R. Renganathan

Spectroscopic studies on the interaction of colloidal capped CdS nanoparticles with bovine serum albumin

Colloidal uncapped and starch capped CdS (SCdS) nanoparticles were prepared and interaction with bovine serum albumin (BSA) have been studied by UV-visible, FT-IR, steady state, time resolved and synchronous fluorescence spectroscopic measurements. BSA molecules adsorbed on the surface of colloidal CdS through the capping agent. The apparent association constant (K(app)=2.54x10(2) M(-1)) and degree of association has been calculated (alpha=1.12) from absorption studies. The binding constant from fluorescence quenching method (6.6x10(2) M(-1)) matches well with that determined from the absorption spectral changes. Static quenching mechanism and conformational changes on BSA molecules were confirmed by time resolved and synchronous fluorescence measurements respectively. The effect of starch capped CdS on the conformation of BSA has been analyzed by means of UV-visible absorption and synchronous fluorescence spectra.

Effect of anchoring group on the photosensitization of colloidal TiO2 nanoparticles with porphyrins

The interaction of porphyrins (TCPP, TSPP, TMeOPP and TPP) with colloidal TiO(2) nanoparticles was studied by infra-red, UV-visible absorption, steady state and time resolved fluorescence spectroscopy. The porphyrins (TCPP, TSPP and TMeOPP) adsorbed on the surface of colloidal TiO(2) nanoparticles through electrostatic interaction. According to absorption and fluorescence changes the apparent association constants (K(app)) were calculated. However, TPP did not interact with surface of colloidal TiO(2) nanoparticles due to the absence of anchoring group. The fluorescence quenching is attributable mainly to electron transfer from the excited state porphyrins to the conduction band of colloidal TiO(2). The rate of electron transfer process (k(et)) was calculated using lifetime measurement. The electron transfer mechanism has been proved by the calculation of free energy change (DeltaG(et)) by applying Rehm-Weller equation. Using all the spectroscopic measurements we confirmed that the presence of anchoring group plays major role in the adsorption as well as the electron transfer processes.

Interaction of anthraquinone dyes with lysozyme: Evidences from spectroscopic and docking studies

The interaction between lysozyme and anthraquinone dyes such as Alizarin Red S, Acid blue 129 and Uniblue was studied using steady state, time resolved fluorescence measurements and docking studies. Addition of anthraquinone dyes effectively quenched the intrinsic fluorescence of lysozyme. Fluorescence quenching of lysozyme by dyes has revealed the formation of complex. The number of binding sites (n) and binding constant (K) for all the three dyes was calculated by relevant fluorescence quenching data. Based on Försters non-radiative energy transfer theory, distance (r(0)) between the donor (lysozyme) and acceptor (dyes) as well as the critical energy transfer distance (R(0)) has also been calculated. The interaction between dyes and lysozyme occurs through static quenching mechanism as confirmed by time resolved spectroscopy. The conformational change of lysozyme has been analyzed using synchronous fluorescence measurement. Finally, docking studies revealed that specific interactions were observed with the residue of Trp 62.

The interaction of sonochemically synthesized gold nanoparticles with serum albumins

Spherical gold nanoparticles of approximately 16nm were synthesized using a sonochemical reduction method and characterized using UV-vis spectroscopy, atomic force microscopy (AFM) and transmission electron microscopy (TEM). The binding of these gold nanoparticles with bovine serum albumin (BSA) and human serum albumin (HSA) was investigated using UV-vis absorption and fluorescence spectroscopic techniques. A strong quenching of the fluorescence from serum albumins was observed due to the formation of a ground state complex with gold nanoparticles (static quenching). The fluorescence quenching constants, number of binding sites and binding constants were determined using Stern-Volmer and Benesi-Hildebrand plots. Using Forster Resonance Energy Transfer (FRET) theory, the distance between the donor (serum albumins) and acceptor (gold nanoparticles) was obtained, which showed that HSA has more affinity towards sonochemically synthesized gold nanoparticles compared to gold nanoparticles synthesized using other methods.

Investigations on the photoinduced interaction of water soluble thioglycolic acid (TGA) capped CdTe quantum dots with certain porphyrins.

The photoinduced interaction of TGA capped CdTe quantum dots (QDs) with porphyrins such as meso-tetrakis(4-sulfonatophenyl)porphyrin [TSPP], meso-tetrakis(4-carboxyphenyl)porphyrin [TCPP], meso-tetrakis (4-N-methylpyridyl)porphyrin [TMPyP] and meso-tetraphenylporphyrin [TPP] has been studied by using absorption, steady state and time resolved fluorescence spectroscopy. The QD surface was negatively charged due to thiol capping agent containing carboxylic group. Positively charged TMPyP interacts with QDs through charge transfer mechanism, negatively charged porphyrins (TCPP and TSPP) interacted through energy transfer mechanism and the neutral one (TPP) does not have any interaction. The Stern-Volmer constant, quenching rate constant, association constants, rate of electron transfer and energy transfer parameters were calculated from the fluorescence data. Effect of molecular structure has also been studied.

Photosensitization of colloidal TiO2 nanoparticles with phycocyanin pigment.

