A series of heteroleptic tridentate ruthenium(II) complexes of composition [(H(2)pbbzim)Ru(tpy-X)](PF(6))(2) (1-7), where H(2)pbbzim = 2,6-bis(benzimidazole-2-yl)pyridine and tpy-X = 4'-substituted terpyridine ligands with X = H, p-methyl phenyl (PhCH(3)), p-bromomethylphenyl (PhCH(2)Br), p-dibromomethylphenyl (PhCHBr(2)), p-cyanomethylphenyl (PhCH(2)CN), p-triphenylphosphonium methylphenyl bromide (PhCH(2)PPh(3)Br), and 4'-phenylformyl (PhCHO) groups, has been synthesized and characterized by using standard analytical and spectroscopic techniques. These compounds were designed to increase the excited-state lifetime of ruthenium(II) bisterpyridine-type complexes. The X-ray crystal structure of a representative compound 2, which crystallized with monoclinic space group P2(1)/c, has been determined. The absorption spectra, redox behavior, and luminescence properties of the ruthenium(II) complexes have been thoroughly investigated. All of the complexes display moderately strong luminescence at room temperature with lifetimes in the range of 10-58 ns. Correlations have been obtained for the Hammett sigma(p) parameter with their MLCT emission energies, lifetimes, redox potentials, proton NMR chemical shifts, etc. The anion binding properties of all the complexes as well as the parent ligand H(2)pbbzim have been studied in acetonitrile using absorption, emission, and (1)H NMR spectral studies, and it has been observed that the metalloreceptors act as sensors for F(-), AcO(-), and to some extent H(2)PO(4)(-). At a relatively lower concentration of anions, a 1:1 H-bonded adduct is formed; however, in the presence of an excess of anions, stepwise deprotonation of the two benzimidazole N-H fragments occurs, an event which is signaled by the development of vivid colors visible with the naked eye. The receptor-anion binding constants have been evaluated. Cyclic voltammetric (CV) measurements carried out in acetonitrile-dimethylformamide (9:1) provided evidence in favor of anion (F(-), AcO(-)) concentration dependent electrochemical responses, enabling 1 - 7 to act as suitable electrochemical sensors for F(-) and AcO(-) ions.

A series of hetero- and homoleptic tridentate ruthenium(II) and osmium(II) complexes of compositions [(tpy-PhCH(3))Ru(tpy-HImzphen)](ClO(4))(2) (1), [(H(2)pbbzim)Ru(tpy-HImzphen)](ClO(4))(2) (2), and [M(tpy-HImzphen)(2)](ClO(4))(2) [M = Ru(II) (3) and Os(II) (4)], where tpy-PhCH(3) = 4'-(4-methylphenyl)-2,2':6',2"-terpyridine, H(2)pbbzim = 2,6-bis(benzimidazole-2-yl)pyridine and tpy-HImzphen = 2-(4-[2,2':6',2"]terpyridine-4'-yl-phenyl)-1H-phenanthro[9,10-d]imidazole, have been synthesized and characterized by using standard analytical and spectroscopic techniques. X-ray crystal structures of three complexes 2, 3, and 4 have been determined. The absorption spectra, redox behavior, and luminescence properties of the complexes have been thoroughly investigated. All of the complexes display moderately strong luminescence at room temperature with lifetimes in the range of 10-55 ns. The effect of solvents on the absorption and emission spectral behavior of the complexes has also been studied in detail. The anion sensing properties of all the complexes have been studied in solution using absorption, emission, and (1)H NMR spectral studies and by cyclic voltammetric (CV) measurements. It has been observed that the complexes 1, 3, and 4 act as sensors for F(-)only, whereas 2 acts as sensor for F(-), AcO(-), and to some extent for H(2)PO(4)(-). It is evident that in the presence of excess of anions deprotonation of the imidazole N-H fragment(s) occurs in all cases, an event which is signaled by the development of vivid colors visible with the naked eye. The receptor-anion binding/equilibrium constants have been evaluated.

