Enhanced Photocatalytic Efficiency of a Least Active Ag-TiO2 by Amine Adsorption.

An Ag-TiO2 photocatalyst with 3.5 atom % silver content, synthesized by a single step sol-gel method, possessed silver nanoparticles (AgNPs; 1-5 nm) on the TiO2 surface, but owing to the nonplasmonic nature of AgNPs and the wide band gap of TiO2, this material exhibited poor activity in a photocatalytic degradation reaction. However, this least active Ag-TiO2 catalyst showed a sudden increase in activity during a photocatalytic amine self-coupling reaction showing the highest activity, which was interpreted as amine (reactant) adsorption-driven activity enhancement. We found that amine adsorption occurred over AgNPs converting into plasmonic AgNPs as well as on the TiO2 surface reducing the band gap and therefore facilitated the visible light excitation and the electron-transfer process efficiently, resulting into overall enhancement in the photocatalytic activity. Thus, a very efficient, stable, and visible light active photocatalyst (amine-adsorbed Ag-TiO2) was developed by simply adsorbing an amine in the least active Ag-TiO2 photocatalyst.

Correlation of Dynamic Surface Tension with Sedimentation of PTFE Particles and Water Penetration in Powders.

The dynamic surface tension of aqueous poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) [(PEO-PPO-PEO)]-type polymeric surfactant (P103, P105, F108, P123, and F127) solutions were correlated with water penetration in packed Teflon powders, the sedimentation of Teflon suspensions in these solutions, foamability, and contact angle measurements on a Teflon surface. The DST trend with bubble lifetime indicated that the overall slowdown in the diffusion process in aqueous solutions is a function of a higher poly(ethylene oxide) (PEO) molecular weight for a given series of block copolymers containing equal PPO molecular weights, favoring slower diffusion kinetics to the air-water interface caused by preferential partitioning in bulk water. The wettability of poly(tetrafluoroethylene) (PTFE) powder illustrates better water penetration for polymers with low molecular weight and lower HLB values. The wettability of F127 solutions decreases with corresponding increases in concentration resulting from higher viscosity, which restrains the diffusion kinetics at the PTFE-water interface. The foamability decreases drastically with higher PEO molecular weight as attributed by slower diffusion kinetics, leading to a decrease in the effective concentration of molecules at the foam interface. The contact angle on glass and the PTFE surface are in good agreement with assumptions made by other analytical techniques showing a lower value of the contact angle with a lower HLB of the Pluronic, which relates to the higher adsorption of molecules at the interface. It is concluded that the adsorption of molecules at the PTFE-water interface decreases in aqueous Pluronic solutions with corresponding increases in the hydrophilic lipophilic balance (HLB), which is consistent with foaming, water penetration in a packed powder of PTFE, the rate of sedimentation, and DST data. A PTFE dispersion containing P123 showed the maximum wettability and lowest sedimentation among the series of block copolymers introduced, which is attributed to faster diffusion kinetics and a higher PPO contribution fostering faster adsorption at the PTFE surface. The dynamic surface tension of aqueous Pluronic solutions seems to correlate well with the adsorption characteristics at the air-water and PTFE-water interfaces.

Synthesis of silver nanoparticles in aqueous aminopolycarboxylic acid solutions via γ-irradiation and hydrogen reduction.

Formation of silver nanoparticles in the presence of various aminipolycarboxylic acids (APCAs) such as iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), and N,N,N',N″,N‴,N‴-triethylenetetraminehexaacetic acid (TTHA) was studied. Monodispersed silver nanoparticles capped by carboxylate groups of APCAs were prepared by the reduction of Ag(+) ions induced by either γ-radiolytic or H2 reduction at room temperature. APCAs act as stabilizer to avoid the aggregation of silver nanoparticles. It has been shown that H2-induced reduction of Ag(+) is possible at room temperature in the presence of APCAs. TTHA stabilized γ-reduced particles showed reactivity towards oxygen. The formed particles were characterized by UV-vis absorption, X-ray diffraction, zetasizer and transmission electron microscopy.

