Yuanhua Ding

Binding Characteristics and Molecular Mechanism of Interaction between Ionic Liquid and DNA

The binding characteristics and molecular mechanism of the interaction between a typical ionic liquid (IL), 1-butyl-3-methylimidazolium chloride ([bmim]Cl), as a green solvent and DNA were investigated for the first time by conductivity measurements, fluorescence spectroscopy, dynamic light scattering (DLS), cryogenic transmission electron microscopy (cryo-TEM), circular dichroism spectroscopy, (31)P nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy, isothermal titration calorimetry (ITC), and quantum chemical calculations. It was found that the critical aggregation concentration of [bmim]Cl is decreased in the presence of DNA, and the addition of [bmim]Cl induced a continuous fluorescence quenching of the intercalated probe ethidium bromide (EtBr), indicating that the interaction between the ionic liquid and DNA is sufficiently strong to exclude EtBr from DNA. DLS results show that [bmim]Cl can induce a coil-to-globule transition of DNA at a low IL concentration, which was confirmed by the cryo-TEM images of DNA-IL complexes. With [bmim]Cl added, the resulting globular DNA structures and the extended DNA coils are first compacted, and then grow in size. During the binding process, DNA maintains the B-form, but the base packing and helical structure of DNA are altered to a certain extent. The (31)P NMR and IR spectra indicate that the cationic headgroups of bmim(+) groups interact with the phosphate groups of DNA through electrostatic attraction, and the hydrocarbon chains of bmim(+) groups interact with the bases through strong hydrophobic association. ITC results reveal the interaction enthalpy between [bmim]Cl and DNA and show that the hydrophobic interaction between the hydrocarbon chains of [bmim]Cl and the bases of DNA provides the dominant driving force in the binding. On the basis of quantum chemical calculations, it can be inferred that at a low IL concentration, the cationic headgroups of [bmim]Cl would be localized within several angstroms of the DNA phosphates, whereas the hydrophobic chains would be arranged parallel to the DNA surface. When the IL concentration is above 0.06 mol/L, the cationic headgroups are near DNA phosphates, and the hydrocarbon chains are perpendicularly attached to the DNA surface.

Comparative studies on adsorption behavior of thionine on gold nanoparticles with different sizes

The adsorption behavior of thionine on gold nanoparticles of two different mean diameters, 18 and 5 nm, was compared by using UV-vis spectroscopy, fluorescence spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), dynamic light scattering (DLS), and quantum chemical calculations. It is found that the addition of small particles makes the monomer peak of thionine finally disappear, and the corresponding dimer peak is significantly increased. Small gold nanoparticles make the equilibrium between the monomer and H-type dimer forms of thionine move largely toward the dimer forms. Due to the stronger binding between thionine and small gold nanoparticles, the fluorescence quenching of thionine by small particles is enhanced compared to large particles, and the quenching is both static and dynamic. TEM images indicate that the addition of thionine results in a heavy clustering for small particles, and the resulting thionine-gold nanoclusters of about 45 nm were obtained. Quantum chemical calculations, which were based on the density functional theory (DFT) at the B3LYP level, and infrared spectroscopic studies show that the nitrogen atoms of the NH(2) moieties of thionine bind to the gold nanoparticle surfaces. For 18 and 5 nm particles, the surface-to-volume atomic ratios are about 0.0597 and 0.2148, respectively. The higher surface-to-volume atomic ratio and the higher surface free energy result in stronger binding of thionine on small particle surfaces, which can be used to modulate the arrangement of dye molecules on particle surfaces, and thus control the properties of organic-inorganic nanocomposite materials.

Diffusion Coefficients and Structure Properties in the Pluronic F127/n‐C4H9OH/H2O System

Abstract Diffusion coefficients of different aggregates in aqueous solutions formed by an amphiphilic block copolymer, Pluronic F127 (F127), were determined by cyclic voltammetry, and the critical micelle concentration (CMC, 4.31 × 10−4 mol L−1) of F127 was obtained. The added n‐butanol facilitates the formation of micelles from the monomers of F127 and makes the critical micelle temperature (CMT) of F127 solutions decrease. The diffusion coefficient of the F127 micelles decreases relatively fast at first with increasing n‐butanol and then the decreasing trend slows after the solubilization of n‐butanol in micelles reaches maximum.

Facile fabrication of pomponlike microarchitectures of lanthanum molybdate via an ultrasound route.

Pomponlike La(2)(MoO(4))(3) microstructures assembled with single-crystalline nanoflakes have been facilely fabricated via a surfactant-assisted ultrasound route for the first time. Various synthesis conditions were examined, such as the surfactant concentration, the molecular structure of surfactants, and the pH value. The obtained pomponlike microstructures were characterized by X-ray diffraction (XRD), (field-emission) scanning electron microscopy [(FE)SEM], transmission electron microscopy (TEM), and nitrogen adsorption/desorption isotherms. It has been revealed that a minimum concentration of sodium dodecylsulfate (SDS) was required for the formation of pomponlike La(2)(MoO(4))(3) microstructures. When the SDS concentration is above 0.02 mol L(-1), the pomponlike microstructures become more perfect, and the size is also increased with the increasing SDS concentration. Under the same sonication, similar pomponlike microstructures were obtained when a cationic surfactant, cetyltrimethyl ammonium bromide (CTAB), was used instead of the anionic surfactant SDS, indicating that the hydrophobic alkyl chains are an important factor for the formation of the pomponlike La(2)(MoO(4))(3) microstructures. It is also found that the pomponlike La(2)(MoO(4))(3) microstructures can only be obtained within an optimal pH range of 8.0-9.0 under sonication. Based on TEM, Fourier transform infrared spectroscopy (FT-IR) and solubilization experiment, a formation mechanism of pomponlike La(2)(MoO(4))(3) microstructures was proposed, in which the collaborative action of surfactants and sonication plays a key role. Furthermore, the porosity of the pomponlike La(2)(MoO(4))(3) microstructures were discussed.