Studies on the Synthesis and Characterization of Pd?TiO2?SiO2 Nanocomposite for Electroanalytical Applications

A nanocomposite of Pd? TiO₂? SiO₂ is developed through a sol‐gel process from the reaction products of titanium isopropoxide followed by mixing the same with palladium linked 3‐glycidoxypropyltrimethoxysilane. The reaction product is sonicated and calcinated to obtain the nanocomposite of Pd? TiO₂? SiO₂. The calcination at 600 °C yielded an amorphous structure whereas at 900 °C it resulted into a nanocrystalline structure. The nanocomposite of palladium was further characterized by TEM, XRD, IR and EDS. The material acts as an efficient electrocatalyst. Electrocatalysis of ascorbic acid is observed at 0.1 V vs. Ag/AgCl, shows linearity between 1 µM and 1 mM in 0.1 M phosphate buffer (pH 7.0).     

Synthesis and thermal behavior of a novel UV‐curable transparent flame retardant film and phosphorus‐nitrogen synergism of flame retardancy

A novel phosphorus monomer (PDHA) has been synthesized through phenyl dichlorophosphate (PDPC) reacting with 2‐hydroxyethyl acrylate (HEA). The structure of PDHA was characterized by Fourier transform infrared spectroscopy (FTIR) and ¹H nuclear magnetic resonance spectroscopy (¹H NMR). A series of UV curable resins were manufactured by blending PDHA with triglycidyl isocyanurate acrylate (TGICA) at different weight ratios. The fire performance was examined by micro‐scale combustion calorimeter (MCC) and limiting oxygen index (LOI). The results obtained from MCC indicated that the addition of PDHA to TGICA reduced the HRR and HRC. In addition, the LOI values varied from 28 to 34. The char residues of the composites were observed by scanning electron microscopy (SEM). Their thermal degradation behavior was investigated by thermogravimetric analysis and real time FTIR analysis (RT‐FTIR). The test results indicated that when the weight ratio of PDHA/TGICA = 1:1, the onset temperature of the composite was highest and the most char residue at 700°C was observed. RT‐FTIR showed that the phosphate group of PDHA first degraded to form poly(phosphoric acid)s at around 300°C, which had the major contribution to form the compact char to protect the sample from further degradation. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of poly(3-thiophene acetic acid)/Fe3O4 nanocomposite

Poly(3-thiophene acetic acid)/Fe₃O₄ nanocomposite is synthesized by the precipitation of Fe₃O₄ in the presence of poly(3-thiophene acetic acid) (P3TAA). Structural, surface, morphological, thermal properties and conductivity characterization/evaluation of the nanocomposite were performed by XRD, FT-IR, TEM, TGA, and conductivity measurements, respectively. The capping of P3TAA around Fe₃O₄ nanoparticles was confirmed by FT-IR spectroscopy, the interaction being via bridging oxygens of the carboxylate and the nanoparticle surface through bidentate binding. The crystallite and particle size were obtained as 9 ± 2 nm and 11 ± 1 nm from XRD line profile fitting and TEM image analysis, respectively, which reveal nearly single crystalline nature of Fe₃O₄ nanoparticles. Magnetization measurements reveal that P3TAA coated magnetite particles do not saturate at higher fields. There is no coercivity and remanence revealing superparamagnetic character. Magnetic particle size calculated from the theoretical fitting as 9.1 nm which coincides the values determined from TEM micrographs and XRD line profile fitting. The comparison to the TEM particle size reveals slightly modified magnetically dead nanoparticle surface.     

Synthesis and characterization of poly(3-thiophenyl acetic acid) (P3TAA)-BaFe12O19 nanocomposite

We have presented a method for the fabrication of poly(3-thiophenyl acetic acid) (P3TAA)-BaFe₁₂O₁₉ nanocomposites by the in situ polymerization of P3TAA in the presence of synthesized BaFe₁₂O₁₉ nanoparticles. The nanoparticles and the nanocomposite were analyzed by XRD, FTIR, TGA, TEM, VSM and conductivity techniques for structural and physicochemical characteristics. Crystallographic analysis revealed the phase as hexaferrite and X-ray line profile fitting yielded a crystallite size of 32 nm. The particles, observed by TEM, exhibit irregular shapes and sizes between 100 and 500 nm, revealing polycrystalline character when compared with the crystallite size from XRD. FTIR and TGA analysis results show that P3TAA is conjugated to the particle surface via a carboxylate group and that the composite has a polymer content of ∼10%. Magnetic hysteresis curves do not saturate at high fields, which is a characteristic feature of fine particle systems with grain sizes smaller than 1 μm. Conductivity measurements showed a semiconductor character of the nanocomposite.     

Hydrothermal Synthesis and Crystal Structure of a Novel Hexanuclear Copper（Ⅱ） Complex：[Cu_6（DPPZ）_4（btc）_4（H_2O）_8]·5H_2O

A new hexanuclear copper(Ⅱ) complex,[Cu 6 (DPPZ) 4 (btc) 4 (H 2 O) 8 ]·5H 2 O (1,DPPZ=dipyrido[3,2-a:2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid),has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489(4),b=14.234(5),c=14.484(5),α=82.848(4),β=79.399(4),γ=73.646(4)°,V=2421.2(13) 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F(000)=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I > 2σ(Ⅰ).In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.     