Formation of gold nanoparticles via a thiol functionalized polyoxometalate.

A useful method for the synthesis of Au nanoparticles is presented. The synthesis of Au nanoparticles with various morphologies was carried out at room temperature using gamma radiolysis and NaBH4 reduction of HAuCl4 in N,N'-dimethylformamide:water solutions containing polyoxometalate (POM). The results demonstrated that by controlling the rate of reduction and ratio of DMF and water, metal particle size and shape can be further tailored. It is shown that gold nanoparticles with controllable size can be synthesized. In principle, the general finding of this work can be extended to other transition/noble metal nanoparticles.

Change of boron substitution improves the lasing performance of Bodipy dyes: a mechanistic rationalisation.

Bodipy laser dyes are highly efficient but degrade rapidly in solution by reacting with in situ generated singlet oxygen ((1)O(2)). To increase the lasing lifetimes of these dyes, we have designed and synthesised two different congeners of the widely studied Pyrromethene 567 (PM567) by substitution at the boron centre and/or at both the boron centre and the meso position. The two new dyes showed high lasing efficiencies with increased photostability. The results of theoretical and pulse radiolysis studies revealed that the substitution at the boron centre reduced the (1)O(2) generation capacity of these dyes as well as their rate of reaction with (1)O(2), thereby enhancing their lifetimes even under lasing conditions.

Hydrogen bonding in neutral and cation dimers of H2Se with H2O, H2S, and H2Se.

Structures, hydrogen bonding, and binding energies of H(4)SeA (A = O, S, Se) dimers and their cation radicals have been studied using DFT-B3LYP, MP2, and CCSD methods with 6-31++G(d,p), cc-pVTZ, and aug-cc-pVTZ basis sets. The binding energy (BE) order of the most stable neutral and cationic dimers have been found to be (H(2)Se···HOH) > (H(2)Se···HSH) > (H(2)Se···HSeH), and (H(2)Se···SeH(2))(+) > (H(2)Se···SH(2))(+) > (HSe···HOH(2))(+), respectively, by B3LYP/6-31++G(d,p) and MP2/aug-cc-pVTZ methods. Higher electronegativity of the heteroatom has been found to result in more stability of the neutral dimer but less of the cationic dimer. Among neutral dimers, structure with more electronegative heteroatom acting as proton donor has been found to be more stable. However, the hemibonded structure has been found to be more stable for the dimer cation radical unless the ionization potentials of the involved heteroatoms are very different, e.g., H(4)SeO(+). Vibrational frequency calculation suggests that an increase in electronegativity of A-atom results in a decrease in Se-H bond strength in H(4)SeA and H(4)SeA(+) dimers. The calculated values of Mulliken atomic charge/spin and hydrogen bond lengths of the dimers and their radical cations have also been discussed.

DFT and surface-enhanced Raman scattering study of tryptophan-silver complex.

Surface-enhanced Raman scattering (SERS) study of tryptophan was carried out in silver hydrosol. The surface adsorption properties of tryptophan were investigated due to its biological importance. Tryptophan is an essential amino acid needed for the normal growth in infants and for nitrogen balance in adults. DFT calculations using B3LYP functional with LANL2DZ basis set was carried out to support the experimental Raman and SERS data. The strong enhancement of 1343 cm(-1) band, assigned to the CO(2) sym. stretching vibration in the SERS spectrum along with a red shift of 63 cm(-1), manifests that chemical mechanism contributes to the SERS activity. Moreover, the observed features in the SERS spectrum as well as theoretical calculations infer that tryptophan is chemisorbed to the silver surface directly through the oxygen and nitrogen atoms of the carboxylate and amino groups with an edge-on orientation with the indole ring lying nearly perpendicular to the silver surface. The SERS enhancement factors for various Raman vibrations of tryptophan were found to be of the order of 10(5)-10(6).

A simple approach for facile synthesis of Ag, anisotropic Au and bimetallic (Ag/Au) nanoparticles using cruciferous vegetable extracts.

