Gold nanoparticles: acceptors for efficient energy transfer from the photoexcited fluorophores

The citrate reduction method of synthesis of gold nanoparticles (AuNP) is standardized with the assistance of instruments like spectrophotometer and TEM. A correlation has been developed between the particle diameter and the fractional concentration of the reductant. This enables one to assess the diameter of the AuNP to be synthesized, in advance, from the composition of the reaction mixture and the diameter of the synthesized particles can be confirmed simply from spectrophotometry. Further, it has been demonstrated that the synthesized AuNPs serve as excellent acceptors for a super-efficient energy transfer (ET) from the donor coumarin 153, leading to a quenching of fluorescence of the latter. The Stern-Volmer constants determined from the fluorescence lifetimes are in the range 107 - 109 mol-1·dm3 and are orders of magnitude higher than the normal photochemical quenching processes. The energy transfer efficiency increases radically with an increase in the size of the metal nanoparticle. The highly efficient energy transfer and the variation of the efficiency of the ET process with a variation of the particle size is ascribed to a large enhancement in the extinction coefficient and an increase in the spectral overlap between the plasmon absorption band of AuNPs and the fluorescence spectrum of C153 with an increase in the size of the nanoparticles. The impact of the work remains in providing a demonstration of a super quenching effect of the AuNPs and projects that they can be exploited for developing biosensors with high degree of sensitivity, if tagged to the biomacromolecules

Photophysics of 2-(2' -hydroxyphenyl) benzoxazole in the presence of α-cyclodextrin: Deactivation of ESIPT through back protonation

55-58The complex photophysics of 2-(2'-hydroxyphenyl)- benzoxazole (HBO) in the presence of α-cyclodextrin (αCD) has been investigated using steady state as well as time-resolved spectroscopy. The 480 nm emission of HBO in aqueous medium has been found to be suppressed meaningfully in the presence of cyclodextrin. Steady state study as well as decay analyses suggest that the tautomer undergoes back protonation reaction in the excited state through the participation of αCD

Interaction of cyclodextrins with human and bovine serum albumins: a combined spectroscopic and computational investigation

Interaction of cyclodextrins (CDs) with the two most abundant proteins, namely human serum albumin (HSA) and bovine serum albumin (BSA), has been investigated using steady-state and time-resolved fluorometric techniques, circular dichroism measurements and molecular docking simulation. The study reveals that the three CDs interact differently on the fluorescence and fluorescence lifetimes of the serum albumins. However, fluorescence anisotropy and circular dichroism are not affected. Depending on their size, different CDs bind to the serum albumins in different positions, resulting in changes in the spectral behaviour of the proteins. Docking study suggests the probable binding sites of the three CDs with the proteins. Combined experimental and computational studies imply that sufficiently high concentration of CDs causes loosening of the rigid structures of these transport proteins, although their secondary structures remain intact. Thus, CDs are found to be safe for the serum proteins from the structural point of view

Excited state deprotonation reactions of aromatic amines: a diffusion-controlled process

The excited state proton transfer reactions of carbazole (CAZL), indole (IND) and diphenylamine (DPA) were studied using a picosecond time-resolved technique. The forward rate constant for deprotonation shows a slight temperature dependence. The activation energy for the process was determined by taking various bases in both aqueous and non-aqueous media. It is of the order of the diffusional barrier in the solution phase. Hence it is concluded that the process is diffusion controlled. The values of the diffusion-controlled rate constants are discussed

Fluorescence resonance energy transfer from tryptophan in human serum albumin to a bioactive indoloquinolizine system

The interaction between a bioactive molecule, 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine (AODIQ), with human serum albumin (HSA) has been studied using steady-state absorption and fluorescence techniques. A 1:1 complex formation has been established and the binding constant (K) and free energy change for the process have been reported. The AODIQ-HSA complex results in fluorescence resonance energy transfer (FRET) from the tryptophan moiety of HSA to the probe. The critical energy-transfer distance (R0) for FRET and the Stern-Volmer constant (Ksv) for the fluorescence quenching of the donor in the presence of the acceptor have been determined. Importantly, KSV has been shown to be equal to the binding constant itself, implying that the fluorescence quenching arises only from the FRET process. The study suggests that the donor and the acceptor are bound to the same protein at different locations but within the quenching distance

Photophysics of 3-hydroxyflavone in supercritical CO2: a probe to study the microenvironment of SCF

The excitation of 3-hydroxyflavone (3HF) to its second excited singlet state (S2) gives rise to dual fluorescence in supercritical carbon dioxide. The ultraviolet fluorescence originated from the S2 state of 3HF is well separated from the green emission emanating from the tautomeric form, produced via the excited state intramolecular proton transfer. The relative intensity of the S2 to the tautomer fluorescence (S2/T) has been studied as a function of pressure and temperature. It is shown that this ratio reflects the microheterogeneity of the supercritical CO2, and confirms the value of fluorometric probes in disclosing the microscopic properties of supercritical fluids.http://www.sciencedirect.com/science/article/B6TFN-4BVP7G9-3/1/02dd61c567fe3e9c8d6ac86a01f79ce

Excited State Proton Transfer of Carbazole. A Convenient Way to Study Microheterogeneous Environments

Abstract: Excited state proton transfer of carbazole gives rise to dual fluorescence from the two prototropic species. Simultaneous consideration of the two emissions takes care of many of the instrumental artifacts. The relative intensity of the two emissions of carbazole is sensitive not only to the pH of the bulk medium but also the microenvironment around the probe. Hence, excited state proton transfer of carbazole has been well studied and exploited extensively to study the detail of microheterogeneous liquid environments like aqueous micelles, cyclodextrins etc. Effect of additive like urea has also been monitored via this photoreaction

Effect of cyclodextrin complexation on excited state proton transfer reactions

Steady state and time-resolved fluorometric investigations of the excited state proton transfer reactions of carbazole and 2-naphthylamine in the presence of β-cyclodextrin are reported in this paper. The results, together with earlier reports, reveal that the prototropic reaction depends not only on the microenvironment of the molecule, which is imposed by cyclodextrin, but also on the nature of the molecule itself. Thus, in comparison with the bare chromophore, the deprotonation rate of the cyclodextrin inclusion complex is enhanced when the guest molecule is carbazole, whereas it is decreased for guests like naphthylamine or naphthols