Synthesis, spectroscopic characterization, DFT studies and biological assays of a novel gold(I) complex with 2-mercaptothiazoline

A new gold(I) complex with 2-mercaptothiazoline (MTZ) with the coordination formula [AuCN(C₃H₅NS₂)] was synthesized and characterized by chemical and spectroscopic measurements, DFT studies and biological assays. Infrared (IR) and ¹H, ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopic measurements indicate coordination of the ligand to gold(I) through the nitrogen atom. Studies based on DFT confirmed nitrogen coordination to gold(I) as a minimum of the potential energy surface with calculations of the hessians showing no imaginary frequencies. Thermal decomposition starts at temperatures near 160 °C, leading to the formation of Au⁰ as the final residue at 1000 °C. The gold(I) complex with 2-mercaptothiazoline (Au-MTZ) is soluble in dimethyl sulfoxide (DMSO), and is insoluble in water, methanol, ethanol, acetonitrile and hexane. The antibacterial activities of the Au-MTZ complex were evaluated by an antibiogram assay using the disc diffusion method. The compound showed an effective antibacterial activity against Staphylococcus aureus (Gram-positive) and Escherichia coli and Pseudomonas aeruginosa (Gram-negative) bacterial cells. Biological analysis for evaluation of the cytotoxic effect of the Au-MTZ complex was performed using HeLa cells derived from human cervical adenocarcinoma. The complex presented a potent cytotoxic activity, inducing 85% of cell death at a concentration of 2.0 μmol L⁻¹.     

Structural studies of Cu(II) binding to the novel peptidyl derivative of quinoxaline: N-(3-(2,3-di(pyridin-2-yl)quinoxalin-6-yl)alanyl)glycine

The coordination properties of the novel conjugate towards copper ions were investigated. The performed studies exhibited the unusual binding properties of the ligand molecule having two potential strong coordination sites, namely dipeptidic chain and pyridyl nitrogens. On the basis of potentiometric and spectroscopic studies the binding at the low pH values to the aromatic entity is suggested, while the rise of pH (including physiological one) yielded the dimeric head-to-tail complex formation. This stable species possesses three nitrogen donors involved in Cu(II) chelation: N(pirydyl), NH₂ and N⁻(amide).     

Factors affecting the reactivity and selectivity in the oxidation of sulfides with tetra-n-butylammonium peroxomonosulfate catalyzed by Mn(III) porphyrins: Significant nitrogen donor effects

The oxidation of aryl sulfides by tetra-n-butylammonium peroxomonosulfate (n-Bu₄NHSO₅) was carried out in the presence of six different manganese (III) tetraarylporphyrins [Mn(Por)s] as biomimetic catalysts and a number of nitrogen donors as co-catalysts. There is no noticeable difference between the reactivity of sulfides, in the presence of electron-rich Mn(por)s, whereas, for electron-deficient catalysts, conversion rates are different. Nevertheless, the over-oxidation of sulfoxide is more sensitive to both the nature of substituents attached to the sulfur atom in substrates as well as porphyrin complex structure. The degree of catalytic activity of Mn(Por)s for the formation of sulfone product increases as the following order: Mn(TPFPP)OAc < Mn[T(4-NO₂P)P]OAc < Mn(TDCPP)OAc < Mn(TPP)OAc < Mn(TMP)OAc < Mn[T(4-OMeP)P]OAc. Our results show that in the presence of electron-rich Mn(Por)s, the strong π-donor N-H imidazoles possess co-catalytic activity greater than that of strong σ-donor amines and weak π-donor pyridines. When electron-deficient Mn(Por)s were employed as catalyst, pyridines demonstrated a higher co-catalytic activity than that of N-H imidazoles. The pronounced effect of protic solvents on the rate and selectivity of oxidation reactions, particularly in the presence of electron-deficient Mn(Por)s has been observed. The outcome of our investigations accompanied by UV-Vis and Raman spectral data confirms the involvement of different active oxidant such as a high valent Mn-oxo species as well as a six-coordinate [(L)(Por)Mn-OHSO₄] complex.     

Phase equilibria of (water-carboxylic acid-diethyl maleate) ternary liquid systems at 298.15 K

Liquid-liquid equilibrium (LLE) data for the ternary systems of (water-formic acid-diethyl maleate), (water-acetic acid-diethyl maleate), (water-propionic acid-diethyl maleate), (water-butyric acid-diethyl maleate), and (water-valeric acid-diethyl maleate) were investigated at 298.15 K and atmospheric pressure. Complete phase diagrams were obtained by determining solubility and the tie-line data. The tie-line data were compared with the results predicted by the UNIFAC and the modified UNIFAC (Dortmund) methods and correlated by means of UNIQUAC model. The reliability of the experimental tie-line data was confirmed by using the Othmer-Tobias correlation. Distribution coefficients and selectivity were evaluated for the immiscibility region.     

正电子发射显像剂O-(2-[18F]氟乙基)-L-酪氨酸的新型前体的合成

设计合成了5种新型正电子发射断层显像剂[O-(2-[¹⁸F]氟乙基)-L-酪氨酸的前体化合物：N-叔丁氧羰基-O-(2-甲磺酰/对硝基苯磺酰)-氧乙基-L-酪氨酸甲酯(9a,11a)和N-叔丁氧羰基-O-(2-甲磺酰/对甲苯磺酰/对硝基苯磺酰)-氧乙基-L-酪氨酸叔丁酯(9b,10b,11b)。 这些化合物以L-酪氨酸为原料,先与甲醇发生酯化反应或与乙酸叔丁酯进行酯交换,再用叔丁氧羰基保护氨基,最后以碳酸钾为碱、18-冠-6为相转移催化剂与乙二醇的磺酸酯在丙酮溶液中加热回流形成目标化合物,总收率为30%～67%。