The primary and secondary relaxation timescales of aging colloidal suspensions of Laponite are estimated from intensity autocorrelation functions obtained in dynamic light scattering (DLS) experiments. The dynamical slowing down of these relaxation processes are compared with observations in fragile supercooled liquids by establishing a one-to-one mapping between the waiting time since filtration of a Laponite suspension and the inverse of the temperature of a supercooled liquid that is rapidly quenched towards its glass transition temperature. New timescales associated with primary and secondary relaxation processes, such as the characteristic timescale associated with the slowdown of the secondary relaxation process and the glass transition time, are extracted to describe the phenomenon of dynamical arrest in Laponite suspensions. In results that are strongly reminiscent of those extracted from supercooled liquids approaching their glass transitions, it is demonstrated that a strong coupling exists between the primary and secondary relaxation processes of aging Laponite suspensions in the cage-forming regime. Furthermore, the experimental data presented here clearly demonstrate the self-similar nature of the aging dynamics of Laponite suspensions within a range of sample concentrations.

Mixed-ligand monometallic ruthenium(II) and osmium(II) complexes of composition [(bipy)(2)M(H(2)Imdc)](ClO(4)), where H(3)Imdc = imidazole-4,5-dicarboxylic acid and bipy = 2,2'-bipyridine, have been synthesized and characterized using standard analytical and spectroscopic techniques. The X-ray crystal structures of the ruthenium(II) complexes, [(bipy)(2)Ru(H(2)Imdc)](ClO(4)) (1) and its corresponding N-H deprotonated form [(bipy)(2)Ru(HImdc)] (3) have been determined. Compound 1 crystallizes in monoclinic form with space group P2(1)/c while 3 is obtained in triclinic form with the space group P1. The anion binding properties of the complexes 1 and 2 have been thoroughly investigated in acetonitrile solution using absorption, emission, and (1)H NMR spectral measurements. Both of the metalloreceptors act as sensors for F(-), AcO(-) and H(2)PO(4)(-) anions. Although at relatively lower concentration of anions, the 1 : 1 H-bonded adduct is formed, in the presence of excess of anions, deprotonation of the imidazole N-H fragment occurs and is accompanied by distinct change of colour. Cyclic voltammetry (CV) measurements carried out in acetonitrile have provided evidence in favour of anion-dependent electrochemical responses of 1 and 2 with F(-) and AcO(-) ions.

The interparticle interactions in colloidal suspensions of charged disks of Laponite clay in water were investigated using dynamic light scattering (DLS) and Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. We studied the effects of clay concentration (C(L)), the concentration of externally added salt (C(S)), and temperature (T) on the microscopic dynamics of the clay suspensions. The fast (τ1) and mean slow relaxation times (⟨τ(ww)⟩) of Laponite suspensions were extracted from intensity autocorrelation functions measured at different waiting times (t(w)) after sample preparation. Comprehensive Laponite concentration-salt concentration-temperature-time superpositions of both the microscopic diffusive time scales and the stretching exponent corresponding to the slow relaxation process highlight the self-similar nature of the energy landscapes of the Laponite suspensions. The evolution of the sodium ion concentration in the aging suspension with tw, measured for several values of CL, CS, and T, was used in a DLVO analysis of the free energy of the suspension for two charged disks parallely approaching one another. This analysis confirms that, in addition to repulsive interparticle interactions, attractive interactions also play a pivotal role in the microscopic dynamics of spontaneously evolving Laponite suspensions.