Bluish phycocyanin is a water soluble pigment having strong visible light absorption at 615 nm. The dynamics of photoinduced electron injection from phycocyanin to colloidal TiO(2) nanoparticles has been studied by absorption, FT-IR, steady state and time-resolved fluorescence spectroscopic methods. The phycocyanin adsorbed on the surface of colloidal TiO(2) nanoparticles, the apparent association constant (K(app)) for the association between colloidal TiO(2) nanoparticles and phycocyanin was measured from both absorption changes (K(app)=4.01x10(2) M(-1)) and fluorescence quenching data (K(app)=5.20x10(2) M(-1)). The value of K(app) obtained from the data of fluorescence quenching matches with that determined from the absorption spectral changes. The good agreement between these values of K(app) highlighted the validity of assumption proposed for the association between phycocyanin and colloidal TiO(2) nanoparticles. The free energy change (DeltaG(et)) for electron injection has been calculated by applying Rehm-Weller equation. Electron injection from excited state phycocyanin into the conduction band of TiO(2) is suggested.

Synthesis, structure, DNA/protein binding and in vitro cytotoxicity of new ruthenium metallates

The reaction of [RuHCl(CO)(PPh3)3] with an equimolar amount of salicylaldehyde-4(N)-methylthiosemicarbazone [H2-(Sal-mtsc)] resulted in two entities, namely [Ru(H-Sal-mtsc)Cl(CO) (PPh3)2] (1) and [Ru(Sal-mtsc)(CO)(PPh3)2] (2) from a single tub. The new complexes were characterized by various spectro (IR, absorption and NMR), analytical and single crystal X-ray diffraction studies. From the crystallographic studies, it is confirmed that in complex 1, the ligand coordinated through the thiolate sulfur and the deprotonated hydrazinic nitrogen N(2), resulting in the formation of an unusual strained four membered chelate ring. The third potential donor, phenolic oxygen, remained uncoordinated. In complex 2, the ligand coordinated as an ONS chelate with the formation of more common five and six membered chelate rings. Complexes 1 and 2 have been tested for their DNA/protein binding properties by taking CT-DNA/lysozyme as models. From the protein binding studies, the alterations in the secondary structure of lysozyme by the ruthenium(II) complexes (1 and 2) were confirmed with synchronous and three-dimensional fluorescence spectroscopic studies. The in vitro cytotoxicity of the newly-synthesized complexes was carried out in two different human tumour cell lines, A549 and HepG2. The cytotoxicity studies showed that complex 2 exhibited higher activity than 1.

An investigation on electron transfer quenching of zinc(II) meso-tetraphenylporphyrin (ZnTPP) by colloidal TiO2

The interaction of zinc(II) meso-tetraphenylporphyrin (ZnTPP) with colloidal TiO(2) was studied by absorption, steady state and time-resolved fluorescence spectroscopy. The quenching was found to obey the Stern-Volmer equation and the corresponding Stern-Volmer plots were linear in the range of quencher concentration used 0-5 x 10(-4)M. The bimolecular quenching rate constants (k(q)) were 20.5 x 10(10)M(-1)s(-1) (steady-state) and 2.85 x 10(10)M(-1)s(-1) (time resolved). The quenching process is suggested to involve electron transfer from the ZnTPP to TiO(2) considering the experimental evidences obtained.

Highly Emissive Luminogens Based on Imidazo[1,2‐a]pyridine for Electroluminescent Applications

A search for novel organic luminogens led us to design and synthesize some N-fused imidazole derivatives based on imidazo[1,2-a]pyridine as the core and arylamine and imidazole as the peripheral groups. The fluorophores were synthesized through a multicomponent cascade reaction (A(3) coupling) of a heterocyclic azine with an aldehyde and alkyne, followed by Suzuki coupling and a multicomponent cyclization reaction. All of the compounds exhibited interesting photophysical responses, especially arylamine-containing derivatives, which displayed strong positive solvatochromism in the emission spectra that indicated a more polar excited state owing to an efficient charge migration from the donor arylamine to the imidazo[1,2-a]pyridine acceptor. The quantum yields ranged from 0.2 to 0.7 and depended on the substitution pattern, most notably that based on the donor group at the C2 position. Moreover, the influence of general and specific solvent effects on the photophysical properties of the fluorophores was discussed with four-parameter Catalán and Kamlet-Taft solvent scales. The excellent thermal, electrochemical, and morphological stability of the compounds was explored by cyclic voltammetry, thermogravimetric analysis, and AFM methods. Furthermore, to understand the structure, bonding, and band gap of the molecules, DFT calculations were performed. The performance of the electroluminescence behavior of the imidazo[1,2-a]pyridine derivative was investigated by fabricating a multilayer organic light-emitting diode with a configuration of ITO/NPB (60 nm)/EML (40 nm)/BCP (15 nm)/Alq3 (20 nm)/LiF (0.5 nm)/Al(100 nm) (ITO=indium tin oxide, EML=emissive layer, BCP=2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, Alq3 =tris(8-hydroxyquinolinato)aluminum), which exhibited white emission with a turn-on voltage of 8 V and a brightness of 22 cd m(-2).

Photoinduced electron transfer from phycoerythrin to colloidal metal semiconductor nanoparticles

Phycoerythrin is a water soluble pigment which absorbs in the visible region at 563 nm. The interaction of phycoerythrin with colloidal metal semiconductors was studied by absorption, FT-IR and fluorescence spectroscopy. Phycoerythrin adsorbed strongly on the surface of TiO(2) nanoparticles, the apparent association constant for the association between colloidal metal-TiO(2) nanoparticles and phycoerythrin was determined from fluorescence quenching data. The free energy change (DeltaG(et)) for electron transfer process has been calculated by applying Rehm-Weller equation.