We present a simple and straightforward approach for the synthesis and stabilization of relatively monodisperse Ag, Au and bimetallic (Ag/Au) nanoparticles by using cruciferous vegetable (green/red) extracts by simply adjusting the pH environment in the aqueous medium. The vegetable extracts act both as reducing and capping agents. The monometallic and bimetallic nanoparticles of Ag and Au so obtained were characterized by UV-visible spectroscopy, X-ray diffraction (XRD), dynamic light scattering (DLS) and transmission electron microscopy (TEM). It is shown that red cabbage extract can be used for the preparation of anisotropic Au nanoparticles. The formation of Au anisotropic nanoparticles was found to depend on a number of environmental factors, such as the pH of the reaction medium, reaction time, and initial reactant concentrations. Additionally, it is shown that these extract-stabilized Au and Ag nanoparticles can be used as a seed for preparation of bimetallic Au/Ag nanoparticles. For bimetallic alloy nanoparticles the absorption peak was observed between the two maxima of the corresponding metallic particles. The surface plasmon absorption maxima for bimetallic nanoparticles changed linearly with increasing Au mole ratio content in various alloy compositions. It has been shown that the formation of hollow Au spheres depends on the experimental conditions.

Effect of ionic size on the structure of cylindrical electric double layers: a systematic study by Monte Carlo simulations and density functional theory.

The effect of ionic size on the diffuse layer characteristics of a cylindrical electric double layer is studied using density functional theory and Monte Carlo simulations for the restricted primitive model and solvent primitive model. The double layer is comprised of an infinitely long, rigid, impenetrable charged cylinder also referred to as the polyion, located at the center of a cylindrical cell containing the electrolyte, which is composed of charged hard spheres and the solvent molecules as neutral hard spheres (in the case of the solvent primitive model). The diameters of all the hard spheres are taken to be the same. The theory is based on a partially perturbative scheme, where perturbation is used to approximate the ionic interactions and the hard sphere contribution is treated within the weighted density approach. The Monte Carlo simulations are performed in the canonical ensemble. The zeta potential profiles as a function of the polyion surface charge density are presented for cylindrical double layers at different ionic concentrations, ionic valences, and different hard sphere (ionic and the solvent) diameters of 2, 3, and 4 Å. The theory agrees quite well with the simulation results for a wide range of system parametric conditions and is capable of showing the maximum and minimum in the zeta potential value for systems having divalent counterions. The steric effects due to the presence of solvent molecules play a major role in characterizing the zeta potential and the ionic density profiles. A noticeable change in the concavity of the zeta potential plots with increasing particle size at very low concentrations of monovalent electrolytes is suggestive of the occurrence of infinite differential capacitance for such systems.

Generation of counter ion radical (Br2(•-)) and its reactions in water-in-oil (CTAB or CPB)/n-butanol/cyclohexane/water) microemulsion.

Herein we report the generation of counterion radicals and their reactions in quaternary water-in-oil microemulsion. Hydrated electrons in the microemulsion CTAB/H(2)O/n-butanol/cyclohexane have a remarkably short half-life (∼1 µs) and lower yield as compared to that in the pure water system. Electrons are solvated in two regions: one is the water core and other the interface; however, the electrons in the water core have a shorter half-life than those in the interface. The decay of the solvated electrons in the interface is found to be water content dependent and it has been interpreted in terms of increased interfacial fluidity with the increase in water content of the microemulsion. Interestingly another species, dibromide radical anion (Br(2)(•-)) in CTAB and CPB microemulsions have been observed after the electron beam irradiation. Assuming that the extinction coefficient of the radicals is the same as that in the aqueous solution, the yields of the radicals per 100 eV are 0.29 and 0.48 for the Br(2)(•-) radical in CTAB and CPB containing microemulsions (W(0) = 40), respectively, under N(2)O saturated conditions. Further, we intended to study electron transfer reactions, which occur at and through the interface. The reaction of the Br(2)(•-) radical anion with ABTS [2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)] has been studied to generate the ABTS radical in the water core, and further, its reaction has been investigated with the water-insoluble molecule vitamin E (tocopherol) and water-soluble vitamin C (ascorbic acid). In the present study, we were able to show that, even for molecules which are completely insoluble in water, ABTS scavenging assay is possible by pulse radiolysis technique. Furthermore, these results show that it is possible to follow the reaction of the hydrated inorganic radical with solutes dissolved in the organic phase in a microemulsion without use of a phase transfer catalyst.

