Xianyong Yu

Spectroscopic studies on the interactions between a bioactive diperoxovanadate complex and pyridine.

Interactions between a bioactive diperoxovanadate complex K3[OV(O2)2(C2O4)].H2O and pyridine in solution were studied by 2D NMR diffusion ordered spectroscopy (DOSY) as well as 1D 1H, 13C, 14N, and 51V NMR, variable temperature 1H NMR and spin-lattice relaxation time. Competitive coordination between C2O(4)(2-) and pyridine to [OV(O2)(2)](-) were observed in solution. A new species [OV(O2)2(Py)](-) was formed and its NMR data were reported for the first time. The experimental results indicated that both of the vanadium atom in species [OV(O2)2(C2O4)](3-) and [OV(O2)2(Py)](-) are six coordinated in solution. The conclusion was further supported by the results of ESI-MS. The newly-formed species is stable under the condition of near physiological pH value.

The investigation of the interaction between Tropicamide and bovine serum albumin by spectroscopic methods

The fluorescence and ultraviolet-visible (UV-Vis) spectroscopy were explored to study the interaction between Tropicamide (TA) and bovine serum albumin (BSA) at three different temperatures (292, 301 and 310K) under imitated physiological conditions. The experimental results showed that the fluorescence quenching mechanism between TA and BSA was static quenching procedure. The binding constant (Ka), binding sites (n) were obtained. The corresponding thermodynamic parameters (ΔH, ΔS and ΔG) of the interaction system were calculated at different temperatures. The results revealed that the binding process is spontaneous, hydrogen binds and vander Waals were the main force to stabilize the complex. According to Förster non-radiation energy transfer theory, the binding distance between TA and BSA was calculated to be 4.90 nm. Synchronous fluorescence spectroscopy indicated the conformation of BSA changed in the presence of TA. Furthermore, the effect of some common metal ions (Mg(2+), Ca(2+), Cu(2+), and Ni(2+)) on the binding constants between TA and BSA were examined.

Preparation and optical properties of worm-like gold nanorods

A type of worm-like nanorods was successfully synthesized through conventional gold nanorods reacting with Na2S2O3 or Na2S. The generated worm-like gold nanorods comprise shrunk nanorod cores and enwrapped shells. Therefore, a gold-gold sulfide core-shell structure is formed in the process, distinguishing from their original counterparts. The formation of the gold chalcogenide layers was confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy. Experimental results showed that the thickness of the gold chalcogenide layers is controllable. Since the increase of shell thickness and decrease of gold nanorod core take place simultaneously, it allows one to tune the plasmon resonance of nanorods. Proper adjustment of reaction time, temperature, additives and other experimental conditions will produce worm-like gold nanorods demonstrating desired longitudinal plasmon wavelength (LPW) with narrow size distributions, only limited by properties of starting original gold nanorods. The approach presented herein is capable of selectively changing LPW of the gold nanorods. Additionally, the formed worm-like nanorods possess higher sensitive property in localized surface plasmon resonance than the original nanorods. Their special properties were characterized by spectroscopic methods such as Vis-NIR, fluorescence and resonance light scattering. These features imply that the gold nanorods have potential applications in biomolecular recognition study and biosensor fabrications.

Investigation on the complex of diperoxovanadate with picolinamide

A novel diperoxovanadate complex NH(4)[OV(O(2))(2)(picolinamide)].H(2)O was synthesized from aqueous solution under physiological conditions. The solution structure of the complex was characterized by multinuclear ((1)H, (13)C, (14)N, and (51)V), variable temperature as well as two-dimensional (DOSY) NMR techniques in the interaction system of NH(4)VO(3)/H(2)O(2)/picolinamide at room temperature. The crystal structure of the complex was determined at 223K by single-crystal X-ray diffraction method. It belongs to the monoclinic space group P21/c with a=7.323(3)A, b=14.255(7)A, c=10.022(5)A, beta=99.524(9) degrees , V=1031.7(8)A(3), and Z=4. The crystal is composed of ammonium ions, picolinamide oxodiperoxovanadate(V) ions, and water molecules, which are held together by ionic and hydrogen bond forces. The species [OV(O(2))(2)(picolinamide)](-) is seven-coordinated with a distorted pentagonal bipyramidal geometry both in solution and in crystal.

NMR and theoretical study on interactions between diperoxovanadate complex and pyrazole-like ligands.

To understand the effects of pyrazole substitution on reaction equilibrium, the interactions between a series of pyrazole-like ligands and [OV(O(2))(2)(D(2)O)](-)/[OV(O(2))(2)(HOD)](-) were explored by using multinuclear ((1)H, (13)C, and (51)V) magnetic resonance, HSQC, and variable temperature NMR in 0.15 mol/L NaCl ionic medium mimicking physiological conditions. These results show that the relative reactivities among the pyrazole-like ligands are 3-methyl-1H-pyrazole approximately 4-methyl-1H-pyrazole approximately 1H-pyrazole>1-methyl-1H-pyrazole. As a result, the main factor which affects the reaction equilibrium is the steric effect instead of the electronic effect of the methyl group of these ligands. A pair of isomers has been formed resulting from the coordination of 3-methyl-1H-pyrazole and a vanadium complex, which is attributed to different types of coordination between the vanadium atom and the ligands. Thus, the competitive coordination leads to the formation of a series of six-coordinate peroxovanadate species [OV(O(2))(2)L](-) (L, pyrazole-like ligands). Moreover, the results of density functional calculations provided a reasonable explanation on the relative reactivity of the pyrazole-like ligands as well as the important role of solvation in these reactions.

NMR and theoretical study on interactions between diperoxovanadate complex and 4-substituted pyridines

To understand the substituting group effects of organic ligands on the reaction equilibrium, the interactions between diperoxovanadate complex [OV(O2)2(D2O)]-/[OV(O2)2(HOD)](-) and a series of 4-substituted pyridines in solution were explored using multinuclear (1H, 13C, and 51V) magnetic resonance, DOSY, and variable temperature NMR in 0.15 mol/L NaCl ionic medium for mimicking the physiological condition. Some direct NMR data are given for the first time. The reactivity among the 4-substituted pyridines is pyridine > isonicotinate > N-methyl isonicotinamide > methyl isonicotinate. The competitive coordination results in the formation of a series of new six-coordinated peroxovanadate species [OV(O2)2L](n-) (L = 4-substituted pyridines, n = 1 or 2). The results of density functional calculations provide a reasonable explanation on the relative reactivity of the 4-substituted pyridines. Solvation effects play an important role in these reactions.

Multinuclear NMR and theoretical investigation on interactions between diperoxovanadate complex and 4-picoline-like ligands

To understand the 4-substituting group effects of organic ligands in pyridine ring on the reaction equilibrium, the interactions between a series of 4-picoline-like ligands and [OV(O(2))(2)(D(2)O)](-)/[OV(O(2))(2)(HOD)](-) in solution were explored by the combined use of multinuclear ((1)H, (13)C, and (51)V) magnetic resonance, DOSY, and variable-temperature NMR in 0.15 mol/L NaCl ionic medium for mimicking the physiological condition. Some direct NMR data are given for the first time. The reactivity among the 4-picoline-like ligands is 4-picoline>isonicotinate>isonicotinamide>ethyl isonicotinate. The competitive coordination results in the formation of a series of new six-coordinated peroxovanadate species [OV(O(2))(2)L](n-) (L=4-picoline-like ligands, n=1 or 2). The results of density functional calculations provide a reasonable explanation on the relative reactivity of the 4-picoline-like ligands. Solvation effects play an important role in these reactions.