Tarasankar Das

Protein-templated gold nanoclusters: size dependent inversion of fluorescence emission in the presence of molecular oxygen

Gold nanoclusters are promising candidates as biological markers without having toxic effects like fluorescent quantum dots. Herein, bovine serum albumin (BSA) protein stabilized gold nanoclusters of two different sizes emitting at 410 and 645 nm have been synthesized. These nanoclusters have been shown to interact with molecular oxygen differentially. Spectroscopic and chemical evidences show that dioxygen molecule gets adsorbed at two different orientations on the nanoclusters. The orientation motifs have been hypothesized to be superoxo and peroxo types on the smaller and the larger gold nanoclusters, respectively. Due to the difference in attachments, the oxygen molecule shows opposite changes in fluorescence intensity for the nanoclusters. The fluorescence intensity of the blue emitting nanocluster shows a profuse enhancement whereas the red emitting species shows quenching of emission. Superoxo type adsorption of the oxygen molecule on the blue emitting gold nanoclusters induce formation of singlet oxygen that in turn enhances the fluorescence intensity of the species. This could be verified by oxidation of diaminobenzidine (DAB) by singlet oxygen. Enhancement in fluorescence intensity of the blue emitting gold nanoclusters with an increase in concentration of molecular oxygen may enable them to be good candidates in bioimaging and detection.

Orientation of a TICT probe trapped in the peripheral confined water created by ionic surfactant envelope around silver nanoparticles.

Ionic surfactants are known to aggregate around the surface of a nanoparticle as a single layer in premicellar and a double layer in micellar concentrations. This motif of arrangement indicates the development of a layer of confined water of lower polarity than bulk water around the surface of the nanoparticle. We have demonstrated the behavior of a twisted intramolecular charge transfer (TICT) probe, trans-2-[4-(dimethylamino)styryl]benzothiazole (DMASBT), in the confined aqueous layer developed at the surface of spherical silver nanoparticles (Ag NPs) at and above the critical micellar concentrations (CMC) of a cationic and an anionic surfactant, namely, cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS). It is observed that the presence of charged surfactant head groups affects DMASBT differentially in the ground and the excited states. In presence of CTAB, DMASBT turns over in the excited state and interacts with the Ag NP surface, whereas in SDS the probe remains in its original orientation during the interaction. Steady-state and time-resolved fluorescence spectral studies provide enough evidence for orientation of the TICT probe in the peripheral water of Ag NP created by the surfactants. The results were confirmed by steady-state anisotropy measurements. The data show the difference between the properties of the confined peripheral water and the bulk aqueous environment. The TICT probe, DMASBT, is proved to be an excellent marker for the phenomenon.

Förster resonance energy transfer between pyrene and bovine serum albumin: Effect of the hydrophobic pockets of cyclodextrins

The phenomenon of Förster resonance energy transfer (FRET) between pyrene and bovine serum albumin (BSA) protein in presence of cyclodextrins (CDs) is explored in the present work. CDs provide hydrophobic environment and thus the aromatic molecules get encapsulated in them depending on the relative size and space. In this work we revealed that along with pyrene monomer, the side chains of amino acids in BSA can get trapped partly in the hydrophobic cavities of CDs if space permits. While being encapsulated by β-CD as pyrene monomer, it can interact with the BSA tryptophan moiety exposed toward the aqueous environment to form a dimer through π-π interaction. This, in turn, affects the energy transfer process by reducing the efficiency. On the other hand, pyrene excimer gets encapsulated in a γ-CD molecule due to availability of enough space. The excimer shows a new band at a higher wavelength. This further reduces FRET efficiency due to scarcity of acceptor for the tryptophan moieties in BSA.

Interaction of a new surface sensitive probe compound with anionic surfactants of varying hydrophobic chain length.

The amide derivative of a bis-phenylethynyl compound meta linked to 2,6-pyridine (BPEAP) poses inherent equilibrium between its neutral and zwitterionic forms in the excited state. BPEAP has been found to bind to the surface of anionic micelles instead of penetrating inside. This phenomenon has been exploited to attempt controlling the process of equilibrium using sodium dodecyl sulfate (SDS) at its pre-micellar and near-micellar aggregation concentrations. The anionic surfactant has been found to alter the equilibrium between the said forms of BPEAP depending on its concentration in solution. The process has been further verified by using sodium decyl sulfate (SDeS), which has smaller hydrophobic chain length than SDS as also varies in the critical micellar concentration (CMC) and aggregation number. The binding constant of the probe to the surfactant aggregates varies depending on the extent of surface available to the fluorophore for attachment.