Preparation, characterization, surface modification and redox reactions of silver nanoparticles in the presence of tryptophan.

The synthesis and characterization of water-soluble dispersions of Ag nanoparticles by the reduction of AgNO(3) using tryptophan under alkaline synthesis conditions are reported. The Ag nanoparticle formation was very slow at low concentration and rapid at extremes. For surface modification and redox reactions, manipulating the interparticles interaction controlled the size of Ag nanoparticles aggregates. Our results suggest that the replacement of the BH(4)(-) ions adsorbed on the nanoparticle surface by tryptophan destabilizes the particles and further caused aggregation. A mechanism is proposed for the formation of silver nanoparticles by tryptophan. The experimental results are supported by theoretical calculations. The Ag nanoparticles were characterized by UV-vis absorption, dynamic light scattering and transmission electron microscopy techniques.

Effect of plant-based phenol derivatives on the formation of Cu and Ag nanoparticles.

The complexes formed on the reaction of various metal ions viz., Cu(II) and Cu(I) with phenol derivatives viz. catechol, chlorogenic acid (CGA), hydroquinone and n-propyl gallate (nPG) were established by UV-visible spectroscopy. The metal/ligand complexing ratio and complexation constants have been determined. Further, we showed that nanoparticles of Cu can be prepared from metal-phenol complexes in the presence of a protein (gelatin) by γ-irradiation showing that the reduction is metal ion centered. Formation of Ag nanoparticles was also observed on photo-irradiation with xenon lamp in the presence of dihydroxy benzene. The Ag and Cu nanoparticles were characterized by transmission electron microscopy (TEM) and UV-visible absorption spectroscopy. TEM technique showed the presence of Cu and Ag nanoparticles with average size of 20 and 30 nm, respectively.

pH and temperature dependent relaxation dynamics of Hoechst-33258: a time resolved fluorescence study.

The photophysical behavior of Hoechst 33258 (H33258) in aqueous solution has been studied by steady-state and time-resolved fluorescence measurements. The intriguing intramolecular geometrical orientations of the dye bring out major modulation on its photophysical behavior, especially in the fluorescence emission characteristics with pH. It has been seen that a change in the solution pH from 7 to 4.5 enhances the emission yield by ~20 fold and this change is ~80-fold on changing the pH from 1.5 to 4.5. While a fast flipping motion among the two benzimidazole rings is considered to be one of the most probable mechanisms for the fast fluorescence decay, a more planar structure of the dicationic form at pH 4.5 having a double bond character between the two benzimidazolium groups is suggested to be the most likely fluorescent species. A similar planar structure is in fact considered to be the fluorescent emitting species of H33258 on minor groove binding to DNA. On the basis of temperature dependent fluorescence decay dynamics explored for the dye in solutions at pH 7 and 4.5, it is understood that a nearly isoenergetic double-well excited state potential is possibly involved in the excited state relaxation dynamics of the dye at pH 7. On increasing the temperature, the conversion to the planar structure is facilitated from the non-planar LE state, enhancing the emission probability of the dye.

Identifying the bond responsible for the fluorescence modulation in an amyloid fibril sensor.

An ultrafast intramolecular bond twisting process is known to be the responsible mechanism for the sensing activity of the extensively used amyloid fibril sensor thioflavin T (ThT). However, it is not yet known which one of the two possible single bonds in ThT is actually involved in the twisting process. To resolve this fundamental issue, two derivatives of ThT have been designed and synthesized and subsequently their photophysical properties have been studied in different solvents. It is understood from the present study that the rotation around the central C-C single bond, and not that around the C-N single bond, is primarily responsible for the sensor activity of ThT. Detailed viscosity-dependent fluorescence studies revealed that the ThT derivative with restricted C-N bond rotation acts as a better sensor than the derivative with free C-N bond rotation. The better sensory activity is directly correlated with a shorter excited-state lifetime. Results obtained from the photophysical studies of the ThT derivatives have also been supported by the results obtained from quantum chemical calculations.

