior of 4-(N,N'-dimethylamino) benzonitrile has been studied in room temperature ionic liquids (ILs) as a function of temperature, excitation wavelength, and exposure time. Dual emission from the locally excited (LE) and intramolecular charge transfer (ICT) states of the molecule has been observed and the relative intensities of the two emission bands and the peak position of the ICT emission are found consistent with the viscosity and polarity of the ILs. Temperature dependence study reveals a blue shift of the ICT emission peak with lowering of temperature indicating that under this condition the emission occurs from incompletely solvated state of the molecule. The observed excitation wavelength dependence of the emission behavior has been attributed to the microheterogeneity of the media. Exposure of the solution to the exciting radiation under very mild condition is found to influence the relative intensities of the two emission bands; an enhancement of the LE emission accompanied by a slight decrease of the ICT emission is observed. The emission intensities, however, return almost to their original values when the exposed solution is kept in the dark. The observation has been attributed to photoreaction of the exposed molecules and the recovery to replenishment of phototransformed molecules by the surrounding unexposed molecules. Fluorescence recovery after photobleaching has been studied by multiphoton confocal fluorescence microscopic technique to obtain insight into the recovery dynamics. The diffusion coefficient estimated from this study is found to be lower than that predicted by the Stokes-Einstein equation by a factor of nearly 7 indicating the microheterogeneous nature of the ILs.