Mixed-ligand monometallic and bimetallic ruthenium(II) complexes of compositions [(bpy)(2)Ru(H(3)Imbzim)](ClO(4))(2) x 2 H(2)O (1) and [(bpy)(2)Ru(H(2)Imbzim)Ru(bpy)(2)](ClO(4))(3) x CH(2)Cl(2) (2), where H(3)Imbzim = 4,5-bis(benzimidazol-2-yl)imidazole and bpy = 2,2'-bipyridine, have been synthesized and characterized using standard analytical and spectroscopic techniques. The X-ray crystal structures of both compounds have been determined and showed that 1 crystallized in the triclinic form with space group P1 and 2 is in the monoclinic form with space group P2(1)/m. The anion binding properties of complexes 1 and 2, as well as those of the parent H(3)Imbzim, were thoroughly investigated in an acetonitrile solution using absorption, emission, and (1)H NMR spectral studies, which revealed that both of the metalloreceptors act as sensors for F(-), for AcO(-), and, to some extent, for H(2)PO(4)(-). At a relatively lower concentration of anions, a 1:1 hydrogen-bonded adduct was formed; however, in the presence of an excess of anions, stepwise deprotonation of the two benzimidazole NH fragments occurred, an event that was signaled by the development of vivid colors visible with the naked eye. Double deprotonation was also observed in the presence of hydroxide. Less basic anions (AcO(-) and H(2)PO(4)(-)) induce deprotonation of only one NH. The effect of solvents on the absorption and emission spectral behavior has also been studied in detail. The binding affinities of different anions toward the receptors were evaluated and showed that the binding constants of 1 and 2 are substantially enhanced relative to free H(3)Imbzim because upon coordination to the Ru(II) center(s), H(3)Imbzim/H(2)Imbzim(-) becomes electron-deficient, thereby rendering the imidazole NH protons more available for hydrogen bonding to the anions. Cyclic voltammetry studies carried out in acetonitrile provided evidence of an anion-dependent electrochemical response with F(-) and AcO(-). Anion-induced lifetime shortening makes complex 2 a suitable lifetime-based sensor for anions.

The interaction of protein and surfactant yields protein–surfactant complexes which have a wide range of applications in the cosmetics, foods, and pharmaceutical industries among others. Ionic and nonionic surfactants are known to interact differently with the protein. The interplay of electrostatic and hydrophobic interactions governs the resultant structure of protein–surfactant complexes. The present study enlightens the paramount role of the hydrophobic interaction, tuned by the hydrophobic tail length of ionic surfactants, in the unfolding of anionic bovine serum albumin (BSA) protein. The unfolding of BSA in the presence of four different tail-length cationic surfactants, that is, C10TAB, C12TAB, C14TAB, and C16TAB, has been investigated by small-angle neutron scattering and dynamic light scattering. All cationic surfactants unfold the protein at a certain concentration range. The propensity of protein unfolding increases with increasing the hydrophobic tail length. The denatured structure of BSA upon addition of cationic surfactants is characterized by the random flight model representing a beads-on-a-string chain-like complex. The unfolded protein binds the surfactant micelles in the protein–surfactant cluster. The micelles get elongated with the increasing concentration of cationic surfactants, whereas the number of micelles per cluster is decreased. In the final stage, the protein–surfactant cluster merges to one large micelle with unfolded protein wrapping the micelle surface. The pathway of protein unfolding is described in terms of the changes in the micellar size, the number of micelles formed per cluster, the separation between the micelles in the cluster, the aggregation number of micelles, and the number of proteins per cluster. The protein–surfactant interaction is further examined in the presence of a nonionic surfactant, that is, C12E10. The nonionic surfactant significantly suppresses the interaction of BSA protein with ionic surfactants by forming mixed micelles. As a result of the mixed micelles formation by ionic–nonionic surfactants, the ionic surfactant moves out from the unfolded BSA protein, and this enables the protein to refold back to its native structure. The propensity of mixed micelle-driven refolding of proteins is significantly changed with changing the tail length of the ionic surfactant.

Synthesis, structural characterization and anion-, cationand solvent-induced tuning of photophysical properties of a bimetallic Ru(II) complex: combined experimental and DFT/TDDFT investigation3