Fluorescence dynamics of double- and single-stranded DNA bound to histone and micellar surfaces.

The study of structure and dynamics of bound DNA has special implications in the context of its biological as well as material functions. It is of fundamental importance to understand how a binding surface affects different positions of DNA with respect to its open ends. Because double-stranded (ds) and single-stranded (ss) DNA are the predominant functional forms, we studied the site-specific dynamics of these DNA forms, bound to the oppositely charged surface of histones, and compared the effects with that of DNA bound to cetyltrimethyl ammonium bromide micelles. We utilized a time-resolved fluorescence technique using fluorescent base analogue 2-aminopurine located at specific positions of synthetic poly-A DNA strands to obtain fluorescence lifetime and anisotropy information. It is observed that the binding leads to overall rigidification of the DNA backbone, and the highly flexible ends show drastic dampening of their internal dynamics as well as the fraying motions. In the case of ds-DNA, we find that the binding not only decreases the flexibility but also leads to significant weakening of base-stacking interactions. An important revelation that strong binding between DNA and the binding agents (histones as well as micelles) does not dampen the internal dynamics of the bases completely suggests that the DNA in its bound form stays in some semiactive state, retaining its full biological activity. Considering that the two binding agents (histones and micelles) are chemically very different, an interesting comparison is made between DNA-histones and DNA-micelle interactions.

Three component model of cylindrical electric double layers containing mixed electrolytes: A systematic study by Monte Carlo simulations and density functional theory.

The structure of electric double layer around a hard rigid impenetrable cylindrical polyion is studied using density functional theory as well as Monte Carlo simulations. The three component model, presented here, is an extension of solvent primitive model where the solvent molecules are treated as the neutral hard spheres, counterions and coions as the charged hard spheres, all of equal diameters, and in addition the mixture of mono- and multivalent counterions are also considered. The theory is partially perturbative where the hard sphere interactions are treated within the weighted density approach and the corresponding ionic interactions have been evaluated through second-order functional Taylor expansion with respect to the bulk electrolyte. The theoretical predictions in terms of the density profiles and the mean electrostatic potential profiles are found to be in good agreement with the simulation results. The presence of neutral hard spheres incorporate the effects of exclude volume interactions (ionic size correlations) while the mixture of mono- and multivalent counterions enhance the ionic charge correlation effects. Thus, this model study shows clear manipulations of ionic size and charge correlations in dictating the ionic density profiles as well as mean electrostatic potential profiles of the diffuse layer. The behavior of diffused double layer has been characterized at varying ionic concentrations, at different concentration ratios of mono- and multivalent counterions of mixed electrolytes, at different diameters of hard spheres, and at varying polyion surface charge density.

Global minimum-energy structure and spectroscopic properties of I2(*-) x n H2O clusters: a Monte Carlo simulated annealing study.

The vibrational (IR and Raman) and photoelectron spectral properties of hydrated iodine-dimer radical-anion clusters, I(2)(*-) x n H(2)O (n=1-10), are presented. Several initial guess structures are considered for each size of cluster to locate the global minimum-energy structure by applying a Monte Carlo simulated annealing procedure including spin-orbit interaction. In the Raman spectrum, hydration reduces the intensity of the I-I stretching band but enhances the intensity of the O-H stretching band of water. Raman spectra of more highly hydrated clusters appear to be simpler than the corresponding IR spectra. Vibrational bands due to simultaneous stretching vibrations of O-H bonds in a cyclic water network are observed for I(2)(*-) x n H(2)O clusters with n > or = 3. The vertical detachment energy (VDE) profile shows stepwise saturation that indicates closing of the geometrical shell in the hydrated clusters on addition of every four water molecules. The calculated VDE of finite-size small hydrated clusters is extrapolated to evaluate the bulk VDE value of I(2)(*-) in aqueous solution as 7.6 eV at the CCSD(T) level of theory. Structure and spectroscopic properties of these hydrated clusters are compared with those of hydrated clusters of Cl(2)(*-) and Br(2)(*-).

Fluorescence behavior of cysteine-mediated Ag@CdS nanocolloids.

Ag@CdS quantum dots were synthesized by a colloidal method. CdS nanoparticles stabilized by L-cysteine were doped with varying silver concentrations. Ag@CdS nanoparticles were characterized by UV-visible spectroscopy, steady-state and time-resolved fluorescence, X-ray diffraction, Fourier transform infrared resonance (FTIR), and transmission electron microscopy. The effect of dopant concentration and effect of aging of Ag@CdS colloids were studied. At low silver content, emission was found to enhance, while at high silver content, emission quenching was observed after aging. Ag-CdS nanocolloids exhibited multiexponential decay with tau2 being a long-lived component. X-ray diffraction spectra of as prepared samples indicated that silver occupies an interstitial position, while for annealed samples, Ag+ ions get oxidized to Ag2+ and substituted for Cd2+ in the CdS lattice. FTIR studies have shown that cysteine acts as a monodentate ligand for cadmium and silver for as-prepared sample, whereas it acts as a tridentate ligand for annealed samples toward silver. Transmission electron microscopy of as-prepared samples showed spherical-shaped composites with a uniform layer of capping molecules.

Structural phase behavior and vibrational spectroscopic studies of biofunctionalized CdS nanoparticles.

Biomodified CdS nanoparticles were synthesized using l-cysteine as a capping agent in the colloidal state as a function of pH. The role of pH on the size and structure of CdS nanoparticles was investigated in detail. At pH 7.4 and 9.1, X-ray diffraction spectra of as prepared samples showed the presence of a mixture of cubic and hexagonal phases while cubic phase was formed at pH 11.2. A gradual transition to the hexagonal phase was observed for refluxed samples at pH 9.1 and 11.2. Whereas, at pH 7.4, the sample remains in a mixture of cubic and hexagonal phase even after refluxing. The particle size of as prepared samples was about 2 nm, and for refluxed samples the size increased up to 10 nm. The binding of cadmium through thiol group is evidenced by infrared spectra. An intense band due to C-C-N vibration was observed after 24 h of reflux. The formation of a specific molecular cluster determines the growth of a particular phase. Transmission electron microscopy (TEM) studies support the X-ray diffraction (XRD) studies and exhibit well separated spherical particles while refluxed samples show clustering.

Host-guest interaction of 1,4-dihydroxy-9,10-anthraquinone (quinizarin) with cyclodextrins.

The interaction of 1,4-dihydroxy-9,10-anthraquinone, (quinizarin; QZ), with alpha-, beta- and gamma-cyclodextrin (CD) hosts, has been investigated using absorption, and steady-state and time-resolved fluorescence measurements, in order to understand the effects of cavity size of CDs on the binding of QZ molecule and the changes in the photophysical properties of QZ in the microenvironment of the hosts. The results demonstrate that QZ forms inclusion complexes with all the CDs. The low binding constants as well as the thermodynamic parameters indicate that the mode of interaction between QZ and CDs is mainly hydrophobic in nature. The relative magnitudes of the binding constants and the differential enhancements in the fluorescence intensity of QZ upon complexation with the CDs can be explained by considering the relative dimensions of the host cavity and the guest molecule, as well as the orientation of the guest molecule inside the CD cavity. It is proposed that the unsubstituted benzene ring of QZ is encapsulated within alpha- and beta-CD cavities whereas the dihydroxy-substituted aromatic ring is encapsulated within the gamma-CD cavity. This is further supported by the complexation studies of the QZ.CD systems with Al(III) ions. It is observed that the complexation of QZ with the metal ion is enhanced in the QZ.alpha-CD and QZ.beta-CD systems whereas it is significantly reduced in the QZ.gamma-CD system, due to shielding of the chelating groups of the dye inside the CD cavity in the latter case.